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2024 Volume 35 Issue 10
2024, 35(10): 109343
doi: 10.1016/j.cclet.2023.109343
Abstract:
A novel Ce-containing poly(tungstobismuthate) Cs18Na8H20[Ce3(H2O)10W8Bi4O28(B-α-BiW9 O33)4]2·64H2O (1) has been synthesized by a facile one-pot self-assembly reaction strategy. Its structural characterization is realized by virtue of single-crystal X-ray diffraction, infrared spectroscopy, powder X-ray diffraction and thermogravimetric analysis. The polyoxoanion of 1 is an octameric architecture consisting of two tetrameric entities [Ce3(H2O)10W8Bi4O28(B-α-BiW9O33)4]23− linked by two CeOW bonds, and adjacent polyoxoanions are further combined together by means of Ce3+ linkers, resulting in an infinite 1D chain architecture. Compound 1 is the currently largest tungstobismuthate, and also represents the first example of lanthanide-encapsulated tungstobismuthate exhibiting an extended structure. Furthermore, compound 1 as a heterogeneous catalyst, exhibits high activity for the oxidative decontamination of a sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES) into 2-chloroethyl ethyl sulfoxide (CEESO).
A novel Ce-containing poly(tungstobismuthate) Cs18Na8H20[Ce3(H2O)10W8Bi4O28(B-α-BiW9 O33)4]2·64H2O (1) has been synthesized by a facile one-pot self-assembly reaction strategy. Its structural characterization is realized by virtue of single-crystal X-ray diffraction, infrared spectroscopy, powder X-ray diffraction and thermogravimetric analysis. The polyoxoanion of 1 is an octameric architecture consisting of two tetrameric entities [Ce3(H2O)10W8Bi4O28(B-α-BiW9O33)4]23− linked by two CeOW bonds, and adjacent polyoxoanions are further combined together by means of Ce3+ linkers, resulting in an infinite 1D chain architecture. Compound 1 is the currently largest tungstobismuthate, and also represents the first example of lanthanide-encapsulated tungstobismuthate exhibiting an extended structure. Furthermore, compound 1 as a heterogeneous catalyst, exhibits high activity for the oxidative decontamination of a sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES) into 2-chloroethyl ethyl sulfoxide (CEESO).
2024, 35(10): 109345
doi: 10.1016/j.cclet.2023.109345
Abstract:
In core-shell silver nanoclusters, the control of core structure presents a more formidable challenge compared to that of the shell structure. Here, we report the successful synthesis and characterization of four distinct silver thiolate nanoclusters [MS4@Ag12@Ag46S24(dppb)12] (M = Mo or W), each incorporating a cup-like [MS4@Ag12]2+ kernel. These nanoclusters were meticulously prepared using (NH4)2MoS4 or (NH4)2WS4 as both a template and a controlled source of S2− ions. Remarkably, we have observed a unique configuration within these eight-electron superatomic Ag58 nanoclusters, where the zero-valent Ag atoms reside exclusively within the inner [MS4@Ag12]2+ kernel. This stands in contrast to other superatomic clusters possessing an Ag(0) core. Notably, the introduction of phenyl-containing compounds during the synthesis process induced a transformation in the space group symmetry from C2/c to I4. This transformative effect was found to originate from the interplay between adjacent 1,4-bis(diphenylphosphino)butane (dppb) ligands, which facilitated enhanced emission through aggregation-induced intermolecular interactions, specifically C−H···π interactions. Collectively, our findings contribute substantively to the understanding of the intricate relationship between nanocluster structures and their corresponding properties, shedding light on the crucial roles played by templates and diphosphine ligands in this context.
In core-shell silver nanoclusters, the control of core structure presents a more formidable challenge compared to that of the shell structure. Here, we report the successful synthesis and characterization of four distinct silver thiolate nanoclusters [MS4@Ag12@Ag46S24(dppb)12] (M = Mo or W), each incorporating a cup-like [MS4@Ag12]2+ kernel. These nanoclusters were meticulously prepared using (NH4)2MoS4 or (NH4)2WS4 as both a template and a controlled source of S2− ions. Remarkably, we have observed a unique configuration within these eight-electron superatomic Ag58 nanoclusters, where the zero-valent Ag atoms reside exclusively within the inner [MS4@Ag12]2+ kernel. This stands in contrast to other superatomic clusters possessing an Ag(0) core. Notably, the introduction of phenyl-containing compounds during the synthesis process induced a transformation in the space group symmetry from C2/c to I4. This transformative effect was found to originate from the interplay between adjacent 1,4-bis(diphenylphosphino)butane (dppb) ligands, which facilitated enhanced emission through aggregation-induced intermolecular interactions, specifically C−H···π interactions. Collectively, our findings contribute substantively to the understanding of the intricate relationship between nanocluster structures and their corresponding properties, shedding light on the crucial roles played by templates and diphosphine ligands in this context.
2024, 35(10): 109352
doi: 10.1016/j.cclet.2023.109352
Abstract:
Understanding the role of perovskite surface passivators in hot carriers transfer dynamics is important to develop highly efficient perovskite solar cells (PSCs). In this work, we have designed and synthesized a naphthalimide-based organic small molecule (NCN) for perovskite surface defect passivator. We reveal that the introduction of NCN not only reduces the density of perovskite defect-state, but also promotes hot carriers (HCs) cooling in perovskite through the transient absorption spectroscopy measurements. Fast HCs cooling permits HCs transfer from perovskite layer into NCN layer, thus resulting in the decreased charge-carrier recombination in NCN-treated device. As expected, the power conversion efficiency (PCE) of PSCs with NCN is enhanced to 22.02% from 19.95% for the control device. The findings are relevant for developing highly efficient PSCs.
Understanding the role of perovskite surface passivators in hot carriers transfer dynamics is important to develop highly efficient perovskite solar cells (PSCs). In this work, we have designed and synthesized a naphthalimide-based organic small molecule (NCN) for perovskite surface defect passivator. We reveal that the introduction of NCN not only reduces the density of perovskite defect-state, but also promotes hot carriers (HCs) cooling in perovskite through the transient absorption spectroscopy measurements. Fast HCs cooling permits HCs transfer from perovskite layer into NCN layer, thus resulting in the decreased charge-carrier recombination in NCN-treated device. As expected, the power conversion efficiency (PCE) of PSCs with NCN is enhanced to 22.02% from 19.95% for the control device. The findings are relevant for developing highly efficient PSCs.
2024, 35(10): 109355
doi: 10.1016/j.cclet.2023.109355
Abstract:
Since the appearance of Rochelle salt, ferroelectrics have received extensive attention from researchers due to they are playing an important role in sensors, memories, mechanical actuation, and so on. In recent years, with the rapid development of molecular ferroelectrics, high-performance molecular ferroelectrics have become effective complement to inorganic ferroelectrics. However, compared with inorganic ferroelectrics, the family of molecular ferroelectrics is relatively scarce, and exploring high-performance ferroelectric materials through new synthesis strategies has become the trend of molecular ferroelectrics. Here, we successfully transformed non-polar material 1 (2-H2PCA)2(H2O)CdCl6 (2-H2PCA = 2-picolylamine cation) into polar material 2 (2-H2PCA)2CdCl6 by single-crystal to single-crystal transformation (SCSCT). Meanwhile, 2 exhibits clear ferroelectricity with a high-temperature Tc of 378 K, a Ps of 1.18 µC/cm2 at 300 K. This work not only realizes the purpose of synthesizing ferroelectrics by forming polar structures by SCSCT, but also realizes the reversibility of SCSCT, which provides ideas for the construction and exploration of new molecular ferroelectrics.
Since the appearance of Rochelle salt, ferroelectrics have received extensive attention from researchers due to they are playing an important role in sensors, memories, mechanical actuation, and so on. In recent years, with the rapid development of molecular ferroelectrics, high-performance molecular ferroelectrics have become effective complement to inorganic ferroelectrics. However, compared with inorganic ferroelectrics, the family of molecular ferroelectrics is relatively scarce, and exploring high-performance ferroelectric materials through new synthesis strategies has become the trend of molecular ferroelectrics. Here, we successfully transformed non-polar material 1 (2-H2PCA)2(H2O)CdCl6 (2-H2PCA = 2-picolylamine cation) into polar material 2 (2-H2PCA)2CdCl6 by single-crystal to single-crystal transformation (SCSCT). Meanwhile, 2 exhibits clear ferroelectricity with a high-temperature Tc of 378 K, a Ps of 1.18 µC/cm2 at 300 K. This work not only realizes the purpose of synthesizing ferroelectrics by forming polar structures by SCSCT, but also realizes the reversibility of SCSCT, which provides ideas for the construction and exploration of new molecular ferroelectrics.
2024, 35(10): 109377
doi: 10.1016/j.cclet.2023.109377
Abstract:
Recently, non-centrosymmetric (NCS) Hg-based chalcogenides have garnered significant interest due to their strong second-harmonic-generation intensities (deff), making them attractive candidates for infrared nonlinear optical (IR-NLO) application. However, achieving both wide band gaps (Eg) and large phase-matched deff simultaneously in these materials remains a challenge due to their inherent constraints on each other. In this research, we have successfully obtained two quaternary NCS Hg-based chalcogenides, Rb2HgGe3S8 and Cs2HgGe3S8, by implementing a bandgap engineering strategy that involves alkali metal introduction and Hg/Ge ratio regulation. Both compounds consist of 2D [HgGe3S8]2– anionic layers made of 1D [HgGeS6]6– chains and dimeric [Ge2S6]4– polyhedra arranged alternately, and the charge-balanced Rb+/Cs+ cations located between these layers. Remarkably, Rb2HgGe3S8 and Cs2HgGe3S8 exhibit overall properties required for promising IR-NLO materials, including sufficient PM deff (0.55–0.70 × AgGaS2@2050 nm), large Eg (3.27–3.41 eV), giant laser-induced damage thresholds (17.4–19.7 × AgGaS2@1064 nm), broad optical transmission intervals (0.32–17.5 µm), and suitable theoretical birefringence (0.069–0.086@2050 nm). Furthermore, in-depth theoretical analysis reveals that the exceptional IR-NLO performance is attributed to the synergy effects of distorted [HgS4] and [GeS4] tetrahedra. Our study provides a useful strategy for enhancing the Eg and advancing Hg-based IR-NLO materials, which is expected to extended and implemented in other chalcogenide systems.
Recently, non-centrosymmetric (NCS) Hg-based chalcogenides have garnered significant interest due to their strong second-harmonic-generation intensities (deff), making them attractive candidates for infrared nonlinear optical (IR-NLO) application. However, achieving both wide band gaps (Eg) and large phase-matched deff simultaneously in these materials remains a challenge due to their inherent constraints on each other. In this research, we have successfully obtained two quaternary NCS Hg-based chalcogenides, Rb2HgGe3S8 and Cs2HgGe3S8, by implementing a bandgap engineering strategy that involves alkali metal introduction and Hg/Ge ratio regulation. Both compounds consist of 2D [HgGe3S8]2– anionic layers made of 1D [HgGeS6]6– chains and dimeric [Ge2S6]4– polyhedra arranged alternately, and the charge-balanced Rb+/Cs+ cations located between these layers. Remarkably, Rb2HgGe3S8 and Cs2HgGe3S8 exhibit overall properties required for promising IR-NLO materials, including sufficient PM deff (0.55–0.70 × AgGaS2@2050 nm), large Eg (3.27–3.41 eV), giant laser-induced damage thresholds (17.4–19.7 × AgGaS2@1064 nm), broad optical transmission intervals (0.32–17.5 µm), and suitable theoretical birefringence (0.069–0.086@2050 nm). Furthermore, in-depth theoretical analysis reveals that the exceptional IR-NLO performance is attributed to the synergy effects of distorted [HgS4] and [GeS4] tetrahedra. Our study provides a useful strategy for enhancing the Eg and advancing Hg-based IR-NLO materials, which is expected to extended and implemented in other chalcogenide systems.
2024, 35(10): 109380
doi: 10.1016/j.cclet.2023.109380
Abstract:
Post-synthetic installation strategy is an effective approach to improve the functions of metal-organic frameworks (MOFs). Herein, a pair of chiral MOFs is successfully constructed through solvothermal subcomponent self-assembly and exhibit circularly polarized luminescence (CPL). These MOFs contain coordinatively unsaturated Zn sites and channels, which allow the installation of pyridyl-terminated pillars into the original structure. Such a post-synthetic installation process reinforces the MOFs' rigidity and increases the photoluminescence quantum yields (PLQYs). Furthermore, the luminescence dissymmetry factors (glum) of these post-modified MOFs are amplified after installing the pillars. This work provides an appealing strategy for boosting the CPL performance of chiral MOFs.
Post-synthetic installation strategy is an effective approach to improve the functions of metal-organic frameworks (MOFs). Herein, a pair of chiral MOFs is successfully constructed through solvothermal subcomponent self-assembly and exhibit circularly polarized luminescence (CPL). These MOFs contain coordinatively unsaturated Zn sites and channels, which allow the installation of pyridyl-terminated pillars into the original structure. Such a post-synthetic installation process reinforces the MOFs' rigidity and increases the photoluminescence quantum yields (PLQYs). Furthermore, the luminescence dissymmetry factors (glum) of these post-modified MOFs are amplified after installing the pillars. This work provides an appealing strategy for boosting the CPL performance of chiral MOFs.
2024, 35(10): 109387
doi: 10.1016/j.cclet.2023.109387
Abstract:
Lithium argyrodites Li6PS5X (X = Cl, Br, I) show great potential as solid electrolytes for solid-state lithium batteries due to their high Li-ion conductivities and excellent electrode compatibility. However, the relatively low conductivity of Li6PS5I (10−6 mS/cm) compared to the other two compositions limits its applications. Herein, Si-doped Li6.5P0.5Si0.5S5I electrolyte is designed and synthesized with superior high conductivity of 3.6 mS/cm. Structural characterization proves the increase due to the anion disorder and volume expansion caused by Si-doping. However, the poor interfacial stability between layered oxide cathode LiNi0.6Co0.2Mn0.2O2 and Li6.5P0.5Si0.5S5I inhibits its battery performance. By introducing Li3InCl6 electrolyte in the configuration, the corresponding battery delivers high initial discharge capacity of 150.2 mAh/g and superior cyclability during 250 cycles at 0.5 C. This work offers design strategy to obtain Li6PS5I-based electrolytes for high performance solid-state batteries.
Lithium argyrodites Li6PS5X (X = Cl, Br, I) show great potential as solid electrolytes for solid-state lithium batteries due to their high Li-ion conductivities and excellent electrode compatibility. However, the relatively low conductivity of Li6PS5I (10−6 mS/cm) compared to the other two compositions limits its applications. Herein, Si-doped Li6.5P0.5Si0.5S5I electrolyte is designed and synthesized with superior high conductivity of 3.6 mS/cm. Structural characterization proves the increase due to the anion disorder and volume expansion caused by Si-doping. However, the poor interfacial stability between layered oxide cathode LiNi0.6Co0.2Mn0.2O2 and Li6.5P0.5Si0.5S5I inhibits its battery performance. By introducing Li3InCl6 electrolyte in the configuration, the corresponding battery delivers high initial discharge capacity of 150.2 mAh/g and superior cyclability during 250 cycles at 0.5 C. This work offers design strategy to obtain Li6PS5I-based electrolytes for high performance solid-state batteries.
2024, 35(10): 109388
doi: 10.1016/j.cclet.2023.109388
Abstract:
Aqueous alkaline zinc batteries (AZBs) exhibit great potential due to their high capacity, high safety and low cost. However, despite these advantages, the lack of high stability and high utilization rate makes the search for high-performance cathode materials a great challenge. Here, an amorphous nickel boride/rGO (NiB/rGO) complex structure was designed. As a result of abundant unsaturated active sites and synergistic electronic effects, amorphous NiB exhibits excellent energy storage properties. As well as having high electrical conductivity, rGO avoids aggregation of NiB nanoparticles, ensuring that NiB/rGO electrodes have a high energy storage capacity. The structure has a strong adhesion between NiB and rGO, which protects its stable structure and extends its life. More importantly, the NiB/rGO//Zn full battery shows remarkable capacity (228.4 mAh/g at 2 A/g), extraordinary cycle durability (93.7% retained after 1000 cycles) and strong energy density 399.7 Wh/kg, when coupled with NiB/rGO cathode. This work will also shed light on other nickel-zinc batteries in order to achieve super durability and capacity.
Aqueous alkaline zinc batteries (AZBs) exhibit great potential due to their high capacity, high safety and low cost. However, despite these advantages, the lack of high stability and high utilization rate makes the search for high-performance cathode materials a great challenge. Here, an amorphous nickel boride/rGO (NiB/rGO) complex structure was designed. As a result of abundant unsaturated active sites and synergistic electronic effects, amorphous NiB exhibits excellent energy storage properties. As well as having high electrical conductivity, rGO avoids aggregation of NiB nanoparticles, ensuring that NiB/rGO electrodes have a high energy storage capacity. The structure has a strong adhesion between NiB and rGO, which protects its stable structure and extends its life. More importantly, the NiB/rGO//Zn full battery shows remarkable capacity (228.4 mAh/g at 2 A/g), extraordinary cycle durability (93.7% retained after 1000 cycles) and strong energy density 399.7 Wh/kg, when coupled with NiB/rGO cathode. This work will also shed light on other nickel-zinc batteries in order to achieve super durability and capacity.
2024, 35(10): 109391
doi: 10.1016/j.cclet.2023.109391
Abstract:
Magnesium rechargeable batteries (MRBs) present opportunities for grid-scale energy storage applications as a complement to Li-ion batteries (LIBS). The major challenges are the low reversible capacity, inferior cycling stability and unsatisfactory energy densities. Na3VCr0.5Fe0.5(PO4)3 with a well-defined NASION-type structure is used as cathode in Mg cell. Two-electrons reaction (~116 mAh/g), 1.5 V average voltage and 65% of capacity retention over 100 cycles are accomplished. Mg is inserted by a biphasic reaction with the participation of V3+/V4+/V5+ redox couples in the electrochemical reaction while the non-active redox couples such as Cr3+/Cr4+ and Fe2+/Fe3+ served as stabilizer to buffer the volume variation. A thermal stability up to ~412 ℃ is also exhibited. Therefore, incorporating a mixture of three transition metal (V/Cr/Fe) in this type of structures will broaden new perspectives for realizing high performance cathodes for MRBs.
Magnesium rechargeable batteries (MRBs) present opportunities for grid-scale energy storage applications as a complement to Li-ion batteries (LIBS). The major challenges are the low reversible capacity, inferior cycling stability and unsatisfactory energy densities. Na3VCr0.5Fe0.5(PO4)3 with a well-defined NASION-type structure is used as cathode in Mg cell. Two-electrons reaction (~116 mAh/g), 1.5 V average voltage and 65% of capacity retention over 100 cycles are accomplished. Mg is inserted by a biphasic reaction with the participation of V3+/V4+/V5+ redox couples in the electrochemical reaction while the non-active redox couples such as Cr3+/Cr4+ and Fe2+/Fe3+ served as stabilizer to buffer the volume variation. A thermal stability up to ~412 ℃ is also exhibited. Therefore, incorporating a mixture of three transition metal (V/Cr/Fe) in this type of structures will broaden new perspectives for realizing high performance cathodes for MRBs.
2024, 35(10): 109405
doi: 10.1016/j.cclet.2023.109405
Abstract:
Na-ion cathode materials with a fast charge and discharge behavior are needed to develop future high-energy sodium-ion batteries (SIBs). However, inevitably complicated phase transitions and sluggish kinetics during insertion and removal of Na+ in P2-type layered transition metal oxides generate structural instability and severe capacity decay. To get rid of such a dilemma, we report a structural optimization strategy to promote P2-type layered transition metal oxides with more (010) active planes as an efficient cathode for SIBs. As a result, as-prepared hexagonal-prism P2-type layered Na0.71Ni0.16Li0.09Co0.16Mn0.6O2 cathode with more (010) active planes delivers a reversible capacity of 120.1 mAh/g at 0.1 C, impressive rate capability of 52.7 mAh/g at 10 C, and long-term cycling stability (capacity retention of 95.6% over 200 cycles). The outstanding electrochemical performance benefited from the unique hexagonal-prism with more (010) active facets, which can effectively shorten the diffusion distances of Na+, increase the Na-ion migration dynamics and nanostructural stability during cycling verified by morphology characterization, Rietveld refinement, GITT, density functional theory calculations and operando XRD.
Na-ion cathode materials with a fast charge and discharge behavior are needed to develop future high-energy sodium-ion batteries (SIBs). However, inevitably complicated phase transitions and sluggish kinetics during insertion and removal of Na+ in P2-type layered transition metal oxides generate structural instability and severe capacity decay. To get rid of such a dilemma, we report a structural optimization strategy to promote P2-type layered transition metal oxides with more (010) active planes as an efficient cathode for SIBs. As a result, as-prepared hexagonal-prism P2-type layered Na0.71Ni0.16Li0.09Co0.16Mn0.6O2 cathode with more (010) active planes delivers a reversible capacity of 120.1 mAh/g at 0.1 C, impressive rate capability of 52.7 mAh/g at 10 C, and long-term cycling stability (capacity retention of 95.6% over 200 cycles). The outstanding electrochemical performance benefited from the unique hexagonal-prism with more (010) active facets, which can effectively shorten the diffusion distances of Na+, increase the Na-ion migration dynamics and nanostructural stability during cycling verified by morphology characterization, Rietveld refinement, GITT, density functional theory calculations and operando XRD.
