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Chinese Chemical Letters
Chinese Chemical Letters
主管 : 中国科学技术协会
刊期 : 月刊主编 : 钱旭红
语种 : 英文主办 : 中国化学会、中国医学科学院药物研究所
ISSN : 1001-8417 CN : 11-2710/O6本刊创办于1990年7月,是由中国化学会主办,中国医学科学院药物研究所承办的核心期刊。本刊由著名化学家梁晓天院士任主编,其内容涵盖化学研究的各个领域,及时报道我国化学界各个研究领域的最新进展及世界上一些化学研究的热点问题。本刊自1993年起为SCI、CA、日本科技文献速报等收录,2000年美国化学文摘引用中国期刊频次中位列第四。展开 > - 影响因子: 8.9
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Synthesis of a new ratiometric emission Ca2+ indicator for in vivo bioimaging
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Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
Oxidation-coupled clusters of [E9]4– are rarely synthesised, and the investigation of their reactivity is profoundly hindered by their high charge and limited yield. In this study, we successfully synthesized two Nb-containing clusters [(Ge9–Ge9)(NbCp2)2]4– (1a) and [(Ge9=Ge9=Ge9)NbCp2]5– (2a), by reacting [Ge9–Ge9]6– and [Ge9=Ge9=Ge9]6– with NbCp4. Theoretical calculations indicate that the formation of 1a and 2a from dimer and trimer is thermodynamically favorable. Furthermore, a Au-containing cluster incorporating the dimeric [Sn9–Sn9]6– cluster, [Au(Sn9–Sn9)]5– (3a), was successfully synthesized, despite the inability to independently synthesize [Sn9–Sn9]6–. A systematic bonding analysis was conducted on these newly synthesized clusters and their parent structures to investigate their bonding patterns.
The rise of antibiotic-resistant bacteria and the formation of biofilms are significant challenges in surgical practice, posing a serious threat to public health due to postoperative wound infections. A promising approach to tackle this issue is the combination of photothermal therapy (PTT) and chemodynamic therapy (CDT), which has shown remarkable effectiveness in treating both cancer and wound infections. In our study, we developed an innovative artificial nanoplatform called Ni-2@F127 by encapsulating Ni-2 in a biocompatible Pluronic. When exposed to 880 nm laser irradiation, Ni-2@F127 exhibited exceptional photothermal performance, achieving a photothermal conversion efficiency of 60.4%, along with significant photocatalytic capabilities. This platform activates a Fenton-like reaction that catalyzes hydrogen peroxide (H₂O₂), producing toxic hydroxyl radicals (•OH) effectively. The synergistic effects of hyperthermia and •OH not only destroy tumor cells but also demonstrate powerful antimicrobial activity, significantly inhibiting the growth of Escherichia coli and Staphylococcus aureus (S. aureus) in vitro under near-infrared (NIR) irradiation. Importantly, in animal models, Ni-2@F127 effectively eliminates S. aureus from deep tissues in cases of subcutaneous abscesses and knife injuries, significantly accelerating abscess resolution and promoting wound healing. The compelling evidence suggests that Ni-based metal complexes could serve as transformative antibacterial agents in phototherapy, unlocking vast potential for their application in wound healing and the treatment of bacterial infections.
Solid-state lithium (Li) metal batteries have attracted significant attention due to their high energy density and improved safety performance. However, sluggish Li-ion transport and rapid anion migration in solid-state electrolytes often result in heterogeneous Li-ion flux distribution and thus Li dendrite growth. Herein, we developed a highly conductive composite solid electrolyte with an elevated Li-ion transference number through incorporating Gd-doped CeO2 (GDC) nanofillers with abundant surface oxygen defects into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrices. The defect concentrations were effectively controlled by regulating the Gd doping ratio in CeO2. As a result, the highest oxygen concentration of 12.2% is achieved for the GDC with 10% Gd doping (GDC-10). The GDC-10 electrolyte demonstrated a high Li-ion transference number of 0.59 and an improved ionic conductivity of 0.40 mS/cm at room temperature, attributed to anion immobilization and enhanced Li-salt dissociation. This was due to the strong interactions between positively charged oxygen vacancies and anions, which effectively reduces surface concentration polarization and homogenizes Li-ion flux. Therefore, LiLi symmetric cells exhibited exceptional cycling stability of 1500 h without noticeable Li dendrite growth at 1 mA/cm2 and 1 mAh/cm2. Furthermore, LiLiFePO4 full cell also stably cycles for 500 cycles with a capacity retention of 90.44% at 1 C. This work provides new insights into the design of composite solid electrolytes through the defect regulation of fillers.
High-entropy alloys (HEAs) have emerged as promising electrocatalysts due to their unique compositional complexity and tunable electronic structures. However, achieving rapid and efficient synthesis of HEA nanoparticles (NPs) with high electrocatalytic activity and understanding their structural and electronic characteristics remains challenging. Here, we report the synthesis of FeCoNiCuCr HEA NPs via an ultrafast carbon thermal shock (CTS) method. Local structural investigations combining synchrotron pair distribution function (PDF) and X-ray absorption fine structure (XAFS) reveal that incorporating Cr introduces local tetragonal distortions, resulting in residual strain that enhances catalytic performance. This local distortion could be attributed to atomic-scale elemental segregation between Cr and Cu, further stabilizing the structure and improving activity. These synergistic effects, combined with uniform carbon-loaded NPs morphology achieved by the CTS process, enable superior OER performance. This study highlights the role of structural and electronic modulation in HEA catalysts, offering valuable insights for the design of next-generation electrocatalysts.
Zero-dimensional (0D) hybrid copper halides have attracted significant attention owing to their unique photophysical properties and remarkable structural diversity. In this work, two 0D self-assemblies compounds of copper iodide dimers were synthesized, namely, (4-MBTP)2(Cu2I4)0.5I (1) and (4-MBTP)(Cu2I4)0.5 (2) (4-MBTP = (4-methylbenzyl)triphenylphosphonium chloride). Compound 1 exhibits blue emission centered at 474 nm, while compound 2 shows yellow emission centered at 559 nm at room temperature. The results combined with crystal structure, spectroscopy analysis, characterization, and theoretical studies reveal that the blue light of compound 1 stems from multiple defect states caused by the presence of I vacancies, while the yellow emission of compound 2 is attributed to through-space charge-transfer (TSCT) and cluster-centered (CC) excited state. Strikingly, the crystal structure can transform from compound 1 into compound 2 with luminescence color change from blue to yellow through treating with methanol. This work provides a structural transformation strategy of hybrid copper halides, as well as realizes the regulation of light emission from defect states to non-defect states, making them feasible candidates for information encryption and optical data storage.
Rechargeable aqueous zinc-ion batteries (RAZIBs) have been considered as viable alternatives to lithium-ion batteries in electrochemical energy storage due to their intrinsic safety, low cost, and environmental friendliness. However, the further practical application of RAZIBs is restricted by the growth of zinc dendrites and severe side reactions during cycling. To address these issues, we proposed a new lysine (Lys) additive to the ZnSO4 electrolyte, the hydrolyzed Lys+ cations can be adsorbed on the Zn anode's surface to modify the interface between the zinc electrode and the ZnSO4 electrolyte. This modification helps weaken the "tip effect" and guides the uniform zinc deposition, effectively alleviating the formation of zinc dendrites. Additionally, introducing alkaline Lys can regulate the pH value of the ZnSO4 electrolyte and suppress side reactions, thereby decreasing the production of by-products. Consequently, the Zn||Zn symmetric cell with Lys additive stably cycled for 4500 h at 1 mA/cm2, and the Zn||NH4V4O10 full cell with Lys additive exhibited improved performance (with a capacity retention of 72% after 1000 cycles) at 5 A/g. This strategy provides valuable insights for developing stable Zn anode toward high-performance RAZIBs.
The dissolution of lithium polysulfides (Li2Sx, 4 ≤ x ≤ 8, LiPSs) intermediates and slow redox kinetics are the main factors leading to the rapid capacity degradation of lithium-sulfur batteries (LSBs), significantly limits the practical development of LSBs. To overcome challenges, NbN embedded in nitrogen-doped carbon nanotubes (NbN@NCNT) composites were synthesized here as sulfur hosts by taking advantage of the superior electrical conductivity and excellent catalytic activity of the metal nitride NbN. The incorporation of NbN enhanced the polysulfides conversion efficiency and suppressed the shuttling effect, thereby enhancing cycling stability in LSBs. XPS results revealed the formation of Li2S, indicating that Li2S8 was sufficiently effectively reduced and catalytically converted to the Li2S. Consequently, after 100 cycles, the capacity retention rate of LSBs using the S/NbN@NCNT electrode reached 71.5% at a current density of 2 mA/cm2 with a high sulfur loading of 3 mg/cm2. More importantly, even at high current density of 8 mA/cm2, the battery assembled with NbN@NCNT was still able to reach the high capacity of 878.14 mAh/g, demonstrating outstanding rate capability. This study offered novel insights into the potential for enhancing the sulfur reaction kinetics in LSBs.
Semiconducting metal oxide based gas sensors exhibit great promise for convenient detection of acetone, a biomarker gas in the exhaled breath of type-Ⅰ diabetes patients. However, the detection usually suffers the interference from exhaled moisture. To overcome this challenge, in this work, a novel hierarchical heterojunction structure consisting of SnO2 nanofiber core and Co3O4 nanosheet shell (denoted as SnO2@Co3O4 core-shell composite) was proposed for fabricating acetone sensor with excellent humidity resistance. Compared with SnO2 nanofibers and Co3O4 nanosheets, the SnO2@Co3O4 showed the highest sensing response, with a response value (Rg/Ra) of 11.27-50 ppm acetone at 110 ℃. In addition, the hierarchical SnO2@Co3O4 core-shell structure shows fast response/recovery speed (19/43 s), lower detection limit (125 ppb), excellent selectivity and stability in a humidity environment (relative humidity 30%-90%) with a relative change of only 3%. The enhanced gas sensing performance toward acetone is attributed to the synergistic effect between the two components, the unique core-shell hierarchical structure and the rich oxygen vacancy density. Density functional theory calculations reveal that the SnO2@Co3O4 has higher acetone adsorption energy than the two components. In addition, a novel SnO2@Co3O4 gas sensing module and smart portable sensor device enable efficient real-time monitoring of acetone concentrations on a smartphone via Bluetooth communication.
Metal-organic framework [Zn2(tz)2(ox)] (CALF-20) has attracted great attention due to its excellent ability to capture carbon dioxide. There are great interests to develop similar adsorbents for gas adsorption and separation. To develop more efficient porous adsorbent, it is essential to study the relationship between these structures and properties. Neutron diffraction has been proved to be an excellent tool for determining both the structural details of MOF host and the precise locations of adsorbed gas within the pore, offering unique opportunities for understanding the structure-properties relationship. Herein, we report the synthesis and structure characterization of MOF [Zn2(mtz)2(ox)], which exhibits high CO2 adsorption capacity. Neutron powder diffraction experiment on the solvated, the activated and CO2 loaded samples unveils the preferred binding sites of CO2 within the MOFs, where CO2 locates toward the center of the pore and interacts with methyl group or triazole via CH···O hydrogen bonding. The adsorption process of CO2 in [Zn2(mtz)2(ox)] is accompanied by the cell volume expansion, so [Zn2(mtz)2(ox)] with more compact structure can show a better adsorption performance. The structure-properties relationship in [Zn2(mtz)2(ox)] elucidated by present study offer a path to develop more advanced porous physisorbent materials.
The replacement of Pt/C catalysts with Pt-based alloy catalysts was considered a promising strategy to reduce platinum-group-metal (PGM) content in proton exchange membrane fuel cell. However, inexpensive transition metal atoms in Pt-based alloy catalysts are subject to metal dissolution issues, leading to stability issues of oxygen reduction reaction (ORR) catalysts. In this work, a PtCuNi/C-WO3-x catalyst is designed employing non-stoichiometric WO3-x with abundant oxygen vacancies (Ovac). The WO3-x can dramatically improve the stability of PtCuNi without sacrificing the activity. Theoretical calculation suggests a decreased vacancy formation energy of W in WO3-x at the presence of Ovac, as well as increased vacancy formation energies of Pt/Cu/Ni in PtCuNi alloy particles with the existence of surface W dopant. Combined with the experimental discovery of slower dissolution rates of metals in PtCuNi/C-WO3-x catalyst, a dissolution-induced stability enhancement mechanism is proposed, whereby facilitated dissolution of W atoms from WO3-x bulk could re-deposit on Pt-alloy surface and inhibit the dissolution of catalytically active metal atoms, revealing a dynamic process that enhances the stability. The PtCuNi/C-WO3-x also shows great potential to be used as cathode catalyst in membrane electrode assembly for high-temperature proton exchange membrane fuel cells.
Structural design is an effective way to realize the functional construction of hole transporting materials (HTMs). In order to have an insight into the relationship between molecular structure and function of HTMs, three isomeric HTMs (RQ1, RQ2 and RQ3) are constructed with functional group of dibenzothiophene which is connected to different positions on the side chains of carbazole-aromatic derivatives. In combination with computational simulation and experimental study, although the isomeric RQ1–RQ3 with the same molecular formula exhibit similar frontier molecular orbital energy levels and optical absorption, their hole transporting ability and interaction at perovskite/HTMs interface in perovskite solar cells (PSCs) are completely different. In comparison with the RQ2 (18.69%) and RQ3 (22.56%), the results indicate that the molecule RQ1 in PSCs application can yield higher power conversion efficiency (23.50%) because of its higher hole mobility and effective charge transfer at perovskite/HTMs interface. Moreover, the mutually corroborating between the computational simulation and the experimental results demonstrate the reliability of the theoretical model for molecular design of isomeric HTMs. This strategy of obtaining high-performance HTMs through simple structural design is expected to inspire researchers to further optimize the efficiency of PSCs.
Traditional polycrystalline P2 layered oxides face challenges such as irreversible phase transitions, poor air stability, and structural distortion, which negatively impact their electrochemical performance. In this study, a single-crystal material, P2-Na2/3Ni1/4Mn2/3Mg1/12O2 (SC-NMM), was synthesized using co-precipitation coupled with the molten salt method. Owing to the strong integrity and high thermal stability of the main {001} planes of the large-sized single crystal, SC-NMM exhibits a high reversible specific capacity (173.5 mAh/g at 20 mA/g) and stable cycle performance (93.38% capacity retention after 100 cycles at 100 mA/g) at high voltage. Additionally, the Na-ion full cell constructed with the SC-NMM cathode and hard carbon anode demonstrates a cathode energy density of 397.4 Wh/kg. The excellent electrochemical performance of SC-NMM originates from the reversible anion redox and single-phase solid solution reaction mechanism. This work provides a reference for synthesizing single-crystal layered transition metal oxides with high electrochemical performance by eliminating irreversible phase transitions through crystal orientation modulation.
Aqueous zinc-ion batteries (AZIBs) have emerged as strong contenders for large-scale energy storage solutions, attributed to their cost-effectiveness and enhanced safety profiles. Nevertheless, their widespread adoption is currently hindered by their poor performance in low-temperature conditions. Herein, an electrolyte is developed by utilizing weakly solvated and film-forming molecule dimethyl sulfite (DMS) to achieve smooth de-solvation and high ionic conductivity at low temperature. The DMS disrupts the hydrogen bonding network of water and lowers the freezing point of the electrolyte to -40.9 ℃. The designed electrolyte achieves ionic conductivity up to 10.75 mS/cm at -30 ℃. Due to the chemical reactivity of DMS and trifluoromethanesulfonate anions in the Zn2+-solvation shell, a ZnF2-ZnS hybrid solid electrolyte interphase (SEI) is successively generated on Zn metal surface. Mechanistic studies reveal that such robust hybrid interphase can promote Zn2+ desolvation and rapid Zn2+ transport. In addition, the addition of DMS effectively suppresses the dendritic growth, hydrogen evolution reaction (HER), and corrosion-induced passivation on the anode surface, facilitating long-term cycling at subzero temperatures. At -40 ℃, the Zn//Zn symmetrical cell cycles for 1200 h at 0.5 mA/cm2 and 0.5 mAh/cm2, and the Zn//NVO cell achieves an ultra-long cycle life of 1000 cycles with a high capacity retention of 82.89% at 1 A/g.
Aqueous zinc-ion batteries (AZIBs) are the low-cost and safe secondary battery technology with great application prospects, but remain hindered by the severe Zn-electrolyte interface compatibility, especially in extreme environmental temperature. Innovative electrolyte design is the key to solving the above problems. Here, we introduce an electrolyte additive of Poloxamer 407 (P407) as a solvation restructuring agent and H2O cluster modulator, effectively stabilizing H2O molecules and suppressing parasitic reactions. Meanwhile, P407 facilitates the formation of a stable solid electrolyte interphase (SEI) composed of organic-inorganic composite, thereby improving the interfacial chemistry. More importantly, the thermoreversible gelation property of P407 enhances the system’s high-temperature stability by forming micelle network structures that effectively retains H2O molecules, while at low temperature, it maintains the fluidity of the electrolyte, ensuring efficient ion transport. By using P407-containing electrolyte, the Zn anode achieves long cycling life of 4000, 850, and 1000 h at 30, 60 and −30 ℃, respectively. Moreover, the modified electrolyte enables the Zn-V2O5 full cells to achieve excellent rate performance and cycling stability in a wide temperature range from −30 ℃ to 60 ℃. This study highlights a simple yet effective strategy for electrolyte modification using P407, providing a pathway toward the development of high-performance AZIBs with broad temperature adaptability.
Solvated-ion co-intercalation mechanism with high-rate capability properties makes graphite anode reconsider as optional anode for sodium-ion batteries and capacitors. The size effect has been widely investigated for various transition metal oxide materials, but such influences on the co-intercalation mechanism remain largely unexplored. In this study, natural graphite anodes with different particle sizes ranging from 25 µm to 1.7 µm for [Na(diglyme)x]+ co-interaction are systematically investigated through detailed kinetics analysis and in-situ X-ray diffraction characterization. Importantly, we find that the reaction pathways of the co-intercalation and co-extraction are quite different. The reduced graphite size results in the loss of phase transitions during the co-extraction process and then the disappearance of the sharp anodic redox peak. The small-sized graphite anodes display boosted capacitor-like responses and provide additional surface adsorption with a slightly increased capacity. Finally, a hybrid sodium-ion capacitor (SIC), using graphite anode and activated carbon cathode, is assembled without complex presodiation treatments. Such optimized hybrid SICs deliver high energy densities of 60 Wh/kg at 240 W/kg and high power density of ~16,000 W/kg with 32 Wh/kg, and ultralong 30,000 stable cycles. This work provides fundamental insights into the Na+-solvent co-intercalation mechanism with tunable capacitor-like kinetics, representing a promising direction for high-power sodium-ion storage.
High-performance electrode materials are of paramount significance for practical applications in energy storage devices, and the design of hollow-structured active electrode materials is a simple effective strategy. Herin, a three-dimensional nickel cobalt cadmium ternary sulfide hollow nanoprism material (NiCoCd-S) was successfully synthesized by combination of refluxing, hydrothermal and calcination methods. The co-existence and synergism of Ni, Co and Cd endow the material surface with abundant catalytic active sites, facilitating the progress of the reaction, enabling it to exhibit better performance than single-metal or bimetallic compounds. The unique hollow structure facilitates increased contact between the electrolyte and more electroactive sites, while the shorter diffusion pathways enable rapid ion/electron transfer rates within the material, synergistically generating enhanced supercapacitive activity. The synthesized NiCoCd-S shows a high specific capacitance (Cg) of 1643.7 F/g@1 A/g, along with a prolonged cycling life (81.6% capacitance retention after 10,000 cycles). When assembling the NiCoCd-S//AC asymmetric supercapacitor, it demonstrates an impressive energy/power density of 105.9 Wh/kg and 919.2 W/kg, respectively. After 10,000 charging-discharging cycles, the initial capacitance can still be maintained at 88.5%. The present work offers a strategy for the rational design of hollow nanostructured polymetallic sulfides with high electrochemical performance and stability.
Electrochemical NO reduction reaction (NORR) has gained extensive attention as a promising approach to achieve both harmful NO removal and ambient NH3 production. Main-group metal-based single-atom catalysts (SACs) hold great promise for electrocatalysis but still lack adequate investigation. Herein, by means of the first-principles calculations, we systematically explore the potential of main-group metal-embedded BC3 monolayer (denoted as M@VB and M@VC, M = Mg, Ca, Al, Ga, In, Ge, Sn, Sb, and Bi) as highly efficient SACs for the NORR toward NH3 synthesis. After examining the structural stability, NO adsorbability, NORR catalytic performance, and NH3 selectivity, we screen Al@VB, Ga@VB, and Ge@VC out of 18 candidate systems. Remarkably, NO can be adsorbed and activated on them with moderate ΔG*NO of -1.27~-1.90 eV, and spontaneously reduced into NH3 without any limiting potential. Moreover, the three screened candidates can effectively inhibit the production of N2O/N2 byproducts under high NO converge, as well as the competing hydrogen evolution reaction (HER). Our work not only offers several high-efficiency NORR electrocatalysts, but also guides the rational design of potential main-group metal-based SACs.
Phenylphosphonate functionalized fully-reduced hourglass-shaped organophosphomolybdate(V) hybrid (H2bib){Ni[Mo6(PO3C6H5)4O15H6]2}·9H2O (bib = 4,4′-bis(imidazolyl)bibpheny) was synthesized as a photoelectrochemical (PEC) sensor. Benefiting from the electron transfer interaction between organic phenyl groups and inorganic {P4Mo6} skeleton, compound achieved a low detection limit of 4.61 nmol/L and high sensitivity of 264.02 µA L/µmol toward the PEC detection of levofloxacin in aqueous solution, together with excellent practicality in milk sample.
In drug discovery, it is extremely important to identify highly potent leads with desirable drug-like profiles. Almost all the marketed phosphodiesterase 5 (PDE5) inhibitors such as sildenafil, vardenafil, and tadalafil have poor selectivity over PDE6 or PDE11 and leading to several side effects. Herein, a metabolites-based scaffold hopping strategy was performed to discover selective PDE5 inhibitors with remarkable metabolic stability. The Eu(OTf)3-catalyzed Mannich-type reaction followed by l-selectride catalyzed reduction was used to prepare chiral 2,3,3a,4,5,6-hexahydro-1H-benzo[b]pyrido[2,3,4-de][1,6] naphthyridines as novel PDE5 inhibitors with high enantioselectivity (> 99% ee and > 30:1 dr). Lead L9 exhibited a half maximal inhibitory concentration (IC50) of 1.03 nmol/L with higher selectivity (> 898-fold) over PDE6 or PDE11 than sildenafil and tadalafil, implying the potential relief from side effects. Especially, the co-crystal binding pattern of L9 with PDE5 is revealed to be different from that of sildenafil, which possibly explain the former's high selectivity. And oral administration of L9·HCl (5.0 mg/kg) exhibited better therapeutic effects than pirfenidone (150 mg/kg) in a bleomycin-induced idiopathic pulmonary fibrosis (IPF) rat model, highlighting the potential of L9·HCl for the treatment of IPF.
Intracerebral hemorrhage (ICH) is a devastating subtype of stroke with high mortality and poor prognosis among survivors. Neuroinflammation after ICH plays a critical role in both secondary brain injury and repair. In the early stages of ICH, excessive activation of microglia triggers pro-inflammation, leading to the release of various pro-inflammatory cytokines that exacerbate neuronal damage and worsen neurological deficits. Pterostilbene (PTE), a natural polyphenol with potent anti-inflammatory and antioxidant properties, is an ideal neuroprotective agent. However, its clinical application is limited by poor bioavailability and low blood-brain barrier (BBB) penetrability following oral administration. Here, we developed PTE-loaded methoxy poly(ethylene glycol)-poly(ε-caprolactone) (mPEG-PCL) nanoparticles (PTE-NPs) to enhance the bioavailability of PTE and performed an intranasal delivery strategy for non-invasive and efficient transport to the ICH lesion. PTE-NPs significantly suppressed pro-inflammatory microglia activation and cytokine release, thereby reducing inflammation-mediated neuronal damage in the peri–hematomal region. In the two ICH mouse models, PTE-NPs demonstrated significant therapeutic efficacy in improving neurological function with good biosafety. This study provides a potential therapeutic strategy for the treatment of ICH and its future clinical translation.
Target therapy represents a paradigm shift to a precise and personalized approach. Unlike the great success of antibody-drug conjugate (ADC) in clinical practice, peptide-drug conjugate (PDC) with good tissue penetration and drug loading capacity exhibits poor stability, quick blood clearance and cellular internalization that limit their translation. In this study, a feasible approach for constructing an in vivo self-assembling peptide-drug conjugate (sPDC) was proposed by rationally designing the combination of tumor-specific targeting peptide module, responsive self-assembling peptide module, and therapeutic drug. Two optimized sPDCs (sPDC1 and sPDC2) capable of specifically targeting human epidermal growth factor receptor 2 (HER2) on the surface of tumors were reported. sPDCs could selectively target HER2-positive tumors and effectively kill HER2 overexpressing tumor cells. In addition, weak but significant efficacy of sPDCs was also observed in HER2-negative tumors, which was likely by-stander effect due to the release of monomethyl auristatin E (MMAE) in the tumor microenvironment. Finally, in HER2-positive xenograft mouse models, sPDC1 showed superior therapeutic efficacy over the clinical HER2-targeted therapeutic agents trastuzumab and lapatinib, and roughly equivalent therapeutic efficacy compared with RC48 even in large tumor-bearing mouse models. Therefore, sPDC1 was promising to serve as a lead compound for further clinical development for oncology therapy.
The poor biofilm colonization, charge transfer, and storage at the anode have long been major obstacles to achieving high power generation in bioelectrochemical systems (BES). To overcome this challenge, we developed electrospun carbon nanofiber-interpenetrated reduced graphene oxide aerogels (CNF/rGO-x, where x denotes the mass ratio of CNF to rGO, with x = 2, 4, 6) to modify the surface of carbon cloth (CC), significantly enhancing its electrochemical performance. The CNF/rGO-6 aerogel featured a porous, interconnected conductive scaffold, endowing the CC electrode with a larger electrochemically active area, higher specific capacitance, and a rougher surface. These properties significantly improved biofilm adhesion, extracellular electron transfer, and charge storage capabilities. As a result, the BES equipped with a CNF/rGO-6 electrode achieved an impressive power density of 3080.3 mW/m2, significantly higher than those of BES with CNF/rGO-4 (2426.3 mW/m2), CNF/rGO-2 (2717 mW/m2), rGO (1978.3 mW/m2), and pure CC (1050.4 mW/m2) electrodes. Furthermore, the CNF/rGO-6 electrode supported a high abundance of electroactive bacteria and enhanced their viability. With its simple fabrication, low weight, and exceptional electrochemical performance, the CNF/rGO-6 aerogel demonstrates significant potential as an electrode material for high-performance and cost-effective BES.
Oral leukoplakia (OLK) is a common and representative malignant disease of oral mucosa, and possess a higher risk of cancer. Compared with traditional surgical treatment, photodynamic therapy (PDT) has great potential in OLK treatment, due to its advantages of minimally invasiveness and low toxic side effects. However, traditional photosensitizer administration suffers from short retention time due to the fluid environment of saliva and extensive tongue movement, leading to poor drug (photosensitizer) utilization and limited therapeutic outcome. To address such issue, here a photosensitive guanosine (G)-based hydrogel system (G@GQD) was constructed, in which graphene quantum dots (GQDs) featuring high photosensitization activity was loaded through three dimensional (3D) fiber network physical encapsulation. The favorable adhesion of the G@GQD hydrogel on the tongue, together with sustained GQDs release, significantly enhanced the retention of GQDs within the oral cavity. As a result, G@GQD hydrogel could continuously generate high levels of reactive oxygen species (ROS) under irradiation, demonstrating a sustained therapeutic efficiency in vitro. Compared with free GQDs, G@GQD exhibited significantly improved PDT efficiency in treating 4-nitroquinoline 1-oxide (4-NQO)-induced OLK animals. This study presented a promising strategy in overcoming the drug retention barrier that caused by saliva and tongue movement, which has far-reaching significance for the future PDT therapies.