2024, 35(10): 109407
doi: 10.1016/j.cclet.2023.109407
Abstract:
Metronidazole (MNZ) is a type of antibiotic that can help people and animals cure bacterial infections, however, abuse of MNZ has posed a threat to human health. Hence, portable and visual detection of MNZ is meaningful for food safety and rational administration of drugs, but full of challenges. Hence, a porous three-dimensional Tb-based metal-organic framework (MOF) {(CH3)2NH2·[Tb5(TDA)8(H2O)2]·6DMF·2C2H5OH}n (TDA-Tb) with good solvent and pH stabilities was prepared, and the framework possesses one-dimensional channels with a diameter of 12 Å along the c-axis. Experiment results suggest that the synthesized TDA-Tb can selectively and sensitively detect MNZ in water, and the limit of detection (LOD) is as low as 4.1 × 10−7 mol/L. Moreover, a flexible sensor TDA-Tb-M was also constructed by incorporating TDA-Tb into membrane materials for convenient usage. And the TDA-Tb-M firstly realized portable and visual detection of MNZ through smartphone scanning, which may inspire more probes with wide application ranges.
Metronidazole (MNZ) is a type of antibiotic that can help people and animals cure bacterial infections, however, abuse of MNZ has posed a threat to human health. Hence, portable and visual detection of MNZ is meaningful for food safety and rational administration of drugs, but full of challenges. Hence, a porous three-dimensional Tb-based metal-organic framework (MOF) {(CH3)2NH2·[Tb5(TDA)8(H2O)2]·6DMF·2C2H5OH}n (TDA-Tb) with good solvent and pH stabilities was prepared, and the framework possesses one-dimensional channels with a diameter of 12 Å along the c-axis. Experiment results suggest that the synthesized TDA-Tb can selectively and sensitively detect MNZ in water, and the limit of detection (LOD) is as low as 4.1 × 10−7 mol/L. Moreover, a flexible sensor TDA-Tb-M was also constructed by incorporating TDA-Tb into membrane materials for convenient usage. And the TDA-Tb-M firstly realized portable and visual detection of MNZ through smartphone scanning, which may inspire more probes with wide application ranges.
2024, 35(10): 109415
doi: 10.1016/j.cclet.2023.109415
Abstract:
The combination of interface engineering and defect engineering is a promising strategy for developing new semiconducting surface-enhanced Raman scattering (SERS) substrate. Herein, an organic/inorganic hybrid g-C3N4/TiO2-X heterojunction with synchronous generation of strong interface effect and abundant surface oxygen vacancy (OV) defect was prepared by a simple sol-hydrothermal procedure with a help of urea. Due to the improved substrate-to-molecule charge transfer (CT) from joint contribution of high-efficiency carrier separation induced by strong interface coupling effect and multiple CT paths derived from abundant surface OV, g-C3N4/TiO2-X substrate exhibits greatly enhanced SERS effect for non-resonant 4-mercaptobenzoic acid (4-MBA) probe. The enhancement factor of g-C3N4/TiO2-X substrate for 4-MBA is as high as 5.57 × 106, and the substrate exhibits ultra-high stability and excellent spectral reproducibility. More meaningfully, the developed g-C3N4/TiO2-X heterojunction can be used to execute an ultrasensitive detection for antibiotic residues in real water system, even comprehensive evaluation of multi-component residues.
The combination of interface engineering and defect engineering is a promising strategy for developing new semiconducting surface-enhanced Raman scattering (SERS) substrate. Herein, an organic/inorganic hybrid g-C3N4/TiO2-X heterojunction with synchronous generation of strong interface effect and abundant surface oxygen vacancy (OV) defect was prepared by a simple sol-hydrothermal procedure with a help of urea. Due to the improved substrate-to-molecule charge transfer (CT) from joint contribution of high-efficiency carrier separation induced by strong interface coupling effect and multiple CT paths derived from abundant surface OV, g-C3N4/TiO2-X substrate exhibits greatly enhanced SERS effect for non-resonant 4-mercaptobenzoic acid (4-MBA) probe. The enhancement factor of g-C3N4/TiO2-X substrate for 4-MBA is as high as 5.57 × 106, and the substrate exhibits ultra-high stability and excellent spectral reproducibility. More meaningfully, the developed g-C3N4/TiO2-X heterojunction can be used to execute an ultrasensitive detection for antibiotic residues in real water system, even comprehensive evaluation of multi-component residues.
2024, 35(10): 109423
doi: 10.1016/j.cclet.2023.109423
Abstract:
The efficient energy conversion of fuel cells is greatly constrained by the slow oxygen reduction reaction (ORR) kinetics, which necessitates the use of highly active metal catalysts such as platinum (Pt). The critical challenge limiting large-scale usage of Pt is the capital cost that can be addressed through a prototypical approach by embedding metal nanoparticles (NPs), e.g., Pt NPs, in the conductive framework. However, previously reported embedding approaches are sophisticated and suffer from limited yields, leading to higher chemical process costs and remaining distant from commercial viability. Here, we report a facile, cost-effective and time-efficient structural tuning approach to synthesizing ultrafine Pt NPs impregnated within a conductive and highly porous carbon framework via a microwave-assisted polyol reduction method. Pt NPs with a uniform size of ~2.27 nm can be successfully integrated within the pores of the carbon framework, enabling homogeneous dispersion. Benefiting from these highly dispersed and ultrafine Pt NPs, the electrochemical surface area (ECSA) is improved to 142.98 m²/gPt, 2.25 times higher than that of the commercial counterpart (63.52 m²/gPt). Furthermore, our structurally optimized catalyst composite features a remarkably catalytic activity with a high half-wave potential (E1/2) of 0.895 V and an improved mass activity (MA) of 0.2289 A/mgPt, 2.39-fold improvement compared to the commercial counterpart. In addition, orthogonal experiments were designed to identify the key process parameters for fabricating Pt/C catalysts, offering insights for scaled-up and industrial production.
The efficient energy conversion of fuel cells is greatly constrained by the slow oxygen reduction reaction (ORR) kinetics, which necessitates the use of highly active metal catalysts such as platinum (Pt). The critical challenge limiting large-scale usage of Pt is the capital cost that can be addressed through a prototypical approach by embedding metal nanoparticles (NPs), e.g., Pt NPs, in the conductive framework. However, previously reported embedding approaches are sophisticated and suffer from limited yields, leading to higher chemical process costs and remaining distant from commercial viability. Here, we report a facile, cost-effective and time-efficient structural tuning approach to synthesizing ultrafine Pt NPs impregnated within a conductive and highly porous carbon framework via a microwave-assisted polyol reduction method. Pt NPs with a uniform size of ~2.27 nm can be successfully integrated within the pores of the carbon framework, enabling homogeneous dispersion. Benefiting from these highly dispersed and ultrafine Pt NPs, the electrochemical surface area (ECSA) is improved to 142.98 m²/gPt, 2.25 times higher than that of the commercial counterpart (63.52 m²/gPt). Furthermore, our structurally optimized catalyst composite features a remarkably catalytic activity with a high half-wave potential (E1/2) of 0.895 V and an improved mass activity (MA) of 0.2289 A/mgPt, 2.39-fold improvement compared to the commercial counterpart. In addition, orthogonal experiments were designed to identify the key process parameters for fabricating Pt/C catalysts, offering insights for scaled-up and industrial production.
2024, 35(10): 109425
doi: 10.1016/j.cclet.2023.109425
Abstract:
Defects at the surface and grain boundaries of the perovskite films are extremely detrimental to both the efficiency and stability of perovskite solar cells (PSCs). Herein, a simple and stable quaternary ammonium halide, named chlormequat chloride (i.e., chlorinated choline chloride, CCC), is introduced to regulate the upper surface chemical environment of perovskite films. The anion (Cl−) and cation [ClCH2CH2N(CH3)3]+ in CCC could effectively self-search and passivate positively and negatively charged ionic defects in perovskites, respectively, which contributes to inhibited nonradiative recombination and reduced energy loss in PSCs. As a result, the champion power conversion efficiency (PCE) of PSCs can be significantly enhanced from 22.82% to 24.07%. Moreover, the unencapsulated device with CCC modification retains 92.0% of its original PCE even subject to thermal aging at 85 ℃ for 2496 h. This work provides guidance for the rational design of functional molecules as defect passivators in PSCs, which is beneficial for the improvements in both device performance and stability.
Defects at the surface and grain boundaries of the perovskite films are extremely detrimental to both the efficiency and stability of perovskite solar cells (PSCs). Herein, a simple and stable quaternary ammonium halide, named chlormequat chloride (i.e., chlorinated choline chloride, CCC), is introduced to regulate the upper surface chemical environment of perovskite films. The anion (Cl−) and cation [ClCH2CH2N(CH3)3]+ in CCC could effectively self-search and passivate positively and negatively charged ionic defects in perovskites, respectively, which contributes to inhibited nonradiative recombination and reduced energy loss in PSCs. As a result, the champion power conversion efficiency (PCE) of PSCs can be significantly enhanced from 22.82% to 24.07%. Moreover, the unencapsulated device with CCC modification retains 92.0% of its original PCE even subject to thermal aging at 85 ℃ for 2496 h. This work provides guidance for the rational design of functional molecules as defect passivators in PSCs, which is beneficial for the improvements in both device performance and stability.
2024, 35(10): 109426
doi: 10.1016/j.cclet.2023.109426
Abstract:
Zinc metal is regarded as one of the most promising anodes for Zn-based batteries in next-generation energy storage systems. However, the dendrite growth and interfacial corrosion lead to poor reversibility and cycle life of Zn anodes. Herein, we synthesize a 2-phosphate-1,2,4-butane tricarboxylic acid modified hyperbranched polyamidoamine containing rich terminal groups of phosphate and carboxyl (HPC) as modified layer for the Zn anodes. Importantly, the in situ acid-etching promotes the exposure of (002)Zn plane and the generated salt-polymer complexes could be adhered to the Zn anodes tightly. This greatly favors the uniform deposition of Zn and inhibits interfacial corrosion. Consequently, stable HPC@Zn anode plating/stripping for over 1200 h at a high areal capacity of 4 mAh/cm2 and a current density of 4 mA/cm2 is obtained. This study provides a new avenue of hyperbranched polymer in interfacial design for highly reversible and stable Zn metal anodes.
Zinc metal is regarded as one of the most promising anodes for Zn-based batteries in next-generation energy storage systems. However, the dendrite growth and interfacial corrosion lead to poor reversibility and cycle life of Zn anodes. Herein, we synthesize a 2-phosphate-1,2,4-butane tricarboxylic acid modified hyperbranched polyamidoamine containing rich terminal groups of phosphate and carboxyl (HPC) as modified layer for the Zn anodes. Importantly, the in situ acid-etching promotes the exposure of (002)Zn plane and the generated salt-polymer complexes could be adhered to the Zn anodes tightly. This greatly favors the uniform deposition of Zn and inhibits interfacial corrosion. Consequently, stable HPC@Zn anode plating/stripping for over 1200 h at a high areal capacity of 4 mAh/cm2 and a current density of 4 mA/cm2 is obtained. This study provides a new avenue of hyperbranched polymer in interfacial design for highly reversible and stable Zn metal anodes.
2024, 35(10): 109430
doi: 10.1016/j.cclet.2023.109430
Abstract:
Carbon dots (CDs), as a solid-state phosphor, have great potential for application in a new solid-state lighting device—laser diode (LD). For high efficiency LD devices, both high photoluminescence quantum yield (PLQY) and high photothermal stability of CDs are essential. Herein, yellow CDs@ZIF-8 composites with high structural stability were prepared by encapsulating CDs in zeolitic imidazolate framework-8 (ZIF-8) through electrostatic adsorption between CDs and ZIF-8, in which CDs with amino groups on the surface were used as luminescent feeders and ZIF-8 was used as a protective layer matrix. The as-prepared CDs@ZIF-8 not only possess a high PLQY of up to 81.17%, but also maintain a high fluorescence intensity of 100% and 80% under long-term illumination (60 min) and high temperature (478 K), respectively. The hydrogen bonding between CDs and ZIF-8 in the encapsulated structure can enhance the degree of electron cloud delocalization, which can improve the PLQY of CDs@ZIF-8. Meanwhile, CDs@ZIF-8 has high photothermal stability due to the binding effect of ZIF-8 on CDs and high thermal stability of ZIF-8. The white LD device, fabricated from CDs@ZIF-8 as a phosphor in combination with 450 nm blue LD, has a color coordinate of (0.37, 0.33), a color temperature of 3762 K, and a high color rendering index of 86. This study provides a new strategy for the construction of solid-state phosphors with high PLQY and high photothermal performance.
Carbon dots (CDs), as a solid-state phosphor, have great potential for application in a new solid-state lighting device—laser diode (LD). For high efficiency LD devices, both high photoluminescence quantum yield (PLQY) and high photothermal stability of CDs are essential. Herein, yellow CDs@ZIF-8 composites with high structural stability were prepared by encapsulating CDs in zeolitic imidazolate framework-8 (ZIF-8) through electrostatic adsorption between CDs and ZIF-8, in which CDs with amino groups on the surface were used as luminescent feeders and ZIF-8 was used as a protective layer matrix. The as-prepared CDs@ZIF-8 not only possess a high PLQY of up to 81.17%, but also maintain a high fluorescence intensity of 100% and 80% under long-term illumination (60 min) and high temperature (478 K), respectively. The hydrogen bonding between CDs and ZIF-8 in the encapsulated structure can enhance the degree of electron cloud delocalization, which can improve the PLQY of CDs@ZIF-8. Meanwhile, CDs@ZIF-8 has high photothermal stability due to the binding effect of ZIF-8 on CDs and high thermal stability of ZIF-8. The white LD device, fabricated from CDs@ZIF-8 as a phosphor in combination with 450 nm blue LD, has a color coordinate of (0.37, 0.33), a color temperature of 3762 K, and a high color rendering index of 86. This study provides a new strategy for the construction of solid-state phosphors with high PLQY and high photothermal performance.
2024, 35(10): 109446
doi: 10.1016/j.cclet.2023.109446
Abstract:
Spin-orbit, charge-transfer intersystem crossing (SOCT-ISC) can directly overcome the disadvantages of the traditional heavy-atom effect and improve the generation efficiency of reactive oxygen species (ROS). Since orthogonal molecular orbitals of donor-acceptor (D-A) pairs favor the SOCT-ISC transition, herein aza-borondipyrromethenes (aza-BODIPYs) with 1,7-di-anthracyl groups (An-azaBDP) was successfully prepared, owing to steric hindrance to produce a big dihedral angle between the two molecular orbital (MO) planes. Moreover, according to density functional theory (DFT) and time-dependent density functional theory (TDDFT), the energy difference between the S1-T1 orbitals of An-azaBDP is small and more inclined towards ISC. An-azaBDP can effectively generate singlet oxygen under light irradiation. An-azaBDP with light irradiation can induce apoptosis in SW620 cells, and can serve as a potential candidate for the treatment of cancer cells and tumors.
Spin-orbit, charge-transfer intersystem crossing (SOCT-ISC) can directly overcome the disadvantages of the traditional heavy-atom effect and improve the generation efficiency of reactive oxygen species (ROS). Since orthogonal molecular orbitals of donor-acceptor (D-A) pairs favor the SOCT-ISC transition, herein aza-borondipyrromethenes (aza-BODIPYs) with 1,7-di-anthracyl groups (An-azaBDP) was successfully prepared, owing to steric hindrance to produce a big dihedral angle between the two molecular orbital (MO) planes. Moreover, according to density functional theory (DFT) and time-dependent density functional theory (TDDFT), the energy difference between the S1-T1 orbitals of An-azaBDP is small and more inclined towards ISC. An-azaBDP can effectively generate singlet oxygen under light irradiation. An-azaBDP with light irradiation can induce apoptosis in SW620 cells, and can serve as a potential candidate for the treatment of cancer cells and tumors.
2024, 35(10): 109448
doi: 10.1016/j.cclet.2023.109448
Abstract:
Solid polymer electrolytes (SPEs) are considered to be one of the most promising systems applied in all-solid-state lithium metal batteries (ASSLMBs) on account of their chemical and electrochemical robustness, mechanical stability, cost-effective and scalable manufacturing techniques. Lately, significant endeavors have been directed towards mitigating the formation of the Li dendrite in SPE-based ASSLMBs, while research on the inactive lithium in the forms of the solid-electrolyte interface has been rarely reported. Herein, a bi-functional GaI3 additive is developed for in-situ generating Li3Ga alloy for suppressing Li dendrite growth, as well as I3− in recovering dead lithium. Relying on the density functional theory (DFT) results, the Li atom prefers to deposit on the Li3Ga surface and then guide uniform Li deposition, while the I3 species features a relatively lower lowest unoccupied molecular orbital (LUMO) energy level (-2.12 eV), meaning a higher electron affinity, which is beneficial for reviving inactive lithium to counterbalance the loss of lithium. As a result, in comparison to cells employing pure PEGDME-based electrolytes, the Li-Li symmetric cells utilizing GaI3-containing solid-state electrolyte exhibited a cycling life nearly 30 times longer at a current density/capacity of 0.2 mA/cm2, 0.2 mAh/cm2. The full batteries of LFP//1%GaI3-SPE//40 µm Li delivered a noteworthy capacity retention of 82% after 1300 cycles at a rate of 1 C.
Solid polymer electrolytes (SPEs) are considered to be one of the most promising systems applied in all-solid-state lithium metal batteries (ASSLMBs) on account of their chemical and electrochemical robustness, mechanical stability, cost-effective and scalable manufacturing techniques. Lately, significant endeavors have been directed towards mitigating the formation of the Li dendrite in SPE-based ASSLMBs, while research on the inactive lithium in the forms of the solid-electrolyte interface has been rarely reported. Herein, a bi-functional GaI3 additive is developed for in-situ generating Li3Ga alloy for suppressing Li dendrite growth, as well as I3− in recovering dead lithium. Relying on the density functional theory (DFT) results, the Li atom prefers to deposit on the Li3Ga surface and then guide uniform Li deposition, while the I3 species features a relatively lower lowest unoccupied molecular orbital (LUMO) energy level (-2.12 eV), meaning a higher electron affinity, which is beneficial for reviving inactive lithium to counterbalance the loss of lithium. As a result, in comparison to cells employing pure PEGDME-based electrolytes, the Li-Li symmetric cells utilizing GaI3-containing solid-state electrolyte exhibited a cycling life nearly 30 times longer at a current density/capacity of 0.2 mA/cm2, 0.2 mAh/cm2. The full batteries of LFP//1%GaI3-SPE//40 µm Li delivered a noteworthy capacity retention of 82% after 1300 cycles at a rate of 1 C.
2024, 35(10): 109450
doi: 10.1016/j.cclet.2023.109450
Abstract:
The occurrence of acquired resistance to cisplatin (DDP) that induces the toxic drug effects has always been a huge challenge and urgently needs to be resolved in the cancer treatment. The combination of anticancer drugs with different mechanisms can remarkably improve the chemotherapeutic efficiency. Given that glutathione (GSH) plays as the driving factors in the resistance of DDP, here we have firstly proposed a “three birds, one stone” based nanoplatform to achieve triple synergetic effects simultaneously addressing DDP resistance in non-small cell lung cancer (NSCLC). Specifically, we initially designed and synthesized a DDP prodrug [Pt(Ⅳ)] bridged silsesquioxane precursor (Pt-Si). Then Pt-Si and bis[3-(triethoxysilyl)propyl]diselenide (BTESePD) were integrated into the framework of mesoporous organosilica nanoparticles (MONs) to obtain a nanocarrier MONPt/Se. After loading with norcantharidin (NCTD) and modifying with the aptamer AS1411 based G-quadruplex (Apt), the Apt@NCTD@MONPt/Se exhibit impressive tumor homing capability. Once being endocytosed, (Ⅰ) the diselenide and -O-Pt(Ⅳ)-O- rich scaffold can be reduced by the excessive GSH, followed by (Ⅱ) breaking the redox homeostasis via GSH depletion and precise release of the DDP. Next, the encapsulated NCTD is also released along with the degradation of the nanocarriers thereby (Ⅲ) achieving the GSH depletion and synergistic anti-tumor effect of NCTD and DDP. Taken together, we believe this “one stone, three birds” strategy may be a promising paradigm to conquer drug resistance for clinical care.
The occurrence of acquired resistance to cisplatin (DDP) that induces the toxic drug effects has always been a huge challenge and urgently needs to be resolved in the cancer treatment. The combination of anticancer drugs with different mechanisms can remarkably improve the chemotherapeutic efficiency. Given that glutathione (GSH) plays as the driving factors in the resistance of DDP, here we have firstly proposed a “three birds, one stone” based nanoplatform to achieve triple synergetic effects simultaneously addressing DDP resistance in non-small cell lung cancer (NSCLC). Specifically, we initially designed and synthesized a DDP prodrug [Pt(Ⅳ)] bridged silsesquioxane precursor (Pt-Si). Then Pt-Si and bis[3-(triethoxysilyl)propyl]diselenide (BTESePD) were integrated into the framework of mesoporous organosilica nanoparticles (MONs) to obtain a nanocarrier MONPt/Se. After loading with norcantharidin (NCTD) and modifying with the aptamer AS1411 based G-quadruplex (Apt), the Apt@NCTD@MONPt/Se exhibit impressive tumor homing capability. Once being endocytosed, (Ⅰ) the diselenide and -O-Pt(Ⅳ)-O- rich scaffold can be reduced by the excessive GSH, followed by (Ⅱ) breaking the redox homeostasis via GSH depletion and precise release of the DDP. Next, the encapsulated NCTD is also released along with the degradation of the nanocarriers thereby (Ⅲ) achieving the GSH depletion and synergistic anti-tumor effect of NCTD and DDP. Taken together, we believe this “one stone, three birds” strategy may be a promising paradigm to conquer drug resistance for clinical care.