Light is a powerful tool for controlling hydrogel formation and drug release, which are essential in tissue engineering and drug delivery. Achieving orthogonal control over hydrogelation and drug release using different wavelengths of light offers precise spatiotemporal regulation but is challenged by limited penetration depth and spectral crosstalk of commonly used visible light. Herein, this work develops an orthogonal light-responsive hydrogel based on dual-wavelength upconversion nanoparticles (UCNPs) for controlled hydrogelation and drug release. Upon 808 nm excitation, these UCNPs emit green light, triggering the photopolymerization of hyaluronic acid-2-aminoethyl methacrylate hydrogels. While 980 nm induces ultraviolet emission, enabling controlled and sustained drug release. Through structural design, the emissions under dual-wavelength excitation exhibit no spectral crosstalk, enabling orthogonal light control of both processes. In vitro and in vivo experiments show that both hydrogel formation and drug release processes can be finely tuned by controlling the power density and excitation durations, significantly enhancing the spatiotemporal precision of drug delivery. This orthogonal light-responsive hydrogel holds significant potential for precise, spatiotemporally controlled drug delivery.
Induction of ferroptosis is a promising strategy for tumor treatment. In light of the fact that the inhibition of ferroptosis suppressor protein 1 (FSP1) can enhance the susceptibility of hepatoma cells to glutathione peroxidase 4 (GPX4) inhibitors, we hypothesized that FSP1 degraders may conspicuously improve the therapeutic efficacy of GPX4 inhibitors against hepatoma. Here, we developed a strategy using an iFSP1 analog (FSP1 inhibitor) and the pomalidomide (E3 ligase ligand) to construct proteolysis targeting chimeras (PROTACs) for degrading FSP1. Among these, C7, the first-in-class PROTAC degrader of FSP1, induced FSP1 degradation with a half-maximal degradation concentration (DC50) value of 0.66 µmol/L. The synergistic application of C7 (1 µmol/L) and the GPX4 inhibitor ML162 (100 nmol/L) markedly induced ferroptosis and effectively inhibited hepatoma cells viability. Further mechanism studies revealed that C7 targets FSP1 and down-regulates it through the ubiquitin-proteasome pathway. In vivo experiments demonstrated that the therapeutic alliance of C7 and ML162 markedly surpassed the efficacy of iFSP1 (FSP1 inhibitor) and ML162 in suppressing tumor proliferation. Collectively, these findings indicated that PROTAC degraders of FSP1 function as potent sensitizers of GPX4 inhibitors to induce ferroptosis, thus representing a promising strategy for hepatoma treatment.
Decellularized amniotic membrane (dAM) holds significant potential in tissue engineering; however, its inherent mechanical limitations and rapid degradation hinder its clinical translation. This study integrates dAM with high molecular weight polymer polycaprolactone (PCL) and natural gelatin (Gel) nanofibers using electrospinning technology and a 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) covalent crosslinking system to produce two composite biomaterials. Both PCL-dAM and Gel-dAM composites demonstrate enhanced strain, tensile strength, and elasticity compared to pure dAM, showcasing improved mechanical properties and significantly reduced degradation rates, with Gel-dAM exhibiting superior overall performance. Gel-dAM also shows considerably better compatibility with fibroblasts, macrophages, and tendon stem cells than PCL-dAM, suggesting that it more effectively supports cell adhesion, proliferation, and differentiation, thus providing a more favorable microenvironment for tissue repair. In macrophage immune modulation, Gel-dAM significantly promotes the polarization of macrophages toward the M2 phenotype, exhibiting potential anti-inflammatory and repair-enhancing effects, thereby offering new insights into the use of dAM in tissue regeneration. These advancements open new possibilities for the clinical application of dAM, particularly in tissue repair and wound dressing.
Patchouli oil (PAO), a traditional herbal remedy with notable anti-inflammatory properties, has demonstrated significant therapeutic potential in gastrointestinal diseases. However, its instability in acidic environments and low bioavailability hinder PAO's clinical application. In this study, we developed a pharmaceutical solid-state form of PAO using a β-cyclodextrin (βCD)-based inclusion cocrystal technology, thus obtaining PAO-βCD cocrystals. PAO-βCD cocrystals exhibited enhanced dissolution and stability. We further encapsulated them in pH-sensitive Eudragit-coated pellets (PAO-βCD@pellet) to achieve site-specific delivery of PAO to the inflamed colon. In vivo results from the dextran sulfate sodium salt (DSS)-induced colitis mouse model showed that PAO-βCD@pellet significantly improved the colonic release of PAO, as evidenced by fluorescence tracking and quantitative analysis of patchouli alcohol, the main active compound of PAO. Furthermore, PAO-βCD@pellet demonstrated superior therapeutic efficacy, reducing disease activity index, preventing intestinal barrier damage, and modulating the gut microbiome. Histological examination confirmed alleviating intestinal epithelial cell damage caused by oxidative stress and inflammation. These findings suggest that PAO-βCD@pellet offers a promising targeted treatment strategy for inflammatory bowel disease (IBD) with enhanced stability, bioavailability, and therapeutic outcomes.
Alzheimer's disease (AD) is a chronic, progressive neurodegenerative disorder with no effective therapeutic agents currently available. Inhibiting phosphodiesterase 4 (PDE4) has emerged as a promising strategy for AD treatment. In this study, we employed a synergistic approach combining generative recurrent neural network (RNN)-driven combinatorial compound design, virtual screening, and structure-activity relationship (SAR) analysis to discover novel PDE4 inhibitors. Utilizing α-mangostin as a hit compound (half maximal inhibitory concentration (IC50) = 1.31 µmol/L), we identified a novel PDE4 inhibitor, 13d (IC50 = 72.8 nmol/L) with moderate liver microsomal stability (rat liver microsomes (RLM), t1/2 = 32.4 min). In vitro activity results indicated that 13d exhibited favorable anti-inflammatory effects and promising neuroprotective activity. In vivo experiments demonstrated that 13d significantly improved AlCl3-induced zebrafish AD model by inhibiting PDE4 and reducing inflammatory cytokine. Further, 13d significantly alleviated AlCl3/d-galactose-induced AD mouse model. These findings highlight the potent PDE4 inhibitor 13d with promising anti-AD activity, underscoring the potential of artificial intelligence-driven drug discovery for novel therapeutic agents for AD.
Tumor-associated carbohydrate antigen (TACA)-based cancer vaccines face clinical challenges due to heterogeneous TACA expression, which compromises antibody-mediated tumor recognition and leads to suboptimal therapeutic outcomes. To address this limitation, we report a combined strategy that integrates vaccination with TACA-based antibody-recruiting molecules. This approach simultaneously redirects anti-TACA antibodies to tumor cells expressing a secondary target, thereby enhancing the efficacy of TACA-based vaccines. Using sialyl-Tn (sTn) as a model TACA and epidermal growth factor receptor (EGFR) and human epidermal growth factor receptor 2 (HER2) as model protein targets, we designed two nanobody (Nb)-sTn conjugates as TACA-based antibody-recruiting molecules: EGFR-targeting 7D12-sTn and HER2-targeting C7b-sTn. These conjugates were synthesized via sortase A-mediated ligation and demonstrated strong binding profiles. Importantly, they effectively redirected anti-sTn antibodies, generated by the Theratope vaccine, to target cells in situ, significantly improving the recognition of tumor cells by anti-sTn antibodies. The synergistic potential of these conjugates in amplifying the therapeutic effect of the sTn-KLH vaccine was further validated through complement-dependent cytotoxicity assays. This innovative strategy represents a highly promising approach to overcome the clinical challenges posed by TACA heterogeneity in cancer vaccine development.
The rapid proliferation of tumor cells is driven by metabolic reprogramming and redox regulation. Real-time monitoring of glutathione (GSH)/adenosine-5′-triphosphate (ATP) provides a dynamic perspective for tumor metabolism and is crucial for guiding precision treatment. We report a dual-site activatable fluorescent probe M901 for simultaneously detecting GSH and ATP without spectral overlap, and the detection range (GSH: 0–7 mmol/L, ATP: 0–6.5 mmol/L) matching the physiological concentration range. Based on this, M901 visualizes a bidirectional regulatory relationship between ATP synthesis↓ (energy imbalance) ↔ electron transport chain dysfunction ↔ reactive oxygen species (ROS)↑ ↔ GSH↓ (oxidative stress). Additionally, M901 reveals for the first time the dynamic compensatory mechanism between GSH and ATP in cellular oxidative stress induced by the inhibition of solute carrier family 7 member 11 (SLC7A11) or glutathione peroxidase 4 (GPX4). In vivo imaging further confirms oxidative stress and mitochondrial dysfunction are core pathological mechanisms leading to liver injury, with treatment efficacy positively correlated with GSH/ATP levels. Importantly, the dynamic visualization of GSH/ATP by M901 enables real-time evaluation of the anti-tumor effects of ferroptosis inducers and cisplatin, guiding successful precision resection of invasive malignant tumors (negative margins <0.2 mm). This study confirms the potential of M901 as a clinical visualization tool for diagnosing, treating and monitoring a variety of diseases.
Molecular networking-guided chemical investigation of the Euphorbia endophyte Malbranchea umbrina D16 led to the isolation of 14 novel unusually cyclized triterpenoids (UCT) involving three different skeletal types. Compounds 1–10 are tricyclic triterpenoids featuring a 1-cyclohexyloctahydro-1H-indene core, in which 1 incoporates an unusual 7,7-dimethyl-6,8-dioxabicyclo[3.1.2]octane motif. Compounds 11–13 represent a rare class of bicyclic triterpenes (6/5 ring system) containing various O-heterocycles at the side chain. Compound 14 is an acyclic triterpenoid with O-heterocycles at both ends. Their structures were assigned by spectroscopic, chemical, computational, and crystallographic means, which also allowed the stereochemical revisions of three previously reported analogues. Compound 1 significantly inhibited the adipogenesis in 3T3-L1 adipocytes via activating the AMP-activated protein kinase (AMPK) signalling.
Ferroptosis is a cell death pathway that plays a crucial role in numerous biological processes. Although closely related to ferrous ion, the execution of ferroptosis was found to be impacted by zinc ion (Zn2+) in recent years. However, most of the related researches focused on the effects of exogenously added Zn2+, while the fundamental understanding of endogenous Zn2+ during ferroptosis still needs further exploration. Herein, a ratiometric fluorescent probe based on pyridine-substituted boron dipyrromethene (BODIPY) fluorophore (BDP-p) was designed to track the endogenous Zn2+ in cells during ferroptosis process. Zn2+ coordination induced an enhancement on the intramolecular charge transfer (ICT), leading to an obvious red shift from 563 nm to 594 nm. In A549 cells, we found fluorescence ratio of the probe elevated in some discrete regions during erastin induced ferroptosis, and this change followed the same trend as the reactive oxygen species (ROS) level. The results suggested that the Zn2+ would be localized in some discrete areas in A549 cells during ferroptosis. This work not only provided a reliable design strategy for developing ratiometric probes of Zn2+, but also supplemented the current understanding of the non-negligible role of Zn2+ in ferroptosis.
Bacteria and stains on tooth and various dental materials severely harm dental health and beauty and require feasible solutions. In this study, a simple strategy was developed to produce nano-coating on different substrates for persistent antibacterial and whitening. The coating is formed by the lysozyme (Lys), hemoglobin (Hb), and glucose oxidase (GOD) via co-assembly, in which the phase transition of Lys initiated the co-assembly to anchor other two proteins. During therapy, the GOD continuously oxidizes glucose in the oral environment to cut off the nutrition of bacteria meanwhile generating H2O2, which would be further catalyzed by the ferrous ions in Hb to produce reactive oxygen species (ROS) for effective decomposition of surrounding bacteria and stains. Moreover, the Hb can perform persistent release of oxygen, which not only enhances the efficiency of glucose oxidation to produce more ROS but directly suppresses anaerobic bacteria via reversing the local hypoxia environment in the mouth. The experimental results indicated that our strategy is able to form nano-film of proteins both on the surface of dental orthosis and human tooth, which further causes obvious reduction of the bacteria not only on the coated substrate but in the surrounding tissue with up to 100% of the bacteriostatic rate. In addition, both the dental orthosis and human tooth were also rapidly cleaned due to the local ROS generation, leading to a sustained anti-staining property in the long term.
Molecular glass refers to amorphous rigid small molecules with certain polymer-like properties. Herein, spirobixanthene is first adopted as the backbone to develop negative photoresist X4Ep with four epoxy moieties. F4Ep based on classical spirobifluorene is also synthesized as a benchmark against X4Ep. Both exhibit good thermostability and similar sensitivity. However, in e-beam lithography, performances of X4Ep completely surpass F4Ep. F4Ep lithography shows inevitably minor bridges no matter how we optimize process conditions. The relatively poor performances of F4Ep may be probably ascribed to its partial crystallization tendency inducing uneven photoacid generator (PAG) distribution and uneven acid diffusion, which thus promotes nonuniform epoxy crosslink to form rough patterns. X4Ep readily achieves dense lines without any defects. The superiority of X4Ep to F4Ep can be ascribed to the exceptional yet apparent structural distortion and asymmetry of spirobixanthene, which guarantees a perfect amorphous state and uniform crosslink. Finally, the optimal line/space (L/S) pattern with half pitch (HP) of 25 nm and line edge roughness (LER) of 2.7 nm is achieved. Therefore, spirobixanthene is a valuable molecular glass backbone for high-performance photoresists in the future.
Layered double hydroxides (LDHs) hold great promise for flexible solid-state supercapacitors owing to their high theoretical capacitance and distinctive architecture. However, their proneness to agglomeration and poor electrical conductivity have long hindered the manifestation of outstanding electrochemical performance. In a groundbreaking approach, we have engineered a hierarchical carbon nanofiber-based NiCo2S4/NiCo-LDH/C nanostructure array. The meticulously crafted hierarchical structure not only imparts remarkable stability to the electrode but also ingeniously harnesses the synergistic interplay among materials. Through density functional theory calculations, we have precisely identified and verified the active sites for charge transfer, unveiling a new understanding of the underlying mechanisms. This unique structure significantly facilitates ion transfer in the vicinity of NiCo-LDH, substantially elevates electrical conductivity, and notably increases the adsorption capacity of OH-. Moreover, it gives a substantial boost to the quantum capacitance. As a result, the electrode showcases a high specific capacitance of 1838.3 F/g. This research pioneers an effective and versatile strategy that can be readily applied to the majority of LDHs, opening up new avenues for enhancing their efficiency of supercapacitor materials.
The advent of the most representative commercially available formulations of paclitaxel, Taxol and Abraxane®, resolved the intravenous challenge of paclitaxel by increasing the water solubility. However, the severe excipient-related toxicity and poor stability of Taxol, along with the low drug loading (10%), complex preparation processes, and poor tumor selectivity of Abraxane®, present significant clinical dilemma. To overcome the challenges, 16-methylheptadecanoic acid (16-MH), with excellent biocompatibility was selected as the assembly module. The paclitaxel-16-MH prodrug nanoassemblies (PSSMH NPs) were constructed by conjugating 16-MH with redox-sensitive disulfide bonds and paclitaxel through an ethylene glycol. PSSMH NPs featured the advantages of easy preparation, high drug loading (> 50%) and superior stability (stable storage for 60 days at 25 ℃). Notably, the area under the concentration−time curve (AUC0–24 h) of PSSMH NPs was 14.95-fold compared with Taxol, indicating a significant improvement in the in vivo fate of paclitaxel. Moreover, the existence of redox-sensitive disulfide bonds endowed PSSMH NPs with increased tumor selectivity, resulting in exceptional tolerance and antitumor efficacy. Overall, the redox-triggered prodrug nano-system with high tumor selectivity and biocompatibility exhibits substantial potential for clinical translation.
The escalating threat of antimicrobial resistance necessitates advanced tools for rapid and selective antibiotic detection in environmental systems. Herein, we report polyphenol-derived carbon dots (P-CDs) synthesized via a one-step solvothermal method using polyphenols and citric acid, enabling dual-mode detection of tetracyclines and quinolones through pH-tunable fluorescence. The P-CDs exhibit distinct fluorescence quenching for tetracyclines (e.g., oxytetracycline (OTC)) and enhancement for quinolones (e.g., norfloxacin (NOR)), driven by synergistic multiple molecular interactions facilitated by surface phenolic groups. With detection limits of 8.19 µmol/L (OTC) and 5.27 µmol/L (NOR), P-CDs achieve 6-fold higher sensitivity compared to conventional carbon dots. Their pH adaptability (pH 2–12), specificity (> 90% selectivity against seven antibiotic classes), and robust performance in real water matrices (e.g., river water and wastewater) underscore their potential as eco-friendly sensors for on-site environmental monitoring. This work highlights a versatile platform to address antibiotic contamination and advance public health safety.
Natural products bearing a bicyclo[3.2.2]nonane motif pose a considerable challenge to chemical synthesis. We developed a europium-promoted inverse-electron-demand Diels–Alder reaction of benzo[2,3]tropone derivatives with electron-rich olefins, which offers an expeditious approach to densely substituted bicyclo[3.2.2]nonanes. This method enabled the concise synthesis of a tetracyclic amine, subsequently identified as a downstream suppressor of autophagy.
Immunotherapy has emerged as a promising strategy for combating tumor metastasis and recurrence, however, its efficacy is often hampered by the immunosuppressive tumor microenvironment (TME). The integration of nanomedicine-based photothermal therapy (PTT) with immunotherapy offers great potential to reshape the immune landscape, thereby enhancing immune responses and therapeutic outcomes. Nevertheless, conventional hyperthermia may induce heat-related damage and excessive inflammation in normal tissues. To address this challenge, we developed a novel therapeutic platform that combines tumor-specific delivery of melittin (MLT) with mild PTT using two-dimensional palladium nanosheets (Pd NSs). This approach allows for selective accumulation of MLT at tumor sites via the enhanced permeability and retention (EPR) effect and TME-responsive release, thereby maximizing antitumor efficacy while minimizing off-target toxicity. The resulting nanocomposite, MLT@Pd@PEG, exhibits excellent biocompatibility and efficient photothermal conversion under 808 nm laser irradiation. The acidic pH and localized heat in the TME synergistically trigger the controlled release of MLT, which disrupts cancer cell membranes and promotes tumor cell apoptosis. Moreover, this treatment facilitates the release of tumor-associated antigens and danger-associated molecular patterns (DAMPs), thereby activating cytotoxic T lymphocytes and natural killer (NK) cells. In vivo studies demonstrate that the combination of immune checkpoint blockade and MLT@Pd@PEG not only eradicates primary and distant tumors in bilateral tumor-bearing mouse models but also prevents tumor recurrence and metastasis by inducing durable immune memory. This comprehensive strategy integrating precise MLT delivery with mild PTT holds significant promise for advancing next-generation cancer immunotherapy.
In the treatment of B-cell lymphoma, chemotherapy as a monotherapy encounters significant challenges like drug resistance, side effects, and limited cytotoxicity. A novel strategy combining chemotherapy and photothermal therapy uses nanomaterials to convert light into heat, locally heating tumor tissues to induce thermal ablation while enhancing the effectiveness of chemotherapeutic agents and reducing toxic side effects on normal cells. Here, we developed a multifunctional black phosphorus nanosheets (BP NSs) for chemo-photothermal synergistic therapy of lymphoma. BP NSs were synthesized from bulk black phosphorus crystal powders utilizing a modified liquid exfoliation technique and functionalized with polyethylene glycol (PEG) to improve stability. The PEGylated BP NSs were loaded with two chemotherapeutic agents, gemcitabine (Gem) and doxorubicin (DOX), forming GD-BP@PEG NSs. The nanosheets exhibit excellent physical stability, efficient photothermal conversion, and pH/near-infrared (NIR) dual-responsive drug release. In vitro cell experiments demonstrated that GD-BP@PEG NSs significantly increased cytotoxicity and apoptosis, especially with NIR laser irradiation. Furthermore, in vivo studies in A20 lymphoma-bearing BALB/c nude mice revealed GD-BP@PEG NSs passively accumulated with high concentrations at the tumor site, efficiently inhibiting lymphoma growth with minimal systemic toxicity, demonstrating significant advantages over single treatments of chemotherapy or photothermal therapy alone. In summary, this pH/NIR dual-triggered BP NSs system could serve as a promising nanoplatform for chemo-photothermal synergistic treatment of B-cell lymphoma.
The low tumor immunogenicity, high immunosuppressive microenvironment, and off-target toxicity severely limit the efficiency of the cyclic guanosine monophosphate-adenosine monophosphate synthase-stimulator of interferon genes (cGAS-STING) pathway that plays an important role in tumor immunotherapy. We herein develop a multifunctional nano-assembly with tumor targeting, double-stranded DNA (dsDNA) releasing, Mn2+ sensitizing and immune microenvironment reprogramming capabilities for improving cGAS-STING to bridge innate and adaptive immunity. The drug-free nano-assembly composed of organic AIE-type photosensitizer and MnO2 can improve the tumor immune microenvironment by consuming glutathione and producing oxygen in the presence of H2O2, concurrently enhancing the release of damaged dsDNA and sensitizing the cGAS by controlled release of Mn2+ to magnify cGAS-STING immunity. In vivo experiments reveal that the multi-mode synergistic activation of STING pathway at the headstream can not only damage the primary tumors to amplify innate immunity, but also facilitate the maturation of dendritic cells, infiltration of cytotoxic T lymphocytes and expansion of adaptive immunity to inhibit primary tumor metastasis and recurrence in the long term.
Chiral phthalides are present in numerous natural products and bioactive molecules. Synthesizing phthalides from alkenes is an effective strategy. However, the challenges of facial-selectivity in the addition to Z/E mixed alkenes and diastereoselectivity at vicinal stereogenic centers have prevented the achievement of a highly selective stereoconvergent synthesis of chiral sulfonyl phthalides from Z/E alkene mixtures. Therefore, we have developed an efficient methodology for the stereoconvergent synthesis of chiral sulfonyl phthalides, using the Cu/PyBim catalytic system. This method enables the asymmetric construction of sulfonyl phthalides with multiple stereocenters for the first time. It exhibits broad applicability across various terminal and internal alkene substrates, and accommodates a diverse array of aryl, alkyl, and nitrogen radical precursors, all under exceptionally mild reaction conditions. The experimental results indicate that the reaction utilizes a Curtin-Hammett kinetic control strategy, leading to the stereoconvergent synthesis of Z/E internal alkene substrates with significant enantioselectivity and diastereoselectivity in the asymmetric construction of chiral sulfonyl phthalides.
Fluoroorganic chemistry is one of the most hectic areas of current chemical research, exerting a profound effect on the most vital industries such as medicine, pesticide, and material science. Synthesis of fluorine-containing organic molecules, particularly those that bear C(sp3)−F bonds, remains a great challenge in modern chemical synthesis. Herein, we disclose a new strategy for the construction of a carbon−fluorine quaternary center, which was accomplished with the silver(Ⅰ)-catalyzed intramolecular Wagner−Meerwein rearrangement fluorination of allylic gem-disubstituted alkene derivatives by using a hypervalent monofluoroiodine(Ⅲ) reagent 1 (AFBI). Interestingly, the tunable five/six-membered heterocycle selectivity is achieved by the intramolecular Wagner−Meerwein rearrangement fluorination via a judicious choice of the group R1 attached to the C−C double bond. This versatile strategy features simple starting materials, mild reaction conditions, good functional-group compatibility, high bond-forming efficiency (e.g., one C−F and one C−O bond), and excellent chemoselectivity. The proposed reaction mechanisms and the roles of the catalyst AgBF4 were understood by control experiments and density functional theory calculations.
Macrocyclic cascade supramolecular assembly could significantly enhance the fluorescence/phosphorescence resonance energy transfer (F/PRET) efficiency through macrocyclic and spatial dual confinement effect. Herein, we reported a cascade supramolecular assembly containing 6-bromoisoquinolinium-modified permethylated cyclodextrin (BQ-PCD), cucurbit[7]uril (CB[7]), and tetra(4-sulfonatophenyl)porphyrin (TPPS), in which the enhanced PRET from 6-bromoisoquinolinium (BQ) to TPPS could be achieved through the dual macrocyclic confinement for multicolor delayed luminescence and information encryption. In TPPS$\subset$BQ-PCD$\subset$CB[7], pure organic room temperature phosphorescence of BQ-PCD at 530 nm is induced by CB[7] macrocyclic confinement, which further transferred to TPPS via spatial confinement, achieving delayed fluorescence at 645 and 715 nm with high PRET efficiency and quantum yield (17.9%). Meanwhile, reversible TPPS concentration-dependent multicolor luminescence was achieved in presence of competitive guest (methionine peptide), followed by porphyrin-photosensitization process, being applied in information encryption. This research presents a facile strategy for efficient PRET through macrocyclic cascade confinement assembly.
The fabrication of three-component supramolecular organic frameworks (SOFs) is a considerable difficulty owing to the intricate noncovalent interactions and the constraints of current synthesis techniques. In this study, we designed and synthesized two photosensitive modules: a naphthalene-modified triphenylamine derivative (NA-TPA) as the donor unit, and a trimethylated viologen-modified triphenylamine (MV-TPA) as the acceptor unit. These modules can self-assemble into a novel two-dimensional SOF via encapsulation-enhanced donor-acceptor interactions with cucurbit[8]uril (CB[8]) in the aqueous solution. The resulting donor-acceptor SOF forms stable two-dimensional nanosheet structures in water. Compared to the individual monomers NA-TPA and MV-TPA, the SOF enhances electron transfer and significantly improves the generation of superoxide anion radicals (O2•−), which in turn effectively promotes the photocatalytic cyclization reaction between o-phenylenediamine and benzaldehyde in water, achieving a yield of up to 94%. This work offers valuable insights into the design and construction of three-component SOFs based on encapsulation-enhanced donor-acceptor interactions for photocatalytic applications.
The generation of transient radical species via carbon–metal bond homolysis is extremely useful, which can be harnessed to promote useful and selective radical-type transformations by the combination of transition metal catalysis. We herein establish a carbon–metal bond homolysis/recombination model for the formation of enantiomerically enriched carbon-metal species, which accounts for the Ni-catalyzed enantioconvergent carboxylation of racemic benzyl ammonium salts with CO2. Theoretical studies suggest a distinct pathway involving a stereoinvertive nucleophilic substitution-type oxidative addition of racemic benzyl ammonium salts to Ni(0), forming a racemic benzyl Ni(Ⅱ) intermediate. Subsequent C–Ni bond homolysis of one enantiomer enables the formation of a transient radical, followed by a dynamic rotation along C–C· bond and radical recombination forming another more thermodynamically favored enantiomer. Geometry analysis suggests less H–H repulsion between the benzyl group and chiral ligand in the more stable isomer. After the reduction and stereoretentive inner-sphere nucleophilic attack on CO2 process, the desired enantiomerically enriched carboxylic acid product is generated. ETS-NOCV analysis reveals a significant back-donation interaction between the dx2-y2 orbital of Ni atom and the unoccupied π* orbital of CO2 in inner-sphere transition state, thus effectively stabilizing the Ni–CO2 complex and facilitating subsequent C–C bond formation. The theoretical calculations provide critical insights into the systematic development of transition metal-catalyzed asymmetric carboxylation, highlighting significant potential for broad applications in synthetic organic chemistry.
Although C2-symmetric C–C atropisomeric diphosphines such as BINAP and SEGPHOS, have achieved tremendous success in enantioselective catalysis in recent centuries, developing diphosphines based on new structural scaffolds is still highly desirable. Here, C2-symmetric N–N atropisomeric diphosphines have been synthesized and comprehensively analyzed. These diphosphines exhibit excellent substituent-dependent tunable dihedral angles comparable to other useful electron-enriched diphosphines. With the aid of these newly developed diphosphines, the transition-metal catalyzed enantioselective dearomatization of heteroaryls is carried out to yield final products with excellent enantioselectivities, indicating their exceptional stereoinduction abilities.
Chiral 1,2,3,4-tetrahydro-1,5-naphthyridines are frequently encountered in many bioactive compounds. However, the methods for their asymmetric synthesis are quite limited. Herein, we developed a straightforward and efficient route to enantioenriched tetrahydro-1,5-naphthyridines from pyridine derivatives tethered with alkene moieties (34 examples, up to 99% yield, 93% ee). The reaction proceeded via Csp2–H activation pathway initiated by site-selective deprotonation with the assistance of La[N(SiMe3)2]3/PyBox, followed by alkene insertion into the resulting La-aryl bond. The potential utility of the current method in organic synthesis was highlighted by scale-up synthesis of chiral product and its further transformations. Moreover, some of the products show a pronounced inhibitory effect on A549 cell activity. In addition, experimental studies and DFT calculations were carried out to elucidate the origin of enantiocontrol.