2024, 35(10): 109451
doi: 10.1016/j.cclet.2023.109451
Abstract:
Hidden natural products are representative of defensive strategies produced in vivo in diseased plants, a process that is induced by the plant immune system. The first transcriptome library of uninfected and pathogen infected Hibiscus tiliaceus stems was constructed by transcriptome sequencing technology, genes related to cadinene-type sesquiterpenoid biosynthesis were screened and combined with ultra-performance liquid chromatography-quadrupole-time of flight mass spectrometry (UPLC-QTOF-MS) analysis data, which indicated pathological tissue had potential to produce novel carbon skeletons of cadinane sesquiterpenoid dimers. Successfully, two cadinane-derived sesquiterpenoid dimers with unprecedented carbon skeletons, hibisceusanols A (1) and B (2) were isolated for the first time from the stems of H. tiliaceus induced by plant-microbial interactions. Their structures and absolute configurations were unambiguously established by spectroscopy, advanced chemistry development (ACD) and electronic circular dichroism (ECD) methods. Compounds 1 and 2 exhibited significant antitumor activity in vitro with half maximal inhibitory concentration (IC50) values of 2.3–7.2 µmol/L. The anticancer effect was generated via the induction of HepG2 cell apoptosis by inhibiting the phosphatidylinositol 3-kinase (PI3K) pathway.
Hidden natural products are representative of defensive strategies produced in vivo in diseased plants, a process that is induced by the plant immune system. The first transcriptome library of uninfected and pathogen infected Hibiscus tiliaceus stems was constructed by transcriptome sequencing technology, genes related to cadinene-type sesquiterpenoid biosynthesis were screened and combined with ultra-performance liquid chromatography-quadrupole-time of flight mass spectrometry (UPLC-QTOF-MS) analysis data, which indicated pathological tissue had potential to produce novel carbon skeletons of cadinane sesquiterpenoid dimers. Successfully, two cadinane-derived sesquiterpenoid dimers with unprecedented carbon skeletons, hibisceusanols A (1) and B (2) were isolated for the first time from the stems of H. tiliaceus induced by plant-microbial interactions. Their structures and absolute configurations were unambiguously established by spectroscopy, advanced chemistry development (ACD) and electronic circular dichroism (ECD) methods. Compounds 1 and 2 exhibited significant antitumor activity in vitro with half maximal inhibitory concentration (IC50) values of 2.3–7.2 µmol/L. The anticancer effect was generated via the induction of HepG2 cell apoptosis by inhibiting the phosphatidylinositol 3-kinase (PI3K) pathway.
2024, 35(10): 109452
doi: 10.1016/j.cclet.2023.109452
Abstract:
Clinical phototheranostic agents suffer from low absorption in near-infrared (NIR) region, decreasing singlet oxygen quantum yield (1O2 QY) caused by aggregation in water, and low photothermal conversion efficiency (PCE), all of which are factors weakening their phototheranostic efficacy. Herein, we designed and synthesized a donor-acceptor-donor (D-A-D) structured boron-dipyrromethene derivative (B-2TPA) which exhibited NIR absorption and fluorescence. After being encapsulated in amphiphilic distearoyl phosphoethanolamine polyethyleneglycol 2000 (DSPE-PEG-2000), the water-soluble B-2TPA nanoparticles (NPs) had increasing 1O2 QY (6.7%) due to the intermolecular aggregation-induced decrease in the energy gap between singlet and triplet excited states. Moreover, the quenched fluorescence and stable twisted intramolecular charge transfer in aggregates further increased the PCE of B-2TPA NPs to 60.1%. In vitro and in vivo studies confirmed that B-2TPA NPs could be used in NIR fluorescence and photoacoustic imaging-guided synergistic photodynamic and photothermal therapy in tumor treatment.
Clinical phototheranostic agents suffer from low absorption in near-infrared (NIR) region, decreasing singlet oxygen quantum yield (1O2 QY) caused by aggregation in water, and low photothermal conversion efficiency (PCE), all of which are factors weakening their phototheranostic efficacy. Herein, we designed and synthesized a donor-acceptor-donor (D-A-D) structured boron-dipyrromethene derivative (B-2TPA) which exhibited NIR absorption and fluorescence. After being encapsulated in amphiphilic distearoyl phosphoethanolamine polyethyleneglycol 2000 (DSPE-PEG-2000), the water-soluble B-2TPA nanoparticles (NPs) had increasing 1O2 QY (6.7%) due to the intermolecular aggregation-induced decrease in the energy gap between singlet and triplet excited states. Moreover, the quenched fluorescence and stable twisted intramolecular charge transfer in aggregates further increased the PCE of B-2TPA NPs to 60.1%. In vitro and in vivo studies confirmed that B-2TPA NPs could be used in NIR fluorescence and photoacoustic imaging-guided synergistic photodynamic and photothermal therapy in tumor treatment.
2024, 35(10): 109456
doi: 10.1016/j.cclet.2023.109456
Abstract:
Three highly oxidized hybrid flavonoids neosophoflavonoids A–C (1, 2a, and 2b) were isolated from the roots of Sophora flavescens. Neosophoflavonoid A possesses a unique highly oxidized heptacyclic 6/6/6/6/6/6/5 system. Neosophoflavonoids B and C are isomers and share the same highly oxidized hexacyclic 6/6/6/6/6/6 systems. Their planar structures were elucidated from 1D/2D nuclear magnetic resonance (NMR), ultraviolet spectroscopy (UV), infrared spectroscopy (IR), and high resolution electrospray ionization mass spectroscopy (HRESIMS) data. Their absolute configurations were determined by thorough GIAO 13C NMR (DP4+) calculation protocol and electronic circular dichroism (ECD) calculation method. The plausible biosynthetic routes for the compounds were also proposed. All compounds exhibited significant protein tyrosine phosphatase-1B (PTP1B) inhibitory activity with half maximal inhibitory concentration (IC50) values 3.94 ± 0.01, 0.38 ± 0.13, and 0.70 ± 0.01 µmol/L, respectively. In addition, compared to a positive control fenofibrate (Feno) at 20 µmol/L, compounds 2a and 2b exhibited stronger inhibitory effects on lipid accumulation in the oleic acid (OA)-induced cell model at 5 and 10 µmol/L.
Three highly oxidized hybrid flavonoids neosophoflavonoids A–C (1, 2a, and 2b) were isolated from the roots of Sophora flavescens. Neosophoflavonoid A possesses a unique highly oxidized heptacyclic 6/6/6/6/6/6/5 system. Neosophoflavonoids B and C are isomers and share the same highly oxidized hexacyclic 6/6/6/6/6/6 systems. Their planar structures were elucidated from 1D/2D nuclear magnetic resonance (NMR), ultraviolet spectroscopy (UV), infrared spectroscopy (IR), and high resolution electrospray ionization mass spectroscopy (HRESIMS) data. Their absolute configurations were determined by thorough GIAO 13C NMR (DP4+) calculation protocol and electronic circular dichroism (ECD) calculation method. The plausible biosynthetic routes for the compounds were also proposed. All compounds exhibited significant protein tyrosine phosphatase-1B (PTP1B) inhibitory activity with half maximal inhibitory concentration (IC50) values 3.94 ± 0.01, 0.38 ± 0.13, and 0.70 ± 0.01 µmol/L, respectively. In addition, compared to a positive control fenofibrate (Feno) at 20 µmol/L, compounds 2a and 2b exhibited stronger inhibitory effects on lipid accumulation in the oleic acid (OA)-induced cell model at 5 and 10 µmol/L.
2024, 35(10): 109458
doi: 10.1016/j.cclet.2023.109458
Abstract:
Monosescinol A (1), the first example of sesquiterpene–polycyclic polyprenylated acylphloroglucinol (PPAP) adduct, which represented a new subclass of PPAP-type natural products, along with two new congeners with normal spiro 6/6/5 tricyclic architecture, were isolated from Hypericum longistylum. Monosescinol A possessed an unprecedented 6/5/5/6/6 pentacyclic carbon skeleton that might be assembled from the 6/6/5 carbon skeleton, via the splitting decomposition of C-3/C-14, and the attack from the C-3 in the PPAP core to C-28 in sesquiterpene section. In addition, we have firstly confirmed that 24R configuration was existed in sec–Bu containing PPAPs by single crystal diffraction data analysis of monosescinol B (2), that might provide an enlightenment in the configurational determination of sec–Bu containing PPAPs. Significantly, further pharmacological research has found that compound 1 exhibited remarkable pharmacological effects against acute myeloid leukemia (AML) cell lines, with direct inhibition of mitochondrial complex Ⅴ and an increase in mitochondrial membrane potential, and led to an induction of oxidative stress, endogenous inflammation, and apoptosis of AML cells.
Monosescinol A (1), the first example of sesquiterpene–polycyclic polyprenylated acylphloroglucinol (PPAP) adduct, which represented a new subclass of PPAP-type natural products, along with two new congeners with normal spiro 6/6/5 tricyclic architecture, were isolated from Hypericum longistylum. Monosescinol A possessed an unprecedented 6/5/5/6/6 pentacyclic carbon skeleton that might be assembled from the 6/6/5 carbon skeleton, via the splitting decomposition of C-3/C-14, and the attack from the C-3 in the PPAP core to C-28 in sesquiterpene section. In addition, we have firstly confirmed that 24R configuration was existed in sec–Bu containing PPAPs by single crystal diffraction data analysis of monosescinol B (2), that might provide an enlightenment in the configurational determination of sec–Bu containing PPAPs. Significantly, further pharmacological research has found that compound 1 exhibited remarkable pharmacological effects against acute myeloid leukemia (AML) cell lines, with direct inhibition of mitochondrial complex Ⅴ and an increase in mitochondrial membrane potential, and led to an induction of oxidative stress, endogenous inflammation, and apoptosis of AML cells.
2024, 35(10): 109459
doi: 10.1016/j.cclet.2023.109459
Abstract:
Infections frequently occur after skin injuries, posing a significant challenge in current clinical care. Frequently changing dressings to minimize wound infections and adhesions results in large amounts of medical waste. Therefore, developing environmentally friendly multifunctional dressings has considerable application and translational significance. This study aimed to prepare a wound dressing with favorable antimicrobial properties and biosafety by grafting a natural antimicrobial peptide, polylysine, onto a traditional cotton textile dressing. The cotton textile dressing offers excellent moisture absorption and softness, while polylysine provides excellent biocompatibility, a broad antimicrobial spectrum, and high stability. Furthermore, both materials are natural and biodegradable, making them ideal for environmentally friendly wound dressings.
Infections frequently occur after skin injuries, posing a significant challenge in current clinical care. Frequently changing dressings to minimize wound infections and adhesions results in large amounts of medical waste. Therefore, developing environmentally friendly multifunctional dressings has considerable application and translational significance. This study aimed to prepare a wound dressing with favorable antimicrobial properties and biosafety by grafting a natural antimicrobial peptide, polylysine, onto a traditional cotton textile dressing. The cotton textile dressing offers excellent moisture absorption and softness, while polylysine provides excellent biocompatibility, a broad antimicrobial spectrum, and high stability. Furthermore, both materials are natural and biodegradable, making them ideal for environmentally friendly wound dressings.
2024, 35(10): 109464
doi: 10.1016/j.cclet.2023.109464
Abstract:
Dual-state emission (DSE) molecules displayed conspicuous fluorescent performance both in solid and solution states. However, the construction of DSE molecules and the regulation of their emission wavelengths remains a great challenge. Based on the structure-function relationship of quinolinonitrile-type fluorophores, this work proposed a feasible strategy for modulating their fluorescent properties into DSE via limiting the torsion angle between the quinoline ring and C=C bond in the range of 4.7° to 30°. Based on this strategy, 53 compounds were obtained which displayed tunable emission wavelengths from 397 nm to 740 nm in solid-state and from 360 nm to 672 nm in solution. The feasibility of the strategy was supported by a series of theoretical calculations, optical characterizations, and crystal analysis, suggesting the compounds have great potential in imaging living cells and tissues with desired wavelengths.
Dual-state emission (DSE) molecules displayed conspicuous fluorescent performance both in solid and solution states. However, the construction of DSE molecules and the regulation of their emission wavelengths remains a great challenge. Based on the structure-function relationship of quinolinonitrile-type fluorophores, this work proposed a feasible strategy for modulating their fluorescent properties into DSE via limiting the torsion angle between the quinoline ring and C=C bond in the range of 4.7° to 30°. Based on this strategy, 53 compounds were obtained which displayed tunable emission wavelengths from 397 nm to 740 nm in solid-state and from 360 nm to 672 nm in solution. The feasibility of the strategy was supported by a series of theoretical calculations, optical characterizations, and crystal analysis, suggesting the compounds have great potential in imaging living cells and tissues with desired wavelengths.
2024, 35(10): 109489
doi: 10.1016/j.cclet.2024.109489
Abstract:
Constructing a smart polymer film with favorable lithium (Li) transport capability and mechanical flexibility for suppressing Li dendrite growth is an effective strategy. Unfortunately, the porosity and the swelling of the polymer membrane cannot completely prevent liquid electrolyte from sweeping through the artificial protection film, severely deteriorating the cyclic performance. Herein, we propose a defect-free hybrid film that consists of Li+ conductive lithium polyacrylate (LiPAA) polymer interface layer and Li-Zn alloy patch to tackle the critical problems of traditional polymer composite passivation film. The pinhole leaks of the polymer matrix are self-filled by Li-Zn alloy patches, enhancing the integrity of LiPAA film. Consequently, a defect-free hybrid film is nailed flat against the Li metal anode, exhibiting extraordinary stability in the liquid electrolyte and enabling perfect protection effect. This facile strategy produces a promising anode for next generation Li batteries.
Constructing a smart polymer film with favorable lithium (Li) transport capability and mechanical flexibility for suppressing Li dendrite growth is an effective strategy. Unfortunately, the porosity and the swelling of the polymer membrane cannot completely prevent liquid electrolyte from sweeping through the artificial protection film, severely deteriorating the cyclic performance. Herein, we propose a defect-free hybrid film that consists of Li+ conductive lithium polyacrylate (LiPAA) polymer interface layer and Li-Zn alloy patch to tackle the critical problems of traditional polymer composite passivation film. The pinhole leaks of the polymer matrix are self-filled by Li-Zn alloy patches, enhancing the integrity of LiPAA film. Consequently, a defect-free hybrid film is nailed flat against the Li metal anode, exhibiting extraordinary stability in the liquid electrolyte and enabling perfect protection effect. This facile strategy produces a promising anode for next generation Li batteries.
2024, 35(10): 109491
doi: 10.1016/j.cclet.2024.109491
Abstract:
Foods are often contaminated by multiple foodborne pathogens, which threatens human health. In this work, we developed a microfluidic biosensor for multiplex immunoassay of foodborne bacteria with agitation driven by programmed audio signals. This agitation, powered by the vibration of a speaker cone during music playing, accelerated the mass transport in the incubation process to form bacterial complexes within 10 min. Immunoassay reagents of the two target bacteria (Escherichia coli O157:H7 and Salmonella typhimurium) were preloaded into the corresponding fore-vacuum storage chamber on the chip, and released to participate in the subsequent immune analysis process by piercing the chambers. All the detection processes were integrated into a single microfluidic chip and controlled by a smartphone through Bluetooth. Under selected conditions, wide linear ranges and low limits of detection (LODs < 2 CFU/mL) were obtained, and real food samples were successfully determined within 30 min. This biosensing method can be extended to wide-ranging applications by loading different recognizing reagents.
Foods are often contaminated by multiple foodborne pathogens, which threatens human health. In this work, we developed a microfluidic biosensor for multiplex immunoassay of foodborne bacteria with agitation driven by programmed audio signals. This agitation, powered by the vibration of a speaker cone during music playing, accelerated the mass transport in the incubation process to form bacterial complexes within 10 min. Immunoassay reagents of the two target bacteria (Escherichia coli O157:H7 and Salmonella typhimurium) were preloaded into the corresponding fore-vacuum storage chamber on the chip, and released to participate in the subsequent immune analysis process by piercing the chambers. All the detection processes were integrated into a single microfluidic chip and controlled by a smartphone through Bluetooth. Under selected conditions, wide linear ranges and low limits of detection (LODs < 2 CFU/mL) were obtained, and real food samples were successfully determined within 30 min. This biosensing method can be extended to wide-ranging applications by loading different recognizing reagents.
2024, 35(10): 109497
doi: 10.1016/j.cclet.2024.109497
Abstract:
Histone H3K79 modifications are essential to regulate chromatin structure and gene transcription, but understanding of the molecular mechanisms is limited. Because H3K79 is at globular domain, short histone peptide cannot mimic H3K79 in chromatin. Instead, reconstituted nucleosome-based chemical tools are ideally used to investigate H3K79 modifications. In consequence, H3K79-modified histone H3 with additional chemical handles are required, but such synthesis is challenging and laborious. Here we report a facile semisynthesis method that enables multifunctional histone H3 readily available. H3K79-containing fragment is short for straight peptide synthesis that was later ligated to recombinant expressed H3 fragments for full-length product in large scale. As a result, nucleosomes with H3K79 modifications as well as photo-reactive group and affinity tag were obtained to investigate potential binding proteins. We believe this method that enhances synthetic accessibility of nucleosome probes will accelerate understanding of the underexplored H3K79 modifications.
Histone H3K79 modifications are essential to regulate chromatin structure and gene transcription, but understanding of the molecular mechanisms is limited. Because H3K79 is at globular domain, short histone peptide cannot mimic H3K79 in chromatin. Instead, reconstituted nucleosome-based chemical tools are ideally used to investigate H3K79 modifications. In consequence, H3K79-modified histone H3 with additional chemical handles are required, but such synthesis is challenging and laborious. Here we report a facile semisynthesis method that enables multifunctional histone H3 readily available. H3K79-containing fragment is short for straight peptide synthesis that was later ligated to recombinant expressed H3 fragments for full-length product in large scale. As a result, nucleosomes with H3K79 modifications as well as photo-reactive group and affinity tag were obtained to investigate potential binding proteins. We believe this method that enhances synthetic accessibility of nucleosome probes will accelerate understanding of the underexplored H3K79 modifications.
2024, 35(10): 109499
doi: 10.1016/j.cclet.2024.109499
Abstract:
Sodium percarbonate (Na2CO3·1.5H2O2, SPC) has been extensively employed as a solid substitute of H2O2 for Fenton process in water treatment, because of its high stability during the production, transport, storage and usage. In addition, SPC can be applied in a wider range of work pH, it is also applied as a buffer in Fenton reaction for preventing a drop in pH. Herein, we have synthesized basic copper molybdate (BCM) nanoblocks with the molecular formula of Cu3(MoO4)2(OH)2 as an efficient and heterogeneous catalyst for antibiotics degradation via percarbonate activation. First, fully physical characterizations confirmed BCM nanocomposite exhibited a structure of nanoblocks. We also found that BCM/SPC system could work in a much wider pH range, compared with H2O2. Then, BCM/SPC system presented a good anti-interference ability for natural organic matter in OTC degradation. EPR results and Quenching tests confirmed that the co-presence of ·CO3−, ·O2−, 1O2 and ·OH in BCM/SPC system.
Sodium percarbonate (Na2CO3·1.5H2O2, SPC) has been extensively employed as a solid substitute of H2O2 for Fenton process in water treatment, because of its high stability during the production, transport, storage and usage. In addition, SPC can be applied in a wider range of work pH, it is also applied as a buffer in Fenton reaction for preventing a drop in pH. Herein, we have synthesized basic copper molybdate (BCM) nanoblocks with the molecular formula of Cu3(MoO4)2(OH)2 as an efficient and heterogeneous catalyst for antibiotics degradation via percarbonate activation. First, fully physical characterizations confirmed BCM nanocomposite exhibited a structure of nanoblocks. We also found that BCM/SPC system could work in a much wider pH range, compared with H2O2. Then, BCM/SPC system presented a good anti-interference ability for natural organic matter in OTC degradation. EPR results and Quenching tests confirmed that the co-presence of ·CO3−, ·O2−, 1O2 and ·OH in BCM/SPC system.
2024, 35(10): 109504
doi: 10.1016/j.cclet.2024.109504
Abstract:
Polyketide synthases (PKSs) are megasynthases with multiple autonomously folding domains, which operate cooperatively in the PKS assemblies to synthesize specific polyketide scaffolds. Any nonreactive intermediates tethered to acyl carrier protein (ACP) domain in the PKS will block the elongation process of polyketide chains. In this study, we systematically elucidate the editing function of fungal type Ⅱ thioesterases (TEIIs) to hydrolyze ACP domain-bounded nonreactive acyl groups, which are uploaded by substrate promiscuous fungal phosphopantetheinyl transferase. Thereof, the TEIIs encoded in gene clusters of nonreducing PKS with reductase domain exhibit universal editing function. Besides, editing function was also found for TEIIs encoded in gene clusters of highly-reducing PKS with condensation domain. Hence, the editing TEIIs with function of recovery PKS are applied to improve the yield of the fungal polyketides in vivo. Our study provides valuable insights into the editing process of fungal PKSs, highlights the crucial role of TEIIs in enhancing polyketide production and introduces a novel metabolic engineering strategy for fungal polyketide biosynthesis by leveraging the editing function of TEIIs.
Polyketide synthases (PKSs) are megasynthases with multiple autonomously folding domains, which operate cooperatively in the PKS assemblies to synthesize specific polyketide scaffolds. Any nonreactive intermediates tethered to acyl carrier protein (ACP) domain in the PKS will block the elongation process of polyketide chains. In this study, we systematically elucidate the editing function of fungal type Ⅱ thioesterases (TEIIs) to hydrolyze ACP domain-bounded nonreactive acyl groups, which are uploaded by substrate promiscuous fungal phosphopantetheinyl transferase. Thereof, the TEIIs encoded in gene clusters of nonreducing PKS with reductase domain exhibit universal editing function. Besides, editing function was also found for TEIIs encoded in gene clusters of highly-reducing PKS with condensation domain. Hence, the editing TEIIs with function of recovery PKS are applied to improve the yield of the fungal polyketides in vivo. Our study provides valuable insights into the editing process of fungal PKSs, highlights the crucial role of TEIIs in enhancing polyketide production and introduces a novel metabolic engineering strategy for fungal polyketide biosynthesis by leveraging the editing function of TEIIs.