A kind of inherently chiral molecular barrels were efficiently constructed by a directional cascade hooping strategy. This strategy involves the anchoring of three nonsymmetric connecting arms onto a cap-dissymmetric bis(tetraoxacalix[2]arene[2]triazine) cage core, followed by hooping via imine condensation and reduction to afford the target molecular barrels with well-defined connectivity. The precise and high-yielding synthesis stems from both the bidirectional Ctriazine-N bond flipping dynamics and the reversible nature of imine formation. The molecular barrels comprise a bis(tetraoxacalix[2]arene[2]triazine) core encircled by a 72-membered loop, forming three fan-shaped cavities with inherent chirality and multiple endo-functionalized sites. The existence of multiple diastereoisomeric conformers due to the restricted Ctriazine-N bond flipping by the constrained loop structure was revealed by variable-temperature NMR studies and DFT calculations.
The typical organic perylenetetracarboxylate (PTC) luminophore suffers from limited bio-application due to its aggregation-caused quenching (ACQ) induced undesirable electrochemiluminescence (ECL) efficiency in aqueous solution. Herein, the ECL emission of PTC was highly improved through the ingenious coordination of PTC (ligand) with Tb3+ (metal ion) to prepare the Tb-PTC metal-organic framework (Tb-PTC MOF), which prevented the π-π stacking and the aggregation of PTC molecules in a homogeneous phase. Moreover, we found that the ECL emission of Tb-PTC MOF was further enhanced by regulating its morphology, pore size and electron transfer ability using different solvents during its synthesis procedure. Notably, under the mixture of DMF, EtOH, and H2O (v/v/v, 1:1:1), a mesoporous Tb-PTC MOF exhibited an outstanding ECL intensity, which may be attributed to two reasons. Firstly, the mesopore and rough surface of Tb-PTC MOF (luminophore) provided abundant active sites and enlarged contact surfaces for S2O82– (coreactant). Secondly, Tb-PTC MOF with higher electron transfer ability could accelerate electron/hole recombination to enhance its ECL emission. Additionally, Tb-PTC MOF with excellent ECL performance was applied as a luminophore to fabricate an ultrasensitive ECL immunosensor for cardiac troponin Ⅰ (cTnI) detection, related to acute myocardial infarction. The constructed ECL immunosensor exhibited a satisfactory linear range (1 fg/mL − 20 ng/mL) and a low detection limit of 0.48 fg/mL. This study provides a new trend for the preparation of PTC-based nanomaterials with highly efficient ECL performance, broadening the scope for sensitive immunoassay in disease diagnosis.
Tertiary N–CF3 compounds have attracted intensive attention due to their great significance in discovery of new lead compounds, however, the synthesis of tertiary diaryl N–CF3 derivatives is still challenging. Herein, we successfully edit diaryl N–H into thiocarbamoyl fluorides with trifluoromethanesulfonyl chloride by use of a PⅢ/PⅤ redox catalyst, leading to the formation of series of diaryl N–CF3 with silver fluoride. In addition, this process is also highly efficient to dialkyl and alkylaryl secondary amines. The mechanism investigation illustrated that the use of hydrosilane is crucial to the success of this transformation. It acts as both terminal reductants to cycle the PⅢ/PⅤ couple and fluoride acceptor to promote the reaction between less reactive amine and thiocarbonyl difluoride intermediate.
The site-selective C(sp3)-H functionalization is of great importance in synthetic chemistry. However, γ-amino C(sp3)-H functionalization of aliphatic amines remains challenging. Herein, we develop an efficient γ-C(sp3)-H acylation of aliphatic amines by cooperative photoredox NHC/Pd catalysis. The process entails the following key steps: (ⅰ) photoinduced palladium-promoted formation of aryl radical, (ⅰ) generation of transient γ-amino alkyl radical through aryl radical-mediated 1,7-HAT, (ⅲ) single-electron oxidation of Breslow enolate intermediate to persistent ketyl radical, and (ⅳ) radical/radical coupling of γ-amino alkyl radical with ketyl radical. The synthetic utility of this γ-amino C(sp3)-H acylation is illustrated by the conversion of readily available aliphatic amines to a diverse collection of γ-aminoketones, which serve as versatile building blocks to enable the synthesis of pyrrolines of interest in medicinal chemistry. The radical mechanism is supported by the results of various control experiments, in situ EPR analysis, radical trapping experiment, and isotopic labeling studies.
Nanobelts have attracted significant attention in both synthetic and supramolecular chemistry due to their distinctive structures and promising applications. However, their synthesis remains challenging due to the high strain inherent in their ribbon-like configurations. A promising approach to mitigate this strain involves incorporating heteroatoms, such as sulfur and oxygen, which not only alleviate strain but also introduce new functionalities. In this study, we report the synthesis of a novel C2-symmetric nanobelt, [7]cyclophenoxathiin ([7]CP), through a multi-step process. The structure of [7]CP was confirmed using NMR, mass spectrometry, and single-crystal X-ray diffraction, revealing a heptagonal frustum-shaped geometry. Host-guest interactions between [7]CP and selected fullerenes were investigated using UV–vis absorption, 1H NMR, and X-ray crystallography. Our findings demonstrate that [7]CP forms 1:1 complexes with fullerenes, exhibiting moderate binding through π−π interactions, with binding constants of 1638, 2534, and 3682 L/mol for C60, C70, and PC61BM, respectively. The reduced cavity size of [7]CP prevents the formation of dimeric complexes observed with [7]cyclophenoxathiin, while still allowing it to function effectively as a molecular container.
Metal-free nanoparticles capable of executing synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) under the action of a single-wavelength laser have garnered considerable attention. Here, a novel type of nitrogen-sulfur co-doped carbon nanoparticles (TG-CNPs) was synthesized from taurine and genipin using a solvothermal method in dimethylformamide. The TG-CNPs, with an average size of approximately 25 nm, demonstrated red and near-infrared absorption/emission in aqueous solution. TG-CNPs exhibited negligible dark cytotoxicity, excellent biocompatibility, and remarkable lysosomal localization ability. Upon 655-nm laser irradiation, TG-CNPs exhibited strong photothermal performance with a photothermal conversion efficiency of 30% along with the efficient generation of superoxide radicals (•O2−). Leveraging the enhanced permeability and retention (EPR) effect, TG-CNPs facilitated passive targeting and accumulation at the tumor site. Notably, following a single round of 655-nm laser treatment, the tumors in the mice were completely eradicated, with no evidence of recurrence observed over the subsequent five months. This study introduces a promising metal-free, heteroatom-doped carbon nanoparticle platform for effective synergistic PTT/PDT in tumor treatment.
Although the incorporation of deuterium has been widely researched, controlled deuterium labelling at precise sites is still very challenging. Herein, efficient catalytic synthesis of deuterated pyrroles is focused, the radical cyclizations of N-propargyl enamines were achieved from photoredox-mediated deuterated water splitting, giving deuterated pyrroles with deuterations at the C(sp2) and C(sp3) precisely. One or two-sites-deuterium incorporation as well as the controllable deuteration label at multi-H/D-exchange-sites, such as a methyl group, have been realized in high selectivity and efficiency via the solvent-controlled divergent deuterations. A halogen effect between solvents and substrates was proposed to initiate different catalytic cycles for the deuterations. The broad tolerance to substrates, the gram scale synthesis under natural sunlight irradiation and its applications in the synthesis of drug analogues further verified their practicality.
A concise asymmetric synthesis of the anti-influenza drug (–)-oseltamivir phosphate (1) has been accomplished in 9 steps with an overall yield of 24%, starting from ethyl propiolate. The key features in this synthesis include an efficient biphasic Pd-catalyzed regioselectively intramolecular Heck-type cyclization to provide access to the highly valued chiral six-membered carbocyclic architecture, a regioselective and diastereoselective nitroso hetero-Diels-Alder reaction to construct the bicyclic oxazine 4 as well as a Cu(OTf)2-mediated regioselective and diastereoselective nucleophilic substitution reaction of bicyclic oxazine 4 with 3-pentanol to yield the trans-1,2-substituted diamino cyclohexyl amyl ether 16 with the correct three contiguous stereocenters. This rapid functionalization of the advanced molecular framework would offer an effective strategy for the asymmetric synthesis of other oseltamivir phosphate analogues.
The intrinsic scintillation property of uranium has recently endowed this heaviest naturally occurring element with new opportunities for X-ray radiation detection and visualization. However, the low radiation stability of most uranium compounds hinders their practical application, particularly in X-ray imaging. Here, we presented a flexible two-dimensional uranium-organic framework (UOF, SCU-334) as an air-stable scintillating material for X-ray detection and, for the first time, a systematic investigation of X-ray imaging in UOFs. Following continuous high dose rate X-ray irradiation exceeding 50 Gy, which equals thousands of chest X-ray diagnoses, SCU-334 retains over 90% of its initial performance, representing a significant improvement over previously reported scintillating UOFs. The upgraded radiation resistance of SCU-334 is attributed to its flexible structure that dissipates energy more efficiently under high-energy particle bombardment through conformation fluctuation and relaxation. This work offers a promising approach to improve the radiation resistance of uranium-based scintillators.
Synthesizing 2-deoxyglycosides, prevalent motifs in bioactive molecules, presents significant challenges in stereocontrol and functional group tolerance. We report a metal-free, photo-induced O-glycosylation of glycals using acridinium salts under visible light. This method effectively couples diverse glycals with both carboxylic acids and alcohols, providing facile access to α-2-deoxyglycosides under mild conditions with broad substrate scope and functional group compatibility. The protocol exhibits high α-stereoselectivity with carboxylic acids and moderate α-selectivity with alcohols, enabling late-stage functionalization of complex molecules, including amino acids, peptides, and drugs. Mechanistic experiments implicate the possible involvement of radical intermediates, potentially operating via a chain reaction. Notably, 2-deoxyglycosylation of NSAIDs using this method enhanced their neuroprotective properties in vitro. This photo-induced strategy offers a practical and versatile platform for accessing complex 2-deoxyglycans relevant to medicinal chemistry and chemical biology.
Glial fibrillary acidic protein (GFAP) can serve as a promising early blood biomarker for Alzheimer's disease (AD). Existing assays mostly rely on antibody-based detection technologies, the preparation of antibodies is relatively complex, costly, and requires high storage conditions. In this study, we screened an aptamer specifically targeting GFAP (KD = 0.621 µmol/L) through systematic evolution of ligands by exponential enrichment (SELEX) technique for the first time and then applied which to develop a simple but sensitive fluorescent sensor by combining isothermal exponential amplification reaction (EXPAR) with hybridization chain reaction (HCR). The platform achieved a broad linear detection range (10 pg/mL to 10 µg/mL) and a low detection limit (0.24 pg/mL). The results detected by the proposed sensor were highly correlated with that detected by ELISA method (R = 0.9989, P < 0.0001). The work overcomes the limitations of antibody-based technologies and provides a promising solution for early diagnosis of AD.
The development of innovative strategies for inert B–H bond functionalization of carboranes and exploration of their potential applications represents a central task in organic chemistry. Here, we demonstrate the facile B–H bond functionalization in carboranes through a cage···Ⅰ(Ⅲ) interaction between a nido-carborane cluster and a hypervalent iodine(Ⅲ) unit. Both experimental and theoretical investigations reveal that the cage···Ⅰ(Ⅲ) interaction induces a charge transfer from the boron cage to the iodine moiety, which leads to a significant decrease of the negative charge at the B(9)–H site of nido-carborane. This facilitates the activation of the B–H bond and subsequent chemical transformations. The unprecedented cage···Ⅰ(Ⅲ) interaction offers a similar B–H bond activation mode as metal mediation. Furthermore, the treatment of nido-carboranes with the iodide(Ⅲ) reagent of PhI(OAc)2 affords nido-carborane-phenyl iodonium zwitterions as versatile synthons, which enable the modular construction of exopolyhedral B–O, B–N, B–P, and B–S bonds of carborane derivatives. This approach provides an efficient and scalable synthetic platform for metal-free and site-selective B–H bond functionalization of nido-carboranes under mild conditions. Notably, the developed 2D-3D fused structures can be used as ligands for the facile construction of novel boron cluster-fused hetero-polycyclic metal complexes in one step. These compounds demonstrate intriguing photophysical properties including aggregation-induced emission, tunable emission wavelength, and oxygen sensing.
Metal-organic frameworks (MOFs) with tunable structures provide a versatile platform for exploring active sites and show great potential in enzyme-like catalysis. In this study, arginine was employed as a modulator to synthesize an arginine-copper metal-organic framework (Arg-Cu-MOF), which demonstrated superior peroxidase-like activity and stability in comparison to unmodified Cu-MOF. The improved activity resulted from an increased density of Cu+ active sites, facilitating efficient •OH generation through H2O2 decomposition. Glyphosate interacts with the copper sites in a way that affects •OH generation and chromogenic substrate oxidation, leading to detectable colorimetric changes. By integrating Arg-Cu-MOF into a needle sensor, we allowed sample handling, reagent mixing, and signal readout, enabling both precise instrumental measurements and semi-quantitative visual detection of glyphosate. This sensor offers a detection range of 0.05–200 µg/mL with a detection limit of 0.049 µg/mL. This work highlights the potential of MOF modulation strategies and integrated detection platforms to enhance analytical performance, improve user-friendliness, and expand the application scope of biomimetic nanomaterials.
The host-guest doped strategy has become the main method for constructing organic phosphorescence materials. In the doped system, guest molecules emit phosphorescence, therefore, improving the luminescence performance of guests is the key to optimizing the phosphorescence property of the doped materials. Herein, we designed to introduce the carbonyl group on the guest molecules. Carbonyl group can effectively promote n-π* transitions, thereby increasing the spin-orbit coupling (SOC) constant of the guests, ultimately improving the phosphorescence performance of the doped materials. Using the indazole derivative (IZ) as the initial guest, two other guests containing carboxyl group (IZ-CG) or ethoxycarbonyl group (IZ-EG) were successfully obtained. Further selected two small molecules and two polymers as the hosts to construct four doped systems. Among these doped systems, the phosphorescence performance of doped materials with IZ-CG or IZ-EG as the guest is significantly better than that of doped materials with IZ as the guest. The phosphorescence lifetime has increased by 2.3-5.0 times, and the phosphorescence quantum yield has increased by 3.0-5.7 times. Theoretical calculations and single crystal structures indicated that carbonyl groups can not only increase the SOC constant, but also enhance the intermolecular interactions of the guests. In addition, doped material can be effectively used for imaging subcutaneous and lymph nodes in mice, achieving a high signal-to-noise ratio.
Coupling photocatalytic H2 generation with antibiotic degradation offers a promising strategy for addressing energy and environmental challenges, leveraging the synergistic benefits of these processes. Herein, a novel heterojunction photocatalyst consisting of ultrafine CeO2 nanoparticles anchored onto CdS nanosheets was prepared using a simple one-pot in-situ hydrothermal method, enabling the simultaneous photocatalytic H2 generation and tetracycline (TC) degradation. The H2 generation efficiency of the optimal CeO2/CdS (CC-0.10) is 3544 µmol g-1 h-1, which surpasses pure CdS by 29.3 times. Additionally, TC is degraded by CC-0.10 at a rate constant (k value) of 0.0352 min-1, 2.73 times faster than CdS (0.0129 min-1). The free radical quenching and electron spin resonance experiments revealed the active involvement of •OH and •O2- radicals in the TC degradation process. Moreover, the unique CeO2/CdS heterojunction photocatalyst was also effective in degrading TC wastewater with an H2 yield of 1374 µmol g-1 h-1, displaying its dual performance in simultaneously degrading antibiotic wastewater and producing H2. The CeO2/CdS type Ⅱ charge transfer mechanism is confirmed by XPS, EPR, KPFM, fs-TAS, and DFT calculations. This work introduces a promising approach to constructing rare-earth oxide/metal sulfide nanocomposites for addressing the interconnected challenges of energy production and environmental pollution.
Regulating gas diffusion is essential for a range of natural and industrial processes, including underwater breathing, aeration reactor and energy device. Natural organisms, e.g., water boatman, utilize their superaerophilic (SAL) abdomen to create a plastron underwater, enabling efficient gas exchange with dissolved oxygen. Herein, inspired by nature, we have developed a superaerophilic stripe that can form an air film underwater to enhance gas diffusion. Increasing the width (w) of the superaerophilic stripe and height (h) of water, along with decreasing the distance between the bubble and the stripe (d), can improve gas diffusion. Due to the improved dissolved gas diffusion, an efficient hydrogen evolution reaction driven by enhanced H2 diffusion was successfully achieved, resulting in an electrode potential decrease ~13 mV at the same current density of 1 mA/cm2 compared to that without the SAL stripe. This research offers important theoretical insights into the dynamics of gas diffusion and presents practical methods for enhancing gas mass transfer.
Exposure to different neonicotinoid insecticides (NNIs) can cause varying degrees of harm to mammals and may even be carcinogenic. Due to their similar molecular structures, it is not only difficult to distinguish NNIs in analysis, but also cross-reactions can also occur. These cross-reactions cause the calibration curves to exhibit strong nonlinearities that cannot be fitted by usual mathematical models. Here, we present an electrochemical sensor array comprising three sensing units for the simultaneous determination of imidacloprid, thiamethoxam, and nitenpyram. The method eliminates cross-reaction with the aid of machine learning. The machine learning model comprises three components: the Douglas-Peucker algorithm for data compression, principal component analysis for classification, and an artificial neural network for quantification. The randomly assigned validation set showed a classification accuracy of 96.3% for the model. The prediction accuracy was 98.77%. The limit of detection was < 0.037 µmol/L, with a detection range from 0.1 µmol/L to 200 µmol/L. Finally, the spiked tea samples were tested, and a satisfactory agreement was obtained between the expected and predicted values.
In this work, bis-trimethylammonium pillar[5]arene (TP5) was synthesized for ionic pair assembly with 4,4′-biphenyldisulfonic acid (BA) to prepare a new kind of ionic single crystals (TP5-BA). The single crystal structure revealed that TP5-BA adopted an ordered cross-stacked arrangement under the combined influence of electrostatic interactions and π-π stacking forces. It is worth noting that TP5-BA exhibited exceptional performance in the adsorption of iodine vapor, with an adsorption capacity as high as 3.27 g/g. After 6 days, its retention rate remained at a high level of 99.71%. This finding may open up a new direction in supramolecular chemistry with ionic pair self-assembly, not only for the development of novel iodine adsorbent materials but also for many other potential applications such as catalysis and energy.
Benzohydroxamic acid (BHA) occurs as recalcitrant organic pollutant discharged from mining industry. While Fenton-like oxidation based on peroxymonosulfate (PMS) has been extensively applied for organic contamination mitigation, its conventional reaction pathway dependent on free radicals needs high energy input with elevated carbon emission. Here, we meticulously developed a novel single-atom catalyst featuring Co-N4 coordination (Cox@NC) to initiate a non-radical Fenton-like oxidation for BHA treatment. Results showed single-atom Co-N4 with the considerable Co content (>2 wt%) and quantitative N coordination displayed exceptional reactivity to activate PMS for BHA degradation with a turnover frequency > 16 min−1. Such single-atom Co-N4 formed a surface-reactive complexes with mild oxidation potential by coordinating with PMS to mediate electron transfer for oxidation of BHA. The mediated ETP further triggered polymerization transformation pathway of BHA through formation and coupling of phenoxy-like radicals, resulting in a considerable recovery yield of BHA polymers (~43%) and superior utilization efficiency of PMS (~434%). Combined with ultrahigh-resolution mass analysis, the identified polymerized products illustrated the related polymerization mechanisms of BHA including hydroxylation, monomer radical generation, dimerization, and chain extension. Such Fenton-like catalysis of single-atom Co-N4 exhibited more remarkable application potentials in mineral processing wastewater treatment compared to traditional Fenton reaction, reducing oxidant consumption and increasing organic carbon recovery. This study enhances development of resource-efficient Fenton-like oxidation technologies for mineral processing wastewater treatment.
Metallocenes are a wide family of organometallic compounds, in which two cyclopentadienyl ligands "sandwich" a metal ion, M(η5-C5R5)2, and have considerable potential for use as components in molecular electronics applications. Here we have studied the electronic transport properties of the matallocenes MCp2 (M = V, Cr, Mn, Fe, Co, Ni, Ru; Cp = η5-C5H5) and MCp*2 (M = Mn, Fe, Co; Cp* = η5-C5Me5). Molecular junctions have been fabricated using either two gold, or one gold and one graphene electrode(s), giving rise to single-molecule conductance values of the order of -4 to -3 log(G/G0)) depending on both the nature of the metallocene and the electrode materials. Calculations on model junctions at the density functional theory level of theory reveal significant charge transfer from the metallocene to the junction electrodes and changes in the nature of the primary charge transport pathways in response to the nature of the metal, supporting ligands, molecular oxidation state and electrode composition.
Nickel-iron double hydroxides are corroded by Cl− during seawater electrolysis, which reduces their catalytic activity and stability. Here, a high-performance bifunctional electrocatalyst (NiFe-LDH/MoNi4) with enhanced chloride corrosion resistance was synthesized. In the OER process, Mo element in the catalyst was reconstructed to form MoO42−, which repelled Cl− to prevent the catalyst from being corroded. Besides, the heterostructure of NiFe-LDH/MoNi4 decreased the reduction of HER active site during HER process (Mo element dissolves easily in alkaline media due to thermodynamic instability). Therefore, based on in-situ self-reconstruction of Mo element and heterostructure in alkaline seawater, NiFe-LDH/MoNi4 delivered a current density of 10 mA/cm2 for the HER (OER) at industrial temperatures (80 ℃) with an overpotential of merely 32 mV (139 mV). Additionally, when NiFe-LDH/MoNi4 is employed as both the anode and cathode, a battery voltage of just 1.39 V (3.13 V) is sufficient to attain a current density of 10 mA/cm2 (1 A/cm2). The system is also capable of sustained operation at a high current density of 500 mA/cm2 for a period of 50 h.
Although periodate (PI) activation via iron-based Fenton-like reactions effectively generates reactive oxygen species (ROS) for pollutant degradation, Fe(Ⅲ) accumulation poses a major challenge to sustained ROS generation. Here, amorphous-boron (AB) was employed as a co-catalyst for boosting Fenton-like activation of PI (primarily Fe(Ⅲ)/PI) towards water decontamination, and the AB/Fe(Ⅲ)/PI process can promptly and steadily oxidize sulfamethoxazole (SMX) during 5 cycling tests. Through integrated qualitative and semi-quantitative analyses of ROS, including EPR, quenching, and chemical probes, AB can directly activate PI to produce hydroxyl radical and indirectly accelerate Fenton-like activation of PI to produce Fe(Ⅳ) by reducing Fe(Ⅲ). The synergetic routes of radical (hydroxyl radical) and non-radical (Fe(Ⅳ)) ensure the high capability of AB/Fe(Ⅲ)/PI for degrading a wide variety of contaminants with diversiform molecular structures. Moreover, characterizations (XPS, EPR, HAADF-STEM, HRTEM, Raman, and XRD) reveals the stepwise boron oxidation via B-B bond cleavage can sustainably donate electron for direct and indirect activation of PI. The self-cleaning surface caused by the synergetic stepwise oxidation of boron and dissolution of boron oxide maintains the high stability of AB for co-catalyzing Fenton-like activation of PI during long-term operation. Therefore, this study proposes a novel Fenton-like technique for eliminating organic contaminants with low iron sludge output and long-term stability.
The utilization of photoelectrocatalytic (PEC) technology for water pollution treatment and value-added chemical production is important in sustainable development strategies. A system combining Ag3PO4/g-C3N4 S-scheme heterojunction photoanodic oxidation with natural air diffusion electrode (NADE) reduction was designed. The PEC system could remove 94.5% of tetracycline (TC) with the first-order kinetic rate constant of 0.148 min-1, while the H2O2 yield in the cathodic chamber reached 4.3 µmol-1 h-1 cm-2 under 2.0 V cell voltage. The rate constant of TC degradation by the Ag3PO4/g-C3N4 coupled NADE PEC system was 4.4 times that of Ag3PO4/g-C3N4 coupled Pt PEC system (0.034 min-1). This was attributed to the synergistic effect between accelerated photoanode carrier transfer and increased H2O2 yield. The production of H2O2 in the cathode chamber of the PEC system with the presence of TC was 2.3 times that of absence of TC (1.9 µmol-1 h-1 cm-2). The active substances playing a major role in this PEC system were mainly h+ followed by •OH. Significantly, the efficient operation of the PEC system under actual sunlight will be conducive to the exploration of practical applications in the future. This study provides new insights for constructing efficient cathode-anode coupled PEC systems for water purification and simultaneous H2O2 production.
Improving the reactivity of Fe(Ⅲ) is the bottleneck in the catalytic activity of persulfate-based Fenton-like chemistry. In this study, the Fe(Ⅲ)-PA catalyst was prepared for the activation of persulfate (PMS) by co-precipitation of phytate with iron ions. In particular, the Fe(Ⅲ)-PA/PMS system achieved efficient degradation of the target pollutant TCH under a wide range of pH conditions from 3.0 to 9.0. In the Fe(Ⅲ) PA/PMS/TCH system, the oxidative degradation of TCH was mainly via the direct electron transfer pathway. Density functional theory (DFT) calculations revealed the mechanism of PMS activation potentiation, that is, phytate reduced the adsorption energy of the catalyst for PMS from -0.43 eV to -2.72 eV by coordination with the ferrihydrite. Moreover, Fe(Ⅲ)-PA functions as an electron shuttle and accelerates the electron transfer process between TCH and PMS. The removal of TCH under the electron transfer process (ETP) mediated by Fe(Ⅲ)-PA was selective, thereby demonstrating less sensitivity to the presence of co-existing ions and natural organic matter (NOMs). This work provides a viable case for ligand-enhanced Fe(Ⅲ) activation of PMS and reveals the critical role of direct electron transfer in pollutant elimination.
Aqueously dispersed nanomaterials exhibiting circularly polarized luminescence (CPL) hold great potentials in biological fields due to the inherent chirality of biological systems and its excellent biocompatibility. However, the limited availability of biodegradable CPL nanoparticles in aqueous media has severely constrained the development of biomedical CPL. Here, we present a facile strategy for achieving tunable CPL of aqueously dispersed nanotoroids through the co-assembly of a homopolypeptide with three achiral triphenylamine derivatives, showing a CPL performance depending on the architecture and doping content of small molecules. Remarkably, a deep-red CPL can be achieved with a record luminescence dissymmetry factor (glum = 1.1 × 10−2) among aqueously polypeptide-based nanoparticles. Furthermore, the densely packed nanostructure completely suppressed the intrinsic reactive oxygen species generation of the chromophores by restricting oxygen diffusion and quenching exciton-energy transfer, thereby eliminating phototoxic risks while preserving imaging fidelity. Overall, this work not only provides a facile method for achieving aqueous CPL from achiral molecules but also establishes a structure-property relationship between chromophore geometry and supramolecular CPL performance, advancing their potential in biological fields.
Lactate (LA) is now recognized as a critical carbon source for tumor metabolism, making its transport blockade a promising anticancer therapeutic strategy. In this study, we incorporated α-cyano-4-hydroxycinnamate (CHC) into hollow-structured CuS@PCN nanoparticles to inhibit LA influx by suppressing the expression of the monocarboxylate transporter 1 (MCT1) in tumor cells. This intervention shifted tumor cell metabolism from LA-fueled oxidative phosphorylation towards anaerobic glycolysis, consequently elevating intratumoral oxygen (O2) levels. The photosensitizer-based metal-organic framework (PCN) component was then able to efficiently convert this elevated O2 into abundant reactive oxygen species (ROS), thereby enhancing photodynamic therapy (PDT) efficacy. Notably, the hollow mesoporous CuS nanoparticle core functioned dually as a high-capacity CHC carrier and a photothermal agent that enables CHC release under near-infrared (NIR) irradiation. Further surface conjugation with folic acid-polyethylene glycol (FA-PEG) imparted tumor-targeting specificity via folate receptor recognition and prolonged systemic circulation. Both in vitro and in vivo evaluations demonstrated the excellent biocompatibility and significantly improved PDT performance of the synthesized CHC-CuS@PCN-FA (CHC-CP-FA) nanoplatform. These findings underscore the considerable potential of CHC-CP-FA for future cancer treatment applications.