2024, 35(10): 109506
doi: 10.1016/j.cclet.2024.109506
Abstract:
The development of resistance against most of the available antibiotics has made Acinetobacter baumannii (A. baumannii) a pathogen of high risk. In this study, thirty novel berberine derivatives are rationally designed, synthesized, and evaluated for their synergistic antibacterial activities against A. baumannii. Among them, compound 2d shows the most potent synergetic effect to aztreonam against A. baumannii, including carbapenem-resistant and extended-spectrum β-lactamases-producing strains. Moreover, synergistic effects were observed for the combinations of 2d and different antibacterial used in clinical practices, indicating its potent broad-spectrum antibiotic-sensitizing effects against A. baumannii. The combination of 2d and aztreonam significantly improves the survival rates of G. mellonella larvae compared with aztreonam treatment alone. Mechanism studies indicate that 2d inhibits the drug efflux and iron acquisition of the bacteria by targeting the AdeB transporter protein, thus achieving a synergistic antimicrobial efficacy with different antibacterial agents. Therefore, berberine derivatives represent a new family of antimicrobial adjuvants against A. baumannii, with the advantage of dual-function antibacterial effect, and are worthy of further investigation.
The development of resistance against most of the available antibiotics has made Acinetobacter baumannii (A. baumannii) a pathogen of high risk. In this study, thirty novel berberine derivatives are rationally designed, synthesized, and evaluated for their synergistic antibacterial activities against A. baumannii. Among them, compound 2d shows the most potent synergetic effect to aztreonam against A. baumannii, including carbapenem-resistant and extended-spectrum β-lactamases-producing strains. Moreover, synergistic effects were observed for the combinations of 2d and different antibacterial used in clinical practices, indicating its potent broad-spectrum antibiotic-sensitizing effects against A. baumannii. The combination of 2d and aztreonam significantly improves the survival rates of G. mellonella larvae compared with aztreonam treatment alone. Mechanism studies indicate that 2d inhibits the drug efflux and iron acquisition of the bacteria by targeting the AdeB transporter protein, thus achieving a synergistic antimicrobial efficacy with different antibacterial agents. Therefore, berberine derivatives represent a new family of antimicrobial adjuvants against A. baumannii, with the advantage of dual-function antibacterial effect, and are worthy of further investigation.
2024, 35(10): 109512
doi: 10.1016/j.cclet.2024.109512
Abstract:
As a promising imaging technology, the low sensitivity of fluorine-19 magnetic resonance imaging (19F MRI) severely hinders its biomedical applications. Herein, we have developed an unprecedented rotaxane-based strategy to improve the sensitivity of 19F MRI agents. By threading the fluorinated macrocycle into 2-blade pinwheel [2]rotaxanes, the 19F longitudinal relaxation rate R1 was dramatically increased, resulting in a significant 19F MRI signal intensity enhancement of up to 79%. Through comparative molecular dynamics studies using a series of solution and solid-state 1H/19F nuclear magnetic resonance (1H/19F NMR) and molecular dynamics simulations, it was found that the formation of mechanical bonds dramatically restricts the motion of the wheel fluorines and thus increasing the R1 for higher 19F MRI sensitivity. Besides a novel strategy for improving 19F MRI sensitivity, this study has established 19F NMR/MRI as a valuable technology for monitoring the molecular dynamics of rotaxanes, which may shed new light on high-performance 19F MRI agents and molecular devices.
As a promising imaging technology, the low sensitivity of fluorine-19 magnetic resonance imaging (19F MRI) severely hinders its biomedical applications. Herein, we have developed an unprecedented rotaxane-based strategy to improve the sensitivity of 19F MRI agents. By threading the fluorinated macrocycle into 2-blade pinwheel [2]rotaxanes, the 19F longitudinal relaxation rate R1 was dramatically increased, resulting in a significant 19F MRI signal intensity enhancement of up to 79%. Through comparative molecular dynamics studies using a series of solution and solid-state 1H/19F nuclear magnetic resonance (1H/19F NMR) and molecular dynamics simulations, it was found that the formation of mechanical bonds dramatically restricts the motion of the wheel fluorines and thus increasing the R1 for higher 19F MRI sensitivity. Besides a novel strategy for improving 19F MRI sensitivity, this study has established 19F NMR/MRI as a valuable technology for monitoring the molecular dynamics of rotaxanes, which may shed new light on high-performance 19F MRI agents and molecular devices.
2024, 35(10): 109519
doi: 10.1016/j.cclet.2024.109519
Abstract:
Hepatocellular carcinoma is a common and fatal malignancy for which there is no effective systemic therapeutic strategy. Dihydroartemisinin (DHA), a derivative of artemisinin, has been shown to exert anti-tumor effects through the production of reactive oxygen species (ROS) and resultant mitochondrial damage. However, clinical translation is limited by several drawbacks, such as insolubility, instability and low bioavailability. Here, based on a nanomedicine-based delivery strategy, we fabricated mitochondria-targeted carrier-free nanoparticles coupling DHA and triphenylphosphonium (TPP), aiming to improve bioavailability and mitochondrial targeting. DHA-TPP nanoparticles can be passively delivered to the tumor site by enhanced penetration and retention and then internalized. Flow cytometry and Western blot analysis showed that DHA-TPP nanoparticles increased intracellular ROS, which increased mitochondrial stress and in turn upregulated the downstream Bcl-2 pathway, leading to apoptosis. In vivo experiments showed that DHA-TPP nanoparticles exhibited anti-tumor effects in a mouse model of hepatocellular carcinoma. These findings suggest carrier-free DHA-TPP nanoparticles as a potential therapeutic strategy for hepatocellular carcinoma.
Hepatocellular carcinoma is a common and fatal malignancy for which there is no effective systemic therapeutic strategy. Dihydroartemisinin (DHA), a derivative of artemisinin, has been shown to exert anti-tumor effects through the production of reactive oxygen species (ROS) and resultant mitochondrial damage. However, clinical translation is limited by several drawbacks, such as insolubility, instability and low bioavailability. Here, based on a nanomedicine-based delivery strategy, we fabricated mitochondria-targeted carrier-free nanoparticles coupling DHA and triphenylphosphonium (TPP), aiming to improve bioavailability and mitochondrial targeting. DHA-TPP nanoparticles can be passively delivered to the tumor site by enhanced penetration and retention and then internalized. Flow cytometry and Western blot analysis showed that DHA-TPP nanoparticles increased intracellular ROS, which increased mitochondrial stress and in turn upregulated the downstream Bcl-2 pathway, leading to apoptosis. In vivo experiments showed that DHA-TPP nanoparticles exhibited anti-tumor effects in a mouse model of hepatocellular carcinoma. These findings suggest carrier-free DHA-TPP nanoparticles as a potential therapeutic strategy for hepatocellular carcinoma.
2024, 35(10): 109521
doi: 10.1016/j.cclet.2024.109521
Abstract:
Photodynamic therapy (PDT) has garnered significant attention as a promising approach to cancer therapy, harnessing the combined benefits of localized light treatment and the accompanying host immune response. In this study, we engineered an immuno-enhanced PDT nanoplatform, denoted as HM@p-MOF (hybrid membrane@porphyrin-metal organic framework). The core porphyrin-MOF was cloaked with a hybrid membrane derived from B16F10 cancer cells and NK cells, resulting in enhanced stability. In both in vitro and in vivo experiments, our finding demonstrated that the hybrid membrane conferred dual targeting capabilities to the nanoplatform, leveraging the unique properties of the B16F10 membrane and NK membrane to augment immunogenic cell death (ICD) induced by photodynamic effects. Additionally, in conjunction with the immunomodulatory functions of the NK cell membrane, we observed an expansion of in situ immune infiltration leading to a systemic immune response. The HM@p-MOF nanoplatform exhibited the capacity to not only inhibit the growth of mouse melanoma but also suppress metastasis. This innovative HM@p-MOF nanoplatform present a viable strategy to enhance phototherapeutic efficacy for both localized and metastatic tumors. It provides a direction for the fabrication of biomimetic nanomedicines possessing immuno-modulatory function.
Photodynamic therapy (PDT) has garnered significant attention as a promising approach to cancer therapy, harnessing the combined benefits of localized light treatment and the accompanying host immune response. In this study, we engineered an immuno-enhanced PDT nanoplatform, denoted as HM@p-MOF (hybrid membrane@porphyrin-metal organic framework). The core porphyrin-MOF was cloaked with a hybrid membrane derived from B16F10 cancer cells and NK cells, resulting in enhanced stability. In both in vitro and in vivo experiments, our finding demonstrated that the hybrid membrane conferred dual targeting capabilities to the nanoplatform, leveraging the unique properties of the B16F10 membrane and NK membrane to augment immunogenic cell death (ICD) induced by photodynamic effects. Additionally, in conjunction with the immunomodulatory functions of the NK cell membrane, we observed an expansion of in situ immune infiltration leading to a systemic immune response. The HM@p-MOF nanoplatform exhibited the capacity to not only inhibit the growth of mouse melanoma but also suppress metastasis. This innovative HM@p-MOF nanoplatform present a viable strategy to enhance phototherapeutic efficacy for both localized and metastatic tumors. It provides a direction for the fabrication of biomimetic nanomedicines possessing immuno-modulatory function.
2024, 35(10): 109523
doi: 10.1016/j.cclet.2024.109523
Abstract:
Long-term fluorescence monitoring of subcellular organelles is crucial for cellular physiology and pathology studies. Lipid droplets (LDs) are increasingly recognized for their involvement in various biological processes, to influence disease development through diverse behaviors However, existing LD probes face challenges in achieving high targeting and long-term monitoring due to poor photostability and long-term phototoxicity. Carbon quantum dots (CQDs) have gained prominence due to their exceptional fluorescence properties, but their prevalent blue excitation wavelength presents difficulties for long-term imaging. Herein, we synthesized red-emissive carbon quantum dot (R-CQDs) with superior photobleaching resistance and red-emission, thus enabling harmlessly fluorescence monitoring of cells longer than 3 h. In addition, R-CQD exhibits suitable amphiphilicity and remarkable solvatochromic effect, allowing rapid targeting to LDs for immediate imaging without cumbersome washing steps. Hence, R-CQD shows high performance for extended observation of dynamic LD behavior in various biological processes, which is confirmed by documenting the course of LDs during starvation as well as lipotoxicity. Compared to commercial probes, R-CQD extends live cell imaging time by at least 9-fold, facilitating the study of LD behavioral characteristics under diverse physiological or pathological conditions. This work provides a reliable fluorescence tool for tracking intercellular microenvironment dynamically thus to understand the divers biological or disease mechanism.
Long-term fluorescence monitoring of subcellular organelles is crucial for cellular physiology and pathology studies. Lipid droplets (LDs) are increasingly recognized for their involvement in various biological processes, to influence disease development through diverse behaviors However, existing LD probes face challenges in achieving high targeting and long-term monitoring due to poor photostability and long-term phototoxicity. Carbon quantum dots (CQDs) have gained prominence due to their exceptional fluorescence properties, but their prevalent blue excitation wavelength presents difficulties for long-term imaging. Herein, we synthesized red-emissive carbon quantum dot (R-CQDs) with superior photobleaching resistance and red-emission, thus enabling harmlessly fluorescence monitoring of cells longer than 3 h. In addition, R-CQD exhibits suitable amphiphilicity and remarkable solvatochromic effect, allowing rapid targeting to LDs for immediate imaging without cumbersome washing steps. Hence, R-CQD shows high performance for extended observation of dynamic LD behavior in various biological processes, which is confirmed by documenting the course of LDs during starvation as well as lipotoxicity. Compared to commercial probes, R-CQD extends live cell imaging time by at least 9-fold, facilitating the study of LD behavioral characteristics under diverse physiological or pathological conditions. This work provides a reliable fluorescence tool for tracking intercellular microenvironment dynamically thus to understand the divers biological or disease mechanism.
2024, 35(10): 109524
doi: 10.1016/j.cclet.2024.109524
Abstract:
Deep oxidation of NO molecules to nitrate species by photocatalysis with virtually no toxic byproduct NO2 generation is a challenging task. In this study, TiO2 in-situ grows based on NH2−MIL-125(Ti) (NM-125) not only inhibited TiO2 agglomeration, but also contacted more tightly to obtain efficient interfacial effects, thus displaying excellent photocatalytic NO removal activity (68.08%). The formation of TiO2 is directly confirmed by characterizations such as X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS). Meanwhile, UV–vis, photoluminescence, and photoelectrochemical analysis indicate that TiO2 formation effectively improves the optical properties. Moreover, the strong electron interaction and electron transport direction between NM-125 and TiO2 are investigated by density functional theoretical (DFT) calculation. Finally, combined with the results of electron spin resonance (ESR) and in-situ FT-IR test, the intermediate processes of NO adsorption and photocatalytic oxidation reaction are discussed in depth, where the production of reactive oxygen species (ROS) under light is the key factor in the successful degradation of NO. Compared with NM-125 which can only produce •OH through photogenerated electrons since the lower valence band position, NMT-2 can directly produce •OH through photogenerated holes, thereby relieving the pressure on photogenerated electrons and producing more ROS. This study will provide reasonable guidance for the modification of NM-125 for photocatalytic removal of ppb-level NO.
Deep oxidation of NO molecules to nitrate species by photocatalysis with virtually no toxic byproduct NO2 generation is a challenging task. In this study, TiO2 in-situ grows based on NH2−MIL-125(Ti) (NM-125) not only inhibited TiO2 agglomeration, but also contacted more tightly to obtain efficient interfacial effects, thus displaying excellent photocatalytic NO removal activity (68.08%). The formation of TiO2 is directly confirmed by characterizations such as X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS). Meanwhile, UV–vis, photoluminescence, and photoelectrochemical analysis indicate that TiO2 formation effectively improves the optical properties. Moreover, the strong electron interaction and electron transport direction between NM-125 and TiO2 are investigated by density functional theoretical (DFT) calculation. Finally, combined with the results of electron spin resonance (ESR) and in-situ FT-IR test, the intermediate processes of NO adsorption and photocatalytic oxidation reaction are discussed in depth, where the production of reactive oxygen species (ROS) under light is the key factor in the successful degradation of NO. Compared with NM-125 which can only produce •OH through photogenerated electrons since the lower valence band position, NMT-2 can directly produce •OH through photogenerated holes, thereby relieving the pressure on photogenerated electrons and producing more ROS. This study will provide reasonable guidance for the modification of NM-125 for photocatalytic removal of ppb-level NO.
2024, 35(10): 109526
doi: 10.1016/j.cclet.2024.109526
Abstract:
Solar-driven H2O2 production and emerging organic pollutants (EOPs) elimination are of great significance from the perspective of environmental sustainability. The efficiency of the photocatalytic reaction system is the key challenge to be addressed. In this work, the strategy of constructing surface ionic local polarization centers to enhance the exciton dissociation of the polymeric photocatalytic is demonstrated. Selected bipyridinium cation (TMAP) is complexed on a K+-incorporated carbon nitride (CNK) framework, and the combination of local polarization centers both on the surface (bipyridinium cation) and bulk (K+ cation) contributes to a superior photocatalytic H2O2 production performance, affording a remarkable H2O2 generation rate of 46.8 µmol h−1 mg−1 and a high apparent quantum yield (AQY) value of 77.5% under irradiation of 405 nm photons. As substantiated experimentally by steady state/transient spectroscopy techniques, the surface local polarization centers increase the population of the long-lived trapped electrons, and thereby promote the interfacial charge transfer process for chemical conversion reaction. The strategy is potentially applicable to the design of a wide range of efficient solar-to-chemical conversion systems.
Solar-driven H2O2 production and emerging organic pollutants (EOPs) elimination are of great significance from the perspective of environmental sustainability. The efficiency of the photocatalytic reaction system is the key challenge to be addressed. In this work, the strategy of constructing surface ionic local polarization centers to enhance the exciton dissociation of the polymeric photocatalytic is demonstrated. Selected bipyridinium cation (TMAP) is complexed on a K+-incorporated carbon nitride (CNK) framework, and the combination of local polarization centers both on the surface (bipyridinium cation) and bulk (K+ cation) contributes to a superior photocatalytic H2O2 production performance, affording a remarkable H2O2 generation rate of 46.8 µmol h−1 mg−1 and a high apparent quantum yield (AQY) value of 77.5% under irradiation of 405 nm photons. As substantiated experimentally by steady state/transient spectroscopy techniques, the surface local polarization centers increase the population of the long-lived trapped electrons, and thereby promote the interfacial charge transfer process for chemical conversion reaction. The strategy is potentially applicable to the design of a wide range of efficient solar-to-chemical conversion systems.
2024, 35(10): 109533
doi: 10.1016/j.cclet.2024.109533
Abstract:
Rhodium-catalyzed C4aryl−H activation and ring-retentive annulation of 2H-imidazoles with internal alkynes to build imidazo[5,1-a]isoquinolinium salts with high yields and broad scope has been disclosed. These novel salts serve as new full-color emissive fluorophores (433−633 nm), just by simply modifying the substituents on C3 and C4 positions of isoquinoline ring. Furthermore, these salts can undergo ring-opening C5aryl−H activation/annulation with a different alkyne to form non-symmetric and AIE-active 1,1′-biisoquinolines, where NH4OAc plays an indispensable role that accounts for Hofmann elimination and imine formation, leading to an unprecedented imine dance: cyclic imine → N-alkenyl imine → NH imine. The 15N labelling experiments indicate that the 2nd annulation includes two pathways: N-exchange (major) and N-retention (minor).
Rhodium-catalyzed C4aryl−H activation and ring-retentive annulation of 2H-imidazoles with internal alkynes to build imidazo[5,1-a]isoquinolinium salts with high yields and broad scope has been disclosed. These novel salts serve as new full-color emissive fluorophores (433−633 nm), just by simply modifying the substituents on C3 and C4 positions of isoquinoline ring. Furthermore, these salts can undergo ring-opening C5aryl−H activation/annulation with a different alkyne to form non-symmetric and AIE-active 1,1′-biisoquinolines, where NH4OAc plays an indispensable role that accounts for Hofmann elimination and imine formation, leading to an unprecedented imine dance: cyclic imine → N-alkenyl imine → NH imine. The 15N labelling experiments indicate that the 2nd annulation includes two pathways: N-exchange (major) and N-retention (minor).
2024, 35(10): 109538
doi: 10.1016/j.cclet.2024.109538
Abstract:
Chemotherapy has been recommended as the standard protocol for triple-negative breast cancer (TNBC) at the advanced stage. However, the current treatment is unsatisfactory due to inefficient drug accumulation and rapid chemo-resistance. Thus, rational design of advanced drug delivery systems that can induce multiple cell death pathways is a promising strategy to combat TNBC. Ferroptosis is a powerful non-apoptotic cell death modality, showing potential in tumor inhibition. Herein, we propose a binary prodrug nanoassemblies that combines chemotherapy with ferroptosis for TNBC treatment. In this system, paclitaxel is linked with paracetamol (ferroptosis activator) by a disulfide linkage to construct self-assembly prodrug. Meanwhile, 2-distearoyl-sn-glycerol-3-phosphoethanolamine-N-methyl(polyethylene glycol)-2000-tyrosine (DSPE-PEG2k-tyrosine) is applied for large neutral amino acid transporter 1 (LAT1) targeting, which is highly expressed in TNBC. The prodrug nanoassemblies exhibit good stability and a glutathione (GSH)-responsive release profile. Furthermore, the LAT1-targeted nanoassemblies show stronger cytotoxicity, higher cellular uptake, and more obvious ferroptosis activation than non-decorated ones. In a TNBC mice model, the prodrug nanoassemblies demonstrate strong anti-tumor efficacy. The application of ferroptosis-assisting chemotherapy may provide a promising strategy for TNBC therapy.
Chemotherapy has been recommended as the standard protocol for triple-negative breast cancer (TNBC) at the advanced stage. However, the current treatment is unsatisfactory due to inefficient drug accumulation and rapid chemo-resistance. Thus, rational design of advanced drug delivery systems that can induce multiple cell death pathways is a promising strategy to combat TNBC. Ferroptosis is a powerful non-apoptotic cell death modality, showing potential in tumor inhibition. Herein, we propose a binary prodrug nanoassemblies that combines chemotherapy with ferroptosis for TNBC treatment. In this system, paclitaxel is linked with paracetamol (ferroptosis activator) by a disulfide linkage to construct self-assembly prodrug. Meanwhile, 2-distearoyl-sn-glycerol-3-phosphoethanolamine-N-methyl(polyethylene glycol)-2000-tyrosine (DSPE-PEG2k-tyrosine) is applied for large neutral amino acid transporter 1 (LAT1) targeting, which is highly expressed in TNBC. The prodrug nanoassemblies exhibit good stability and a glutathione (GSH)-responsive release profile. Furthermore, the LAT1-targeted nanoassemblies show stronger cytotoxicity, higher cellular uptake, and more obvious ferroptosis activation than non-decorated ones. In a TNBC mice model, the prodrug nanoassemblies demonstrate strong anti-tumor efficacy. The application of ferroptosis-assisting chemotherapy may provide a promising strategy for TNBC therapy.
2024, 35(10): 109539
doi: 10.1016/j.cclet.2024.109539
Abstract:
Using hydrogen-bonded organic frameworks (HOFs) as photosensitizers to perform photocatalytic oxidation reactions under green and mild conditions is still a challenge for the application of HOFs materials. This study presents a novel approach that exploits HOFs to enhance the efficiency of photocatalytic oxidation for achieving visible light catalytic oxidation of styrene and its derivatives in the aqueous environment. By using 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H4TBAPy) as the monomer, a pyrene-based hydrogen-bonded organic framework (PFC-1) with a microporous structure was successfully prepared. Compared with monomer H4TBAPy, due to the exciton effect and the interlayer confinement of HOFs, the singlet oxygen (1O2) production efficiency is significantly improved, which has great potential in photocatalytic oxidation reactions. Subsequently, the practicality of PFC-1 as a photocatalyst was studied, and the photocatalytic oxidation of styrene and its derivatives in aqueous solution was achieved under visible light with high catalytic efficiency, indicating that PFC-1 has significant potential to promote photocatalytic oxidation reactions under mild conditions. The utilization of HOFs as photosensitizers in this straightforward approach enables the attainment of green photocatalytic oxidation, hence expanding the potential applications of HOFs materials within the realm of photocatalysis.