Chemical scavengers are frequently used to quantify the contribution of target radicals to contaminant removal in natural and engineered waters. While favored for their ease of use and versatility across systems, improper selection can lead to significant kinetic and mechanistic misinterpretations. This study presents a critical evaluation of chemical scavengers in radical-induced reactions across various environmental scenarios. Specifically, we demonstrate that in systems containing both target and coexisting radicals, commonly used scavengers can react with both species, complicating the measurement of reaction kinetics and leading to misinterpretation of target radical contributions. In addition, we discuss the challenges associated with applying scavengers in heterogeneous systems, where the distribution of scavengers and target compounds across interfaces significantly impacts the evaluation of radical contributions. Further, our insights from non-steady-state systems into radicals' dynamic behavior and transient phenomena are often overlooked in other steady-state conditions. We address interactions between scavengers and triplet excited-state compounds in photochemical systems, emphasizing the importance of selecting appropriate scavengers to ensure accurate kinetic profiling and radical quantification. These findings hold significant implications for advancing scavenger research across a broad range of chemical research and practical applications.
Chlorine is not only widely used as an important basic chemical, but also shows promising in-situ electrochemical remediation. Unfortunately, its electrochemical production usually relies on expensive noble-metal dimensionally stable anode (DSA). Herein, a high-performance non-noble metal Co3O4/Ti anode was developed by a simple electrodeposition-calcination method, demonstrating a high efficiency in producing active chlorine in a wide pH range (3–11) and at relatively low Cl- concentration close to different real environmental requirements due to its abundant surface area and active sites provided by the interlaced nanosheet structure anode. Compared with commercial DSA, the Co3O4/Ti anode offered significant advantages in terms of Faraday efficiency, electric energy consumption and economic cost, achieving the rate of active chlorine production of 14.97 mg L-1 min-1 in 0.5 mol/L NaCl electrolyte solution (pH 6) with a Faraday efficiency of 96.8% and low energy consumption of 2.49 kWh/kg. Moreover, the robust backbone structure of the anode enabled the Faraday efficiency to be maintained at about 92.2% without deactivation after ten cycles of reaction. In addition, this Co3O4/Ti electrode demonstrated effectiveness in treating organic pollutants and mariculture wastewater and seawater rapid sterilization. This study provides new inspirations for the construction of highly efficient, low-cost, and low energy consumption non-noble metal cobalt-based anode for the in-situ environmental remediation application.
Per- and polyfluoroalkyl substances (PFASs), especially perfluorooctanoic acid (PFOA), pose a significant threat to ecosystems and human health due to their extreme persistence and bioaccumulative properties. Although metal-organic frameworks (MOFs) show potential for adsorption, their efficiency is limited by insufficient active sites and the inability to control the design of adsorption centers, which is a key bottleneck for practical application. In this study, defect engineering was employed to synthesize NH2-UiO-66 derivatives with gradient defect densities (NH2-UiO-66, -LD, -HD), exposing unsaturated Zr sites to enhance PFOA capture. The optimized NH2-UiO-66-HD exhibited ultrafast kinetics, achieving 95% removal within 30 min and a theoretical adsorption capacity of up to 739.31 mg/g, surpassing most MOFs and traditional adsorbents. Mechanistic studies revealed that defect-induced unsaturated Zr sites act as high-affinity anchors, strongly coordinating with the -COO- group of PFOA, while forming a triple interaction mechanism with N–H···F hydrogen bonds and electrostatic interactions (-NH3+), a synergy not previously reported. The material maintained over 90% efficiency through seven cycles, addressing long-standing regenerability challenges in PFAS remediation. This research pioneers a programmable defect-control approach to create hierarchical active sites in MOFs and first demonstrates the synergy of Zr coordination, hydrogen bonding, and electrostatic attraction for ultra-efficient PFAS removal.
The high sensitivity of platinum (Pt)-based catalysts to CO during the hydrogen oxidation reaction (HOR) at the anode is one of the key issues for the long-term stable development of proton exchange membrane fuel cells (PEMFCs). Modulating the electronic structure of Pt is considered an effective approach to enhancing HOR activity and improving CO tolerance. Herein, we utilized the synergistic effect between the transition metal interstitial compounds (TMICs) of VN and Pt to develop a Pt-VN heterojunction-loaded carbon nanofiber catalyst (Pt-VN/NCNF) for CO tolerance in HOR. The introduction of VN causes electronic orbitals rearrangement of Pt, thereby optimizing the adsorption of H on the Pt surface. Meanwhile, the overlap of the d-band of the electron-deficient Pt with the 1π and 5σ bonding orbitals of CO was significantly reduced, which suppresses the strong CO adsorption on Pt surfaces and leave more active sites for H2 adsorption and oxidation. As a result, Pt-VN/NCNF exhibits a mass activity of 1.26 mA/µgPt, 41 times higher than that of commercial Pt/C. Encouragingly, Pt-VN/NCNF maintains 96.7% of its original activity even in the presence of 1000 ppm CO. As anticipated, Pt-VN/NCNF-based PEMFCs demonstrate superior CO tolerance to Pt/C in H2/CO mixtures with CO concentrations ranging from 10 ppm to 1000 ppm.
To elucidate the regulatory mechanisms of interlayers on interfacial polymerization (IP) dynamics and thin-film composite (TFC) membrane performance, UiO-66 and its derivatives with tailored properties were synthesized and employed as interlayers to fabricate TFC membranes. The influence of interlayer's charge and porosity on IP reaction was systematically investigated based on the forward osmosis (FO) system. Results showed that the introduction of the UiO-66 interlayer promoted the diffusion of the reactive monomer during the initial stage of the IP reaction, resulting in a wrinkled and thin polyamide (PA) layer. Compared to the pristine TFC membrane, the UiO-66–0% interlayered TFC membrane exhibited 2.7-fold enhanced water permeability (21.67 L m−2 h−1 (LMH)) but reduced salt rejection (3.69 g m−2 h−1 (gMH)). Incorporation of amino-functionalized UiO-66–30% with enhanced positive charge induced a double-layer PA structure, reducing water flux to 15.13 LMH. Engineering hierarchically porous UiO-66 (HP-UiO-66–30%) achieved balanced performance, maintaining high flux (21.04 LMH) while significantly improving rejection (1.39 gMH). This study demonstrates that strategic modulation of nanomaterial functionality and porosity enables precise PA layer engineering for high-performance TFC membranes with simultaneously enhanced permeability and selectivity.
Porous liquids (PLs), as a new class of porous materials with permanent porosity and liquid fluidity, have attracted extensive research interest due to their excellent physical and chemical properties. Herein, we synthesized a chiral porous liquid D-his-ZIF-8-[Bpy][NTf2] based on a metal-organic framework (MOF) and used it as a new stationary phase to investigate its separation performance by high-resolution gas chromatography. The porosity of this porous liquid system was verified through Brunauer-Emmett-Teller (BET) and positron (e+) annihilation lifetime spectroscopy (PALS). The results showed that the D-his-ZIF-8-[Bpy][NTf2] coated capillary column (column A) exhibited excellent separation performance for n-alkanes, n-alcohols, alkylbenzens, isomers, and racemic compounds. Among them, fifteen pairs of enantiomers including alcohols, esters, epoxides, ketones, haloalkanes, and amino acid derivatives were well separated on column A with good reproducibility and stability. The relative standard deviations (RSDs) of the retention time and peak area of two analytes (3-butyne-2-ol and dichlorobenzene) were <1.80% and 0.80%, respectively. By comparing the chiral recognition ability of D-his-ZIF-8-[Bpy][NTf2] coated column A with D-his-ZIF-8 coated column B, the column A has better separation efficiency for chiral compounds than column B. In addition, the chiral recognition ability of column A is complementary to that of commercially available β-DEX 120 column (column C). Compared with the commercial HP-35 column and the previously reported P5A-C10–2NH2 column for the separation of organic mixtures and/or isomers, column A exhibits similar separation performance and has a good separation complementarity to these two columns. Hence, this work opens up a new way for the practical application of porous framework solid materials in gas chromatography.
Geometrical configurations at the nanometer scale are inherently linked to electronic properties, offering exciting opportunity to engineer the latter through precise structural control. The honeycomb structure, a prominent geometry in two-dimensional materials like graphene, has become a versatile platform for advancing energy technologies, quantum computing, and nanoscale sensing. Achieving a perfect honeycomb network at large scale remains challenging but desired, especially when atomic defects and disorder can severely impact materials' properties and performances. Intrinsic topological defects often persist due to the conformational flexibility of the precursor skeletons, which allows precursor monomers to deform despite variations in preparation parameters. To address this challenge, we employ a tripod molecular precursor, pTBPT, combined with ultrahigh vacuum on-surface synthesis. Networks comprising rings of different edges are initially formed after deposition of pTBPT on Cu (111) at room temperature to 420 K. At low coverage (~0.015 monolayer) selenium doping, we achieve the fabrication of ordered honeycomb networks with much improved structural homogeneity. Selenium doping facilitated the formation of ordered two-dimensional metal-organic nanostructure from 360 K to 480 K. The disorder−order transition of molecular networks through selenium doping on Cu (111) is explored through high-resolution scanning tunneling microscopy (STM). A persistent homology method is resorted to quantify the degree of order of our patterns. The regulation of energy diagrams in the absence or presence of the selenium atom is revealed by density functional theory (DFT) calculations. These findings can enrich the on-surface synthesis toolbox of conformationally flexible precursors, for the design of ordered nanoarchitectures, and for future development of engineered honeycomb nanomaterials.
In light of the prevalent issues associated with metal ion dissolution, secondary pollution, and poor stability in traditional metal-based Fenton catalysts, this study innovatively developed a metal-free carbon-based catalyst co-doped with Si-O bonds and graphitic nitrogen using natural diatomite as the precursor. By leveraging the synergistic effects of Si-O bonds and graphitic nitrogen, the electronic structure of the carbon matrix was effectively modulated, establishing an efficient electron transport channel for peroxymonosulfate (PMS) activation. Results showed that the Fenton-like performance of the resulting catalysts was far superior to those of traditional metal catalysts and can be comparable to various single-atom catalysts. Both the radical and 1O2 pathways exhibited a negligible role in the metal-free Si-O/N@DM/PMS systems. In contrast, electron transfer process (ETP) was the predominate oxidation pathway for acetaminophen (PCM) degradation in the Si-O/N@DM/PMS systems. To facilitate engineering applications, we further designed a proton membrane reactor integrated with a four-channel PMS system, which could introduce an enlarged ETP pathway for pollutant degradation; this addresses the key issues of both sulfate pollution and metal leaching in water caused by traditional metal-based Fenton systems.
Eliminating heavy metals from industrial high-salinity wastewater is imperative for sustainable industrial development and environmental protection. Herein, a citrate-modified biochar that demonstrated robust anti-salt interference was developed. The sorbent achieved an adsorption capacity of 252.14 mg/g in 4.1 mol/L NaCl solution and 232.55 mg/g in 1.4 mol/L Na2SO4 solution, maintaining efficient Cu(Ⅱ) adsorption over four cycles. It retained an adsorption capacity of 236.89 mg/g in real waste salt-derived brine. Adsorption followed pseudo-first-order kinetics (k = 0.0901 min-1) and conformed to the Langmuir isotherm (qmax = 251.21 mg/g) model, indicating that physical adsorption on a homogeneous surface primarily governs the adsorption mechanisms. Thermodynamic analysis revealed that the adsorption is spontaneous and endothermic, with enhanced affinity for Cu(Ⅱ) at higher temperatures. Oxygen-containing groups, especially the hydroxyl group, drove adsorption via surface precipitation/complexation, ultimately generating posnjakite (Cu4(SO4)(OH)6·2H2O). Cost analysis showed that the total expenditure for treating 1000 L of wastewater (300 mgCu/L) was $28.89 ($0.0963/gCu(Ⅱ)) and the treatment capacity using fixed-bed columns was 120 L/kg. These findings offer a viable and cost-effective strategy for Cu(Ⅱ) elimination from high-salinity wastewater.
Non-noble metal catalysts have garnered significant attention as sustainable alternatives to precious metal catalysts for the abatement of hydrocarbon emissions and mitigating environmental pollution. In this study, we employed an in-situ exsolution strategy coupled with oxidation stabilization to engineer the surface of cobalt-doped LaFeO3-δ catalysts, successfully extending their application in an oxygen-rich scenario. The formed unique socket-like structure facilitates the exposure of highly reactive CoOx particles with superior homogeneity in both size and distribution. The optimized catalyst, CoOx@LFCO-3, achieved 90% toluene conversion at a notably lower temperature of 237 ℃ with a space velocity of 20,000 mL g−1 h−1. Mechanistic studies revealed that the enhanced interaction between exsolved cobalt oxides and the perovskite support, along with abundant active sites, significantly improved the catalyst's performance in low-temperature toluene oxidation. This work presents a scalable approach for developing cost-effective, high-performance perovskite oxide catalysts for environmental applications.
The preparation of porous molecularly imprinted polymers (MIPs) from starch, a natural product, presents significant challenges. In this study, we developed a straightforward method for preparing porous MIPs (DFP-MIPs) by crosslinking short amylose as a functional monomer with decafluorobiphenyl (DFP) as a cross-linker. Experimental results indicated that DFP-MIPs exhibited a larger specific surface area (14.06 m2/g) and adsorption capacity (26.3 mg/g), and a high imprinting factor of 3.14 for estradiol (E2), compared to MIPs prepared using tetrafluorobenzenediamine with a single benzene ring as the cross-linker. A method for detecting E2 in milk and meat samples was also established using DFP-MIPs as the adsorbent in conjunction with high-performance liquid chromatography. Under optimal conditions, this method demonstrated a linear range of 0.0200–0.400 µg/g, a detection limit of 0.00300 µg/g, and a recovery rate of 85.2% to 101.4%. The proposed method for preparing DFP-MIPs is expected to provide a new pathway for the development of porous and highly selective MIPs using amylose.
Developing a supramolecular polymer gel based on carbonized polymer dots with highly efficient lubrication properties is very challenging. Here, we obtained a kind of carbonized polymer dots (CPDs) by thermal reflux of long-chain aliphatic amines in halogenated benzene solvents. The CPDs nano-gel achieved high lubrication performance due to entangling effect of long chain and reversible thixotropic behavior after gel formation. Two-dimensional correlation synchronous (2D-COS) showed the CPDs connect small carbon dots into large hydrophobic structures through their own dense chain entanglement, thus trapping oil to form gel. Chain entanglement, as a non-permanent crosslinking, can slide under stress, and this flexible and dynamic characteristic allows it to maintain efficient and long-lasting lubrication without hysteresis during friction. The tribological test results showed a significant reduction of 38.14% in the coefficient of friction and 93.71% in wear scar diameter after lubrication with CPDs nano-gel. Moreover, the serial analysis for the friction interface and computational methodologies revealed that the formation of tribochemical film between friction pairs is the key to reduce wear. This study underscored the possibility of utilizing carbonized polymer dots for self-assembly applications, and we anticipate that supramolecular carbonized polymer dots gels have great potential in lubrication and emission reduction, ultimately contributing to the development of a sustainable society.
Rational design of nonmetallic heteroatom-doped biochar catalysts for peroxymonosulfate (PMS) activation faces dual challenges in regulating electronic structures and clarifying non-radical pathways. This study addressed this through a nitrogen-oxygen co-doped biochar (NOBCBM) synthesized via mechanochemical ball milling and chemical doping. Co-doping of C=O, pyridinic N, and graphitic N synergistically enhanced electron transfer and PMS activation efficiency compared to single N-doped biochar systems. The optimized NOBCBM removed 94% oxytetracycline (OTC) (20 mg/L) in 30 min, with a kinetic constant (kobs = 0.1523 min−1) over twice that of NSBCBM (0.0664 min−1). Radical quenching and electron paramagnetic resonance identified singlet oxygen (1O2) and electron transfer as dominant non-radical pathways. Density functional theory (DFT) calculations revealed oxygen doping elevates local electrostatic potential and redistributes electron density at N-active sites, amplifying catalytic activity. The system demonstrated robust catalytic performance across pH 3–11, high salinity, and complex water matrices, maintaining > 80% OTC removal over 72 h. Plant growth assays and life cycle assessment (LCA) confirmed minimal ecological impacts, with purified water supporting normal seedling development. This work elucidates the critical role of N/O co-doping in steering PMS activation toward non-radical mechanisms while establishing a sustainable paradigm for metal-free biochar catalysis in water remediation.
Spontaneous resolution is a way for constructing chiral compounds from achiral modules, but the products are usually stochastic, which is unsuitable for enantioselective applications. Herein, a pair of chiral hydrogen-bonded frameworks assembled from achiral modules was reported. By introducing reusable chiral inducers, enantiomerically enriched NKU-777-xD/xL were obtained and exhibited superior enantioselective sensing performance. Notably, the amount of chiral inducer shows a positive correlation with the enantioselective sensing function, reflecting the degree of enantiomeric excess of NKU-777-xD/xL. Molecular-level mechanism studies reveal that competitive absorption governs the sensing functions of NKU-777-xD/xL, and the enantioselectivity is due to the enantioselective interactions of the hydrogen-bonded frameworks with targeting chiral molecules. This work not only provides a facile way to synthesize enantiomerically enriched chiral hydrogen-bonded frameworks from achiral modules using reusable chiral inducer but also gains insights into the inducer-controlled enantiomerically enriched chiral compounds for enantioselective applications.
Molecular glues (MGs) represent a promising approach in protein regulation, especially for "undruggable" targets. Despite the advantages over traditional protein inhibitors and proteolysis-targeting chimeras (PROTACs), MGs show various off-target effects, inducing general toxicities in patients. Herein, we describe a structure-guided design of visible-light photocaged MGs (vc-MGs), which precisely and spatiotemporally control the G1 to S phase transition 1 (GSPT1) protein level and Burkitt's lymphoma through visible-light irradiation in vitro and in vivo. Notably, activated VL-MG-9 showed a potent antitumor effect in the RAMOS xenograft mouse model, while VL-MG-9 alone has no GSPT1 degradation activity or general toxicity in various organs even at high dose. Furthermore, proteomics assay and apoptosis analysis confirmed the selectivity and safety of VL-MG-9. Significantly, pharmacokinetic results demonstrated the enhanced permeability and bioavailability (F%) of VL-MG-9. These data clearly reveal the practicality and importance of vc-MGs as preliminary tool for the targeted therapy of malignancies with reduced systemic toxicity and improved druggability.
The visible light photocatalytic gem‑carboamination reactions of α-diazo esters by using o-hydroxyaryl enaminones and amines as reaction partners have been realized, leading to the straightforward synthesis of chromone derived α-amino esters which could be easily hydrolyzed to functionalized α-amino acids. The reactions mediated by molecular iodine proceed via free radical pathway under metal-free conditions. Unlike the conventional carbene-based functionalization of diazo compounds involving nucleophilic/electrophilic or two electron neutral groups, the current protocol allows the installation of two nucleophilic functional structures to the carbon center, providing practical new tool for the synthesis of amino acids.
The unstable solid electrolyte interphase (SEI) characterized by sluggish ion transport kinetics and consecutive side reactions poses a major challenge to the commercialization of sodium-ion batteries (SIBs). Here, ethoxy (pentafluoro) cyclotriphosphazene (PFPN) as a multifunctional electrolyte additive is reported to construct stable and highly ion-conductive SEI. PFPN decomposes preferentially to form the NaF, Na3N-rich SEI with fast Na+ migration kinetics due to its low lowest unoccupied molecular orbital energy and strong adsorption on hard carbon (HC) anode. Meanwhile, the incorporation of PFPN effectively suppresses exothermic reactions at the electrode/electrolyte interface, thereby reducing the risk of thermal runaway. As expected, the HCNa cell with PFPN additive demonstrates homogeneous sodium deposition on HC anode and delivers a high reversible capacity of 248.5 mAh/g with negligible capacity decay after 1000 cycles at 0.1 A/g. The NaNi0.33Fe0.33Mn0.33O2 (NFM)HC full cell also yields enhanced cycling stability under -20 ℃. This study proposes a simple and effective SEI regulation strategy for high-performance and safe SIBs.
A homogeneous dual catalytic system that synergistically merges photochemical and halogen-bond catalysis has been developed for the radical sulfonylation-annulation of (hetero)arene-tethered alkynes and alkenes with RSO2Cl. This protocol efficiently constructs a variety of sulfonylated fused-(hetero)arenes with good functional group compatibility under mild and eco-friendly conditions. The process is initiated by halogen-bond activation of RSO2Cl, which facilitates subsequent photocatalyzed heterolytic S-Cl cleavage via a SET pathway to generate RSO2 radicals; an alternative EnT pathway for radical generation was also identified.
Despite the enormous potential of heteroatom-doped carbon materials for sodium storage applications, direct doping strategies still face two critical unresolved challenges: Elucidating the modulation mechanism of heteroatom doping on the hybrid energy storage behavior of sodium-ion hybrid capacitors (SIHCs), and maintaining structural integrity while achieving high sulfur-nitrogen (S, N) co-doping levels. Herein, we report a facile and controllable synthetic approach for preparing highly S, N co-doped porous carbon (denoted as SNGN-1), using sodium gallate, pre-synthesized via the neutralization reaction of gallic acid with sodium hydroxide, as the precursor. The as-fabricated SNGN-1 possesses a high nitrogen content of 4.02 at% and a sulfur content of 1.31 at%, coupled with abundant structural defects, a large specific surface area, superior electronic conductivity, exceptional sodium storage capability and robust cycling stability. Computational results demonstrate that the Na+ adsorption energy (Ead) of SNGN-1 is -1.936 eV, corresponding to a substantial increase in the absolute value relative to its undoped counterpart; additionally, the incorporation of heteroatoms leads to a marked intensification of the valence and conduction band peaks near the Fermi level. When employed as the anode for sodium-ion half-cells, SNGN-1 delivers a high reversible capacity of 585 mAh/g at a current density of 0.1 A/g, and retains stable cycling performance even after 1000 cycles at 2 A/g. More impressively, the SIHC device assembled with SNGN-1 as the anode achieves remarkable energy/power density metrics, delivering a high energy density of 165.2 Wh/kg at a power density of 218.6 W/kg. These findings highlight the great potential of SNGN-1 as a high-performance anode material for advanced sodium-ion batteries and SIHCs, thereby paving the way for the development of next-generation low-cost energy storage systems.
In the context of the continuously increasing energy demand, the ongoing advancement of innovative energy storage technologies is regarded as an important strategy to alleviate the energy crisis. Among various energy storage technologies, supercapacitors (SCs) demonstrate significant potential in the future energy storage sector due to their exceptional high-power density and long cycle life. As the core component of SCs, the choice of electrode materials is crucial to their performance, with carbon materials being favored for their excellent electrical conductivity and large specific surface area. In particular, porous carbon materials derived from biomass-based polymers have become a research hotspot due to their unique advantages. Through chemical modification and high-temperature carbonization, these materials can form more stable and optimized porous structures, significantly enhancing their electrochemical performance while meeting environmental protection requirements, thereby highlighting their superiority as electrode materials. This article aims to review the sources, production, and applications of carbon materials derived from biomass-based polymers. We have deeply summarized the preparation and activation methods of carbon from different biomass-based polymer sources. In addition, a comprehensive analysis and systematic comparison of novel modification techniques, such as heteroatom doping, copolymerization, and the incorporation of nanomaterials, were performed to enhance the performance of SCs. Finally, according to the technical challenges to be solved, the goal of large-scale development of biomass-based polymer-derived porous carbon in the field of energy storage is proposed, which is crucial for coping with the global energy crisis and reducing environmental impact.
Solid-state batteries that present lower risk factors and higher energy density are promising for advanced energy storage and applications. In particular, solid-state electrolytes (SSEs) are the critical components that responsible for ionic transport between negative electrodes and positive electrodes. It is crucial to fundamentally understand the ionic transport models and behaviors in the SSEs, with purpose of enhancing ion transport rate and stability of SSEs. To rationally improve the solid-state ion transport behavior of electrolytes, this review summarizes recent progresses on the transport principles and multiscale characterization methods of ion transport in SSEs, including traditional electrochemical methods, frequency-dependent spectroscopy, two-dimensional morphological imaging and three-dimensional morphological imaging. It is emphasized that combination of multiscale and multiple methods would be a developing trend for fundamentally understanding the mechanism of ion transport in SSEs. According to comprehensive transport principle and behaviors, hierarchical fillers are designed for composite electrolytes with fast ionic transport abilities. The remaining challenges for establishing advanced multiscale characterization methods are also discussed.
Inflammatory bowel disease (IBD), which includes Crohn’s disease and ulcerative colitis, represents a significant health challenge due to its intricate interplay of genetic, environmental, and immunological factors. While current treatments are effective at managing symptoms, they are not without drawbacks, such as potential side effects, the financial strain on patients, and the risk of complications. Nanotechnology presents an innovative solution to these challenges, offering the potential to improve the bioavailability, stability, and precise delivery of natural compounds with potent anti-inflammatory properties. This review examines the array of nanoparticle (NP) delivery systems that are revolutionizing IBD treatment, including lipid-based NPs, polymeric NPs, metallic NPs, plant-derived exosomes, and mesoporous silica NPs. Furthermore, the review explores the various responsive mechanisms of NPs, including pH-responsive, reactive oxygen species (ROS)-responsive, enzyme-responsive, charge-mediated, ligand-receptor targeted, and multi-responsive systems. The therapeutic potential of nanomedicines derived from natural products is highlighted, with a focus on their roles in immunomodulation, reducing inflammation, repairing the intestinal barrier, and modulating the gut microbiota. Nanotechnology boosts IBD treatment with novel natural NPs. NPs delivery systems offer notable benefits, such as improving drug solubility, increasing the efficiency of absorption, alongside providing a controlled and sustained release of therapeutic agents directly at the inflammation site. Despite the promising capabilities of nanotechnology in IBD treatment, obstacles remain. These include the necessity for comprehensive toxicological assessments, formulating strategies to guarantee the safety and effectiveness of these innovative treatments. Therefore, this review provides a systematic analysis that provides guidance for the research and development of NPs based natural products.
Infected bone defects (IBD) are intricate and formidable conditions characterized by elevated rates of infection recurrence and delayed healing, resulting from dysregulation of the bone immune microenvironment (IME) mediated by microbes. The conventional approaches including surgical intervention and antibiotic therapy encounter challenges such as antibiotic resistance and susceptibility to postoperative infections. Considering the diverse impacts of various immune cells (ICs) and cytokines, the investigations into the IME have been conducted to offer potential strategies for treating IBD by addressing the requirements of infection eradication and bone regeneration (BREG). However, there is still a lack of review discussing the impacts of IME on IBD in light of its diverse components. Hydrogels, as promising materials in the treatment of IBD, can mimic the extracellular matrix of natural tissues, providing an optimal environment for cell growth and tissue regeneration. Recent studies have focused on investigating immune modulation through hydrogel delivery for treating IBD. This review aims to discuss the effects of different types of ICs and cytokines on the IME in IBD while summarizing current progress and strategies targeting this microenvironment using hydrogels. The insights gained from this review will aid the development of future immunomodulatory approaches for IBD treatment.
Hepatocellular carcinoma (HCC) is the most common type of primary liver cancer and is among the leading causes of cancer-related mortality. Immunotherapy strategies targeting HCC are widely used in clinical practice. However, the pronounced immunosuppressive characteristics of the tumor microenvironment in HCC significantly hinder the efficacy of immunotherapy, often leading to suboptimal therapeutic outcomes. Innovative immunomodulatory delivery systems offer a promising path for HCC therapy by enabling precise targeting of tumor sites and significantly reducing the chances of systemic toxicity and side effects. This study describes the immune microenvironment of HCC and the mechanisms leading to immune evasion. This study then explores the issues and restrictions of current mainstream immunotherapies, highlighting the breakthroughs achieved through drug delivery systems crafted with innovative micro-nanomaterials for HCC immunotherapy. Besides, the application scenarios and challenges encountered by micro-nanomaterials in clinical translational applications were also discussed, and future development trends in this field were prospected, offering a theoretical foundation for the design of efficient HCC treatment strategies.
Ocular posterior segment diseases (OPSDs), including uveitis, glaucoma, retinitis pigmentosa (RP), fundus neovascular diseases (FNDs), and age-related macular degeneration (AMD), are major causes of global blindness. The eye's biological barriers often prevent conventional drugs from reaching the posterior segment effectively, while potentially causing adverse effects. Nanocarrier-based drug delivery systems (DDS) offer promising solutions, with their small size, tunable properties, and high biocompatibility enhancing drug permeability, stability, and targeted delivery. These systems may reduce administration frequency, prolong therapeutic effects, minimize side effects, and improve patient compliance. Unlike previous reviews, this article comprehensively examines novel nanocarriers for OPSD treatment. We first analyze small molecules, their nanocarriers, and administration methods based on recent two-decade research. Next, we compare nanocarrier stability, biocompatibility, ocular penetration, drug release kinetics, and formulation ease, emphasizing recent advances in design, preparation, and functional modification. Finally, by evaluating clinical applications and challenges, we discuss translational hurdles and future prospects for OPSD nanotherapeutics. Greater research efforts are needed to realize nanocarriers' full potential in OPSD treatment.