Using hydrogen-bonded organic frameworks (HOFs) as photosensitizers to perform photocatalytic oxidation reactions under green and mild conditions is still a challenge for the application of HOFs materials. This study presents a novel approach that exploits HOFs to enhance the efficiency of photocatalytic oxidation for achieving visible light catalytic oxidation of styrene and its derivatives in the aqueous environment. By using 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H4TBAPy) as the monomer, a pyrene-based hydrogen-bonded organic framework (PFC-1) with a microporous structure was successfully prepared. Compared with monomer H4TBAPy, due to the exciton effect and the interlayer confinement of HOFs, the singlet oxygen (1O2) production efficiency is significantly improved, which has great potential in photocatalytic oxidation reactions. Subsequently, the practicality of PFC-1 as a photocatalyst was studied, and the photocatalytic oxidation of styrene and its derivatives in aqueous solution was achieved under visible light with high catalytic efficiency, indicating that PFC-1 has significant potential to promote photocatalytic oxidation reactions under mild conditions. The utilization of HOFs as photosensitizers in this straightforward approach enables the attainment of green photocatalytic oxidation, hence expanding the potential applications of HOFs materials within the realm of photocatalysis.
2024, 35(10): 109540
doi: 10.1016/j.cclet.2024.109540
Abstract:
Oligo[n]rotaxanes are one of the most extensively studied categories of mechanically bonded macromolecules. In this study, a supramolecular oligo[2]rotaxane is successfully constructed driven by platinum(Ⅱ) metallacycle and pillar[5]arene-based host–guest interactions in an orthogonal way. The supramolecular oligo[2]rotaxane is further applied in fabricating a light harvesting system.
Oligo[n]rotaxanes are one of the most extensively studied categories of mechanically bonded macromolecules. In this study, a supramolecular oligo[2]rotaxane is successfully constructed driven by platinum(Ⅱ) metallacycle and pillar[5]arene-based host–guest interactions in an orthogonal way. The supramolecular oligo[2]rotaxane is further applied in fabricating a light harvesting system.
2024, 35(10): 109544
doi: 10.1016/j.cclet.2024.109544
Abstract:
A rhodium-catalyzed desymmetrization reaction for enantioselective methyl C−H arylation is achieved by utilizing an in situ arylating reagent via nucleophilic cyclization of o-aminoaryl alkyne. The reaction results in chiral indoles containing all-carbon quaternary stereocenters under atmospheric conditions, with a wide range of substrates exhibiting good enantioselectivity (44 examples). Mechnism and DFT studies show that the stereocontrol is reasonably achieved through the collaborative control of a large silicon substituted chiral ligand and C−H···π, LP···π interactions between aryl rings of the carboxylate group and the substrate. Control experiments demonstrate that Rh-aryl bond formation via in situ nucleophilic cyclization is more critical for reaction efficiency than via C−H activation of the nucleophilic cyclization byproduct.
A rhodium-catalyzed desymmetrization reaction for enantioselective methyl C−H arylation is achieved by utilizing an in situ arylating reagent via nucleophilic cyclization of o-aminoaryl alkyne. The reaction results in chiral indoles containing all-carbon quaternary stereocenters under atmospheric conditions, with a wide range of substrates exhibiting good enantioselectivity (44 examples). Mechnism and DFT studies show that the stereocontrol is reasonably achieved through the collaborative control of a large silicon substituted chiral ligand and C−H···π, LP···π interactions between aryl rings of the carboxylate group and the substrate. Control experiments demonstrate that Rh-aryl bond formation via in situ nucleophilic cyclization is more critical for reaction efficiency than via C−H activation of the nucleophilic cyclization byproduct.
2024, 35(10): 109548
doi: 10.1016/j.cclet.2024.109548
Abstract:
Molecular-based ferroelastics with dielectric switching properties are highly desirable for their applications on microelectronic dielectric switches, sensors, data storage, and so on. However, the current reports mostly focus on organic-inorganic hybrids containing toxic heavy metal atoms, and the relatively low phase transition temperature limits their application. In this paper, low-toxic organic salt ferroelastic enantiomers (R/S)-4-fluoro-1-azabicyclo[3.2.1]octonium chloride [(R/S)-F-321] were designed and synthesized under the introducing chirality strategy. They undergo a 432F422-type ferroelastic phase transition with a high Curie temperature (Tc) of 470 K, simultaneously exhibiting excellent dielectric switching characteristics. In addition to the ordered-disordered movement of cations, the significant displacement of anions is also responsible for such high Tc and large dielectric switching ratios, which is very rare in molecular-based switching materials. This work enriches the development of molecular ferroelastic switching materials and gives inspiration for the exploration of environmentally friendly high Tc organic salt ferroelastics with prominent switching performances.
Molecular-based ferroelastics with dielectric switching properties are highly desirable for their applications on microelectronic dielectric switches, sensors, data storage, and so on. However, the current reports mostly focus on organic-inorganic hybrids containing toxic heavy metal atoms, and the relatively low phase transition temperature limits their application. In this paper, low-toxic organic salt ferroelastic enantiomers (R/S)-4-fluoro-1-azabicyclo[3.2.1]octonium chloride [(R/S)-F-321] were designed and synthesized under the introducing chirality strategy. They undergo a 432F422-type ferroelastic phase transition with a high Curie temperature (Tc) of 470 K, simultaneously exhibiting excellent dielectric switching characteristics. In addition to the ordered-disordered movement of cations, the significant displacement of anions is also responsible for such high Tc and large dielectric switching ratios, which is very rare in molecular-based switching materials. This work enriches the development of molecular ferroelastic switching materials and gives inspiration for the exploration of environmentally friendly high Tc organic salt ferroelastics with prominent switching performances.
2024, 35(10): 109554
doi: 10.1016/j.cclet.2024.109554
Abstract:
Triphenylamine (TPA)-containing 2-(2′-hydroxyphenyl)benzoxazoles (2a-2c) have been synthesized via a highly efficient rhodium-catalyzed C–H/C–H cross-coupling reaction. Compound 2a is a novel mechanofluorochromic material with blue-shifted mechanochromic properties. Compounds 2b and 2c presented opposite mechanochromic trends. For 2b, the enol-form emission enhanced, and the keto-form emission blue-shift after grinding. In contrast, 2c exhibited the weak enol-form emission disappeared and the keto-form emission slightly red-shift after grinding treatments. The estrone-containing 2b-based water-dispersed nanoparticles (NPs) exhibit apparent dual-emission and were applied for fluorescence images. In addition, bis(TPA)-containing 2c-based devices exhibit dual-emission with good performance and a singlet exciton yield of 92%, which breaks through the theoretical upper limit of 25% in conventional fluorescent OLEDs. This is one of the highest exciton utilization values recorded for the ESIPT molecules with a dual emission system.
Triphenylamine (TPA)-containing 2-(2′-hydroxyphenyl)benzoxazoles (2a-2c) have been synthesized via a highly efficient rhodium-catalyzed C–H/C–H cross-coupling reaction. Compound 2a is a novel mechanofluorochromic material with blue-shifted mechanochromic properties. Compounds 2b and 2c presented opposite mechanochromic trends. For 2b, the enol-form emission enhanced, and the keto-form emission blue-shift after grinding. In contrast, 2c exhibited the weak enol-form emission disappeared and the keto-form emission slightly red-shift after grinding treatments. The estrone-containing 2b-based water-dispersed nanoparticles (NPs) exhibit apparent dual-emission and were applied for fluorescence images. In addition, bis(TPA)-containing 2c-based devices exhibit dual-emission with good performance and a singlet exciton yield of 92%, which breaks through the theoretical upper limit of 25% in conventional fluorescent OLEDs. This is one of the highest exciton utilization values recorded for the ESIPT molecules with a dual emission system.
2024, 35(10): 109560
doi: 10.1016/j.cclet.2024.109560
Abstract:
Reliable and selective sensing of dopamine (DA) is essential for early diagnosis of mental diseases. Among the various potential methods, nanozyme-based sensing systems have demonstrated promising sensitivity and reliability. However, owing to the lack of substrate specificity, it is challenging to selectively detect DA using nanozymes. Herein, based on the reactivity of the DA oxidation intermediates, we report a cascade colorimetric sensing system for the selective detection of DA using only a single nanozyme. It was disclosed that the oxidation product of DA catalyzed by Co-N-doped carbon sheets (Co-N-C, a common oxidase-like nanozyme), dopamine quinone (DAQ), showed significant biocatalytic electron-donating activity in the reduction of O2 to generate O2•−. Further using O2•− to oxidize 3,3′,5,5′-tetramethylbenzidine (TMB), a colorimetric sensing platform for DA was constructed with a linear detection range of 50 nmol/L to 50 µmol/L and a low limit of detection of 4 nmol/L. Thanks to the reactivity of the oxidation product, without any biometric units (such as nucleic acids, enzymes, and antibodies/antigens), the reaction selectivity of DA against other interferences (e.g., ascorbic acid, adrenaline, 5-hydroxytryptamine, and glutathione) was enhanced up to 71-fold. Beyond complicated cascade systems requiring at least two nanozymes, sophisticated artificial recognition via multiple interactions was simplified by exploiting the oxidative properties of product intermediates; thus, only a single common oxidase-like nanozyme was needed. This work offers a new strategy to enhance the selectivity of nanozymes for bioanalytical applications.
Reliable and selective sensing of dopamine (DA) is essential for early diagnosis of mental diseases. Among the various potential methods, nanozyme-based sensing systems have demonstrated promising sensitivity and reliability. However, owing to the lack of substrate specificity, it is challenging to selectively detect DA using nanozymes. Herein, based on the reactivity of the DA oxidation intermediates, we report a cascade colorimetric sensing system for the selective detection of DA using only a single nanozyme. It was disclosed that the oxidation product of DA catalyzed by Co-N-doped carbon sheets (Co-N-C, a common oxidase-like nanozyme), dopamine quinone (DAQ), showed significant biocatalytic electron-donating activity in the reduction of O2 to generate O2•−. Further using O2•− to oxidize 3,3′,5,5′-tetramethylbenzidine (TMB), a colorimetric sensing platform for DA was constructed with a linear detection range of 50 nmol/L to 50 µmol/L and a low limit of detection of 4 nmol/L. Thanks to the reactivity of the oxidation product, without any biometric units (such as nucleic acids, enzymes, and antibodies/antigens), the reaction selectivity of DA against other interferences (e.g., ascorbic acid, adrenaline, 5-hydroxytryptamine, and glutathione) was enhanced up to 71-fold. Beyond complicated cascade systems requiring at least two nanozymes, sophisticated artificial recognition via multiple interactions was simplified by exploiting the oxidative properties of product intermediates; thus, only a single common oxidase-like nanozyme was needed. This work offers a new strategy to enhance the selectivity of nanozymes for bioanalytical applications.
2024, 35(10): 109565
doi: 10.1016/j.cclet.2024.109565
Abstract:
An oxidative annulation of 2-arylidene-1,3-indanediones with Meldrum's acid has been developed for the divergent syntheses of spirolactones with a spirocenter located at the γ-position with respect to the carbonyl group. This heteroannulation protocol tolerates various functional groups and delivers moderate-to-good product yields. Interestingly, the reaction outcomes are exclusively controlled by the reaction oxidant/medium. This annulation strategy can also be executed in the flow system with decent product yields. Control experiments revealed that the reaction proceeds via a radical tandem annulation pathway.
An oxidative annulation of 2-arylidene-1,3-indanediones with Meldrum's acid has been developed for the divergent syntheses of spirolactones with a spirocenter located at the γ-position with respect to the carbonyl group. This heteroannulation protocol tolerates various functional groups and delivers moderate-to-good product yields. Interestingly, the reaction outcomes are exclusively controlled by the reaction oxidant/medium. This annulation strategy can also be executed in the flow system with decent product yields. Control experiments revealed that the reaction proceeds via a radical tandem annulation pathway.
2024, 35(10): 109567
doi: 10.1016/j.cclet.2024.109567
Abstract:
Silicon-based anodes including Si, SiOx and SiO2 could deliver ultra-large capacities, but degrade fast owing to huge volume change and low conductivity. Generally, large amounts of elastic binder and conductive additives were composited with nanosized silicon-based materials to yield reasonable cycling stability, which nevertheless not only decrease specific capacity but also induce inhomogeneous lithiation/delithiation as well as uneven stress variations. Artificial nanolattice has exhibited superior mechanical properties which could be ideal structure for silicon-based anodes, but yet faces challenges in integration of chemical reactivity, conductivity and mechanical stability. Herein, we fabricate artificial SiO2 honeycomb nanolattice consisting of numerous nanoscale SiO2 cells interconnected by through-holes, and conformal coating of highly graphitic carbon on the nanolattice is achieved through in situ catalytic graphitization. Moreover, the nanolattice is firmly bonded on Cu substrate through atomic interdiffusion irrespective of surface roughness. This unique structure allows fast charge transportation and homogeneous lithiation/delithiation throughout the micron-meter nanolattice, which results in excellent stability and large reversible capacity over 500 cycles at 1 A/g. The results highlight design and constructing artificial nanolattice can be an effective way to prevent chemo-mechanical degradation of silicon-based anode materials.
Silicon-based anodes including Si, SiOx and SiO2 could deliver ultra-large capacities, but degrade fast owing to huge volume change and low conductivity. Generally, large amounts of elastic binder and conductive additives were composited with nanosized silicon-based materials to yield reasonable cycling stability, which nevertheless not only decrease specific capacity but also induce inhomogeneous lithiation/delithiation as well as uneven stress variations. Artificial nanolattice has exhibited superior mechanical properties which could be ideal structure for silicon-based anodes, but yet faces challenges in integration of chemical reactivity, conductivity and mechanical stability. Herein, we fabricate artificial SiO2 honeycomb nanolattice consisting of numerous nanoscale SiO2 cells interconnected by through-holes, and conformal coating of highly graphitic carbon on the nanolattice is achieved through in situ catalytic graphitization. Moreover, the nanolattice is firmly bonded on Cu substrate through atomic interdiffusion irrespective of surface roughness. This unique structure allows fast charge transportation and homogeneous lithiation/delithiation throughout the micron-meter nanolattice, which results in excellent stability and large reversible capacity over 500 cycles at 1 A/g. The results highlight design and constructing artificial nanolattice can be an effective way to prevent chemo-mechanical degradation of silicon-based anode materials.
2024, 35(10): 109571
doi: 10.1016/j.cclet.2024.109571
Abstract:
The topology of conjugated macrocycles had significant impacts on their photo-physical and photo-chemical properties. Herein, a series of π-conjugated macrocycles with diverse topology were synthesized via intramolecular McMurry coupling. Their chemical structure and macrocyclic topology were unambiguously confirmed via NMR, MALDI-TOF mass spectra, crystal analysis and scanning tunneling microscopy (STM). Depending on the structural topology and structural rigidity, these cyclic compounds display obviously distinctive emission behavior and photochemical reactions in the solution and in the solid state. Monocyclic phenylene vinylene macrocycle (denoted as MST) exhibiting aggregation-induced emission behavior, was more vulnerable to photo-cyclization in solution and triplet sensitizer promoted photo-dimerization due to lower strain and more flourishing intramolecular motions. After UV light irradiation, relatively more flexible MST could yield the anti-dimer via triplet excimer on the HOPG surface confirmed by STM investigation. By contrast, highly constrained bicyclic analogue (named as DMTPE) with central tetraphenylethene core, displayed high emission quantum yields of 68% both in solution and in the solid state, and was relatively inert to photochemical reactions and yield syn-dimer on the surface via singlet excimer involved [2 + 2] photo-dimerization. Based on the solution-mediated photo-polymerization of MST moiety, multicyclic porous carbon-rich ribbon connected with four-membered ring was successfully constructed and validated via STM imaging.
The topology of conjugated macrocycles had significant impacts on their photo-physical and photo-chemical properties. Herein, a series of π-conjugated macrocycles with diverse topology were synthesized via intramolecular McMurry coupling. Their chemical structure and macrocyclic topology were unambiguously confirmed via NMR, MALDI-TOF mass spectra, crystal analysis and scanning tunneling microscopy (STM). Depending on the structural topology and structural rigidity, these cyclic compounds display obviously distinctive emission behavior and photochemical reactions in the solution and in the solid state. Monocyclic phenylene vinylene macrocycle (denoted as MST) exhibiting aggregation-induced emission behavior, was more vulnerable to photo-cyclization in solution and triplet sensitizer promoted photo-dimerization due to lower strain and more flourishing intramolecular motions. After UV light irradiation, relatively more flexible MST could yield the anti-dimer via triplet excimer on the HOPG surface confirmed by STM investigation. By contrast, highly constrained bicyclic analogue (named as DMTPE) with central tetraphenylethene core, displayed high emission quantum yields of 68% both in solution and in the solid state, and was relatively inert to photochemical reactions and yield syn-dimer on the surface via singlet excimer involved [2 + 2] photo-dimerization. Based on the solution-mediated photo-polymerization of MST moiety, multicyclic porous carbon-rich ribbon connected with four-membered ring was successfully constructed and validated via STM imaging.
2024, 35(10): 109572
doi: 10.1016/j.cclet.2024.109572
Abstract:
Epilepsy, as a chronic neurological disease of the brain, is closely related to oxidative stress, and the peroxynitrite (ONOO−) significantly rise up in this event. Therefore, ONOO− is considered as a potential biomarker for early prediction of epilepsy. However, some potential diagnostic reagents for epilepsy are hindered by the blood-brain barrier (BBB). Meanwhile, “drug repurposing” is attracting a growing interest. Edaravone (EDA), as a first-line drug in the clinical treatment of cerebral ischemia, plays antioxidant roles in scavenging free radicals, promising potential antiepileptic activity. Thus, it is imperative to develop fluorescent probes for monitoring ONOO− fluctuations in the epileptic brain. Hence, we proposed a novel fluorescent probe with the thiocarbonate as the promising recognition unit for ONOO− and dicyanoisophorone derivative as the fluorophore. Moreover, by the “three-in-one” strategy, the introduction of trifluoromethyl into DCI-ONOO-3 can extend the emission wavelength of the fluorophore, shorten the response and increase lipophilicity. Consequently, DCI-ONOO-3 was used for monitoring ONOO− fluxes in brain of epileptic mice and evaluating the antiepileptic efficacy of EDA. It opens up a new way for the design of BBB permeable fluorescent probes, and provides a convincing new method for the diagnosis and treatment of epilepsy.
Epilepsy, as a chronic neurological disease of the brain, is closely related to oxidative stress, and the peroxynitrite (ONOO−) significantly rise up in this event. Therefore, ONOO− is considered as a potential biomarker for early prediction of epilepsy. However, some potential diagnostic reagents for epilepsy are hindered by the blood-brain barrier (BBB). Meanwhile, “drug repurposing” is attracting a growing interest. Edaravone (EDA), as a first-line drug in the clinical treatment of cerebral ischemia, plays antioxidant roles in scavenging free radicals, promising potential antiepileptic activity. Thus, it is imperative to develop fluorescent probes for monitoring ONOO− fluctuations in the epileptic brain. Hence, we proposed a novel fluorescent probe with the thiocarbonate as the promising recognition unit for ONOO− and dicyanoisophorone derivative as the fluorophore. Moreover, by the “three-in-one” strategy, the introduction of trifluoromethyl into DCI-ONOO-3 can extend the emission wavelength of the fluorophore, shorten the response and increase lipophilicity. Consequently, DCI-ONOO-3 was used for monitoring ONOO− fluxes in brain of epileptic mice and evaluating the antiepileptic efficacy of EDA. It opens up a new way for the design of BBB permeable fluorescent probes, and provides a convincing new method for the diagnosis and treatment of epilepsy.
2024, 35(10): 109575
doi: 10.1016/j.cclet.2024.109575
Abstract:
Trifluoroacetic acid (TFA) catalyzed condensation reaction between tetraaminooxacalix[4]arene and N-alkylcarbazole-3,6-dicarbaldehyde in CH2Cl2 afforded a single product in 87%–89% yield. Well-defined yet undissolvable 1H NMR spectra suggested formation of robust and discrete structures in solution. X-ray single crystal analysis further revealed a giant twisted double-layer chiral macrocycle in the solid state, which was formed from [4 + 8] condensation of the two reactants via 16 imine bonds. DFT calculations discovered that only the [4 + 8] twisted product is thermodynamically favorable, which accounts for its highly selective and efficient formation out of a library of many other combinations.
Trifluoroacetic acid (TFA) catalyzed condensation reaction between tetraaminooxacalix[4]arene and N-alkylcarbazole-3,6-dicarbaldehyde in CH2Cl2 afforded a single product in 87%–89% yield. Well-defined yet undissolvable 1H NMR spectra suggested formation of robust and discrete structures in solution. X-ray single crystal analysis further revealed a giant twisted double-layer chiral macrocycle in the solid state, which was formed from [4 + 8] condensation of the two reactants via 16 imine bonds. DFT calculations discovered that only the [4 + 8] twisted product is thermodynamically favorable, which accounts for its highly selective and efficient formation out of a library of many other combinations.
2024, 35(10): 109581
doi: 10.1016/j.cclet.2024.109581
Abstract:
Post-synthetic modifications (PSM) have drawn great attention as a vigoroso tool to tune or enhance the performance of metal-organic frameworks (MOFs). However, the current PSM method usually have to sacrifice the porosity of MOFs to enrich their functionality, such as pore space partition (PSP) and post-synthetic elimination and insertion (PSE&I), causing a trade-off in this aspect. To address this issue, we herein propose a new PSM strategy of using the size-matching ligands as the bolts to lock MOFs’ pores, which could be anchored onto open metal sites (OMSs) after guest loading through a stepwise manipulation. As a result, the loaded cargoes undergo a controlled releasing process with respect to different bolt ligands. Our proposed strategy provides a promising way to balance the functionality and porosity of MOFs.