Tetrahedral framework nucleic acids (tFNAs), a novel class of nanodelivery carriers, demonstrate significant potential due to their well-defined topological structure, programmable molecular recognition capabilities, and exceptional biocompatibility. This article systematically reviews the dynamic behavior of tFNAs across multi-scale delivery processes. At the macroscale, it elucidates the organ accumulation and metabolism of tFNAs following various routes of administration. At the microscale, it delves into the transmembrane transport mechanisms and subcellular localization characteristics of tFNAs. Furthermore, this review discusses the current research status of strategies aimed at improving the delivery efficiency of tFNAs through active targeted modifications and proposes cutting-edge approaches to developing precision delivery systems leveraging engineering modifications and intelligent response designs.
Hydrogels, soft materials made from polymer networks capable of absorbing water, demonstrate remarkable compatibility in diverse hybridizations. When the fillers that can undergo reversible crystallization are used for incorporation, the materials’ mechanical properties and functions would be significantly improved. Therefore, these hydrogels, named crystal hydrogels, are emerging as a class of new advanced functional materials. This review offers a comprehensive examination of these materials from five distinct angles. We first discuss their fundamental characteristics and then elaborate on the synthesis methods of crystal hydrogels, categorizing them into three types based on their crystal formation mechanisms. The third section is dedicated to describing the properties of crystal hydrogels. Furthermore, we explore the diverse and remarkable applications that have emerged with the advancement of crystal hydrogels. The review concludes by summarizing the core concepts and assessing the recent opportunities and challenges faced by crystal hydrogels.
Myocardial infarction (MI) is a disease with a very high mortality rate among cardiovascular diseases. It causes extensive damage to myocardial cells due to prolonged and repeated ischemia and hypoxia. Early coronary revascularization is the best method for treating MI. However, the reperfusion process in MI can produce reactive oxygen species, further damaging myocardial tissue, and triggering MI-reperfusion injury (MI/RI). Although various traditional treatment strategies exist, the treatment of myocardial ischemia including MI and MI/RI remain a significant challenge. Mitochondrial dysfunction plays an important role in the emergence and development of myocardial ischemia. In recent years, with the advancement of nanobiomedicine, therapeutic strategies for targeting mitochondria have gained increasing attentions in diseases' therapy. Thus, nanobiomedicine targeting mitochondria has shown great promise in the treatment of myocardial ischemia. This review first comprehensively elaborates on the mechanisms of mitochondrial homeostasis in MI and MI/RI, and then focuses on the application progress of nanomaterials targeting mitochondrial homeostasis (oxidative stress, mitophagy, mitochondrial fusion and fission, etc.) in improving myocardial ischemia. Ultimately, this article looks forward to the prospects of nanomaterials in the targeting treatment of MI and MI/RI, aiming to provide more effective and innovative ideas for clinical treatments.
The electrochemical CO2 reduction (CO2R) holds the potential to manufacture carbon-based chemicals and fuels while advancing toward carbon neutrality. On the path to achieving practical CO2R, a significant challenge lies in the formation of carbonate salts due to the interplay between CO2, local alkalinity and metal cations. The carbonate issue leads to the wastage of CO2 reactant, thus resulting in low carbon utilization efficiency and high costs for carbonate regeneration. Additionally, such salt formation can threaten the operation stability of the CO2R in electrolyzers equipped with gas diffusion electrodes (GDE). These challenges motivate us to conduct the present review, aiming to provide a comprehensive understanding and propose solution strategies for the carbonate problem. We start from the mechanism insights into carbonate formation with specific analysis on the kinetics of carbonate formation, mass transfer process, and the influence of interfacial pH, followed by the exposition of advanced techniques to monitor the carbonate accumulation. Next, the design strategies to solve the carbonate problem including the optimization of electrolyte, electrode, membranes and operation conditions, are presented, with a highlight on acidic CO2 electrolysis system without introducing metal cations into electrolyte systems. We finally end up by offering future opportunities in this evolving field. These timely and inspiring perspectives can guide researchers in addressing carbonate-related issues and advance CO2R toward practical feasibility.
Organophosphorus (OPs) compounds are extensively utilized in pesticides, chemical warfare agents, pharmaceuticals, and industrial applications due to their distinctive chemical properties, including biological activity, persistence, and hydrophobicity. However, their excessive use has led to significant environmental toxicity and pollution concerns, underscoring the urgent need for sustainable methods to monitor OPs pollutants. Traditional detection relies on bulky instruments, whereas organic fluorescent probes present advantages such as high selectivity, sensitivity, and portability. This review summarizes recent advancements in these probes for OPs detection, outlines characterization strategies based on underlying mechanisms, discusses challenges and future directions, and introduces OPs’ features, probe mechanisms, and design guidelines, providing theoretical insights and technical references for the development of novel organic fluorescent probes.
Electrocatalytic CO2 reduction to formate using renewable energy offers a promising route for sustainable chemical production and carbon utilization. Bismuth-based catalysts stand out for their exceptional selectivity towards formate, combining intrinsic advantages with practical viability. This review critically examines recent advances in strategically tailoring bismuth-based catalysts for selective CO2-to-formate conversion. Moving beyond conventional material classifications, we emphasize mechanistic understanding of the reaction pathways and active sites governing formate generation. Crucially, we dissect the synthesis strategies enabling precise control over catalyst properties—ranging from metallic bismuth nanostructures and single atoms to tailored compounds, heterostructures, and alloys—and link these design principles to performance optimization. In addition, we incorporate operando characterization and computational insights within catalyst-specific case studies to examine selected dynamic reaction mechanisms and key enhancement mechanisms under operational conditions. Finally, we outline forward-looking research trajectories, addressing critical challenges like achieving industrially relevant performance and stability, and proposing innovative pathways focused on advanced catalyst architectures, microenvironment engineering, and predictive frameworks for scalable implementation.
Electrocatalytic oxygen reduction reaction (ORR) is a key sustainable energy process, but its efficiency and durability are severely affected by reactive oxygen species (ROS) such as hydroxyl radicals and superoxide anions. Understanding the kinetics of these transient intermediates is crucial for revealing the ORR mechanism and designing novel electrocatalysts. Many new in situ and operando characterization techniques have emerged in ROS detection. This article reviews recent progress in the detection and quantification methods for ROS during the electrocatalytic ORR, including fluorescence spectroscopy, UV–vis absorption spectroscopy, electron paramagnetic spectroscopy, scanning electrochemical microscopy, and electrochemiluminescence related technologies. The aim is to provide latest references for researchers in this field and promote further development of electrocatalytic ORR related research.
Asymmetric reduction of unsaturated compounds via dynamic kinetic resolution (DKR) has significantly enhanced the efficiency and selectivity of synthesizing enantiomerically pure compounds from racemic substrates. This approach combines the simultaneous racemization of substrates with enantioselective reduction, enabling quantitative yields and high enantiomeric excess. In the past several years, remarkable advances in this field have been achieved, ranging from the development of innovative catalytic systems, novel synthetic strategies, expansion of substrate scope, deeper mechanistic understanding, and their applications. These advancements offer alternative and efficient methods in the asymmetric synthesis of chiral molecules bearing multiple consecutive stereogenic centers, particularly beneficial for the synthesis of natural products or chiral intermediates in pharmaceuticals and fine chemicals. In this review, we summarize the recent advances during the last several years according to the substrate types in this powerful and productive field, with an emphasis on the development of new catalytic systems and the insight into the DKR process.
The growing global demand for sustainable energy makes biodiesel an important renewable alternative to alleviate the energy crisis and reduce greenhouse gas emissions. Therefore, there is an urgent need to develop efficient, environmentally friendly and economically viable biodiesel production methods. Hypercrosslinked polymers (HCPs), as aromatic porous organic polymers, are solid frameworks that can be used as heterogeneous catalyst, and they are a promising platform for biodiesel catalytic conversion due to their low cost, highly accessible active site, tunable catalytic site types. In addition, innovative green synthesis strategies make environmentally begin production of HCPs possible. In recent years, HCPs has developed rapidly in the field of biomass catalysis. Unfortunately, to the best of our knowledge, there are no publications focusing on the green synthesis and application of HCPs-based materials for biodiesel production. This review provides an update on the synthesis and utilisation of green and efficient HCPs for catalytic biodiesel production. Initially, the green routes for HCPs synthesis are described, followed by a comprehensive summary of the various approaches to biodiesel production. The primary focus is on the utilisation of HCPs as carriers of active sites in the catalytic conversion of biodiesel, with particular emphasis on catalyst design, morphology control, and intelligent management in terms of application extension. Ultimately, thought-provoking recommendations are proposed to utilize improved green HCPs in combination with advanced production processes to achieve more efficient and sustainable development.
Hydrogen-bonded frameworks (HOFs) are attracting interest for industrial and environmental applications. This review emphasizes recent developments in HOFs, concentrating on their structural characteristics, types of hydrogen bonding, and the connections that affect their mechanical properties and environmental responsiveness. It highlights hinge-like flexibility, rigidity, and framework retention, which enhance adaptability and structural integrity while trapping gases. A proposed mechanism for the selective adsorption of noble gases and light hydrocarbons emphasizes their potential in gas storage and environmental remediation. Overall, HOFs are presented as versatile materials ready to tackle emerging industrial challenges.
The stereoselective synthesis of 1,2-cis-galacturonic acid and 2-amino-2-deoxy-galacturonic acid glycosides remains a critical challenge in carbohydrate chemistry owing to the electronic and steric effects imposed by the C5-carboxyl group and C2 substituents. The available synthetic strategies can be divided into two divergent pathways: the construction of the glycan backbone before introducing the carboxyl group and the use of pre-formed uronic acid donors during glycosylation. Key advances include the use of remotely participating acyl groups, conformational control via 3,6-lactone intermediates, chelation-directed anomerisation and steric shielding by bulky protecting groups such as 4,6-O-di-tert-butylsilylene and 4,6-O-benzylidene. This review comprehensively overviews the current strategies that overcome stereo-chemical challenges in the synthesis of 1,2-cis-galacturonic and aminogalacturonic acid–containing glycans. In addition, the application of these methodologies to the synthesis of biologically relevant carbohydrates is examined.
This research explores the influence of crystallinity on gas chromatographic (GC) separation using covalent organic frameworks (COFs) as stationary phases. Three COF materials (CTF-DCBs) with varying crystallinity were synthesized and characterized. CTF-DCB-1, with superior crystallinity, demonstrated high-selectivity GC separation of benzene isomers as well as styrene/phenylacetylene mixtures, while CTF-DCB-2 and CTF-DCB-3 exhibited lower crystallinity and worse separation performance. Thermodynamic and kinetic tests showed that CTF-DCB-1 had the worst thermodynamic adsorption but low diffusion mass transfer resistance, which resulted in the best separation. Therefore, optimizing the crystallinity of COFs is necessary for balancing the kinetic diffusion and thermodynamic interactions towards the analytes, achieving high-performance GC stationary phases.
Regulation of apoptosis represents a key parameter in all living organisms. In this paper, an input-induced logic-gated modular nanocalculator is designed to regulate cancer cell apoptosis by programmatically combining and connecting logic gate modules with different functions. Via rational design of the various logic gate modules of the nanocalculator, different apoptosis related operations including cancer cell targeting, apoptosis induction, and apoptosis monitoring could be performed. Importantly, each of these logic gate modules could independently perform apoptosis related YES logic operations when ran separately. After combining each YES logic gate module into a logic circuit and connecting it to the GO scaffold to construct a logic-gated nanocalculator, the input-induced logic-gated modular nanocalculator could selectively enter cancer cells and control the drug release to logically apoptosis (output), by performing AND logic gate operations when inputs (nucleolin and H+) were included at the same time. Moreover, evidence suggests that these efficient logical calculations proceed in cancer cell apoptosis regulation without the general limiations of lithography in nanotechnology. As such, this work provides a new vision for the construction of a logic-gated modular nanocalculator with logical calculation proficiency potentially useful in cancer therapy and the regulation of life.
Magnesium hydride (MgH2) demonstrates immense potential as a solid-state hydrogen storage material, while its commercial utilization is impeded by the elevated operating temperature and sluggish reaction kinetics. Herein, a MOF derived multi-phase FeNi3-S catalyst was specially designed for efficient hydrogen storage in MgH2. Experiments confirmed that the incorporation of FeNi3-S into MgH2 significantly lowered the desorption temperature and accelerated the kinetics of hydrogen desorption and reabsorption. The initial dehydrogenation temperature of the MgH2 + 10 wt% FeNi3-S composite was 202 °C, which was 123 °C lower than that of pure MgH2. At 325 °C, the MgH2 + 10 wt% FeNi3-S composite released 6.57 wt% H2 (fully dehydrogenated) within 1000 s. Remarkably, MgH2 + 10 wt% FeNi3-S composite initiated rehydrogenation at room temperature and rapidly absorbed 2.49 wt% H2 within 30 min at 100 °C. Moreover, 6.3 wt% H2 was still retained after 20 cycles at 300 °C, demonstrating the superior cycling performance of the MgH2 + 10 wt% FeNi3-S composite. The activation energy fitting calculations further evidenced the addition of FeNi3-S enhanced the de/resorption kinetics of MgH2 (Ea = 98.6 kJ/mol and 43.3 kJ/mol, respectively). Through phase and microstructural analysis, it was determined that the exceptional hydrogen storage performance of the composite was attributed to the in-situ formation of Mg/Mg2Ni + Fe/MgS and MgH2/Mg2NiH4 + Fe/MgS hydrogen storage systems. Further mechanistic analysis revealed that Mg2Ni/Mg2NiH4 served as “hydrogen pump” and Fe/MgS served as “hydrogen diffusion channel”, thus accelerating the dissociation and recombination of hydrogen molecules. In conclusion, this work offers insight into catalysts combining transition metal alloys and transition metal sulfide for exerting muti-phase synergistic effect on boosting the dehydrogenation/hydrogenation reactions of MgH2, which can also inspire future pioneering work on designing and fabricating high efficient catalysts in other energy storage related areas.
The rate-limited activation of NN triple bonds with high bond energies has been a bottleneck in photoctalytic nitrogen fixation. Here, polymeric carbon nitride with frustrated Lewis pairs (FLPs) was constructed by inserting electron-deficient magnesium into g-C3N4 (CN). The synergistic interactions between Mg and amino groups in CN led to a 7.2 fold increase in the photoreactivity of nitrogen (N2) fixation by carbon nitride.
Photocatalytic fuel cells provide promising opportunities for sustainable wastewater treatment and energy conversion. However, their applications are challenged by the sluggish oxygen reducton reaction (ORR) kinetics at cathodes owning to the low O2 solubility and diffusion rate. Herein, we proposed a photo-biocatalytic fuel cell (PBFC) with a novel hybrid biocathode based on artificially engineered algal cells coated by ZIF-8 confined carbon dots/bilirubin oxidase (ZIF-8/CDs/BOD@algae). Microalgae absorbed CO2 and provided O2 in situ for BOD catalysts. Due to effective absorption of O2 by imidazole and confinement of hydrophobic porous ZIF-8, oxygen diffusion has been accelerated in MOF/enzyme systems. Importantly, the introduction of CDs alleviated the poor conductivity of ZIF-8 and improved the electron transfer rate of BOD. Thus, the biocathode exhibited a high current density of 1767 µA/cm2, a 2.26-fold increase compared with that of CDs/BOD/algae biocathode. Also, it displayed enduring operational stability for up to 60 h since the firmly wrapped ZIF-8 shells could encapsulate proteins and protect algae from the external stimulation. When coupled with Mo: BiVO4 photoanodes, the PBFC exhibited a remarkable power output of 131.8 µW/cm2 using tetracycline hydrochloride (TCH) as a fuel and an increased degradation rate of TCH. Therefore, this work not only establishs an effective confinement strategy for enzyme to enrich oxygen, but also unveils new possibilities for modified microalgal cells aiding photoelectrocatalytic systems to recover energy from wastewater treatment.
Converting CO2 into methanol (CH3OH), a high-value-added liquid-phase product, through efficient and highly selective photocatalysis remains a significant challenge. Herein, we present a straightforward cation exchange strategy for the in-situ growth of BiVO4 on an InVO4 substrate to generate a Z-scheme heterojunction of InVO4/BiVO4. This in-situ partial transformation approach endows the InVO4/BiVO4 heterojunction with a tightly connected interface, resulting in a significant improvement in charge separation efficiency between InVO4 and BiVO4. Moreover, the construction of the heterojunction reduces the formation energy barrier of the *COOH intermediate during the photoreduction of CO2 and increases the desorption energy barrier of the *CO intermediate, facilitating the deep reduction of *CO. Consequently, the InVO4/BiVO4 heterojunction is capable of photocatalytic CO2 reduction to CH3OH with high efficiency and selectivity. Under conditions where water serves as the electron source and a light intensity of 100 mW/cm2, the yield of CH3OH reaches 130.5 µmol g−1 h−1 with a selectivity of 92 %, outperforming photocatalysts reported under similar conditions.
Many labdane-related diterpenoids (LRDs) exhibit high values in drug development. Their diversity in structure and bioactivity, to a large extent, arise from oxidative modifications which are mainly catalyzed by cytochrome P450s (CYPs). The medicinal plant Euphorbia fischeriana Steud. is rich in LRDs with distinct scaffolds. Herein, we characterized three cytochrome P450s involved in LRD biosynthesis from this plant. Notably, CYP71D450 and CYP701A148 are two substrate-promiscuity CYPs. The former is the first example of CYPs which can oxidize C-3 of ent–atisane skeleton and ent–isopimara-7(8),15-diene, and the latter is the first example of CYPs which can oxidize C-19 of ent–abietane and ent–pimarane skeletons. This study expands the toolkit for bioproduction of diverse LRDs.
Owing to their intricate molecular frameworks and copious chiral centers, the structural identification and configurational assignment of natural products are challenging tasks. Comprehensive spectral data analysis is crucial for the confirmation of absolute configurations. Ignoring critical parameters will lead to false structure, which may confuse the total synthesis and drug development. Herein, the configurations of seven heterogeneous Pallavicinia diterpenoids (PDs) isolated from Pallavicinia liverworts are revised using a combination of single-crystal X-ray diffraction and electronic circular dichroism (ECD) calculations. Meanwhile, identification of five unprecedented PD heterodimers PD-dimers A–E (18–22) along with eleven previously undescribed PDs (5–9, 13–17, 23) obtained by the reinvestigation of the Chinese liverwort Pallavicinia subciliata have resulted in corrections and support the revised conclusions.
Overproduction of reactive oxygen species (ROS) following ischemic injury triggers an inflammatory response, significantly impeding neurological functional recovery. Nanozymes with potent antioxidative and anti-inflammatory effects thus offer great potential for ischemic stroke treatment. In this study, we developed an ischemia-homing nanozyme by combining melatonin (MT)-loaded honeycomb manganese dioxide (MnO2) nanoflowers with M2-type microglia membranes to rescue the ischemic penumbra. The surface-engineered M2-type microglia membranes provided intrinsic ischemia-homing and blood-brain barrier (BBB)-crossing properties to the biomimetic nanozymes. This nanozyme can not only transforms harmfulsuperoxide anion radicals (•O2–) and hydrogen peroxide (H2O2) into harmless water and oxygen but also scavenges highly toxic hydroxyl radicals (•OH), dramatically lowering intracellular ROS levels. More importantly, the biomimetic nanoparticles reduce cerebral infarct areas and provide significant neuroprotection against ischemic stroke by lowering oxidative stress, inhibiting cell apoptosis, and decreasing inflammation. This study may offer a viable approach for the use of nanozymes in treating ischemic stroke.
Metal ion homeostasis plays a pivotal role in maintaining cellular functions, and its disruption can initiate regulated cell death pathways. Despite its therapeutic potential, metal ion therapy for breast cancer has been hampered by inefficient ion delivery and the intrinsic resistance mechanisms of cancer cells. In this work, a cuproptosis amplifier of copper-telaglenastat coordinate (denoted as Cu-CB) is developed to trigger cell ferroptosis for synergistic breast cancer treatment. Telaglenastat (CB-839), a glutaminase inhibitor, is identified as an effective copper ionophore that facilitates the formation of Cu-CB. Specially, Cu-CB can promote the aggregation of lipoylated proteins to initiate cuproptosis, while also inhibiting glutathione (GSH) synthesis and downregulating glutathione peroxidase 4 (GPX4) to trigger ferroptosis. The interplay between these cuproptosis and apoptosis pathways, mediated by Cu-CB, significantly amplifies reactive oxygen species (ROS) production and lipid peroxidation, culminating in the synergistic suppression of breast cancer. Both in vitro and in vivo studies validate the superior antitumor effects of Cu-CB through the induction of cuproptosis and ferroptosis, which may provide a new insight for metal ion delivery systems and metal ion-based tumor therapies.
Alzheimer’s disease (AD) is a common neurodegenerative disorder among the elderly population. There are currently no effective therapeutic drugs available, the multi-target-directed ligands (MTDLs) strategy has been considered as the promising approach. Given the structural diversity of natural products, Rivastigmine’s pharmacophore was integrated with diverse natural product scaffolds to construct a combinatorial compound library. This library was subsequently screened and optimized to identify a novel butyrylcholinesterase (BuChE) inhibitor, compound 3c. The results showed that compound 3c exhibited favorable BuChE inhibitory activity (half-maximal inhibitory concentration (IC50) = 0.43 µmol/L), potential anti-inflammatory potency, good Aβ1–42 aggregation inhibitory capacity and remarkable neuroprotective effects. The in vivo study exhibited that 3c significantly ameliorated AlCl3-induced zebrafish AD model and scopolamine-induced memory impairment. Collectively, compound 3c was the artificial intelligence (AI)-driven promising multifunctional agent with BuChE inhibition for the treatment of AD.
The study of target proteins is crucial for understanding molecular interactions and developing analytical platforms, therapeutic agents and functional tools. Herein, we present a novel nanoplatform activated by near-infrared (NIR) light for triple-modal proteins study, which enabling target protein labeling, enrichment and visualization. Azido-naphthalimide-coated upconversion nanoparticles (UCNPs) serve as NIR light-responsive nanoplatforms, showing promising applications in studying interactions between various bioactive molecules and proteins in living systems. Under NIR light irradiation, azido-naphthalimides are activated by ultraviolet (UV) and blue light emitted from UCNPs and the resulting amino-naphthalimides intermediate not only crosslink nearby target proteins but also enable imaging performance. We demonstrate that this nanoplatform is capable of selective protein labeling and imaging in complex protein environments, achieving specific labeling and imaging of both intracellular and extracellular proteins in mammalian cells as well as bacteria. Furthermore, in vivo protein labeling has been achieved using this novel NIR light-activatable nanoplatform. This technique will open new avenues for discoveries and mechanistic interrogation in chemical biology.
The field of nanomedicine has been revolutionized by the concept of immunogenic cell death (ICD)-enhanced cancer therapy, which holds immense promise for the efficient treatment of cancer. However, precise delivery of ICD inducer is severely hindered by complex biological barriers. How to design and build intelligent nanoplatform for adaptive and dynamic cancer therapy remains a big challenge. Herein, this article presents the design and preparation of CD44-targeting and ZIF-8 gated gold nanocage (Au@ZH) for programmed delivery of the 1,2-diaminocyclohexane-Pt(Ⅱ) (DACHPt) as ICD inducer. After actively targeting the CD44 on the surface of 4T1 tumor cell, this Pt-Au@ZH can be effectively endocytosed by the 4T1 cell and release the DACHPt in tumor acidic environment, resulting in ICD effect and superior antitumor efficacy both in vitro and in vivo in the presence of mild 808 nm laser irradiation. By integration of internal and external stimuli intelligently, this programmed nanoplatform is poised to become a cornerstone in the pursuit of effective and targeted cancer therapy in the foreseeable future.
Fluorescent probes based on intramolecular charge transfer (ICT) have obvious advantages for accurate quantitative analysis. To obtain high-performance ratiometric probes requires distinct photophysical properties during recognition reaction process, which is closely related to their ICT characteristics. 1,8-Naphthalimide is known as a typical fluorophore with desirable ICT property when functionalized with an electron-donating moiety at the para-position of the naphthalene chromophore. Although the photophysical properties of para-substituted 1,8-naphthalimide have been well studied, its meta-substituted counterpart has not been fully evaluated since the meta-position is conventionally thought to be weakly conjugated. Herein, combined experimental and theoretical studies are performed which consistently indicate that stronger charge transfer (CT) is exhibited by the meta-amino substituted 1,8-naphthalimide (m-NH2) compared to the para-amino substituted one (p-NH2). The ratiometric response of fluorescence with significant changes in wavelength and intensity upon acetylation (m-NAc and p-NAc) can be attributed to the larger ICT and stronger -NH2 vibrations. This observation is further demonstrated by deuterium oxide experiments, viscosity experiments and quantum chemical calculations. The practical application of meta-amino-1,8-naphthalimide ICT-based probes is also confirmed. This research is expected to bring an in-depth understanding of π-conjugated systems with ICT characteristics, and facilitates the design of sensitive ICT fluorescent probes with meta-amino substitution.
Sulfur dioxide (SO2) and its derivatives have been recognized as harmful environmental pollutants. However, they are often produced during the processing of traditional Chinese medicines, potentially compromising the quality of these medicinal materials and contributing to various health issues. Due to a lack of effective monitoring and imaging tools, the physiological effects of excessive SO2 residues in traditional Chinese medicine remain unclear. Therefore, developing a rapid and effective tool for detecting SO2 is crucial for understanding its metabolic pathways and effects in vivo. In this study, we developed a near infrared (NIR) and ratiometric fluorescent probe, NIR-RS, which exhibits high sensitivity, selectivity, and rapid response for SO2 detection. Notably, NIR-RS accurately quantifies SO2 contents in Pinelliae rhizoma (P. rhizoma) samples, with recovery rates from 98.46% to 102.40%, and relative standard deviations (RSDs) < 5.0%. For bioimaging applications, NIR-RS has low cytotoxicity and good mitochondrial-targeting ability, making it suitable for imaging exogenous and endogenous SO2 in mitochondria. Additionally, NIR-RS was successfully applied to image SO2 content of P. rhizoma samples within cells, revealing that high SO2 residue elevated mitochondria adenosine triphosphate (ATP) content, these findings reveal that P. rhizoma with excessive SO2 can affect the organism's growth mechanisms through alterations in ATP pathways. In vivo, SO2 was found to predominantly accumulate in the liver following gavage with P. rhizoma solution, with accumulation levels increasing in proportion to SO2 residue concentration. High SO2 concentrations in P. rhizoma can cause pulmonary fibrosis and gastric mucosal damage. This work provides a valuable tool for regulating SO2 content in P. rhizoma and may help researcher better understand the metabolism of SO2 derivatives and explore their physiological roles in biological systems.
Poor solubility often results in low efficacy of antitumor drugs. Nevertheless, limited research has been conducted on the potential decrease in drug efficacy following the self-assembly of hydrophobic pure drugs into nanodrugs, and solutions to this problem are even rarer. Loading water-insoluble antitumor drugs into nanocarriers offers a promising solution. However, intricate carrier preparation, limited drug loading capacity, and carrier-associated safety remain key challenges. In this study, based on the discovery that hydrophobic gambogic acid (GA) self-assembles into nanostructures with diminished antitumor efficacy in aqueous environments, we developed a carrier-free nanodrug system, designated as GA-S-S-AS nanoparticles (NPs), characterized by straightforward preparation, high drug loading, fluorescence imaging, tumor-targeting, and responsive drug release in reducing environments. Specifically, the hydrophobic GA was covalently linked to the hydrophilic aptamer through a disulfide bond and then self-assembled into the nanodrugs. About 92% of drug was encapsulated in self-assembled NPs, demonstrating remarkable stability under physiological conditions and controlled release of GA in the high-glutathione environment characteristic of tumor sites. Furthermore, by utilizing the synergistic interaction between the enhanced permeability and retention (EPR) effect and ligand-receptor active targeting mechanisms, the nanodrugs significantly increased the accumulation of GA at tumor locations. Consequently, the nanodrugs exhibited optimal therapeutic efficacy against the tumor both in vitro and in vivo, significantly inhibiting tumor growth. Furthermore, the nanodrugs demonstrated enhanced biosafety compared to free GA, effectively reducing GA-induced hepatotoxicity. Taken together, these findings underscore the significant potential of this multifunctional carrier-free nanodrugs for the targeted delivery of GA, thereby laying a foundation for future endeavors aimed at developing novel formulations of hydrophobic antitumor drugs.
Mangicol-type sesterterpenoids possess potent anti-inflammatory activity, characterized by a 5–5–6–5 tetracyclic carbon skeleton formed by mangicdiene synthase FgMS. Two proposed mechanisms for mangicdiene formation involve either C6-C10 cyclization (path a) or C2-C10 cyclization (path b) after the C10 carbocation formation, but neither has been experimentally validated. Here, we have identified a second mangicdiene synthase ManD, which is derived from Fusarium sp. JNU-XJ070152–01 and shares high amino acid sequence identity with FgMS. Through heterologous expression of manD in Aspergillus oryzae NSAR1, we observed production not only of mangicdiene (1) and variecoltetraene (2), previously identified by expression of FgMS in Escherichia coli, but also two novel sesterterpene skeletons fusadiene (3) and fusatriene (4). The identification of fusadiene and fusatriene supports the occurrence of two key carbocation intermediates in path b, thus experimentally confirming that mangicdiene is built via path b for the first time, consistent with previous density functional theory (DFT) calculation results.
Bicyclo[2.1.1]hexanes (BCHs) are structurally unique C(sp3)-rich bicyclic hydrocarbons that are gaining prominence in the field of medicinal chemistry as bioisosteres of benzenoids. The nitrile is an important functionality in drug development due to its ability to improve physicochemical and pharmacokinetic properties and facilitate potential noncovalent interactions with drug targets. Consequently, cyano-arene motifs are commonly found in drug development. The introduction of cyano-BCHs as potential bioisosteres of cyano-arenes shows great promise; however, there are currently no catalytic methods available for their synthesis. Herein, we report a palladium-catalyzed enantioselective [2σ + 2π] cycloadditions of bicyclo[1.1.0]butanes with arylidenemalononitriles for the preparation of chiral cyano-BCHs. This method accommodated a wide range of substrates and tolerated various functional groups. The cyano-BCH products could be transformed to molecules with diverse functionality. Control experiments suggest that the reaction proceeds via a zwitterionic intermediate generated by palladium-mediated ring opening of vinyl-carbonyl bicyclo[1.1.0]butanes followed by stereoselective 1,2-addition and intramolecular allylic substitution reactions.
The large volume expansion and rapid capacity attenuation of tin-based electrodes are the main factors limiting their commercial application. The reasonable design of electrode material structure is particularly important for improving its electrochemical performance. Herein, phosphorus-modified graphene encapsulated Sn6O4(OH)4 nanoparticles composite (P-Sn6O4(OH)4@RGO) with crystalline-amorphous heterostructure has been successfully designed and prepared. The design of crystalline-amorphous structure has largely enhanced the active sites, and the construction of a graphene encapsulation structure has greatly alleviated volume expansion. Notably, P-Sn6O4(OH)4@RGO obtained an excellent high-rate long-term cycling performance for lithium-ion batteries anode, reaching a high specific capacity of 970 mAh/g at 1.0 A/g after 1450 cycles. This work demonstrates that restructuring the electrode material's structure and phase through phosphorus modification can effectively improve the electrochemical performance of tin-based electrode materials.
Ln@MOFs by anchoring rare metal ions (Ln) into metal–organic frameworks (MOFs) are proved to have great potential in the field of luminescent molecular thermometer. Nevertheless, the current research indicated that the poor structural stability and low sensitivity hindered their application scope. In this work, a new MOF Zn-450 luminescent thermometer with multiple emission fluorescence characteristics was synthesized by the combination of 3,3′,5,5′-biphenyl tetracarboxylic acid (H4L) and Zn2+ ion under solvothermal conditions. Interestingly, a high relative sensitivity of 1.43 % K−1 was found within 80–300 K based on Zn-450. Subsequently, two high-sensitivity luminescent Ln@MOFs (Ln = Eu and Tb) were further fabricated by doping rare earth ions into Zn-450 based on the post-synthesis strategy. Among them, the Eu@Zn-450 demonstrates various luminous behaviors while achieving an increased relative sensitivity of 1.63 % K−1. In addition, the continuously visible red, pink, and purple luminescent emissions at the same temperature range were observed, suggesting that the Eu@Zn-450 could be utilized as a luminescent colorimetric molecular thermometer. Importantly, this work can present new possibilities for the development of rare earth-doped luminescence and its temperature sensing properties.
In this study, we meticulously designed a layered carbon-based catalytic material to induce the degradation of a series of organic pollutants by activating peroxymonosulfate (PMS) in the PMS-based advanced oxidation processes (AOPs). Results indicated that the silicon and oxygen elements from the montmorillonite were incorporated into the catalyst matrix to form the Si-O-C structure. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array, achieving over 90% removal rate of most pollutants within 60 min. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array. The salt bridge system confirmed that pollutants can provide electrons to the Si-O-C/PMS system, and we verified that the electron transfer process (ETP) mechanism was the main pathway for the degradation of pollutants in the Si-O-C/PMS system via the open-circuit potential analysis. In combination with the structural properties of different pollutants, we discovered that electron-donating pollutants can supply more electrons to the Si-O-C/PMS system, thereby enhancing the ETP process. The findings of this study are anticipated to advance the development and practical application of layered carbonaceous materials-based catalysts and support the design and implementation of nanoconfined catalysts in the field of AOPs.
Photocatalysis uses solar energy to convert nitrogen and water directly into ammonia, helping reduce dependence on fossil fuels and offering a way to integrate the nitrogen cycle into a clean energy network. Ohmic junctions between metals and semiconductors have demonstrated significant advantages in enhancing stability and reducing carrier recombination, but their application in photocatalytic nitrogen fixation is limited due to the difficulty of work function matching and the complexity of fabrication processes. In this study, density functional theory (DFT) calculations were used to confirm the work function matching between Bi and Bi2Ti2O7 (BTO), ensuring the formation of an Ohmic junction. A Bi-Bi2Ti2O7 (B-BTO) composite was successfully synthesized via a one-step hydrothermal method, using bismuth nitrate and titanium sulfate as precursors. Compared to pure BTO, the B-BTO heterojunction, driven by dual electron injection from both metal Bi and BTO, significantly increased the ammonia synthesis rate to 686.95 µmol g−1 h−1, making it the most active nitrogen fixation material among similar pyrochlore-based catalysts to date. The differential charge density calculations, photocurrent (i-t) measurements, and photoluminescence (PL) tests further validate the role of Ohmic contacts in enhancing charge transfer and prolonging carrier lifetimes. This research provides valuable insight into the application of Ohmic junctions in photocatalytic nitrogen fixation and contributes to advancements in this field.
The development of catalytic multicomponent reactions for constructing complex organic scaffolds from readily accessible commodity chemicals is a key pursuit in contemporary synthetic chemistry. Current methods for synthesizing thioesters primarily rely on the acylation of thiols, which produces substantial waste and requires malodorous, unstable sulfur sources. In this work, we introduce a photocatalyzed hydrogen transfer strategy that enables a three-component synthesis of thioesters using abundant primary alcohols, easily available alkenes and elemental sulfur under mild conditions. This protocol demonstrates broad applicability and high chemo- and regioselectivity for both primary alcohols and alkenes, highlighting the advantage and potential of photo-mediated hydrogen transfer in facilitating multicomponent reactions using primary alcohol and elemental sulfur feedstocks.
The deuterium labeling has garnered significant interest in drug discovery due to its critical role on improving pharmacokinetic and metabolic properties. However, despite its pharmaceutical value, the general and rapid syntheses of aromatic scaffolds that contains deuterium remain an important yet elusive task. State-of-the-art approaches mainly relied on the transition metal-catalyzed C–H deuteration via the assistance of directing groups (DGs), which often suffered from over-deuteration and lengthy step counts required for installation and/or removal of DG. Herein, we report a generalizable synthetic linchpin strategy for the facile preparation of the ortho-deuterated aromatic core. Through capture of aryne-derived 1,3-zwitterion with heavy water, we synthesized an array of ortho-deuterated aryl sulfonium salts. These novel linchpins not only participated the transition metal catalyzed cross-coupling reaction as nucleophiles, but also served as aryl radical reservoirs under photochemical or electrochemical conditions, enabling facile and precise access to structurally diverse deuterated aromatics. Moreover, we have disclosed a novel EDA complex enabled direct arylation of phosphines under visible-light irradiation, further expanding the utility of our platform approach.
The recovery of gold from waste electronic and electric equipment (WEEE) has gained great attention with the increased number of WEEE, because it can largely alleviate the pressure on the environment and resources. Covalent organic frameworks (COFs) are ideal adsorbents for gold recovery owing to their large surface area, good stability, easily functionalized ability, periodic structures, and definitive nanopores. Herein, a cyano-functionalized COF (COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold. The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance, which possesses fast adsorption kinetics, high cycling stability, and adsorption capacity up to 663.67 mg/g. Excitingly, COF-CN showed extremely high selectivity for gold ions, even in the presence of various competing cations and anions. The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE. The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.
Triclosan (TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects. Therefore, developing an efficient and sustainable technology to degrade TCS is urgently needed. Herein, cobalt oxyhydroxide @covalent organic frameworks (CoOOH@COFs) S−scheme heterojunction was synthesized, which combined the visible-light-driven photocatalysis and peroxymonosulfate (PMS) activation to synergistically generate abundant reactive oxygen species (ROSs) for TCS degradation. The degradation efficiency of TCS reached 100% within 8 min in the Vis-CoOOH@COFs/PMS system, and the reaction rate constant was 0.456 min−1, which was nearly 1.90 and 2.85 times that of single CoOOH and COFs, and 2.36 times that under dark condition, respectively. The density functional theory (DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to CoOOH. Both experimental and theoretical analyses indicated that CoOOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation, enhanced interfacial electron transfer, accelerated PMS activation, and generated multiple ROSs. In particular, photogenerated electrons (e−) accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle, while the PMS captured the e−, which significantly decreased the charge combination of CoOOH@COFs. Radicals (O2•−, •OH, and SO4•−) and non-radicals (such as 1O2, h+, and e−) were both presented in the Vis-CoOOH@COFs/PMS system, with O2− playing a dominant role in TCS degradation. Furthermore, the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification. Importantly, the environmentally friendly CoOOH@COFs S−scheme heterojunction exhibited excellent stability and reusability. In conclusion, this study innovatively designed an S−scheme heterojunction in the photocatalytic-PMS activation system, providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.
Developing a chiral material as versatile and universal chiral stationary phase (CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance. In this study, we demonstrated for the first time that a chiral metal-organic cage (MOC), [Zn6M4], as a universal chiral recognition material for both multi-mode high-performance liquid chromatography (HPLC) and capillary gas chromatography (GC) enantioseparation. Two novel HPLC CSPs with different bonding arms (CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn6M4] onto thiolated silica via thiol-ene click chemistry. Meanwhile, a capillary GC column statically coated with the chiral MOC [Zn6M4] was also fabricated. The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC (NP-HPLC) and reversed phase (RP-HPLC) but also in GC, and various racemates were well separated, including alcohols, diols, esters, ketones, ethers, amines, and epoxides. Importantly, CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation, which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns, suggesting the great potential of the two prepared CSPs in enantioseparation. This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC, and also paves the way to expand the potential applications of MOCs.
Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials. Herein, we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission, which is constructed by cucurbit[7]uril (CB[7]), cyanostilbene derivative (DAC) and Laponite XLG (LP) via supramolecular cascade assembly. Compared with the free guest molecule DAC, the confinement of macrocycle CB[7] achieve effective near-infrared fluorescence in the aqueous phase from scratch, and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC, which not only result in a substantial enhancement of the fluorescence intensity, but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states. Further, 8–hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt (HPTS) is introduced in the cascade assembly to fabricated photo-controllable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer, which is successfully employed in reversible multiple information encryption.
The brain's functions are governed by molecular metabolic networks. However, due to the sophisticated spatial organization and diverse activities of the brain, characterizing both the minute and large-scale metabolic activity across the entire brain and its numerous micro-regions remains incredibly challenging. Here, we offer a high-definition spatially resolved metabolomics technique to better understand the metabolic specialization and interconnection throughout the mouse brain using improved ambient mass spectrometry imaging. This method allows for the simultaneous mapping of thousands of metabolites at a 30 µm spatial resolution across the mouse brain, ranging from structural lipids to functional neurotransmitters. This approach effectively reveals the distribution patterns of delicate microregions and their distinctive metabolic characteristics. Using an integrated database, we annotated 259 metabolites, demonstrating that the metabolome and metabolic pathways are unique to each brain microregion. The distribution of metabolites, closely linked to functionally connected brain regions and their interactions, offers profound insights into the complexity of chemical processes and their roles in brain function. An initial dataset for future metabolomics research might be obtained from the high-definition mouse brain's spatial metabolome atlas.
RNA binding proteins (RBPs) are a crucial class of proteins that interact with RNA and play a key role in various biological process. Deficiencies or abnormalities of RBPs are closely linked to the occurrence and progression of numerous diseases, making RBPs potential therapeutic targets. However, the limited tissue penetration of 254 nm UV irradiation makes it difficult to efficiently crosslink weak and dynamic RNA–protein interactions in mammal tissues. Additionally, RNA degradation in metal catalyzed click reaction further hinders the enrichment of RNA-protein complexes (RPCs). Due to these inherent limitations, globally profiling the RNA binding proteome in mammal organs has long been a challenge. Herein, we proposed a novel method, which utilized a dual crosslinking with formaldehyde and 254 nm UV irradiation, metabolic labeling and metal-free thiol-yne click reaction to enable large-scale enrichment and identification of RBPs in mouse liver, called FTYc_UV. In this method, formaldehyde is first used to crosslink the crude RNA-protein complexes (cRPCs) in situ to address the problem of poor tissue penetration of 254 nm UV irradiation. Furthermore, this method integrates metabolic labeling with a metal-free thiol-yne click reaction to achieve non-destructive RNA tagging. After specifically RNA-RBPs crosslinking by 254 nm UV irradiation in tissue lysates, formaldehyde decrosslinking is employed to remove non-specific proteins, leading to effective enrichment of RPCs from mouse liver and thereby overcoming the poor specificity of formaldehyde crosslinking. Application of FTYc_UV in mouse liver successfully identified over 1600 RBPs covering approximately 75% of previously reported RBPs. Furthermore, 420 candidate RBPs, including 151 metabolic enzymes, were also obtained, demonstrating the sensitivity of FTYc_UV and the potential of this method for in-depth exploration of RNA–protein interactions in biological and clinical research.
Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives. However, it is challenging to develop environmentally friendly catalytic systems, especially in constructing efficient and recyclable catalysts under water or solvent-free conditions. Here, we designed two novel coordination polymers Cd–CPs and Fe–CPs to investigate their catalytic performance in water. Gratifyingly, it was observed that Cd-CPs as a multifunctional catalyst was successfully applied to establish a universal pathway for direct fabrication of 1,8-naphthyridine derivatives under water conditions, while it was effective for the synthesis of 1,3,5-triazines through acceptorless dehydrogenative coupling strategies. The features of broad substrate, high atom efficiency, and good catalyst reusability highlight the feasibility of this transformation. In additional, we demonstrated the spindle-like structures Fe-P, derived from the Fe–CPs via phosphorylation, which can be used as an efficient electrocatalyst for oxygen evolution reaction with good stability. This work provides two highly efficient non-noble metal catalysts for functionalized 1,8-naphthyridine derivatives production and oxygen evolution reaction, and opens a new avenue to further fabricate diverse metal catalysts with high catalytic performance in water.
Fractal assembly in discrete structures, especially for artificial supramolecular species, has attracted significantly increased interest over the past two decades. In this study, we present the precisely controlled fractal expanding synthesis of a novel triangular prism supramolecule featuring Sierpiński triangular face, which was achieved through a module-intervened self-expansion strategy. The homoleptic S1 was firstly synthesized through the assembly of ligand L1 with Zn2+ ions. Based on the triangular-faced prism S1, we further introduced Sierpiński triangular faces on the section of the heteroleptic supramolecular cage S2 with an expanded inner cavity and more abundant active sites for photocatalytic properties. The topotactic architectures for both S1 and S2 were fully characterized by nuclear magnetic resonance spectroscopy, high-resolution electrospray ionization mass spectrometry, transmission electron microscopy, and atomic force microscopy. Furthermore, the enhanced photocatalytic activity of the fractal expanded S2 was performed via the superior amine oxidative efficiency over S1. This study proposes the unprecedented fractal expanding strategy for three-dimensional supramolecular species with higher complexity, potentially opening new avenues for structural regulation of artificial fractal molecules.
The Jellium closed-shell model, a cornerstone of cluster science, has long guided the design of superatoms by dictating electron-counting rules. However, its reliance on precise control of cluster composition and electron shell occupancy presents significant experimental challenges. Here, we introduce a ligation strategy that circumvents these limitations by demonstrating that the adiabatic electron affinity (AEA) of aluminum-based clusters, whether with filled or partially filled electron shells, can be dramatically enhanced through the attachment of organic Lewis acid ligands. It was evidenced that the AEA of PAl12 can be significantly increased by 2.17 eV after the ligation of two ligands, indicating a remarkable improvement in its electron-accepting ability. This approach yields superhalogen species, offering a versatile and practical means to tune the electronic properties of clusters while preserving their superatomic states, independent of shell occupancy. Remarkably, this ligand-induced modulation is not confined to naked clusters but also extends to nano-confined systems, hinting at its broader applicability. Given the indispensable role of ligands in cluster synthesis, this strategy holds promise for advancing the field of condensed-phase superatom synthesis, potentially complementing traditional electron-counting rules in a broader range of applications.
DNA methylation is an important promising biomarker for cancer diagnosis and monitoring. Therefore, the assessment of DNA methylation levels is helpful for the prognosis and diagnosis of cancer. However, it is still a huge challenge to sensitively and accurately quantify the levels of DNA methylation in clinical sample. In this work, we proposed a protospacer adjacent motif (PAM)-free mediated CRISPR-Cas12a ultra-sensitive and quantitative DNA methylation detection method. Through recognizing the dsDNA with toehold region, CRISPR-Cas12a not only got rid of the limitation of PAM, but also improved its distinction ability for single CpG site methylation, nearly 5-fold that of conventional PAM-containing dsDNA. We further introduced assist-strand and design an artificial mismatch to greatly improve the ability to distinguish single CpG methylation site. Our results showed that the discrimination factor was > 200. Then, we constructed toe-dsDNA by using "heating and freezing", which made our method universally applicable and feasible. In addition, we greatly simplified the difficulty of primer design. Our method detected four highly methylated genes acyl carrier protein (ACP), CLV3/ESR-related (CLE), Disabled (DAB) and Homeobox (HOX) with a detection limit of 0.01% and excellent linearity in DNA methylation standards. Then, we verified the clinical utility of this method in 29 hepatocellular carcinomas, 11 ovarian cancers and 4 health people. In conclusion, we have successfully constructed a PAM-free CRISPR-Cas12a DNA methylation quantification method, which achieves high congruence in sensitivity, specificity and universality, fully demonstrating its significant clinical application value.
Metal organic framework (MOF) assembled with coordination bonds has the disadvantage of poor stability that limits its application in the field of stationary phase, while covalent organic framework (COF) assembled through covalent bonds exhibits excellent structural stability. It has been shown that the stationary phases prepared by combining MOF and COF can make up for the poor stability of MOF@SiO2, and the MOF/COF composites have superior chromatographic separation performance. However, the traditional methods for preparing COF/MOF based stationary phases are generally solvent thermal synthesis. In this study, a green and low-cost synthesis method was proposed for the preparation of MOF/COF@SiO2 stationary phase. Firstly, COF@SiO2 was prepared in a choline chloride/ethylene glycol based deep eutectic solvent (DES). Secondly, another acid-base tunable DES prepared by mixing p-toluenesulfonic acid (PTSA) and 2-methylimidazole in different proportions was introduced as the reaction solvent and reactant for rapid synthesis of MOF/COF@SiO2. Compared with the toxic transition metal-based MOFs selected in most previous studies, a lightweight and non-toxic S-zone metal (calcium) based MOF was employed in this study. PTSA and calcium will form the calcium/oxygen-containing organic acid framework in acidic DES, which assembles with terephthalic acid dissolved in basic DES to form MOF. The strong hydrogen bonding effect of DES can facilitate rapid assembly of Ca-MOF. The obtained Ca-MOF/COF@SiO2 can be used for multi-mode chromatography to efficiently separate multiple isomeric/hydrophilic/hydrophobic analytes. The synthesis method of Ca-MOF/COF@SiO2 is green and mild, especially the use of acid-base tunable DES promotes the rapid synthesis of non-toxic Ca-MOF/COF@silica composites, which offers an innovative approach of greenly synthesizing novel MOF/COF stationary phases and extends their applications in the field of chromatography.
Cuprous oxide (Cu2O) is one of the most promising catalysts for electrochemical conversion of CO2 into value-added C2 products. The efficiency of CO2-to-C2 conversion is highly dependent on the Cu2O crystal plane orientation and the corresponding adsorbed *CO species. Herein, we constructed high-index crystal planes (311) in Cu2O (CO–Cu2O) via a facile self-selective CO-induced strategy under a CO atmosphere, which was verified by high-resolution transmission electron microscopy (HR-TEM) and atomic force microscopy (AFM) results. By exploiting the high surface energy of the high index crystal planes, *CO species are stabilized in CO–Cu2O during CO2RR, resulting in exceptional catalytic performance for CO2-to-C2 products. In situ infrared spectroscopy revealed that both atop-type (*COatop) and hollow-type (*COhollow) adsorption of *CO species occurred on the CO–Cu2O. The asymmetric C–C coupling energy barrier between *COatop and *COhollow in (311) crystal plane decreases by 47.8% compared to the symmetric coupling of *COatop in conventional (100) crystal planes. Consequently, the Faradaic efficiency of C2 products generated with CO–Cu2O was increased by as high as 100% compared to that with pristine Cu2O.
The direct transformation of dinitrogen (N2) into nitrogen-containing organic compounds holds substantial importance. In this work, we report a titanium-promoted method for the conversion of N2 to N-methylimides. Initially, the N2-bridging end-on dititanium side-on dipotassium complex [{(TrenTMS)Ti}2(μ-η1:η1:η2:η2-N2K2)] underwent simultaneous disproportionation and N-methylation reactions in the presence of methyl trifluoromethanesulfonate (MeOTf), yielding [{(NMe, TMSNN2TMS)Ti}(μ-NMe)]2 with complete cleavage of the N≡N bond. The nucleophilicity of the N-methylated intermediate allowed it to react with electrophilic reagents such as trimethylchlorosilane (TMSCl) to form heptamethyldisilazane, or with acyl chlorides to generate N-methylimides. Moreover, nitrogen-15 (15N) labeled experiments provided a novel approach to synthesizing 15N-labeled methylimides.
The excessive use of pesticides has exacerbated environmental pollution due to herbicide residues, while their persistent toxicity poses serious challenges to global ecological security. A magnetically recyclable CoFe2O4/BiOBr S-scheme heterojunctions was prepared by microwave-assisted co-precipitation method for photocatalytic degradation of Diuron (DUR) in water. The formation of S-scheme heterojunction enhances electron transfer and charge separation, which was demonstrated by free radical trapping, electrochemical experiments, and DFT calculations. The magnetic CoFe2O4/BiOBr catalysts can achieve 99.9% removal of diuron in 50 min under visible light irradiation. Furthermore, the system maintains stable performance across a broad pH range (3–9), enabling adaptation to diverse water environments, effective elimination of multiple pollutants, and strong resistance to ionic interference. Using magnetic recovery, CoFe2O4/BiOBr exhibits a high removal rate of 99% and a markedly low ion leaching rate (< 20 µg/L) after six cycles photocatalytic process, confirming its excellent stability and durability. According to HPLC-QTOF-MS and DFT calculation, the main ways of DUR degradation include dechlorinated hydroxylation, dealkylation and hydroxylation of aromatic ring and side chain. Toxicity analysis showed that the toxicity of the intermediates generated during degradation was generally lower than that of DUR. The magnetic CoFe2O4/BiOBr S-scheme heterojunction developed in this study exhibits excellent photocatalytic performance, high applicability, good stability, and durability, providing an effective magnetic for the removal of refractory pollutants.
Albeit notable endeavors in the construction of organophosphorodithioates, the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge. Herein, an efficient organocatalytic enantioselective nucleophilic addition of vinylidene ortho-quinone methide with phosphinothioic thioanhydride as nucleophilic reagent has been achieved by the dual catalysis of cinchona alkaloid-derived squaramide and 4-dimethylaminopyridine. This protocol provides a straightforward approach for accessing a variety of axially chiral phosphorodithiolated styrenes in good yields (up to 98% yield) with high stereoselectivities (up to 97% ee and >99:1 E/Z).
T-cell acute lymphoblastic leukemia (T-ALL) is a common yet severe pediatric cancer treated with L-asparaginase (ASP). To boost the treatment's effectiveness and lessen its toxicity, enzyme@MOF nanoparticles were engineered with a hyaluronic acid (HA)-targeted polyethylene glycol (PEG) surface. These nanoparticles, termed ASP@MOF/PEG-HA, showed efficient uptake by drug-resistant T-ALL cells. The pH-sensitive zeolitic imidazolate framework-8 (ZIF-8) based metal-organic framework (MOF) nanoparticles allowed the encapsulated ASP to significantly increase cytotoxicity against T-ALL cells. Furthermore, HA's ability to bind to T-ALL cells with elevated CD44 expression further induced apoptosis in CD44+ T-ALL cells with poor prognosis. In animal models, the nanoparticles improved survival rates and reduced the burden of leukemia, demonstrating substantial anti-leukemia effects. Thus, these nanoparticles offer an effective treatment approach for drug-resistant T-ALL cells characterized by increased CD44 expression.
Hepatic fibrosis is regulated by the synergistic actions of various cells and cytokines, with the activation and proliferation of hepatic stellate cells (HSCs) being considered the central event in this process. To achieve specific targeting of activated hepatic stellate cells (aHSCs) and precise treatment of hepatic fibrosis, this study developed a dual-functional drug delivery system (SIL/cRGD-PEG-PPS PMs) with both targeting and responsive release capabilities. It aims to target the αvβ3 receptor specifically expressed on the surface of aHSCs using the cyclic peptide c(RGDyk), and to exploit the high reactive oxygen species (ROS) level in the cellular microenvironment to achieve concentrated burst release of drugs at the pathological sites of hepatic fibrosis. Based on multiple assessments, SIL/cRGD-PEG-PPS PMs specifically enhanced the targeted delivery of silybin (SIL) to aHSCs, inhibited the proliferation and migration of aHSCs, and exhibited good biosafety. Additionally, it demonstrated excellent anti-fibrotic activity in fibrotic mice. In summary, this study shows great potential in targeted treatment of hepatic fibrosis and provides a multifunctional tool for advancing the research and therapeutic strategies of hepatic fibrosis.
Nanofiltration (NF) technology, with its capacity for nanoscale filtration and controllable selectivity, holds significant promise in diverse applications. However, the current upper bound of permeance and selectivity of NF membranes is intrinsically constrained by the morphology and structure of the polyamide (PA) selective layer. This issue arises because NF membranes typically exhibit relatively smooth nodular structures, which theoretically impede efficient water transport. In this study, we enhanced the formation of nanobubbles by synergistically regulating with surfactant and low temperatures, resulting in the fabrication of PA NF membranes with a crumpled morphology. We observed that lower temperatures promote enhanced gas solubility in the aqueous phase, facilitating increased nanobubble formation through the foaming effect of surfactant sodium dodecylbenzene sulfonate (SDBS). Consequently, this resulted in the creation of PA NF membranes with more crumpled structures and superior performance, with pure water permeance reaching 36.25 ± 0.42 L m-2 h-1 bar-1, representing an improvement of 14.47 L m-2 h-1 bar-1 compared to the control group. Additionally, it maintains a high Na2SO4 rejection rate of 97.00% ± 0.58%. The PA NF membranes produced by eliminating nanobubbles and free interfaces exhibited a smooth structure, whereas introducing nanobubbles (through NaHCO3 addition, N2 pressurization, and ultrasonication) resulted in the formation of crumpled membranes. This emphasized that the large amount of nanobubbles generated by SDBS and low temperature in the interfacial process played a critical role in shaping crumpled PA NF membranes and enhancing membrane performance. This approach has the potential to provide valuable insights into customizing the structural design of TFC PA NF membranes, contributing to further advancements in this field.