Post-synthetic modifications (PSM) have drawn great attention as a vigoroso tool to tune or enhance the performance of metal-organic frameworks (MOFs). However, the current PSM method usually have to sacrifice the porosity of MOFs to enrich their functionality, such as pore space partition (PSP) and post-synthetic elimination and insertion (PSE&I), causing a trade-off in this aspect. To address this issue, we herein propose a new PSM strategy of using the size-matching ligands as the bolts to lock MOFs’ pores, which could be anchored onto open metal sites (OMSs) after guest loading through a stepwise manipulation. As a result, the loaded cargoes undergo a controlled releasing process with respect to different bolt ligands. Our proposed strategy provides a promising way to balance the functionality and porosity of MOFs.
2024, 35(10): 109582
doi: 10.1016/j.cclet.2024.109582
Abstract:
The first example of metal Sn-fused perylene diimides (PDI) derivative (Sn-PDI) was designed, synthesized, and investigated. To obtain this type compound, a simple one-pot synthesis, named stannylative cycloaddition reaction, has been successfully developed via a palladium-based catalyst system. The novel mechanism exhibits that the reaction experiences oxidative addition, Pd-cyclization, stannylation, Pd-Sn-cyclization, and reductive elimination processes successively. This stannylative cycloaddition does realize unique σ-π hyperconjugation effect and therefore significantly influencing on the photophysical, electrochemical and excited state properties. Compared with those of PDI, both of the absorption and fluorescence spectra of Sn-PDI display large red-shifts over 20 nm. The electron energy levels of Sn-PDI have changed with an uncommon regulation. And Sn-PDI gives a considerably raised highest occupied molecular orbital (HOMO) level of -6.00 eV More importantly, the singlet excitons of Sn-PDI could efficiently intersystem cross (ISC) into triplet state with a long lifetime of 17.8 µs, which is far longer than that (4.4 ns) of PDI.
The first example of metal Sn-fused perylene diimides (PDI) derivative (Sn-PDI) was designed, synthesized, and investigated. To obtain this type compound, a simple one-pot synthesis, named stannylative cycloaddition reaction, has been successfully developed via a palladium-based catalyst system. The novel mechanism exhibits that the reaction experiences oxidative addition, Pd-cyclization, stannylation, Pd-Sn-cyclization, and reductive elimination processes successively. This stannylative cycloaddition does realize unique σ-π hyperconjugation effect and therefore significantly influencing on the photophysical, electrochemical and excited state properties. Compared with those of PDI, both of the absorption and fluorescence spectra of Sn-PDI display large red-shifts over 20 nm. The electron energy levels of Sn-PDI have changed with an uncommon regulation. And Sn-PDI gives a considerably raised highest occupied molecular orbital (HOMO) level of -6.00 eV More importantly, the singlet excitons of Sn-PDI could efficiently intersystem cross (ISC) into triplet state with a long lifetime of 17.8 µs, which is far longer than that (4.4 ns) of PDI.
2024, 35(10): 109583
doi: 10.1016/j.cclet.2024.109583
Abstract:
Activated pancreatic stellate cells (PSCs) are the main source of collagen layer deposition and the key target in pancreatic fibrosis. However, no effective treatment specific to pancreatic fibrosis clinically, owing to the drug accumulation blocked by the collagen barrier and thus it is difficult to inhibit activated PSCs precisely. Herein, a PSCs-targeting nano-system based on “nanodrill” strategy (LA-PC) was designed to enhance the accumulation of all-trans retinoic acid (ATRA) in PSCs, relying on the platelet-derived growth factor receptor beta (PDGFRβ)-targeting peptide (pPB: C*SRNLIDC*) and collagenase (Col). After being injected into fibrotic mice via tail vein, the Col modified on LA-PC can remove the excess collagen layer, and the drug delivery efficiency through pPB targeting peptide was more than 5 times higher than that of free ATRA, as well as the degree of fibrosis significantly reduced. Notably, this nano-system effectively inhibited platelet-derived growth factor subunit B (PDGF-BB)/PDGFRβ axis on PSCs via a down-regulated extracellular signal-regulated protein kinase (ERK) pathway, and accordingly reduced the level of PDGF-BB. Thus, the smart platform provided a promising strategy for the treatment of pancreatic fibrosis to achieve the precise regulation of PSCs.
Activated pancreatic stellate cells (PSCs) are the main source of collagen layer deposition and the key target in pancreatic fibrosis. However, no effective treatment specific to pancreatic fibrosis clinically, owing to the drug accumulation blocked by the collagen barrier and thus it is difficult to inhibit activated PSCs precisely. Herein, a PSCs-targeting nano-system based on “nanodrill” strategy (LA-PC) was designed to enhance the accumulation of all-trans retinoic acid (ATRA) in PSCs, relying on the platelet-derived growth factor receptor beta (PDGFRβ)-targeting peptide (pPB: C*SRNLIDC*) and collagenase (Col). After being injected into fibrotic mice via tail vein, the Col modified on LA-PC can remove the excess collagen layer, and the drug delivery efficiency through pPB targeting peptide was more than 5 times higher than that of free ATRA, as well as the degree of fibrosis significantly reduced. Notably, this nano-system effectively inhibited platelet-derived growth factor subunit B (PDGF-BB)/PDGFRβ axis on PSCs via a down-regulated extracellular signal-regulated protein kinase (ERK) pathway, and accordingly reduced the level of PDGF-BB. Thus, the smart platform provided a promising strategy for the treatment of pancreatic fibrosis to achieve the precise regulation of PSCs.
2024, 35(10): 109599
doi: 10.1016/j.cclet.2024.109599
Abstract:
Tetracycline (TC) as a typical emerging pollutant is becoming a serious threat to the environment and human health. A combined advanced oxidation technology of UV/Ozone (O3)/peroxydisulfate (PDS) process was developed to explore an efficient and economic treatment process of TC in wastewater. Furthermore, the reactive sites and transformation pathways of TC were explored and the toxicity of the intermediates was quantified with a quantitative structure-activity relationship (QSAR) assessment. The degradation performance of TC was substantially enhanced in UV/O3/PDS process with a kobs of 0.0949 min−1, which was 2.3 times higher than UV/O3 and 3.2 times than sole UV. The results demonstrated that there was a superior synergistic effect of PDS on UV/O3 processes for the degradation of TC. Electron paramagnetic resonance (EPR) analysis and quenching experiments show that •OH, SO4•−, O2•− and 1O2 all contributed to TC degradation in the UV/O3/PDS process and exhibited a synergistic effect, which inhibited the generation of harmful products. In addition, the UV/O3/PDS system can effectively degrade TC in a wide range of substrate concentrations and pH, and also showed excellent adaptability to various concentrations of anions (Cl− and HCO3−). This study proves the feasibility of UV/O3/PDS process for treating TC contaminated wastewater with complicated water matrix.
Tetracycline (TC) as a typical emerging pollutant is becoming a serious threat to the environment and human health. A combined advanced oxidation technology of UV/Ozone (O3)/peroxydisulfate (PDS) process was developed to explore an efficient and economic treatment process of TC in wastewater. Furthermore, the reactive sites and transformation pathways of TC were explored and the toxicity of the intermediates was quantified with a quantitative structure-activity relationship (QSAR) assessment. The degradation performance of TC was substantially enhanced in UV/O3/PDS process with a kobs of 0.0949 min−1, which was 2.3 times higher than UV/O3 and 3.2 times than sole UV. The results demonstrated that there was a superior synergistic effect of PDS on UV/O3 processes for the degradation of TC. Electron paramagnetic resonance (EPR) analysis and quenching experiments show that •OH, SO4•−, O2•− and 1O2 all contributed to TC degradation in the UV/O3/PDS process and exhibited a synergistic effect, which inhibited the generation of harmful products. In addition, the UV/O3/PDS system can effectively degrade TC in a wide range of substrate concentrations and pH, and also showed excellent adaptability to various concentrations of anions (Cl− and HCO3−). This study proves the feasibility of UV/O3/PDS process for treating TC contaminated wastewater with complicated water matrix.
2024, 35(10): 109618
doi: 10.1016/j.cclet.2024.109618
Abstract:
The existence of adsorbed water and structural water in the crystal structure of attapulgite (ATP) endows it with poor capability to store lithium ions. Herein, the chloride molten salt method was developed to function ATP materials based on theoretical calculations, which exhibit ground-breaking electrochemical performance. After the modification process, the metal ions in chloride molten salt occupy the vertices of the Mg-O octahedral structure from the liberation of structural water and hydroxyl groups in ATP, forming MaMgbAlcSixOy (M = Li, Na, or K). Using LiCl molten salt-modified ATP (Li-ATP) as a proof-of-concept, the detailed phase transition, physicochemical properties, and lithium storage capacity were investigated. Compared to the original ATP, Li-ATP achieves a nearly 7-fold increase in lithium storage capacity (498 mAh/g), featuring a promising low-cost polyanionic type anode material.
The existence of adsorbed water and structural water in the crystal structure of attapulgite (ATP) endows it with poor capability to store lithium ions. Herein, the chloride molten salt method was developed to function ATP materials based on theoretical calculations, which exhibit ground-breaking electrochemical performance. After the modification process, the metal ions in chloride molten salt occupy the vertices of the Mg-O octahedral structure from the liberation of structural water and hydroxyl groups in ATP, forming MaMgbAlcSixOy (M = Li, Na, or K). Using LiCl molten salt-modified ATP (Li-ATP) as a proof-of-concept, the detailed phase transition, physicochemical properties, and lithium storage capacity were investigated. Compared to the original ATP, Li-ATP achieves a nearly 7-fold increase in lithium storage capacity (498 mAh/g), featuring a promising low-cost polyanionic type anode material.
2024, 35(10): 109625
doi: 10.1016/j.cclet.2024.109625
Abstract:
When zero-valent iron (ZVI) is prepared and applied under neutral conditions, it is easy to form oxides or hydroxides on its surface, which hinders the electron release of ZVI. To this end, a nucleophile was introduced into the ZVI system to inhibit the precipitation of iron ions, improve the conductivity of the solution, and promote the removal efficiency of electrophilic functional groups in organic compounds. In this study, the addition of nucleophiles such as ethylenediamine, methylamine and dimethylamine to the ZVI/H2O2 system resulted in an enhanced removal efficiency of tetracycline (TC) under neutral condition, while electrophiles such as EDTA-2Na and oxalic acid dihydrate impeded the removal of TC. Experimental results demonstrated that the presence of nucleophiles could effectively promote the release of iron ions and increase the proportion of ferrous in both aqueous solution and solid surface of ZVI. Experimental and theoretical calculation results revealed that the electrophilic functional group was eliminated in the TC molecule, and the toxicity of the treated solution was reduced significantly. Overall, this work provides a selection of the conditions and pollutants applicable to ZVI under neutral pH conditions.
When zero-valent iron (ZVI) is prepared and applied under neutral conditions, it is easy to form oxides or hydroxides on its surface, which hinders the electron release of ZVI. To this end, a nucleophile was introduced into the ZVI system to inhibit the precipitation of iron ions, improve the conductivity of the solution, and promote the removal efficiency of electrophilic functional groups in organic compounds. In this study, the addition of nucleophiles such as ethylenediamine, methylamine and dimethylamine to the ZVI/H2O2 system resulted in an enhanced removal efficiency of tetracycline (TC) under neutral condition, while electrophiles such as EDTA-2Na and oxalic acid dihydrate impeded the removal of TC. Experimental results demonstrated that the presence of nucleophiles could effectively promote the release of iron ions and increase the proportion of ferrous in both aqueous solution and solid surface of ZVI. Experimental and theoretical calculation results revealed that the electrophilic functional group was eliminated in the TC molecule, and the toxicity of the treated solution was reduced significantly. Overall, this work provides a selection of the conditions and pollutants applicable to ZVI under neutral pH conditions.
2024, 35(10): 109635
doi: 10.1016/j.cclet.2024.109635
Abstract:
A novel biodegradable material, Se@PLA, was designed and prepared via the selenization reaction of polylactic acid using NaHSe as the selenization reagent. This material shows excellent antibacterial activity (EC50 = 13.38 µg/mL) against Xanthomonas oryzae pv. Oryzae, which is a highly destructive pathogen responsible for rice bacterial blight. Se@PLA induces oxidative stress in bacteria, leading to the rupture of bacterial cell membranes and eventual death. Moreover, Se@PLA can significantly inhibit the motility of bacteria and is low toxic to soil and aquatic organisms. This work provides an effective method for preventing and controlling rice bacterial blight, and reveals the great potential of using Se@PLA as an alternative next generation plant bactericide.
A novel biodegradable material, Se@PLA, was designed and prepared via the selenization reaction of polylactic acid using NaHSe as the selenization reagent. This material shows excellent antibacterial activity (EC50 = 13.38 µg/mL) against Xanthomonas oryzae pv. Oryzae, which is a highly destructive pathogen responsible for rice bacterial blight. Se@PLA induces oxidative stress in bacteria, leading to the rupture of bacterial cell membranes and eventual death. Moreover, Se@PLA can significantly inhibit the motility of bacteria and is low toxic to soil and aquatic organisms. This work provides an effective method for preventing and controlling rice bacterial blight, and reveals the great potential of using Se@PLA as an alternative next generation plant bactericide.
2024, 35(10): 109645
doi: 10.1016/j.cclet.2024.109645
Abstract:
In recent years, multicolor cascade supramolecular assemblies with controllable topological morphology have become a research hotspot due to their wide application in light-emitting materials, cell imaging and other fields. Herein, several kinds of macrocycles including cucurbiturils, calixarene and cyclodextrins are used as building blocks to construct fluorescent assemblies with anthryl-conjugated phenylpyridine (G), wherein cucurbit[8]uril (CB[8]) and G can form nanowires at a stoichiometric ratio of n: n through host-guest encapsulation to form a non-covalent heterodimer. Significantly, the macrocycle confinement effect drastically enhances the fluorescence emission of G and emission peak generated bathochromic shift from 500 nm to 600 nm. When the supramolecular polymer is further assembled with amphiphilic calix[4]arene (SC4A8), the fluorescence emission of G⊂CB[8] further increases to 1.4 times, accompanied by the morphological transformation from linear structure to nanorod structure. Subsequently, a very small amount of dye Cy5 is added to the assembly solution as an energy receptor, and the negatively charged G⊂CB[8]@SC4A8 system is regarded as an energy donor. The efficient energy transfer process enables near-infrared (NIR) emission at 675 nm with 71% energy transfer efficiency (ΦET) at a donor/receptor ratio of 100:1. Finally, the cascade supramolecular assembly has been successfully applied to targeted imaging in the nucleus of HeLa and A549 cancer cells.
In recent years, multicolor cascade supramolecular assemblies with controllable topological morphology have become a research hotspot due to their wide application in light-emitting materials, cell imaging and other fields. Herein, several kinds of macrocycles including cucurbiturils, calixarene and cyclodextrins are used as building blocks to construct fluorescent assemblies with anthryl-conjugated phenylpyridine (G), wherein cucurbit[8]uril (CB[8]) and G can form nanowires at a stoichiometric ratio of n: n through host-guest encapsulation to form a non-covalent heterodimer. Significantly, the macrocycle confinement effect drastically enhances the fluorescence emission of G and emission peak generated bathochromic shift from 500 nm to 600 nm. When the supramolecular polymer is further assembled with amphiphilic calix[4]arene (SC4A8), the fluorescence emission of G⊂CB[8] further increases to 1.4 times, accompanied by the morphological transformation from linear structure to nanorod structure. Subsequently, a very small amount of dye Cy5 is added to the assembly solution as an energy receptor, and the negatively charged G⊂CB[8]@SC4A8 system is regarded as an energy donor. The efficient energy transfer process enables near-infrared (NIR) emission at 675 nm with 71% energy transfer efficiency (ΦET) at a donor/receptor ratio of 100:1. Finally, the cascade supramolecular assembly has been successfully applied to targeted imaging in the nucleus of HeLa and A549 cancer cells.
2024, 35(10): 109648
doi: 10.1016/j.cclet.2024.109648
Abstract:
Sequential C-H bond addition with two different coupling partners is a powerful method for the rapid and modular construction of complex molecules based on simple starting materials. Herein, an efficient ruthenium-catalysed multicomponent long-range C-H functionalization of 2H-imidazoles was developed. This protocol showed good substrate suitability and yielded alkyl arylation products with potential biological activity.
Sequential C-H bond addition with two different coupling partners is a powerful method for the rapid and modular construction of complex molecules based on simple starting materials. Herein, an efficient ruthenium-catalysed multicomponent long-range C-H functionalization of 2H-imidazoles was developed. This protocol showed good substrate suitability and yielded alkyl arylation products with potential biological activity.
2024, 35(10): 109652
doi: 10.1016/j.cclet.2024.109652
Abstract:
The adsorption of peroxymonosulfate (PMS) is crucial for PMS activation in the heterogeneous advanced oxidation processes. However, the investigation of PMS adsorption on the piezocatalysts still remains insufficient. In this work, bismuth oxychloride (BiOCl) nanosheets were prepared as the piezocatalysts for PMS activation under ultrasonic vibration to remove carbamazepine (CBZ) in aqueous solutions. Up to 92.5% of CBZ was degraded for 40 min in BiOCl piezo-activated PMS system with the reaction rate constant of 0.0741 min−1, being 1.63 times that of the sum of BiOCl piezocatalysis, BiOCl-activated PMS, and vibration-activated PMS. PMS adsorption on the surface of BiOCl was specifically studied by comparing the microscopic structure change of the fresh and used BiOCl. The results suggested that the piezoelectric field of BiOCl was able to promote the tight adsorption of PMS on the surface, thus facilitating the fast activation of PMS through electrons transfer to produce reactive species (HO•, SO4•−, O2•−, 1O2). This work presents an in-depth understanding for the role of piezoelectric effect on the adsorption and activation of PMS.
The adsorption of peroxymonosulfate (PMS) is crucial for PMS activation in the heterogeneous advanced oxidation processes. However, the investigation of PMS adsorption on the piezocatalysts still remains insufficient. In this work, bismuth oxychloride (BiOCl) nanosheets were prepared as the piezocatalysts for PMS activation under ultrasonic vibration to remove carbamazepine (CBZ) in aqueous solutions. Up to 92.5% of CBZ was degraded for 40 min in BiOCl piezo-activated PMS system with the reaction rate constant of 0.0741 min−1, being 1.63 times that of the sum of BiOCl piezocatalysis, BiOCl-activated PMS, and vibration-activated PMS. PMS adsorption on the surface of BiOCl was specifically studied by comparing the microscopic structure change of the fresh and used BiOCl. The results suggested that the piezoelectric field of BiOCl was able to promote the tight adsorption of PMS on the surface, thus facilitating the fast activation of PMS through electrons transfer to produce reactive species (HO•, SO4•−, O2•−, 1O2). This work presents an in-depth understanding for the role of piezoelectric effect on the adsorption and activation of PMS.
2024, 35(10): 109792
doi: 10.1016/j.cclet.2024.109792
Abstract:
GPCRs are dominant targets for approved drugs and the discovery of lead compound targeting them is still challengeable. Affinity-based screening technique is a promising platform to uncover GPCR ligands. However, the intrinsic activities of them are seldom simultaneously determined during the screening. Taking beta2-adrenoceptor (β2AR) as a probe, this work created a strategy for screening GPCR ligands with simultaneous characterization of their downstream G protein binding responses associated with GTP. The strategy included (ⅰ) the design and expression of a protein miniature formed by β2AR and G protein α-subunit (Gαs) using circularly permuted HaloTag (cpHalo) as a flexible linker; (ⅱ) immobilization of the miniature onto silica gel by a click dehalogenation reaction; (ⅲ) systematic characterization of the immobilized miniature by fluorescent and chromatographic studies, and (ⅳ) simulating of ligand-induced β2AR-Gαs signaling cascade by chromatographic assays using GTP as an indicator. The immobilized miniature exhibited specificity to β2AR and Gαs antibodies and ligands. The specificity is stable at least within fifteen days with the variation less than 1%. The intrinsic activities of β2AR ligands were distinguished by the changes of GTP chromatographic behaviors on Gαs-cpHalo-β2AR column. Agonists strengthened the binding affinity and kinetics of GTP with Gαs, while antagonist did not give any effect on them. With the intrinsic activity evaluation, we believe, it will improve the attributes of chromatographic methods for drug discovery efforts with minimizing false-positive results.
GPCRs are dominant targets for approved drugs and the discovery of lead compound targeting them is still challengeable. Affinity-based screening technique is a promising platform to uncover GPCR ligands. However, the intrinsic activities of them are seldom simultaneously determined during the screening. Taking beta2-adrenoceptor (β2AR) as a probe, this work created a strategy for screening GPCR ligands with simultaneous characterization of their downstream G protein binding responses associated with GTP. The strategy included (ⅰ) the design and expression of a protein miniature formed by β2AR and G protein α-subunit (Gαs) using circularly permuted HaloTag (cpHalo) as a flexible linker; (ⅱ) immobilization of the miniature onto silica gel by a click dehalogenation reaction; (ⅲ) systematic characterization of the immobilized miniature by fluorescent and chromatographic studies, and (ⅳ) simulating of ligand-induced β2AR-Gαs signaling cascade by chromatographic assays using GTP as an indicator. The immobilized miniature exhibited specificity to β2AR and Gαs antibodies and ligands. The specificity is stable at least within fifteen days with the variation less than 1%. The intrinsic activities of β2AR ligands were distinguished by the changes of GTP chromatographic behaviors on Gαs-cpHalo-β2AR column. Agonists strengthened the binding affinity and kinetics of GTP with Gαs, while antagonist did not give any effect on them. With the intrinsic activity evaluation, we believe, it will improve the attributes of chromatographic methods for drug discovery efforts with minimizing false-positive results.
2024, 35(10): 109805
doi: 10.1016/j.cclet.2024.109805
Abstract:
Directed self-assembly has been used to create micro-nano scale patterns, including chiral periodic structures of organic molecules, for potential applications in optics, photonics, metamaterials, and medical and sensing technologies. This study presents a straightforward approach for fabricating large-scale chiral grating porphyrin assemblies through template-assisted techniques. The solution of tetrakis(4-sulfonatophenyl)porphyrin (TPPS) was induced by chiral amino acids (L/D-arginine and L/D-serine) to self-assemble into highly ordered chiral grating structures with the assistance of sodium dodecyl sulfate (SDS). The structures show precise line widths (5.5 µm) and gaps (18 µm). Using in situ optical microscopy and second harmonic generation (SHG) microscopy, the chiral characteristics and dynamic evolution of the template-assisted self-assembly are investigated. It is found that the chirality of amino acids induced TPPS self-assembled into chiral structures and the liquid contraction interface significantly enhanced the chirality of the assemblies. This study is significant for understanding the mechanism of chiral evolution and designing novel micro-nano materials with predetermined chiral properties.
Directed self-assembly has been used to create micro-nano scale patterns, including chiral periodic structures of organic molecules, for potential applications in optics, photonics, metamaterials, and medical and sensing technologies. This study presents a straightforward approach for fabricating large-scale chiral grating porphyrin assemblies through template-assisted techniques. The solution of tetrakis(4-sulfonatophenyl)porphyrin (TPPS) was induced by chiral amino acids (L/D-arginine and L/D-serine) to self-assemble into highly ordered chiral grating structures with the assistance of sodium dodecyl sulfate (SDS). The structures show precise line widths (5.5 µm) and gaps (18 µm). Using in situ optical microscopy and second harmonic generation (SHG) microscopy, the chiral characteristics and dynamic evolution of the template-assisted self-assembly are investigated. It is found that the chirality of amino acids induced TPPS self-assembled into chiral structures and the liquid contraction interface significantly enhanced the chirality of the assemblies. This study is significant for understanding the mechanism of chiral evolution and designing novel micro-nano materials with predetermined chiral properties.
2024, 35(10): 109808
doi: 10.1016/j.cclet.2024.109808
Abstract:
Charge-transfer (CT) stoichiometric cocrystals are promising choice of organic materials for unveiling the structure-property relationship. However, due to the contradiction between large CT degree required for strong NIR absorption and flexible molecular stacking, construction of stoichiomorphism-based cocystals with near-infrared (NIR) photothermal property remains challenging. Herein, the first example of stoichiomorphism-based photothermal cocrystals were accomplished through the adaptive assembly of 3,3′,5,5′-tetramethylbenzidine (TMB) donor and 1,2,4,5-tetracyanobenzene (TCNB) acceptor. The selective cocrystallization could be controlled by varying the donor-acceptor stoichiometries via a surfactant-assisted method, resulting in two cocrystals with 1:1 (T1C1) and 1:2 (T2C1) stoichiometries. The absorbance intensity of T1C1 at 808 nm was nearly twice that of T2C1, while the photothermal conversion efficiency (PCE) of the former was 60.3% ± 0.6%, approximately 80% of that for the latter (75.5% ± 2.6%), which might be caused by the different intermolecular interactions in distinct molecular stacking patterns. Notably, both excellent PCEs of stoichiometric cocrystals were attributed to the nonradiative transition process, including internal conversion and charge dissociation processes, as elucidated by femtosecond transient absorption spectroscopy measurements. Furthermore, T1C1 was used as an NIR heater for preparing agarose-based photothermal hydrogel, showing great potential for light-controlled in-situ gelation. This strategy of balancing the CT degree and molecular packing orientation not only uncovered the relationship between stoichiometric stacking and photothermal property, but also provided an opportunity to develop advanced organic optoelectronic materials.
Charge-transfer (CT) stoichiometric cocrystals are promising choice of organic materials for unveiling the structure-property relationship. However, due to the contradiction between large CT degree required for strong NIR absorption and flexible molecular stacking, construction of stoichiomorphism-based cocystals with near-infrared (NIR) photothermal property remains challenging. Herein, the first example of stoichiomorphism-based photothermal cocrystals were accomplished through the adaptive assembly of 3,3′,5,5′-tetramethylbenzidine (TMB) donor and 1,2,4,5-tetracyanobenzene (TCNB) acceptor. The selective cocrystallization could be controlled by varying the donor-acceptor stoichiometries via a surfactant-assisted method, resulting in two cocrystals with 1:1 (T1C1) and 1:2 (T2C1) stoichiometries. The absorbance intensity of T1C1 at 808 nm was nearly twice that of T2C1, while the photothermal conversion efficiency (PCE) of the former was 60.3% ± 0.6%, approximately 80% of that for the latter (75.5% ± 2.6%), which might be caused by the different intermolecular interactions in distinct molecular stacking patterns. Notably, both excellent PCEs of stoichiometric cocrystals were attributed to the nonradiative transition process, including internal conversion and charge dissociation processes, as elucidated by femtosecond transient absorption spectroscopy measurements. Furthermore, T1C1 was used as an NIR heater for preparing agarose-based photothermal hydrogel, showing great potential for light-controlled in-situ gelation. This strategy of balancing the CT degree and molecular packing orientation not only uncovered the relationship between stoichiometric stacking and photothermal property, but also provided an opportunity to develop advanced organic optoelectronic materials.
2024, 35(10): 109809
doi: 10.1016/j.cclet.2024.109809
Abstract:
Deep-blue emitter with high photoluminescence efficiency (PLQY) is highly desirable in ultra-high definition displays and white solid-state lightings. In this work, two deep-blue phenanthro[9,10]imidazole derivatives, PPIS and PPPIS, with hot exciton property are successfully developed. Compared to PPIS, the embedded phenyl bridge in PPPIS is able to effectively increase the overlap of frontier molecular orbitals. In consequence, PPPIS shows higher oscillator strength and significantly enhanced PLQY. PPPIS also achieves better electroluminescence performance in non-doped device, showing deep-blue emission with Commission International de l'Eclairage (CIE) coordinates of (0.153, 0.087) and the maximum external quantum efficiency (EQEmax) of 8.5% with minuscule efficiency roll-off. Meanwhile, when PPPIS serves as the host for phosphor PO-01, high-efficiency orange phosphorescent device is obtained with high EQEmax of 29.8% and negligible efficiency roll-off at 1000 cd/m2. Further, efficient single-emissive-layer white device is assembled via utilizing PPPIS as a blue emitter as well as the host for PO-01 simultaneously, providing warm-white emission with CIE coordinates of (0.429, 0.433) at 1000 cd/m2, the forward-viewing EQEmax of 27.2% and maximum power efficiency (PEmax) of 80.1 lm/W, respectively. Our studies can establish a viable design strategy for deep-blue emitters in high-performance non-doped blue OLEDs and hybrid WOLEDs.
Deep-blue emitter with high photoluminescence efficiency (PLQY) is highly desirable in ultra-high definition displays and white solid-state lightings. In this work, two deep-blue phenanthro[9,10]imidazole derivatives, PPIS and PPPIS, with hot exciton property are successfully developed. Compared to PPIS, the embedded phenyl bridge in PPPIS is able to effectively increase the overlap of frontier molecular orbitals. In consequence, PPPIS shows higher oscillator strength and significantly enhanced PLQY. PPPIS also achieves better electroluminescence performance in non-doped device, showing deep-blue emission with Commission International de l'Eclairage (CIE) coordinates of (0.153, 0.087) and the maximum external quantum efficiency (EQEmax) of 8.5% with minuscule efficiency roll-off. Meanwhile, when PPPIS serves as the host for phosphor PO-01, high-efficiency orange phosphorescent device is obtained with high EQEmax of 29.8% and negligible efficiency roll-off at 1000 cd/m2. Further, efficient single-emissive-layer white device is assembled via utilizing PPPIS as a blue emitter as well as the host for PO-01 simultaneously, providing warm-white emission with CIE coordinates of (0.429, 0.433) at 1000 cd/m2, the forward-viewing EQEmax of 27.2% and maximum power efficiency (PEmax) of 80.1 lm/W, respectively. Our studies can establish a viable design strategy for deep-blue emitters in high-performance non-doped blue OLEDs and hybrid WOLEDs.
2024, 35(10): 109821
doi: 10.1016/j.cclet.2024.109821
Abstract:
It has been widely recognized that hole transporting materials (HTMs) play a key role in the rapid progress of perovskite solar cells (PVSCs). However, common organic HTMs such as spiro-OMeTAD not only suffer from high synthetic costs, but also usually require the additional chemical doping process to improve their hole transport ability, which unfortunately induces the terrible stability issue. Therefore, it is urgent to develop low-cost dopant-free HTMs for efficient and stable PVSCs. In this work, we have successfully developed a new class of efficient dopant-free fluoranthene-based HTMs (TPF1–5) with quite low lab synthetic costs by combining donor-acceptor and branched structure designs. The detailed structure-property study revealed that tuning the twisted arms at different substitution sites would regulate the intermolecular interactions and film-forming ability, thereby significantly affecting the performance of the HTMs. By applying these HTMs in conventional PVSCs, the dopant-free TPF1-based devices not only achieved the best efficiency of 21.76%, which is comparable to that of the doped spiro-OMeTAD control devices, but also showed much better operational stability, which maintained over 87% of the initial efficiency under maximum power point tracking after 1038 h.
It has been widely recognized that hole transporting materials (HTMs) play a key role in the rapid progress of perovskite solar cells (PVSCs). However, common organic HTMs such as spiro-OMeTAD not only suffer from high synthetic costs, but also usually require the additional chemical doping process to improve their hole transport ability, which unfortunately induces the terrible stability issue. Therefore, it is urgent to develop low-cost dopant-free HTMs for efficient and stable PVSCs. In this work, we have successfully developed a new class of efficient dopant-free fluoranthene-based HTMs (TPF1–5) with quite low lab synthetic costs by combining donor-acceptor and branched structure designs. The detailed structure-property study revealed that tuning the twisted arms at different substitution sites would regulate the intermolecular interactions and film-forming ability, thereby significantly affecting the performance of the HTMs. By applying these HTMs in conventional PVSCs, the dopant-free TPF1-based devices not only achieved the best efficiency of 21.76%, which is comparable to that of the doped spiro-OMeTAD control devices, but also showed much better operational stability, which maintained over 87% of the initial efficiency under maximum power point tracking after 1038 h.
2024, 35(10): 109838
doi: 10.1016/j.cclet.2024.109838
Abstract:
As a hydrolase, chymotrypsin (CHT) is involved in many physiological activities, and its abnormal activity is closely related to diabetes, pancreatic fibrosis, chronic pancreatitis and pancreatic cancer. In this work, an innovative long-wavelength emission fluorescent probe TCF-CHT was designed and synthesized for the high specificity detection of CHT, which utilized TCF-OH and a mimetic peptide substrate 4-bromobutyryl as chromogenic group and recognition group, respectively. TCF-CHT exhibited excellent selectivity and eye-catching sensitivity (8.91 ng/mL) towards CHT, "off-on" long-wavelength emission at 670 nm and large Stokes shift (140 nm). Furthermore, the successful fulfillment and perfect performance in imaging endogenous CHT in complex organisms (P815 cells, HepG2 cells, zebrafish and tumor-bearing mice) verified its potential as a powerful tool for the recognition of CHT in complicated biological environments.
As a hydrolase, chymotrypsin (CHT) is involved in many physiological activities, and its abnormal activity is closely related to diabetes, pancreatic fibrosis, chronic pancreatitis and pancreatic cancer. In this work, an innovative long-wavelength emission fluorescent probe TCF-CHT was designed and synthesized for the high specificity detection of CHT, which utilized TCF-OH and a mimetic peptide substrate 4-bromobutyryl as chromogenic group and recognition group, respectively. TCF-CHT exhibited excellent selectivity and eye-catching sensitivity (8.91 ng/mL) towards CHT, "off-on" long-wavelength emission at 670 nm and large Stokes shift (140 nm). Furthermore, the successful fulfillment and perfect performance in imaging endogenous CHT in complex organisms (P815 cells, HepG2 cells, zebrafish and tumor-bearing mice) verified its potential as a powerful tool for the recognition of CHT in complicated biological environments.
2024, 35(10): 109862
doi: 10.1016/j.cclet.2024.109862
Abstract:
A novel and readily available binaphthyl-based fluorescent probe (S)-1 was designed and synthesized. (S)-1 can be used to not only chemoselectively discriminate 3 basic amino acids out of common amino acids, but also enantioselectively recognize histidine. Encouragingly, enantioselective imaging of histidine in cells was achieved for the first time by the probe (S)-1. These performances endowed it potential application in the chiral analysis of basic amino acids in asymmetric synthesis and cell imaging for diagnosis of diseases caused by racemization of histidine. Nuclear magnetic resonance (NMR) and mass spectrometry investigations suggested that different reaction extent of (S)-1 with l/d-histidine and different product structures generated the observed enantioselective fluorescent response. The molecular structures and thermodynamic stability of the complexes, formed from (S)-1 + Zn2+ and enantiomers of histidine, were calculated by Gaussian 16 based on density functional theory (DFT) to validate the above action mechanism.
A novel and readily available binaphthyl-based fluorescent probe (S)-1 was designed and synthesized. (S)-1 can be used to not only chemoselectively discriminate 3 basic amino acids out of common amino acids, but also enantioselectively recognize histidine. Encouragingly, enantioselective imaging of histidine in cells was achieved for the first time by the probe (S)-1. These performances endowed it potential application in the chiral analysis of basic amino acids in asymmetric synthesis and cell imaging for diagnosis of diseases caused by racemization of histidine. Nuclear magnetic resonance (NMR) and mass spectrometry investigations suggested that different reaction extent of (S)-1 with l/d-histidine and different product structures generated the observed enantioselective fluorescent response. The molecular structures and thermodynamic stability of the complexes, formed from (S)-1 + Zn2+ and enantiomers of histidine, were calculated by Gaussian 16 based on density functional theory (DFT) to validate the above action mechanism.
2024, 35(10): 109863
doi: 10.1016/j.cclet.2024.109863
Abstract:
The development of efficient and stable bifunctional overall water-splitting is a crucial goal for clean and renewable energy, which is a challenging task. Herein, we report an Mn-incorporated RuO2 (Mn-RuO2) catalyst for highly efficient electrocatalytic oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in acid and alkaline media. Benefiting from a more electrochemical active area with the incorporation of Mn, the Mn-RuO2 required an overpotential of 200 mV to attain a current density of 10 mA/cm2 for OER in acid. DFT result indicates that the doping of Mn into RuO2 can enhance the OER activity. An acidic overall water-splitting electrolyzer with good stability constructed by bifunctional Mn-RuO2 only requires a cell voltage of 1.50 V to afford 10 mA/cm2 and can operate stably for 50 h at 50 mA/cm2, which is better than the state-of-the-art Ru-based catalyst. Additionally, the Mn-RuO2 exhibits excellent HER and OER activity in alkaline media, and it shows superior activity and durability for overall water-splitting, only needing a cell voltage of 1.49 V to attain 10 mA/cm2. The present work provides an efficient approach to designing and constructing efficient Ru-based electrocatalysts for overall water-splitting.
The development of efficient and stable bifunctional overall water-splitting is a crucial goal for clean and renewable energy, which is a challenging task. Herein, we report an Mn-incorporated RuO2 (Mn-RuO2) catalyst for highly efficient electrocatalytic oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in acid and alkaline media. Benefiting from a more electrochemical active area with the incorporation of Mn, the Mn-RuO2 required an overpotential of 200 mV to attain a current density of 10 mA/cm2 for OER in acid. DFT result indicates that the doping of Mn into RuO2 can enhance the OER activity. An acidic overall water-splitting electrolyzer with good stability constructed by bifunctional Mn-RuO2 only requires a cell voltage of 1.50 V to afford 10 mA/cm2 and can operate stably for 50 h at 50 mA/cm2, which is better than the state-of-the-art Ru-based catalyst. Additionally, the Mn-RuO2 exhibits excellent HER and OER activity in alkaline media, and it shows superior activity and durability for overall water-splitting, only needing a cell voltage of 1.49 V to attain 10 mA/cm2. The present work provides an efficient approach to designing and constructing efficient Ru-based electrocatalysts for overall water-splitting.
2024, 35(10): 110038
doi: 10.1016/j.cclet.2024.110038
Abstract:
The first example of sono-photocatalytic bond formation was reported. With both visible light and ultrasound wave as the energy, various 3-aminoquinoxalin-2(1H)-ones were efficiently obtained with good functional group tolerance in the absence of any additive or external photocatalyst. Compared with the conventional photocatalysis, sono-photocatalysis not only dramatically improved the reaction rates and yields, but also reduced energy consumption.
The first example of sono-photocatalytic bond formation was reported. With both visible light and ultrasound wave as the energy, various 3-aminoquinoxalin-2(1H)-ones were efficiently obtained with good functional group tolerance in the absence of any additive or external photocatalyst. Compared with the conventional photocatalysis, sono-photocatalysis not only dramatically improved the reaction rates and yields, but also reduced energy consumption.
2024, 35(10): 109347
doi: 10.1016/j.cclet.2023.109347
Abstract:
Polymeric carbon nitride (PCN) has garnered increasing attention as a metal-free photocatalyst with a suitable band gap. In efforts to enhance its photocatalytic performance, researchers have examined various PCN materials, including poly(heptazine imide) (PHI) and poly(triazine imide) (PTI), two isomers within the PCN family that exhibit distinct and superior photocatalytic activity compared to other forms. The challenge, however, lies in the common practice among researchers to categorize PHI and PTI along with other PCN types under the overarching term "g-C3N4, " which significantly impedes optimization efforts. The objective of this review is to provide comprehensive insights into the structural features, photoelectrochemical properties, and effective characterization methods employed for distinguishing between PHI and PTI materials. The review also summarizes various optimization strategies, such as crystallinity adjustments, defect engineering, morphology control, constructing heterojunction, and atomic-level metal loading dispersion, to elevate the photocatalytic activity of PHI and PTI, in addition to summarizing the history of carbon nitride development. Furthermore, this review highlights the primary applications of PHI and PTI, encompassing nitrogen fixation, biomass conversion, organic synthesis, CO2 reduction, pollutant degradation, H2O2 production, and photocatalytic water splitting. Lastly, the prospects and challenges associated with further advancing PHI and PTI are thoroughly examined.
Polymeric carbon nitride (PCN) has garnered increasing attention as a metal-free photocatalyst with a suitable band gap. In efforts to enhance its photocatalytic performance, researchers have examined various PCN materials, including poly(heptazine imide) (PHI) and poly(triazine imide) (PTI), two isomers within the PCN family that exhibit distinct and superior photocatalytic activity compared to other forms. The challenge, however, lies in the common practice among researchers to categorize PHI and PTI along with other PCN types under the overarching term "g-C3N4, " which significantly impedes optimization efforts. The objective of this review is to provide comprehensive insights into the structural features, photoelectrochemical properties, and effective characterization methods employed for distinguishing between PHI and PTI materials. The review also summarizes various optimization strategies, such as crystallinity adjustments, defect engineering, morphology control, constructing heterojunction, and atomic-level metal loading dispersion, to elevate the photocatalytic activity of PHI and PTI, in addition to summarizing the history of carbon nitride development. Furthermore, this review highlights the primary applications of PHI and PTI, encompassing nitrogen fixation, biomass conversion, organic synthesis, CO2 reduction, pollutant degradation, H2O2 production, and photocatalytic water splitting. Lastly, the prospects and challenges associated with further advancing PHI and PTI are thoroughly examined.
2024, 35(10): 109416
doi: 10.1016/j.cclet.2023.109416
Abstract:
Water splitting with proton exchange membrane water electrolyzers (PEMWE) is regarded as a promising pathway for sustainable hydrogen conversion. Additionally, oxygen evolution reaction (OER) is considered as the dominant factor during the whole process due to the sluggish kinetics. Among the catalysts, Ru-based catalysts draw special attention because of their excellent activity and relatively low price. However, the limited stability impedes their further commercialization and tremendous efforts have been devoted to overcome this challenge. This review firstly introduces the basic mechanisms of OER. Then the evaluation protocols and techniques to investigate the stability of Ru-based catalysts are summarized. A detailed elucidation of the possible degradation mechanisms is also critically analyzed. Furthermore, effective strategies to design durable Ru-based catalysts for acidic OER are discussed. Such as heteroatom doping, phase and facet engineering, heterostructure building and support optimization. Finally, promises, perspectives and challenges in developing highly durable Ru-based catalysts for acidic OER are outlined.
Water splitting with proton exchange membrane water electrolyzers (PEMWE) is regarded as a promising pathway for sustainable hydrogen conversion. Additionally, oxygen evolution reaction (OER) is considered as the dominant factor during the whole process due to the sluggish kinetics. Among the catalysts, Ru-based catalysts draw special attention because of their excellent activity and relatively low price. However, the limited stability impedes their further commercialization and tremendous efforts have been devoted to overcome this challenge. This review firstly introduces the basic mechanisms of OER. Then the evaluation protocols and techniques to investigate the stability of Ru-based catalysts are summarized. A detailed elucidation of the possible degradation mechanisms is also critically analyzed. Furthermore, effective strategies to design durable Ru-based catalysts for acidic OER are discussed. Such as heteroatom doping, phase and facet engineering, heterostructure building and support optimization. Finally, promises, perspectives and challenges in developing highly durable Ru-based catalysts for acidic OER are outlined.