As an important class of phenanthroline derivatives containing soft N and hard O donor atoms, the laborious syntheses of unsymmetrical 1, 10-phenanthroline-derived diamide ligands (DAPhen) have hindered its extensive study. In this work, we first report a convenient synthetic method for the construction of DAPhen using Friedländer reaction by two facile steps (vs. previous 12 steps). A variety of DAPhen ligands are readily available, especially unsymmetrical ones, which give us a platform to systematically study the substituent effect on f-block elements extraction performance. The performance of unsymmetrical extractants is experimentally confirmed to falls between that of their corresponding symmetrical extractants by extracting UO22+ as the representative f-block element. This work provides a direct and versatile method to synthesize symmetrical and unsymmetrical DAPhen, which paves way for the investigations on their coordination properties with metal ions and other applications.
Integration of single-atom catalysts (SACs) onto metal-organic frameworks (MOFs) with porous channels has garnered significant interest in the field of CO2 reduction. However, MOFs are usually bulky can impede the diffusion of intermediates with substrates and maximizing catalytic site utilization remains a challenge. In this study, we utilized firstly the post-synthetic single-atom chelation sites on zirconium-based metal-organic cages (Zr-MOCs) to anchor cobalt (Co) atom to synthesize single-dispersible ZrT-1-NH2-IS-Co molecular cages for CO2 photoreduction. Experimental results demonstrate that ZrT-1-NH2-IS-Co exhibits impressive catalytic performance, achieving syngas yields of up to 30.9 mmol g-1 h-1, ranking among the highest values of reported crystalline porous catalysts. Mechanistic insights reveal the newly introduced metal serving as the catalytic site and *COOH acts as a crucial intermediate in the CO2 reduction process. Furthermore, the successful synthesis of ZrT-1-NH2-IS-Ni and ZrT-1-NH2-IS-Mn show the universality of the modification strategies, with their CO2 catalytic activity surpassing that of ZrT-1-NH2.
Ferroptosis has exhibited great potential in therapies and intracellular reducing agents of sulfur species (RSSs) in the thiol-dependent redox systems are crucial in ferroptosis. This makes the simultaneous detection of multiple RSSs significant for evaluating ferroptosis therapy. However, the traditional techniques, including fluorescent (FL) imaging and electrospray ionization-based mass spectrometry (MS) detection, cannot achieve the discrimination of different RSSs. Herein, simultaneous MS detection of multiple RSSs, including cysteine (Cys), homocysteine (Hcy), glutathione (GSH) and hydrogen sulfide (H2S), was obtained upon enhancing ionization efficiency by a fluorescent probe (NBD-O-1). Based on the interaction between NBD-O-1 and RSSs, the complex of RSSs with a fragment of NBD-O-1 can be generated, which can be easily ionized for MS detection in the negative mode. Therefore, the intracellular RSSs can be well detected upon the incubation of HeLa cells with the probe of NBD-O-1, exhibiting the total RSS levels by the FL imaging and further providing expression of each RSS by enhanced MS detection. Furthermore, the RSSs during ferroptosis in HeLa cells have been evaluated using the present strategy, demonstrating the potential for ferroptosis examinations. This work has made an unconventional application of a fluorescent probe to enhance the detection of multiple RSSs by MS, providing significant molecular information for addressing the ferroptosis mechanism.
Traditional strategies for designing hyperhalogens, superatoms with exceptional electron-withdrawing capacity, rely on complex superhalogen assembly, posing significant experimental challenges. Here, we introduce a non-invasive dual external field (DEF) approach combining solvent effects and an oriented external electric field (OEEF) to construct hyperhalogens, as demonstrated by density functional theory (DFT) calculations. Our DEF strategy proves versatile, successfully designing hyperhalogens not only in simplified Agn− model systems but also in the experimentally synthesized Ag25 nanocluster. Using the 3D Ag19− structure as a model, we further reveal the DEF's pivotal role in O2 activation, where solvent-OEEF synergy induces tunable O–O bond elongation and charge transfer, proportional to field strength. Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition, providing a theoretical foundation for tailoring high-performance catalysts through precise active-site modulation.
This study investigates the properties of high-purity starches extracted from Polygonum multiflorum (PMS) and Smilax glabra (SGS). The starches were characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, high-performance anion-exchange chromatography, and differential scanning calorimetry. Significant differences were observed in their morphological, physicochemical, and functional properties. PMS had a smaller particle size (13.68 µm), irregular polygonal shape, A-type, lower water absorption (62.67%), and higher oil absorption (51.17%). In contrast, SGS exhibited larger particles (31.75 µm), a nearly spherical shape, B-type, higher crystallinity (50.66%), and greater amylose content (21.54%), with superior thermal stability, shear resistance, and gelatinization enthalpy. SGS also contained higher resistant starch (83.28%) and longer average chain length (20.58%), but showed lower solubility, swelling power, light transmittance, and freeze-thaw stability. The physicochemical properties differences in crystal pattern and particle morphology between PMS and SGS lead to distinct behaviors during in vitro digestion and fermentation. These findings highlight the potential of medicinal plant starches in functional ingredients and industrial processes.
To enhance the anti-resistance efficacy of our previously disclosed naphthyl-triazine 5, structure-based drug design strategy was rationally conducted to design a series of novel biphenyl-piperidine-triazine-containing non-nucleoside reverse transcriptase inhibitors. Remarkably, several of these compounds demonstrated single-digit nanomolar antiviral potency against both wild-type (WT) human immunodeficiency virus-1 (HIV-1) and five clinically relevant mutant strains. Among these, compound 11s emerged as the most potent inhibitor, showing remarkable efficacy against WT HIV-1 (50% effective concentration (EC50) = 2 nmol/L) and five mutant strains (EC50 = 0.003–0.073 µmol/L), which was significantly superior to that of compound 5. This optimized derivative demonstrated substantially improved pharmacological properties compared to existing drugs etravirine (ETR) and rilpivirine (RPV), showing a 4-fold reduction in cytotoxicity alongside 6-fold enhancement in selectivity index (50% cytotoxic concentration (CC50) = 19.69 µmol/L, selectivity index (SI) = 7438). The compound’s metabolic profile revealed exceptional stability, with an elimination half-life (t1/2 = 41.4 min) more than double that of RPV (t1/2 = 16.03 min). Comprehensive safety evaluation indicated minimal cytochrome P450 (CYP) enzymes interference, low cardiac ion channel activity, and no observable acute toxicity, collectively suggesting a reduced risk profile for therapeutic applications. These promising characteristics significantly advance the development potential of biphenyl-piperidine-triazine derivatives as next-generation non-nucleoside reverse transcriptase inhibitors (NNRTIs), offering enhanced efficacy, improved safety, and favorable pharmacokinetic properties for antiretroviral therapy.
Electrochemical CO2 reduction reaction (CO2RR) into valuable formate provides a strategy for carbon neutrality. Bismuth (Bi) catalysts, attributed to their appropriate energy barrier of OCHO* intermediate, have demonstrated substantial potential for the advancement of electrocatalytic CO2 reduction to formate. However, due to the weak bonding of protons (H*) of Bi, the available protonate of CO2 on Bi is insufficient, which limits the formation of OCHO*. Prediction by theoretical calculation, chlorine doping can effectively promote the dissociation of H2O and thus achieve effective proton supply. We prepare chlorine-doped Bi (Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO2. An obvious improvement of faradaic efficiency (FE) of formate (96.7% at −0.95 V vs. RHE) can be achieved on Cl-Bi, higher than that of Bi (89.4%). Meanwhile, Cl-Bi has the highest formate production rate of 275 µmol h−1 cm−2 at −0.95 V vs. RHE, which is 1.2 times higher than that of Bi (224 µmol h−1 cm−2). In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H2O and supply sufficient protons to promote the protonation of CO2 to OCHO*, which is consistent with theoretical calculation. The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.
The hydrogen evolution reaction (HER) is a key process in electrocatalytic water splitting for hydrogen production, yet it is often limited by sluggish H*-OH adsorption and H* binding kinetics. We obtained Ru-modified NiO nanoparticles (Ru-NiO/NF) with enhanced HER properties by substituting ruthenium (Ru) for Ni atoms in the NiO (200) crystalline facets on nickel foam by a one-step electrodeposition technique. This novel catalyst exhibits a significantly reduced H*-OH adsorption energy and improved kinetics, with an overpotential of only 60 mV at 10 mA/cm2 and a Tafel slope of 26.19 mV/dec. The Ru-NiO/NF maintains its activity for over 115 h, outperforming NiO/NF by reducing the overpotential by 177 mV. DFT calculations confirm that the addition of Ru to NiO enhances the HER kinetics by modifying the electronic structure, optimizing the surface chemistry, stabilizing the intermediates, lowering the energy barriers, and facilitating efficient charge transfer through a robust three-dimensional structure, resulting in a change in the rate-limiting step and a significant reduction in the Gibbs free energy. This study presents a highly efficient HER catalyst and offers insights into designing advanced NiO-based electrocatalysts by reducing reaction energy barriers.
The first hemiterpene-quassinoid adducts, bruquass A and B (1 and 2), were rapidly isolated and identified from Brucea javanica using an integrated analytical strategy. They possessed unusual carbon skeletons formed by the coupling of quassinoids with hemiterpene units via vinylogous aldol reactions. Their structural configurations were determined through comprehensive spectroscopic analysis and electronic circular dichroism (ECD) calculations. Plausible biosynthetic pathways for 1 and 2 were proposed, and guided by these biogenetic insights, the biomimetic synthesis of compound 1 was successfully achieved. Furthermore, compounds 1 and 2 exhibited significant antifeedant activity against Plutella xylostella. The bioactivity assessment results open up the prospects of 1 and 2 as a promising new class of botanical insecticide.
Two supramolecular organic frameworks (SOFs) have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water. Dynamic light scattering and 1H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature. One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice, which improves by 40% compared with the highest value of the reported SOFs. In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrug-resistant MDR A549/ADR tumor cells to realize intracellular delivery, leading to enhanced antitumor efficacy. Moreover, it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism. As the first examples that undergo room-temperature reversible assembly and disassembly, the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
Achieving non-centrosymmetric (NCS) configurations in ABX3-type hybrid halides remains a critical challenge for nonlinear optical (NLO) materials due to the conflicting requirements of high second-harmonic generation (SHG) response, wide bandgap, and phase-matching capabilities. Herein, we propose a triple-site modulation strategy by synergistically tailoring the A-site cations (2-methylimidazole cation/1-ethyl-3-methylimidazole cation), B-site metals (Sn2+/Pb2+), and X-site halogens (Cl/Br), which effectively disrupts lattice symmetry and enables NCS crystallization. Our results demonstrate a strong SHG response, an expanded optical bandgap and increased birefringence. The optimized compound C6H11N2PbCl3 exhibits a moderately strong SHG efficiency of 3.8 × KDP, a wide bandgap (3.87 eV), and enhanced birefringence (0.139@1064 nm), surpassing majority hybrid NLO materials. The innovative anionic framework introduced here broadens the scope of hybrid NLO crystals, facilitating the integration of various aromatic heterocyclic cations. This research provides a robust strategic framework for the development of advanced NLO materials.
Aqueous zinc-ion batteries (AZIBs) have advantages including low economic cost and high safety. Nevertheless, the serious hydrogen evolution reactions (HER) and rampant growth of Zn dendrite hinder their further development. Herein, potassium acetate (KAc) additive with cation/anion synergy effect is added into the ZnSO4 electrolyte to effectively promote the oriented uniform Zn deposition and suppress side reactions. According to density functional theory calculation and experimental results, CH3COO− (Ac−) anions are capable of forming stronger hydrogen bonds with H2O molecules, leading to an expanded electrochemical stability window, reduced the reactivity of H2O, and hence suppressing HER. Meanwhile, Ac− anions can also preferentially adsorb onto the Zn anode, promoting dense deposition towards the (100) crystal plane. Besides, dissociated K+ ions serve as electrostatic shielding cations, which significantly promote uniform Zn deposition and prevent dendrite formation. Thus, the ZnZn symmetric cell demonstrates an impressive cycle lifespan of 3000 h at 1.0 mA/cm2. Furthermore, the ZnMnO2 full battery exhibits superior stability with a capacity retention of 86.95% at 2.0 A/g after 4000 cycles. Therefore, the cation/anion synergy effect in KAc additive offers a viable solution to address HER and hinder dendrite growth at the interface of Zn anodes.
Effective treatment of subcutaneous tumors remains a focal point in cancer therapy. Photothermal therapy, a novel therapeutic approach, has emerged as a promising alternative, offering a less invasive option for the treatment of subcutaneous tumors. This study reports the exploration of novel supramolecular halogen-bonded organic frameworks (XOFs) based on [N···Br+···N] halogen bonds through the ligand exchange strategy and their application in photothermal therapy. Through ligand exchange, XOF(Br)-TPy was successfully prepared, and its structure and properties were thoroughly characterized using NMR, XPS, FT-IR, and XRD techniques. Due to their cationic characteristics, these XOFs serve as effective carriers for the photothermal agent IR820. In vitro experiments demonstrated that the IR820@XOF(Br)-TPy composite exhibits excellent photothermal conversion efficiency under NIR irradiation, effectively inducing tumor cell ablation. Furthermore, in vivo studies confirmed the remarkable antitumor efficacy of the composite material in a subcutaneous tumor model. This work demonstrates that the ligand exchange strategy is a versatile and facile approach for constructing XOFs(Br) and provides a novel strategy for developing advanced photothermal therapeutic agents with significant application potential.
Cisplatin (CDDP)-based chemotherapy is an effective strategy for the treatment of advanced nasopharyngeal carcinoma (NPC). However, serious toxic side effects of CDDP limit patient tolerance and treatment compliance, which urgently needs to be addressed in clinical application. Liposomes have been considered ideal vehicles for reducing CDDP toxicity due to their high biocompatibility, low toxicity and passive targeting ability. Nevertheless, CDDP's poor water/lipid solubility usually results in a low liposome drug-lipid ratio, limiting tumor delivery ability. Herein, a CDDP-polyphenol complex liposome was designed to increase the drug loading capacity of CDDP to realize the reduction of toxicity and effective antitumor effect simultaneously. The complex was prepared via complexation reaction of different stoichiometric ratios of CDDP and polyphenolic substances (gallic acid, epigallocatechin gallate and tannic acid), followed by encapsulation of complex in liposomes to improve tumor targeting. Notably, the molecular interaction forces between CDDP and polyphenolic substances were intensively investigated through a binding force disruption assay. In vitro studies demonstrated that the optimal formulation of CDDP-epigallocatechin gallate complex liposome (CDDP-EGCG Lips) showed the highest CDDP encapsulation efficiency, favorable stability, pH-sensitive release, enhanced cellular uptake and apoptosis effect. In vivo studies revealed that CDDP-EGCG Lips retarded the elimination of CDDP to prolong their circulation time, inhibited the growth of tumors, and significantly reduced the toxic side effects compared to CDDP monotherapy. This delivery strategy holds great promise for improving the clinical use of platinum-based drugs.
Aqueous zinc-ion batteries (AZIBs) are regarded as one of the most promising energy conversion and storage devices. Nevertheless, side reactions and dendrite growth on the zinc metal anode hinder their widespread application. In this study, hemin was employed as a multi-functional artificial interface for the first time to inhibit the disordered growth of zinc dendrites and mitigate side reactions. Theoretical calculations indicate that hemin is preferentially adsorbed onto the zinc anode, thus blocking the interaction between the active zinc anode and electrolyte. Compared with zinc foil, the Hemin@Zn anode demonstrates enhanced corrosion resistance, a decrease in hydrogen evolution, and more orderly deposition of zinc. As expected, the symmetric cell with Hemin@Zn anode can sustain up to 4000 h at 0.2 mA/cm2, 0.2 mAh/cm2. Asymmetric Zn//Cu cells exhibit an average coulombic efficiency exceeding 99.72% during 500 cycles. Moreover, the full cell Hemin@Zn//NH4V4O10 delivers a superior capacity up to 367 mAh/g and the discharge capacity retention reaches 124 mAh/g after 1200 cycles even at a current density of 5 A/g. This work provides a simple and effective method for constructing a robust artificial interface to promote the application of long-life AZIBs.
Schizophrenia (SCZ) is a severe mental disorder with an unclear pathogenesis. Increasing evidence suggests that oxidative stress (OS) may contribute to the neuropathological processes underlying SCZ. Biothiols, key endogenous antioxidants, have been proposed as potential biomarkers for the disease. However, due to the presence of the blood-brain barrier (BBB), fluorescent probes are rarely used to image biothiols in the brain of SCZ models. In this study, a series of fluorescent probes for biothiols were developed using dicyanoisophorone derivatives as fluorophores known for their excellent optical properties, and carboxylic esters as recognition units. A parallel synthesis and rapid screening strategy was employed to construct and optimize these probes. By introducing trifluoromethyl and benzothiazole groups into the fluorophore, the emission wavelength was successfully shifted into the near-infrared region. Additionally, various trifluoromethyl-substituted aromatic and nitrogen heterocyclic compounds were incorporated to optimize the carboxylic esters, thereby improving the probes' reactivity and lipophilicity. Systematic evaluation of the physicochemical characteristics, and optical performance led to the identification of DCI-BT-11 as the most promising candidate. DCI-BT-11 demonstrated excellent BBB permeability and a good response to biothiols both in vitro and in vivo. Notably, DCI-BT-11 was used for the first time to visualize biothiol flux and assess the therapeutic effects of the antioxidant N-acetylcysteine (NAC) in the brains of SCZ mouse models, offering new insights into the role of OS in the pathogenesis and treatment of SCZ.
By using carbohydrates as the biomass carbon sources, Se/C materials could be easily prepared. The materials could catalyze the oxidative deoximation reactions, which are significant transformations in both pharmaceutical industry and fine chemical production. Compared with the reported organoselenium-catalyzed ionic reactions, the Se/C-catalyzed deoximation reactions occurred via unique free radical mechanisms, endowing the Se species high catalytic reactivity. The Se/C catalysts were recyclable and their turnover numbers (TONs) were high (>104), making the reactions practical for industrial grade preparation. The unique free radical mechanisms of the reaction and green and practical features of the catalysts are the characteristics and advantages of the work.
The detection of amino acid enantiomers holds significant importance in biomedical, chemical, food, and other fields. Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensity changes, which can compromise accuracy and repeatability. In this study, we report a novel fluorescent probe (R)-Z1 that achieves effective enantioselective recognition of chiral amino acids in water by altering emission wavelengths (> 60 nm). This water-soluble probe (R)-Z1 exhibits cyan or yellow-green luminescence upon interaction with amino acid enantiomers, enabling reliable chiral detection of 14 natural amino acids. It also allows for the determination of enantiomeric excess through monitoring changes in luminescent color. Additionally, a logic operation with two inputs and three outputs was constructed based on these optical properties. Notably, amino acid enantiomers were successfully detected via dual-channel analysis at both the food and cellular levels. This study provides a new dynamic luminescence-based tool for the accurate sensing and detection of amino acid enantiomers.
Metal-support interaction (MSI) is crucial for fine-tuning the active-site structure of supported catalysts and enhancing performance. Here, we present an ammonia-directed reactive gas-metal-support interaction (RGMSI), in which NH3 reduces ZnO and assembles an anti-perovskite Ni3ZnN structure with interstitial nitrogen, significantly boosting hydrogenation efficiency. Nitrogen incorporation expands the lattice parameter, increasing the (111) lattice spacing from 2.04 Å in Ni to 2.18 Å in Ni3ZnN, with an extended Ni-Ni interatomic distance from 2.49 Å to 2.65 Å. Additionally, Ni-N coordination shifts the d-band center downward and induces electron deficiency in Ni via charge transfer. These modifications optimize reactant adsorption on the tailored Ni3ZnN structure compared to Ni, leading to a remarkable increase in 1,3-butadiene hydrogenation selectivity from 30.0% to 92.9%, along with an enhanced TOF from 0.067 s−1 to 0.079 s−1. These findings highlight RGMSI as a versatile and effective strategy for designing supported metal catalysts, offering new insights into selective hydrogenation catalysis.
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes (PLEDs). Herein, we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors (PG and PDG) via metal-free CN coupling polymerization for the fabrication of deep-blue PLEDs. The steric, rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state. Due to the different length of electron-deficient diphenyl sulfone monomers, PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films. Interestingly, similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation. Finally, PLEDs based on PG are fabricated with a stable deep-blue emission of CIE (0.15, 0.10), and corresponding EL spectral profile is also completely identical to PL ones of diluted solution, revealed the intrachain emission without obvious interchain excited state, confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications, e.g., encapsulating enzymes to enhance their stability, activity, and reusability. However, precise control and tune the pore size of such frameworks still remains a significant challenge to date. In this study, we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block. First, a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization. Then 2-ureido-4[1H]-pyrimidinone (Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization. Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units, well-ordered supramolecular polymer frameworks were readily obtained. Notably, the pore size was dependent on the chain length of the polyisocyanide arms. Precisely control the chain length of polyisocyanide arms, supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved. These frameworks, with tunable and large pore apertures, demonstrated exceptional capabilities in encapsulating enzymes of different sizes, such as lipase (TL), horseradish peroxidase (HRP), and glucose oxidase (GOx). The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability. Moreover, the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes, enabling efficient dual-enzyme cascade reactions.
Despite demonstrating significant anti-tumor potential as an artemisinin derivative, artesunate faces delivery efficiency challenges due to low water solubility and insufficient targeting specificity. To improve the delivery efficiency, we engineered three artesunate (ART) derivatives, AC15-L (linear), AC15-B (branched), and AC15-C (cyclic) with distinct aliphatic chain architectures. Unexpectedly, we observed that AC15-C exhibited superior cytotoxicity against 4T1 breast cancer cells, and had the highest binding affinity for Lon protease 1 (LONP1) (−72.6 kcal/mol). Subsequently, disulfide bond-containing lipid-PEG (DSPE-SS-PEG2K) modified chain architecture-engineered ART derivatives nanoassemblies (NAs) were developed to mitigate solubility-related limitations while enhancing targeting precision. Molecular docking and experimental validation demonstrated that ART derivatives inhibited LONP1 through hydrophobic interactions while preserved Fe2+-mediated Fenton-like reaction activity. In vitro and in vivo evaluations demonstrated that AC15-C NAs outperformed free ART and other NAs, suppressing 4T1 tumor growth via dual action: LONP1-directed mitochondrial proteostasis collapse and reactive oxygen species (ROS) amplification through Fe2+-ART interactions. This study elucidated a novel anti-tumor mechanism of ART through the rational design of derivatives with spatially configured aliphatic chains, and developed reduction-responsive NAs to provide an advanced delivery strategy.
The fluorination strategy has been proven effective in significantly enhancing the photovoltaic performance of organic solar cells (OSCs) based on non-fused ring electron acceptors (NFREAs). However, research on the impact of fluorination positions at side chains on NFREAs device performance remains scant. In this study, we introduce two isomeric NFREAs, designated as GA-2F-E and GA-2F, distinguished by their fluorination positions at the side chains. Both NFREAs share a thiophene[3,2-b]thiophene core, but their side chains differ: GA-2F-E features two (4-butylphenyl)-N-(4-fluorophenyl) amino groups, whereas GA-2F’s side chains consist of bis(4-fluorophenyl)amino and bis(4-butylphenyl)amino groups attached to opposite sides of the core. To delve into the influence of fluorination positions on the optoelectronic properties, aggregation behavior, and overall efficiency of the acceptor molecules, a comprehensive investigation was conducted. The findings reveal that, despite similar photophysical properties and comparable absorption bandwidths, GA-2F-E, with fluorine atoms positioned on both sides of the molecular framework, demonstrates more compact π-π stacking, reduced bimolecular recombination, superior exciton transport, and a more balanced, higher mobility. As a result of these advantages, OSCs optimized with D18:GA-2F-E achieve a remarkable power conversion efficiency (PCE) of 16.45%, surpassing the 15.83% PCE of devices utilizing D18:GA-2F. This research underscores the potential of NFREAs in future applications and highlights the significance of fluorination positions in enhancing OSC performance, paving the way for the development of more efficient NFREAs.
Field-effect nanofluidic transistors (FENTs), biomimicking the structure and functionality of neuron, act as biological transistors with the ability to gate switching responses to external stimuli. The switching ratio has been verified to evaluate the performance of FENTs, but until recently, the response time, another crucial indicator, has been ignored. Employing finite-element method, we investigated the relationship among gate charge, switching ratio and response time by divisionally manipulating gate charge, including entrance surface and the surface of confinement space, for ion transport to optimize switching capability. The dual-split gate charge on FENTs exhibits synergistic effect on switching response. Based on the two regional gate charge on FENTs, multivalence ions in lower concentration, high aspect ratio and single channel show higher switching ratio but longer response time compared to monovalent ions. The findings highlight the necessity of balancing these two signals in FENTs and offer insights for optimizing their design and expanding applications to dual-signal-detection iontronics.
Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction (OER). However, the correlation among catalyst structure, magnetic property, and magnetic field enhanced-electrochemical activity remains to be fully elucidated. Herein, single-domain CoFe2O4 catalysts with tunable oxygen vacancies (CFO-VO) were synthesized to probe how VO mediates magnetism and OER activity under magnetic field. The introduction of VO can simultaneously modulate saturation magnetization (Ms) and coercivity (Hc), where the increased Ms dominates the magnetic field-enhanced OER activity. Under a 14,000 G magnetic field, the optimized CFO-VO exhibits up to 16.1% reduction in overpotential and 365% enhancement in magnetocurrent (MC). Electrochemical analyses and post-OER characterization reveal that the magnetic field synergistically improves OER kinetics through lattice distortion induction, magnetohydrodynamic effect, and spin charge transfer effect. Importantly, the magnetic field promotes additional Co3+ generation to compensate for charge imbalance caused by VO filling, maintaining dynamic equilibrium of VO and effective reactant adsorption-conversion processes. This work unveils the synergistic mechanism of VO and magnetic parameters for enhancing OER performance under the magnetic field, providing new insights into the design of high-efficiency spin-regulated OER catalysts.
Structural instability and sluggish lithium-ion (Li+) kinetics of spinel NiCo2O4 anodes severely hinder their applications in high-energy-density lithium-ion batteries. Mesocrystalline structures exhibit promising potential in balancing structural stability and enhancing reaction kinetics. However, their controlled synthesis mechanisms remain elusive. Herein, a substrate interface engineering strategy is developed to achieve controllable synthesis of mesocrystalline and polycrystalline NiCo2O4 nanorods. Remarkably, mesocrystalline NiCo2O4 exhibits a high capacity retention rate of 85.7% after 500 cycles at 2 A/g, attributed to its porous structure facilitating Li+ transport kinetics and unique stress-buffering effect validated by ex-situ TEM. Theoretical calculations and interfacial chemical analysis reveal that substrate-crystal surface engineering regulates the nucleation-growth pathways: Acid-treated nickel foam enables epitaxial growth via lattice matching, acting as a low-interfacial-energy template to reduce nucleation barriers and promote low-temperature oriented crystallization. In contrast, carbon cloth requires high-temperature thermal activation to overcome surface diffusion barriers induced by elevated interfacial energy. This substrate-driven crystallization kinetic modulation overcomes the limitations of random nucleation in conventional hydrothermal synthesis. The established substrate-crystal interfacial interaction model not only clarifies the kinetic essence of crystal orientation regulation but also provides a universal theoretical framework for lattice-matching design and mesostructural optimization of advanced electrode materials.
In this study, electrochemical C-H carboxylation of benzylamines with CO2 was reported. This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids (α-AAs) under mild conditions. Various substituted benzylamines containing diverse functional groups and even highly reactive moieties, such as cyano, amide and alkene groups could be successfully transformed to the carboxylated products. Notably, this method proved to be applicable to the late-stage modification of biorelevant compounds, highlighting its potential for synthetic chemistry. Mechanistic studies such as radical trapping experiments, kinetic isotope effect (KIE) tests and cyclic voltammetry (CV) studies provided useful insight into this transformation.
Thermally activated delayed fluorescence (TADF) emitters show great potential in photodynamic therapy (PDT) and bioimaging, leveraging their structural adaptability, efficient reverse intersystem crossing (RISC), robust photosensitizing capability, and high photoluminescence quantum yields (PLQYs). Herein, we developed a new class of donor–acceptor–donor (D-A-D)-type TADF materials by connecting the highly twisted indolizine-benzophenone electron acceptors with a series of electron donors including phenoxazine, phenothiazine and 9,9-dimethyl-9,10-dihydroacridine. These materials exhibit enhanced TADF properties, aggregation-induced emission (AIE), alongside high reactive oxygen species (ROS) generation efficiency, effectively mitigating aggregation-caused quenching observed in traditional fluorophores. Among them, IDP-p-PXZ, incorporating the phenoxazine donor, stands out with the smallest singlet–triplet splitting energy (ΔEST) and the highest spin-orbit coupling matrix elements (SOCMEs). Upon encapsulation into 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000] (DSPE-PEG2000) nanoparticles (NPs), IDP-p-PXZ demonstrates extended delayed fluorescence lifetimes in air, an exceptionally fast intersystem crossing (ISC) rate constant (kISC) of 3.4 × 107 s−1, and a radiative rate constant (kr) of 5.05 × 106 s−1. These NPs exhibit superior biocompatibility, efficient cellular internalization, and potent ROS production, enabling effective simultaneous PDT and confocal fluorescence imaging in HeLa cells.
Herein, we have developed a straightforward wet-chemical method to synthesize a series of Pd-based alloy nanowires (NWs), including PdPt NWs, PdAu NWs, PdIr NWs, and PdRu NWs, which exhibits high mass activity and turnover frequency (TOF) for HER, surpassing Pt/C by 4.6-fold and 1.5-fold in acidic and alkaline electrolytes, respectively. It also demonstrates high stability in alkaline electrolyte at a current density of 220 mA/cm2 for 280 h, highlighting its potential for practical applications under industrial current conditions. PdPt NWs exhibited ultrathin structures with head-to-tail kinks and inherent defects, significantly increasing the density of active sites and precisely tuning the electronic structure, which could accelerate reaction kinetics and boost water-splitting electrocatalytic performance. This study highlights the potential of PdPt NWs as highly efficient catalysts, offering outstanding catalytic performance and stability for practical applications.
Co-assembling chiral molecules with achiral compounds via non-covalent interactions like arene-perfluoroarene (AP) interactions offers an effective approach for fabricating chiral functional materials. Herein, chiral molecules L/D-PF1 and L/D-PF2 with pyrene groups were synthesized and its chiroptical properties upon co-assembly with achiral compound octafluoronaphthalene (OFN) through AP interaction were systemically studied. The co-assembly of L/D-PF1/OFN and L/D-PF2/OFN exhibited distinct chiroptical properties such as circular dichroism (CD) and circularly polarized luminescence (CPL) signals. Chirality transfer from the chirality center of L/D-PF1 and L/D-PF2 to the achiral OFN and chiral amplification were successfully achieved. Besides, no significant CPL signal was observed in the self-assembly of L/D-PF1 or L/D-PF2 while co-assembly with OFN exhibited obvious CPL amplification induced by AP interaction. Notably, a reversal CD signal and CPL signal could be observed in L/D-PF2/OFN when the molar ratio changed from 1:1 to 1:2 while not found in L/D-PF1/OFN, indicating that that minor structural changes of molecules could cause large changes in assembly. In addition, a series of computational calculations were conducted to verify the AP interaction between L-PF1/L-PF2 and OFN. This work demonstrated that arene-perfluoroarene interaction could drive chiral transfer, chiral amplification and chiral inversion and provided a new method for the preparation of chiroptical materials.
By means the in situ halogenation of the vinyl C-H bond in o-hydroxyphenyl enaminones, the step efficient synthesis of 3-diphenylphosphinyl chromones has been realized through the challenging construction of C-P(Ⅲ) bond by using diphenyl phosphine as reaction partner. In addition, the tunable synthesis of 2-phosphoryl chromanones has been achieved via hydrophosphorylation by simply modifying reaction conditions without using metal reagent.
The photocatalytic oxidation of methane (CH4) to valuable chemicals like low alcohols (CH3OH and C2H5OH) represents a significant technological advancement with implications for energy conversion and environmental purification. A major challenge in this field is the chemical inertness of methane and the strong oxidizing nature of photogenerated holes, which can lead to over-oxidation and reduced selectivity and efficiency. To address these issues, we have developed a sodium-doped zinc oxide (Na-ZnO) modified with cobalt oxide (CoO) catalyst. This catalyst has demonstrated excellent performance in converting methane to low alcohols, achieving a yield of 130 µmol g−1 h−1 and a selectivity of up to 96 %. The doping of Na in ZnO significantly enhances methane adsorption, while the surface-modified CoO effectively captures photogenerated holes, activates water molecules, and uses hydroxyl radicals to activate methane, thus controlling the dehydrogenation degree of methane and preventing the formation of over-oxidized products. This strategy has successfully improved the efficiency and selectivity of photocatalytic methane oxidation to low alcohols, offering a new perspective for the application of photocatalytic technology in energy and environmental fields.
The three-dimensional (3D) Pd-based nanoflower structures, assembled from two-dimensional (2D) nanosheets, are characterized by their stable and ordered configurations. These structures have been extensively designed as anode materials for fuel cells. However, the exploration of trimetallic nanoflowers with porous architectures remains limited. In this study, we present a straightforward one-step solvothermal method for the synthesis of trimetallic PdCuNi porous nanoflowers (PNFs). Leveraging several unique advantages, such as an open superstructure, high porosity, and enhanced electronic interactions among the trimetals, the resulting PdCuNi PNFs demonstrate significantly improved electrochemical performance, with mass activities reaching 5.94 and 10.14 A/mg for the ethanol oxidation reaction (EOR) and the ethylene glycol oxidation reaction (EGOR), respectively. Furthermore, the PdCuNi PNFs exhibit optimized d-band centers and the most negative onset oxidation potential, indicating enhanced antitoxicity and stability. This study not only provides a novel perspective on the synthesis of 3D porous nanomaterials but also highlights the potential application value of trimetallic nanoalloys in catalysis.
α-Chiral amides are common in pharmaceuticals, agrochemicals, natural products, and peptides, prompting the need for new synthetic methods. Here, we introduce a nickel-catalyzed asymmetric reductive amidation method to synthesize α-chiral amides from benzyl ammonium salts and isocyanates. The key to success is using a chiral 2,2′-bipyridine ligand (-)-Ph-SBpy, enabling high yield (up to 95%) and enantiomeric ratio (up to 98:2 er) under mild conditions. Addition of phenol prevents isocyanate polymerization by reversibly forming a carbamate intermediate, enhancing selectivity and efficiency. The synthetic utility is showcased through transformations of the enantioenriched amides, and the mechanism and enantioselectivity are supported by experimental and computational studies.
In the field of organic solar cells (OSCs), side-chain engineering is a key strategy for developing high-performance non-fullerene small molecule acceptors (SMAs), which could adjust the material solubility and modulate the intermolecular stacking properties, profoundly impacting the film morphology and thus acting on the final power conversion efficiency (PCE) of the materials. In this study, two asymmetric acceptor molecules, Qx-PhBr-BO and Qx-PhBr-X, were synthesized by migrating the branching site of the outer side chain from the β-site to the γ-site. The branching site located at the γ-site could reduce the steric-hindrance effect and enhance the molecular aggregation behavior, giving rise to redshifted absorption and tight π-π stacking. Morphology analysis shows that the Qx-PhBr-X-based devices have smoother surfaces and a phase-separated structure, which is more favorable for charge transport and extraction. The Qx-PhBr-X-based devices exhibit balanced hole-electron mobility, efficient exciton dissociation, and low charge recombination. As a result, Qx-PhBr-X with γ-site branching exhibits superior photovoltaic performance with a PCE of 17.16%, which is significantly higher than that of Qx-PhBr-BO at 16.28%. These results highlight the importance of side-chain modifications for optimizing OSC efficiency and provide an important reference for precise tuning of side-chain structures in future molecular design.
Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction (OER) is crucial for advancing overall water splitting (OWS) systems. In this study, we synthesized the electrode material Ce-NiCo-LDHs@SnO2/NF through a two-step hydrothermal reaction, where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO2 layer. Ce doping adjusts the internal electronic distribution of NiCo-LDHs, while the introduction of the SnO2 layer enhances electron transfer capability. Together, these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism (LOM). Consequently, Ce-NiCo-LDHs@SnO2/NF exhibits high level electrochemical performance in OER, requiring only 234 mV overpotential to achieve a current density of 10 mA/cm2, with a Tafel slope of just 27.39 mV/dec. When paired with Pt/C/NF, an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 mA/cm2. Furthermore, the catalyst demonstrates stability for 100 h during the OWS stability test. This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO2 layer.
Rational design of nanozymes with enhanced catalytic efficiency remains a central challenge in the development of artificial enzymes. Herein, we report the construction of ultrasmall gold nanocluster-based nanoassemblies (Dp-AuNCs@Fe2+) through the coordination of Fe2+ ions by a dopa-containing peptidomimetic ligand (DpCDp). This nanoarchitecture simultaneously integrates catalytically active gold cores and redox-active Fe2+ centers, bridged by DpCDp to facilitate directional electron transfer. Comprehensive spectroscopic and kinetic analyses reveal that DpCDp promotes efficient charge migration from the Au core to surface-bound Fe2+, significantly enhancing H2O2-mediated peroxidase-like activity. Compared to bare Dp-AuNCs, Dp-AuNCs@Fe2+ display a 4.3-fold improvement in detection sensitivity, a 6.7-fold increase in catalytic efficiency, and markedly stronger hydroxyl radical generation. Mechanistically, this activity stems from a synergistic triad: direct H2O2 oxidation at gold surfaces, radical generation at Fe2+ sites, and DpCDp-facilitated electron shuttling. This work presents a robust strategy for nanozyme enhancement via electronic and structural co-engineering, offering valuable insights for the future design of bioinspired catalytic systems.
Conversion of ammonia into hydrogen, a crucial pathway for the hydrogen economy, is severely constrained by the intricacy of the required equipment and the low efficiency. Herein, Pd@PtNiCoRuIr core-shell mesoporous bifunctional electrocatalysts were fabricated via a one-step wet-chemical reduction approach. By utilizing the limiting effect of triblock copolymers, gradient distribution control of six metal elements (Pd core and Pt/Ni/Co/Ru/Ir high-entropy alloys shell) was achieved, where the high-entropy alloy shell forms high-density active sites through lattice distortion effect. With the help of lattice distortion and mesoporous-confinement-enabled interfacial coupling effects, Pd@PtNiCoRuIr catalyst exhibited exceptional bifunctional performance in alkaline media: A low hydrogen evolution reaction (HER) overpotential of 30.5 mV at 10 mA/cm2 and a high ammonia oxidation reaction (AOR) peak current density of 19.6 mA/cm2 at 0.7 V vs. RHE, representing a 3.83-fold enhancement over commercial Pt/C. Moreover, a rechargeable Zn-NH3 battery system was constructed and achieved 92.3% Faradaic efficiency (FE) for NH3-to-H2 conversion with outstanding stability at 16 mA/cm2, thereby providing an innovative solution for efficient ammonia decomposition-based hydrogen production.
Developing advanced electrocatalysts to convert CO2 into liquid fuels such as C2H5OH is critical for utilizing intermittent renewable energy. The formation of C2H5OH, however, is generally less favored compared with the other hydrocarbon products from Cu-based electrocatalysts. In this work, an alkanethiol-modified Cu2O nanowire array (OTT-Cu2O) was constructed with asymmetric Cu sites consisting of paired Cu–O and Cu–S motifs to overcome previous limitations of C2H5OH electrosynthesis via CO2RR pathway. This catalyst achieves a high Faradaic efficiency of 45% for CO2-to-C2H5OH conversion at 300 mA/cm2, representing a more than two-fold enhancement over the Cu2O electrode. Mechanistic investigations reveal that the Cu–S site exhibits distinct C-binding capability that stabilizes key intermediates (*OCH2 and *CO), in contrast to the O-affinitive Cu–O site. The asymmetric S–Cu–O configuration promotes thermodynamically favorable asymmetric C–C coupling between *CO and *OCH2, forming the critical CO–OCH2 intermediate and facilitating C2H5OH production, as opposed to symmetric O–Cu–O sites that mainly generate HCOOH. This work offers an effective strategy for designing multi-active-site catalysts toward highly selective CO2 reduction to C2H5OH and provides fundamental insight into the reaction mechanism.
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science. Multi-nuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mono-nuclear catalysts, but which substantially involve multi-step, tedious, and difficult synthesis. Herein, this study reports an intriguing approach to construct multi-nuclear catalysts for the milestone α-diimine nickel catalysts using an oligomeric strategy. A polymerizable norbornene unit is incorporated into the α-diimine ligand backbone, leading to the formation of the monomeric nickel catalyst Ni1 and its corresponding oligomeric nickel catalysts (Ni3 and Ni5) with varying degrees of polymerization (DP = 3 and 5). Notably, the oligomeric catalyst Ni5 was facilely scaled up (50 g-level), showed enhanced thermal stability, exhibited 4.6 times higher activity, and yielded polyethylene elastomer with a 379% increased molecular weight in ethylene polymerization, compared to the monomeric catalyst Ni1. Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent. The kilogram-scale polyethylene, produced using Ni5 in a 20 L reactor, presented a highly branched all-hydrocarbon structure, which demonstrated typical elastic properties (tensile strength: 4 MPa, elastic recovery: SR = 72%) along with great processability (MFI = 3.0 g/10 min), insulating characteristics (volume resistivity = 2 × 1016 Ω/m), and hydrophobicity (water vapor permeability: 0.03 g/m2/day), suggesting potentially practical applications.
Detecting biomarkers in body fluids by optical lateral flow immune assay (LFIA) technology provides rapid access to disease information for early diagnosis. LFIA is based on an antigen-antibody reaction and is rapidly becoming the preferred choice of physicians and patients for point-of-care testing due to its simplicity, cost-effectiveness, and rapid detection. Observing the optical signal change from the colloidal gold of the traditional LFIA strip has been widely applied for various biomarkers detection in body fluids. Despite the significant progress, rapid real-time detection of color changes in the colloidal gold by the naked eye still faces many limitations, such as large errors and the inability to quantify and accurately detect. New optical LFIA strip technology has emerged in recent years to extend its application scenarios for achieving quantitative detection such as fluorescence, afterglow, and chemiluminescence. Herein, we summarized the development of optical LFIA technology from single to hyphenated optical signals for biomarkers detection in body fluids from invasive and non-invasive sources. Moreover, the challenge and outlook of optical LFIA strip technology are highlighted to inspire the designing of next-generation diagnostic platforms.
Groundwater is a key part of the terrestrial ecosystem, but it is vulnerable to pollution in the context of chemical industry development. Treating contaminated groundwater is challenging due to its stable water quality, hidden contamination, and complex treatment requirements. Current research focuses on advanced treatment technologies, among which the advanced oxidation process (AOPs) of peroxomonosulfate (PMS) has great potential. Although there are many reviews of PMS-based AOP, most of them focus on surface water. This review aims to explore the activation reaction of PMS to groundwater by in-situ chemical oxidation (ISCO) technology, further study the reaction mechanism, compare the treatment effect of characteristic pollutants in the groundwater of the chemical industry park, propose new activation methods and catalyst selection, and provide guidance for future groundwater treatment research.
Antibiotic resistance genes (ARGs) are recognized as a primary threat to the sustainability of environment and human health in the 21st century. Nanomaterials (NMs) have attracted substantial attention due to their unique dimensions and structures. Unfortunately, emerging evidence suggests that NMs may facilitate the transmission of ARGs. It is crucial to elucidate how NMs affect the evolution and dissemination of ARGs. The current review comprehensively examines the role of NMs in the widespread transmission of ARGs in aquatic environments and the underlying mechanisms involved in the process. It aims to clarify the effects and mechanisms of NMs on the horizontal gene transfer processes that are associated with ARGs, including the enhancement of cell membrane permeability, the formation of nanopores on membranes, promotion of mutagenesis, and the generation of reactive oxygen species (ROSs). Furthermore, the trade-off between the removal of ARGs and horizontal transfer has been elucidated. The review aspires to guide future research directions, advance knowledge on the implications of NMs in the field of ARGs' transmission, and provide a theoretical foundation for the development of safer and more effective applications of NMs.
The development of highly effective therapeutics is a priority in addressing the escalating threat that cancer poses to human health. Cyclodextrins (CDs) with exceptional biocompatibility and devisable structural hierarchy are emerging as versatile building blocks for engineered drug delivery systems, showing a promising prospect in cancer therapy. CDs enable precise synthesis of functionalized polymers with tailored architectures, endowing their excellent stability and large surface area to prolong drug circulation, enhance solubility, and increase targeting efficiency. Recently, CD-based nanotherapeutics has shown transformative potential in chemotherapy, phototherapy, immunotherapy, gene therapy and other co-delivery systems of combination therapy. This review will introduce the types of CD-based nanotherapeutics, systematically summarize their design methods and anticancer application, and further discuss the prospects and challenges, providing a roadmap for advancing CD nanotechnology toward cancer therapeutics.
The escalating global issues of water scarcity and pollution emphasize the critical need for the rapid development of efficient and eco-friendly water treatment technologies. Photoelectrocatalytic technology has emerged as a promising solution for effectively degrading refractory organic pollutants in water under light conditions. This review delves into the advancements made in the field, focusing on strategies to enhance the generation of active species by modulating the micro-interface of the photoanode. Strategies, such as morphological control, element doping, introduction of surface oxygen vacancies, and construction of heterostructures, significantly improve the separation efficiency of photogenerated charges and the generation of active species, thereby boosting the efficiency of photoelectrocatalytic performance. Furthermore, the review explores the potential applications of photoelectrocatalytic technology in organic pollutant degradation in solutions. It also outlines the current challenges and future development directions. Despite its remarkable laboratory success, practical implementation of photoelectrocatalytic technology encounters obstacles related to stability, cost-effectiveness, and operational efficiency. Future investigations need to focus on optimizing the performance of photoelectrocatalytic materials and exploring strategies for upscaling their application in real water treatment scenarios.
Chitosan (CS), a natural polymer derived from chitin found in the exoskeletons of crustaceans, has garnered significant interest in the pharmaceutical field due to its unique properties, including biocompatibility and biodegradability. In recent years, various studies have reported that CS can affect drug bioavailability, and interestingly, it works as an oral absorption enhancer and inhibitor. This review offers an in-depth analysis of the mechanisms underlying such a phenomenon and supports its application as a pharmaceutical excipient. CS enhances oral drug absorption through various mechanisms, such as interaction with the intestinal mucosa, tight junction modulation, inhibition of efflux transporters, enzyme inhibition, solubility and stability enhancement, and complexation. On the other side, CS exhibits the ability to inhibit the absorption of certain drugs by adsorbing to lipids and sterols, modulating bile acids and gut microbiota, altering drug-cell interaction at the polar interface, and mucus-mediated entrapment and interference. Future potential pharmaceutical research in this field includes elucidating the underneath absorption relevant mechanisms, rational use in formulations as excipient, exploring functional CS derivatives, and developing CS-based drug delivery systems. This comprehensive review highlights CS’s versatile and significant role in enhancing and inhibiting oral drug absorption, providing insights into the complexities of drug delivery and the potential of CS to improve therapeutic outcomes.
The diagnostic efficacy of contemporary bioimaging technologies remains constrained by inherent limitations of conventional imaging agents, including suboptimal sensitivity, off-target biodistribution, and inherent cytotoxicity. These limitations have catalyzed the development of intelligent stimuli-responsive block copolymers-based bioimaging agents, which was engineered to dynamically respond to endogenous biochemical cues (e.g., pH gradients, redox potential, enzyme activity, hypoxia environment) or exogenous physical triggers (e.g., photoirradiation, thermal gradients, ultrasound (US)/magnetic stimuli). Through spatiotemporally controlled structural transformations, stimuli-responsive block copolymers enable precise contrast targeting, activatable signal amplification, and theranostic integration, thereby substantially enhancing signal-to-noise ratios of bioimaging and diagnostic specificity. Hence, this mini-review systematically examines molecular engineering principles for designing pH-, redox-, enzyme-, light-, thermo-, and US/magnetic-responsive polymers, with emphasis on structure-property relationships governing imaging performance modulation. Furthermore, we critically analyze emerging strategies for optical imaging, US synergies, and magnetic resonance imaging (MRI). Multimodal bioimaging has also been elaborated, which could overcome the inherent trade-offs between resolution, penetration depth, and functional specificity in single-modal approaches. By elucidating mechanistic insights and translational challenges, this mini-review aims to establish a design framework of stimuli-responsive block copolymers-based for high fidelity bioimaging agents and accelerate their clinical translation in precise diagnosis and therapy.
Malignant pleural effusion (MPE) is a serious disease caused by malignant tumors with high morbidity and mortality. Chemotherapy, immunotherapy, and antiangiogenic therapy are common treatments for MPE at present. However, traditional chemotherapeutic drugs have many side effects and can easily lead to drug resistance in patients. The complex tumor microenvironment (TME) of MPE directly reduces the antitumor efficacy of immunotherapy. Fortunately, drug delivery systems (DDSs) based on biomaterials have the ability to overcome some of the drawbacks of conventional treatments by improving drug stability, increasing the accuracy of tumor cell targeting, reducing toxic side effects, and remodeling TME, ultimately improving drug efficacy. Therefore, the purpose of this review is to provide an overview and discussion of the latest progress in biomaterial-based DDSs for the treatment of MPE. We discuss the application of biomaterials in the treatment of MPE from multiple perspectives, including chemotherapy, immunotherapy, combination therapy, and pleurodesis, where microspheres, cell membrane-derived microparticles (MPs), micelles, nanoparticles, and liposomes, are involved. The application of these biomaterials has been proven to have great potential in the treatment of MPE, providing a new idea for follow-up research.
In recent years, development of strategies to treat central nervous system (CNS) diseases has attracted extensive attention. A major obstacle in this field is the blood-brain barrier (BBB), which significantly limits the efficient delivery of therapeutic agents to the brain and hinders the treatment of CNS diseases. Overcoming the restrictive nature of the BBB has thus emerged as a key objective in CNS drug development. Nanomaterials have garnered growing interest due to their unique physicochemical properties and potential to traverse the BBB, enabling targeted drug delivery to brain tissue and improving therapeutic efficacy. In this review, we present current insights into the structure and function of the BBB and highlight a range of nanomaterial-based strategies for BBB penetration, including receptor-mediated transport (RMT), adsorptive-mediated transcytosis, reversible BBB disruption, and intranasal administration. Finally, we summarize recent advances in enhancing BBB permeability for CNS therapeutics and discuss persisting challenges, offering perspectives for future research in this field.
Plant bacterial diseases cause significant harm to agricultural production because of their frequent, intermittent and regional outbreaks. Currently, chemical control is still a more effective method for bacterial disease. To develop new, efficient and safe antibacterial agrochemicals, we summarize the research progress of compounds with antibacterial activities in the past ten years, classify them according to their active skeletons, and discuss their structure-activity relationships and mechanisms of action. Finally, the development trend of antibacterial agrochemicals was prospected. This review provides valuable information for the development of antibacterial agrochemicals.
Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry, significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access this valuable scaffold. Catalyzed direct Csp2–H functionalization provides an effective and cost-efficient approach to synthesizing carbazoles from simple and readily available starting materials, ensuring a promising path characterized by excellent atom and step economy. This review highlights the substantial progress made in the last 10 years in advancing catalytic Csp2–H functionalization techniques for synthesizing carbazoles.
In recent years, different drugs therapies for treatment pulmonary fibrosis (PF) have gained much attention due to development of drug delivery technology and urgent clinical needs. PF treatment existed a variety of currently clinical problem but PF could be treated with different drugs potentially though drug delivery technology. This review systematically expounds its basic theory, various drug delivery technologies, and future development directions. In the introduction, the relationship between the pathological mechanism of PF and drug delivery, the basic principles of the drug delivery system and the biological barriers faced by pulmonary drug delivery are analyzed. This review details delivery of small molecule drug, macromolecular drug and cells, including chemical synthesis and natural small molecule drug delivery, as well as RNA and cell-based delivery. Finally, the challenges and perspectives of these drugs to treat PF delivery technologies are discussed and key aspects in the development of PF drugs are considered. We hoped that this review can provide comprehensive and in-depth theoretical reference and technical support for the drug treatment of PF.
Hydrogen peroxide (H2O2) has been recognized as a green and nonpolluting multifunctional oxidant with extensive applications in environmental protection, metal etching, textile printing and dyeing, chemical synthesis and food processing. However, over 90% of industrial H2O2 is currently produced through the multi-step anthraquinone oxidation process, which suffers from a process with some drawbacks such as complex, high-energy consumption, and toxic byproducts emissions. Compared to the traditional anthraquinone method, artificial photosynthesis of H2O2 using semiconductor photocatalysts has emerged as a sustainable alternative due to its use of water and O2 as the clean reactants and sole energy as the driving force. In recent years, metal-free photocatalysts mainly including covalent organic frameworks (COFs), covalent triazine frameworks (CTFs) and carbon nitrile (g-C3N4) have garnered significant interest due to their superior thermal and chemical stability, diverse synthesis methods, tunable functionality, light weight nature and non-toxicity. These materials also exhibit adjustable band structure and unique photoelectric properties. Sustainable efforts have been made to advance metal-free photocatalysts for artificial photosynthesis of H2O2, however, a comprehensive summary of current research status on metal-free-based photocatalytic overall H2O2 production remain scarce. This review outlines recent process in overall H2O2 photosynthesis based on metal-free photocatalysts. First, we introduced the fundamental concepts of photocatalytic overall H2O2 production. Then, we analyze representative studies on photocatalytic overall H2O2 synthesis using metal-free materials. Finally, we discuss the challenges and future perspectives in this field to guide the design and synthesis of metal-free systems for H2O2 generation.
The catalytic transferred of small molecules into high-value chemical products in green methods are highly perused, and has obtained huge attention. In this field, great progress has been achieved during the past five years. Followed by the roadmap (Chinese Chemical Letters, 2019, 30, 2089–2109) written by us before five years, we think that it should be updated to give more insights in this field. Thus, we write the present roadmap based on the fast changed background. In this roadmap, oxygen and carbon dioxide reduction reactions (including at high temperature), photocatalytic hydrogen generation and carbon dioxide reduction reactions, (photo)electrocatalytic reduction of O2 to H2O2 and NH3 generated from N2 are discussed. The progress and challenges in above catalytic processes are given. We believe this manuscript will give the researchers more suggestions and help them to obtain useful information in this field.
The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals, where electron transfer at the electrode produces catalysts with more valence states. Among these transition metal catalysts, electrochemical conversions catalyzed by inexpensive copper metals have received considerable attention. This article systematically investigated this field and reviewed the electrochemical copper catalytic methods applied in organic synthesis from the different activation modes of substrates, which can be broadly classified into the functionalization of C = C bonds, C−H bond activation, C−C and C−X bond activation, and so on.
Radical cycloaddition reactions (RCRs) are highly effective methods for constructing complex carbo- and heterocycles, which are frequently encountered in natural products that exhibit intriguing biological properties and hold significant potential for applications in medicinal chemistry. Radical-mediated cycloaddition strategies, which recycle radical character, are particularly appealing because they require only a catalytic amount of reagent and promise reactions with theoretically high atom economy. This review focuses on recent developments and synthetic applications in RCRs, with an emphasis on visible light-induced radical photocycloaddition reactions (RPCRs), transition metal-catalyzed approaches, and small molecule-catalyzed methods. By highlighting some outstanding innovations and addressing current challenges, this review aims to identify potential areas for improvement. These advancements will provide more efficient pathways for the synthesis of natural product molecules and offer valuable insights for the development of new synthetic methodologies.
Interlocked covalent organic cages have aesthetic skeletons endowed with structural and topological complexity. Their self-assembly provides a unique possibility to mimic the hierarchical self-assembly of biomacromolecules. In recent years, significant progresses in interlocked covalent organic cages have been witnessed. Different topological structures have been fabricated via various non-template induced methods, and diverse weak interactions are demonstrated to play critical roles in guiding the formation of interlocked structures. Therefore, this article systematically summarizes the recent advances in interlocked covalent organic cages, especially their design, synthesis, and self-assembly properties. Depending on different types of chemical reactions, irreversible and reversible reactions are separately introduced. In each section, proper monomer selection, critical topology design, key driving forces as well as detailed interlocked mechanisms for the formation of interlocked structures, and their self-assembly behaviors in single crystals are discussed detailedly. Finally, the challenge and future development of interlocked covalent organic cages are briefly prospected.