2024, 35(10): 109420
doi: 10.1016/j.cclet.2023.109420
Abstract:
For a significant duration, enhancing the efficacy of cancer therapy has remained a critical concern. Magnetotactic bacteria (MTB), often likened to micro-robots, hold substantial promise as a drug delivery system. MTB, classified as anaerobic, aquatic, and gram-negative microorganisms, exhibit remarkable motility and precise control over their internal biomineralization processes. This unique ability results in the formation of magnetic nanoparticles arranged along filamentous structures in a catenary fashion, enclosed within a membrane. These bacteria possess distinctive biochemical properties that facilitate their precise positioning within complex environments. By harnessing these biochemical attributes, MTB could potentially offer substantial advantages in the realm of cancer therapy. This article reviews the drug delivery capabilities of MTB in tumor treatment and explores various applications based on their inherent properties. The objective is to provide a comprehensive understanding of MTB-driven drug delivery and stimulate innovative insights in this field.
For a significant duration, enhancing the efficacy of cancer therapy has remained a critical concern. Magnetotactic bacteria (MTB), often likened to micro-robots, hold substantial promise as a drug delivery system. MTB, classified as anaerobic, aquatic, and gram-negative microorganisms, exhibit remarkable motility and precise control over their internal biomineralization processes. This unique ability results in the formation of magnetic nanoparticles arranged along filamentous structures in a catenary fashion, enclosed within a membrane. These bacteria possess distinctive biochemical properties that facilitate their precise positioning within complex environments. By harnessing these biochemical attributes, MTB could potentially offer substantial advantages in the realm of cancer therapy. This article reviews the drug delivery capabilities of MTB in tumor treatment and explores various applications based on their inherent properties. The objective is to provide a comprehensive understanding of MTB-driven drug delivery and stimulate innovative insights in this field.
2024, 35(10): 109442
doi: 10.1016/j.cclet.2023.109442
Abstract:
Natural hydrogels have emerged as a pivotal innovation in wound care, offering a unique combination of high absorbency, biocompatibility, and versatility. However, due to the complexity of wound healing, the physiological state of the wound varies dynamically, and the mechanism of natural hydrogels that boost wound healing is still unclear. In this review, we firstly provide a comprehensive introduction to the biological process of wound healing, emphasizing the critical stages and factors affecting healing. This work concludes the composition and properties of natural hydrogels, including collagen, gelatin, hyaluronic acid, chitosan, alginates, cellulose, and fibroin, highlighting their biocompatibility and biodegradability. The focus shifts to the various crosslinking strategies employed to enhance the structural integrity and functionality of natural hydrogels. This review further investigates the biological effects of natural hydrogels in wound healing, detailing their antibacterial, antioxidant, anti-inflammatory, adhesive, and hemostatic functions. Furthermore, we propose the challenges and future perspectives of natural hydrogels in practical applications. This review offers a comprehensive overview of the current state and potential future advancements in natural hydrogel dressings for wound care, highlighting their critical role in addressing complex and hard-to-heal wounds.
Natural hydrogels have emerged as a pivotal innovation in wound care, offering a unique combination of high absorbency, biocompatibility, and versatility. However, due to the complexity of wound healing, the physiological state of the wound varies dynamically, and the mechanism of natural hydrogels that boost wound healing is still unclear. In this review, we firstly provide a comprehensive introduction to the biological process of wound healing, emphasizing the critical stages and factors affecting healing. This work concludes the composition and properties of natural hydrogels, including collagen, gelatin, hyaluronic acid, chitosan, alginates, cellulose, and fibroin, highlighting their biocompatibility and biodegradability. The focus shifts to the various crosslinking strategies employed to enhance the structural integrity and functionality of natural hydrogels. This review further investigates the biological effects of natural hydrogels in wound healing, detailing their antibacterial, antioxidant, anti-inflammatory, adhesive, and hemostatic functions. Furthermore, we propose the challenges and future perspectives of natural hydrogels in practical applications. This review offers a comprehensive overview of the current state and potential future advancements in natural hydrogel dressings for wound care, highlighting their critical role in addressing complex and hard-to-heal wounds.
2024, 35(10): 109492
doi: 10.1016/j.cclet.2024.109492
Abstract:
Amorphous alloys, with unique atomic structures and metastable nature, are treated as superior candidates for environmental wastewater remediation due to their superior catalytic capabilities. Given the strong demand for environmental protection, the field of amorphous alloys in wastewater treatment has great development prospects, and numerous research results have been published in recent years. As a promising catalyst, it was demonstrated that amorphous alloys could exhibit many excellent properties in wastewater treatment, such as high catalytic efficiency, easily adjustable parameters and reliable sustainability. This paper aims to summarize recent research trends regarding amorphous alloys in the field of catalysis, focusing on the preparation methods, physical performance, catalytic mechanisms and environmental application. Meanwhile, this review also investigates the challenges encountered and future perspectives of amorphous alloys, offering new research opportunities to enlarge their applicability spectra.
Amorphous alloys, with unique atomic structures and metastable nature, are treated as superior candidates for environmental wastewater remediation due to their superior catalytic capabilities. Given the strong demand for environmental protection, the field of amorphous alloys in wastewater treatment has great development prospects, and numerous research results have been published in recent years. As a promising catalyst, it was demonstrated that amorphous alloys could exhibit many excellent properties in wastewater treatment, such as high catalytic efficiency, easily adjustable parameters and reliable sustainability. This paper aims to summarize recent research trends regarding amorphous alloys in the field of catalysis, focusing on the preparation methods, physical performance, catalytic mechanisms and environmental application. Meanwhile, this review also investigates the challenges encountered and future perspectives of amorphous alloys, offering new research opportunities to enlarge their applicability spectra.
2024, 35(10): 109503
doi: 10.1016/j.cclet.2024.109503
Abstract:
Air pollution, including airborne pathogens and particulate matter (PM), has become a prominent issue affecting human health and safety. Conventional air filtration materials do not meet the requirements for efficient PM capture or do not instantly kill pathogens, leading to increased risk of direct/indirect contact transmission and infection due to the accumulation of pathogens during filtration. Electrospun nanofibrous membranes have emerged as a promising platform due to their rich porous structure, finer fiber diameters, good internal connectivity, and the ability to easily incorporate active chemicals for antimicrobial function. In this review, antimicrobial mechanisms of nanofibrous membranes for air filtration and PM capture mechanisms of nanofibers were firstly investigated, and various types of electrospun nanofibrous membranes with different antimicrobial agents for efficient air filtration were described in detail, including organic antimicrobial agents, inorganic antimicrobial agents and metal−organic frameworks. We hope this work could provide a better practical insight for designing novel electrospun nanofibrous membranes with antimicrobial efficacy for efficient air filtration.
Air pollution, including airborne pathogens and particulate matter (PM), has become a prominent issue affecting human health and safety. Conventional air filtration materials do not meet the requirements for efficient PM capture or do not instantly kill pathogens, leading to increased risk of direct/indirect contact transmission and infection due to the accumulation of pathogens during filtration. Electrospun nanofibrous membranes have emerged as a promising platform due to their rich porous structure, finer fiber diameters, good internal connectivity, and the ability to easily incorporate active chemicals for antimicrobial function. In this review, antimicrobial mechanisms of nanofibrous membranes for air filtration and PM capture mechanisms of nanofibers were firstly investigated, and various types of electrospun nanofibrous membranes with different antimicrobial agents for efficient air filtration were described in detail, including organic antimicrobial agents, inorganic antimicrobial agents and metal−organic frameworks. We hope this work could provide a better practical insight for designing novel electrospun nanofibrous membranes with antimicrobial efficacy for efficient air filtration.
2024, 35(10): 109511
doi: 10.1016/j.cclet.2024.109511
Abstract:
The application of nanotechnologies in formulation has significantly promoted the development of modern medical and pharmacological science, especially for nanoparticle-based drug delivery, bioimaging, and theranostics. The advancement of engineering particle design and fabrication is largely supported by a better understanding of how their apparent characteristics (e.g., size and size distribution, surface morphology, colloidal stability, chemical composition) influence their in vivo biological performance, which raises an urgent need for practical nanoformulation methods. Based on turbulent flow mixing and the self-assembly of molecules in fluids, flash technologies emerged as effective bottom-up fabrication strategies for effective nanoformulation. Among the flash technology family, flash nanocomplexation (FNC) is considered a novel and promising candidate that can promote and optimize formulation processes in a precise spatiotemporal manner, thus obtaining excellent fabrication efficiency, reproducibility and expandability. This review presents an overview of recent advances in fabricating drug-delivery nanoparticles using FNC platforms. Firstly, brief introductions to the basic principles of FNC technology were carried out, followed by descriptions of turbulent microvolume mixers that have significantly promoted the efficiency of FNC-based fabrications. Applications of real formulation cases were then categorized according to the self-assembly-driven interactions (including electrostatic interaction, coordination interaction, hydrogen bonding and hydrophobic interaction) and discussed to reveal the progressiveness of fabricating nanoparticles and discuss how its flexibility will provide advances and replenish the philosophy of nanomedicine formulation. In the end, the commercial potential, current limitations, and prospects of FNC technology for nanoformulation will be summarized and discussed.
The application of nanotechnologies in formulation has significantly promoted the development of modern medical and pharmacological science, especially for nanoparticle-based drug delivery, bioimaging, and theranostics. The advancement of engineering particle design and fabrication is largely supported by a better understanding of how their apparent characteristics (e.g., size and size distribution, surface morphology, colloidal stability, chemical composition) influence their in vivo biological performance, which raises an urgent need for practical nanoformulation methods. Based on turbulent flow mixing and the self-assembly of molecules in fluids, flash technologies emerged as effective bottom-up fabrication strategies for effective nanoformulation. Among the flash technology family, flash nanocomplexation (FNC) is considered a novel and promising candidate that can promote and optimize formulation processes in a precise spatiotemporal manner, thus obtaining excellent fabrication efficiency, reproducibility and expandability. This review presents an overview of recent advances in fabricating drug-delivery nanoparticles using FNC platforms. Firstly, brief introductions to the basic principles of FNC technology were carried out, followed by descriptions of turbulent microvolume mixers that have significantly promoted the efficiency of FNC-based fabrications. Applications of real formulation cases were then categorized according to the self-assembly-driven interactions (including electrostatic interaction, coordination interaction, hydrogen bonding and hydrophobic interaction) and discussed to reveal the progressiveness of fabricating nanoparticles and discuss how its flexibility will provide advances and replenish the philosophy of nanomedicine formulation. In the end, the commercial potential, current limitations, and prospects of FNC technology for nanoformulation will be summarized and discussed.
2024, 35(10): 109527
doi: 10.1016/j.cclet.2024.109527
Abstract:
Photothermal hydrogels with excellent photo responsive and thermal conversion ability had attract a great deal of attention from researchers to explore their biological applications. This review aimed to provide a comprehensive overview of photothermal hydrogels, focusing on their design principles, various functions, and biological applications. Firstly, several classifications of photothermal hydrogels were given according to different photothermal agents (metal, metal sulfide/oxide, MXene, carbon-based, dyes, black phosphorus, and polymer) utilized in hydrogel construction. The photothermal conversion mechanism and hydrogel fabrication were also discussed in detail. Then, the relationship between their photothermal conversion property and functions, together with some indispensable property such as biocompatibility, adhesion, mechanical properties, and self-healing properties was fully introduced. Furthermore, the applications of photothermal hydrogels in the biomedical (i.e., wound healing, antibacterial treatments, controlled drug release, bone repair, and tumor treatment) was summarized. Finally, the future opportunities and challenges of photothermal hydrogels were proposed. We believe that this review could provide a new horizon for further preparation of photothermal hydrogels, and could promote their applications in wider fields.
Photothermal hydrogels with excellent photo responsive and thermal conversion ability had attract a great deal of attention from researchers to explore their biological applications. This review aimed to provide a comprehensive overview of photothermal hydrogels, focusing on their design principles, various functions, and biological applications. Firstly, several classifications of photothermal hydrogels were given according to different photothermal agents (metal, metal sulfide/oxide, MXene, carbon-based, dyes, black phosphorus, and polymer) utilized in hydrogel construction. The photothermal conversion mechanism and hydrogel fabrication were also discussed in detail. Then, the relationship between their photothermal conversion property and functions, together with some indispensable property such as biocompatibility, adhesion, mechanical properties, and self-healing properties was fully introduced. Furthermore, the applications of photothermal hydrogels in the biomedical (i.e., wound healing, antibacterial treatments, controlled drug release, bone repair, and tumor treatment) was summarized. Finally, the future opportunities and challenges of photothermal hydrogels were proposed. We believe that this review could provide a new horizon for further preparation of photothermal hydrogels, and could promote their applications in wider fields.
2024, 35(10): 109541
doi: 10.1016/j.cclet.2024.109541
Abstract:
Antibiotics, as widely used antibacterial drug, exist in various environmental media. Antibiotic residues can affect biological metabolism and lead to bacterial resistance and the formation of antibiotic-resistance genes, posing a threat to human health and ecological safety. Establishing efficient detection methods for antibiotics and antibiotic-resistance genes has great environmental significance. Fluorescence detection methods, due to their fast response, high sensitivity and specificity, and low-cost, are widely used in chemical and biological sensing. This review first summarizes the pre-treatment methods for different types of environmental samples, and then focuses on the recent advances of fluorescence methods for the detection of antibiotics and antibiotic-resistance genes. Finally, main challenges and future research directions of fluorescence methods for antibiotic and antibiotic-resistance genes detection are discussed. This review highlights the promising prospect of fluorescence methods in-situ detection and monitoring of antibiotics and antibiotic-resistance genes, and provides guidance for the construction of overall risk assessment system of environmental media.
Antibiotics, as widely used antibacterial drug, exist in various environmental media. Antibiotic residues can affect biological metabolism and lead to bacterial resistance and the formation of antibiotic-resistance genes, posing a threat to human health and ecological safety. Establishing efficient detection methods for antibiotics and antibiotic-resistance genes has great environmental significance. Fluorescence detection methods, due to their fast response, high sensitivity and specificity, and low-cost, are widely used in chemical and biological sensing. This review first summarizes the pre-treatment methods for different types of environmental samples, and then focuses on the recent advances of fluorescence methods for the detection of antibiotics and antibiotic-resistance genes. Finally, main challenges and future research directions of fluorescence methods for antibiotic and antibiotic-resistance genes detection are discussed. This review highlights the promising prospect of fluorescence methods in-situ detection and monitoring of antibiotics and antibiotic-resistance genes, and provides guidance for the construction of overall risk assessment system of environmental media.
2024, 35(10): 109558
doi: 10.1016/j.cclet.2024.109558
Abstract:
DNA-based hydrogels are exceptional materials for biological applications because of their numerous advantages such as biodegradability, biocompatibility, hydrophilicity, super absorbency, porosity, and swelling. Among these advantages, the ability of DNA-based hydrogels to respond to specific physical and chemical triggers and undergo reversible phase transitions has garnered significant attention in the fields of disease diagnosis (biosensors) and treatment (drug delivery). This article focuses on the recent advancements in the research of DNA-based hydrogels and discusses the different types of these hydrogels, the synthetic methods, their unique properties, and their applications in biosensors and drug delivery. The types of DNA hydrogels are categorized based on their building blocks, and the process of synthesis as well as the unique characteristics of DNA-based hydrogels are described. Then, DNA-based responsive hydrogels utilized as intelligent materials for the development of biosensors are reviewed. Furthermore, this article also presents the current status of DNA-based responsive hydrogels in drug delivery for cancer treatment, wound healing, and other therapeutic applications. Ultimately, this paper discusses the current challenges in expanding the practical application of DNA-based hydrogels.
DNA-based hydrogels are exceptional materials for biological applications because of their numerous advantages such as biodegradability, biocompatibility, hydrophilicity, super absorbency, porosity, and swelling. Among these advantages, the ability of DNA-based hydrogels to respond to specific physical and chemical triggers and undergo reversible phase transitions has garnered significant attention in the fields of disease diagnosis (biosensors) and treatment (drug delivery). This article focuses on the recent advancements in the research of DNA-based hydrogels and discusses the different types of these hydrogels, the synthetic methods, their unique properties, and their applications in biosensors and drug delivery. The types of DNA hydrogels are categorized based on their building blocks, and the process of synthesis as well as the unique characteristics of DNA-based hydrogels are described. Then, DNA-based responsive hydrogels utilized as intelligent materials for the development of biosensors are reviewed. Furthermore, this article also presents the current status of DNA-based responsive hydrogels in drug delivery for cancer treatment, wound healing, and other therapeutic applications. Ultimately, this paper discusses the current challenges in expanding the practical application of DNA-based hydrogels.
2024, 35(10): 109579
doi: 10.1016/j.cclet.2024.109579
Abstract:
Reactive oxygen species (ROSs) in Fenton process are of great importance in treating contaminants in wastewater. It is crucial to understand their chemical properties, formation, and reaction mechanisms with contaminants. This review summarizes the reactive oxygen species in Fenton process, including hydroxyl radical (•OH), superoxide radical (O2•−), singlet oxygen (1O2), hydroperoxyl radical (HO2•), and high-valent iron. •OH shows a trend to react with chemistry groups with abundant electrons through H-atom abstraction, radical adduct formation and single electron transfer. Electron transfer is discovered to be an important pathway when 1O2 degrades organic pollutants. Ring-opening and β-scission are proposed to be the possible ways of 1O2 to certain contaminants. Proton abstraction, nucleophilic substitution, and single electron transfer are proposed to explain how O2•− degrade pollutants. As the conjugated acid of O2•−, radical adduct formation and H-atom abstraction are reported for the reaction mechanisms of hydroperoxyl radical. High-valent iron in Fenton, namely Fe(Ⅳ), reacts with certain pollutants via single- or two-electron transfer. This review is important for researchers to understand the ROSs produced in Fenton and how they react with pollutants.
Reactive oxygen species (ROSs) in Fenton process are of great importance in treating contaminants in wastewater. It is crucial to understand their chemical properties, formation, and reaction mechanisms with contaminants. This review summarizes the reactive oxygen species in Fenton process, including hydroxyl radical (•OH), superoxide radical (O2•−), singlet oxygen (1O2), hydroperoxyl radical (HO2•), and high-valent iron. •OH shows a trend to react with chemistry groups with abundant electrons through H-atom abstraction, radical adduct formation and single electron transfer. Electron transfer is discovered to be an important pathway when 1O2 degrades organic pollutants. Ring-opening and β-scission are proposed to be the possible ways of 1O2 to certain contaminants. Proton abstraction, nucleophilic substitution, and single electron transfer are proposed to explain how O2•− degrade pollutants. As the conjugated acid of O2•−, radical adduct formation and H-atom abstraction are reported for the reaction mechanisms of hydroperoxyl radical. High-valent iron in Fenton, namely Fe(Ⅳ), reacts with certain pollutants via single- or two-electron transfer. This review is important for researchers to understand the ROSs produced in Fenton and how they react with pollutants.
2024, 35(10): 109727
doi: 10.1016/j.cclet.2024.109727
Abstract:
Sonodynamic therapy (SDT) exhibits promising clinical applications in cancer treatment owing to its advantages, including ultrasonic cavitation effect, mechanical effect, and deep tissue penetration. Titanium dioxide (TiO2) nanomaterials, recognized as excellent sonosensitizers, have been extensively studied in cancer SDT. This review first outlines the mechanism of TiO2-based SDT, then systematically discusses the regulation of TiO2 sonosensitivity, covering aspects such as morphology, particle size, element doping, defect engineering, heterojunction structure, and interactions with the tumor microenvironment. Furthermore, the review generalizes ultrasound-responsive TiO2-based therapeutic modalities for tumor treatment, including SDT, SDT combined with chemotherapy, chemodynamic therapy, photothermal therapy, immunotherapy, and treatment visualization. Finally, the review navigates the ongoing challenges and prospects in TiO2-based cancer SDT.
Sonodynamic therapy (SDT) exhibits promising clinical applications in cancer treatment owing to its advantages, including ultrasonic cavitation effect, mechanical effect, and deep tissue penetration. Titanium dioxide (TiO2) nanomaterials, recognized as excellent sonosensitizers, have been extensively studied in cancer SDT. This review first outlines the mechanism of TiO2-based SDT, then systematically discusses the regulation of TiO2 sonosensitivity, covering aspects such as morphology, particle size, element doping, defect engineering, heterojunction structure, and interactions with the tumor microenvironment. Furthermore, the review generalizes ultrasound-responsive TiO2-based therapeutic modalities for tumor treatment, including SDT, SDT combined with chemotherapy, chemodynamic therapy, photothermal therapy, immunotherapy, and treatment visualization. Finally, the review navigates the ongoing challenges and prospects in TiO2-based cancer SDT.
2024, 35(10): 109810
doi: 10.1016/j.cclet.2024.109810
Abstract:
Bioelectronics have gained substantial research attention owing to their potential applications in health monitoring and diagnose, and greatly promoted the development of biomedicine. Recently, poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) hydrogels have arose as a promising candidate for the next-generation bioelectronic interface due to its high-conductivity, versatility, flexibility and biocompatibility. In this review, we highlight the recent advances of PEDOT:PSS hydrogels, including the gelation methods and modification strategies, and summarize their wide applications in different type of sensors and tissue engineering in detail. We expect that this work will provide valuable information regarding the functionalizations and applications of PEDOT:PSS hydrogels.
Bioelectronics have gained substantial research attention owing to their potential applications in health monitoring and diagnose, and greatly promoted the development of biomedicine. Recently, poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) hydrogels have arose as a promising candidate for the next-generation bioelectronic interface due to its high-conductivity, versatility, flexibility and biocompatibility. In this review, we highlight the recent advances of PEDOT:PSS hydrogels, including the gelation methods and modification strategies, and summarize their wide applications in different type of sensors and tissue engineering in detail. We expect that this work will provide valuable information regarding the functionalizations and applications of PEDOT:PSS hydrogels.
2024, 35(10): 109550
doi: 10.1016/j.cclet.2024.109550
Abstract:
2024, 35(10): 110026
doi: 10.1016/j.cclet.2024.110026
Abstract:
2024, 35(10): 110060
doi: 10.1016/j.cclet.2024.110060
Abstract:
2024, 35(10): 110061
doi: 10.1016/j.cclet.2024.110061
Abstract:
2024, 35(10): 110115
doi: 10.1016/j.cclet.2024.110115
Abstract:
