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2024 Volume 35 Issue 11
2024, 35(11): 109285
doi: 10.1016/j.cclet.2023.109285
Abstract:
Effective design of nanoheterostructure anode with high ion/electron migration kinetics can give electrode with superior electrochemical performance. However, the design and preparation of nanoheterostructure composites with high-capacity and long cycling life in half and pouch full cells remain a big challenge. Here, a novel micro-pore MnS/Mn2SnS4 heterostructure nanowire were in situ encapsulated into the N and S elements co-doped amorphous carbon tubes (abbreviated as (MnS/Mn2SnS4)@N,S-ACTs) and showed superior energy storage properties in Na-/Li-ion half cells and pouch full cells. The Na-/Li-storage capabilities improvement are attribute to the strong synergistic effect between MnS/Mn2SnS4 heterostructure and N,S-ACTs protective layer, the former induces an local built-in electric field between Mn2SnS4 and MnS during charging/discharging, accelerating interfacial ion/electron diffusion dynamics, the latter effective maintains the morphology and volume evolution during Na+/Li+ charging/discharging, achieving a long-term cycling stability (e.g., high discharge capacity of 79.2 mAh/g with the capacity retention of 79.3% can be gained after 2200 cycles at 3 C in (MnS/Mn2SnS4)@N,S-ACTs//LiFePO4 pouch full cells; a high capacity of ~34 mAh/g at 10 C can be got with a Coulombic efficiency of 100% after 1000 cycles in pouch (MnS/Mn2SnS4)@N,S-ACTs//Na3V2(PO4)2O2F full cells.
Effective design of nanoheterostructure anode with high ion/electron migration kinetics can give electrode with superior electrochemical performance. However, the design and preparation of nanoheterostructure composites with high-capacity and long cycling life in half and pouch full cells remain a big challenge. Here, a novel micro-pore MnS/Mn2SnS4 heterostructure nanowire were in situ encapsulated into the N and S elements co-doped amorphous carbon tubes (abbreviated as (MnS/Mn2SnS4)@N,S-ACTs) and showed superior energy storage properties in Na-/Li-ion half cells and pouch full cells. The Na-/Li-storage capabilities improvement are attribute to the strong synergistic effect between MnS/Mn2SnS4 heterostructure and N,S-ACTs protective layer, the former induces an local built-in electric field between Mn2SnS4 and MnS during charging/discharging, accelerating interfacial ion/electron diffusion dynamics, the latter effective maintains the morphology and volume evolution during Na+/Li+ charging/discharging, achieving a long-term cycling stability (e.g., high discharge capacity of 79.2 mAh/g with the capacity retention of 79.3% can be gained after 2200 cycles at 3 C in (MnS/Mn2SnS4)@N,S-ACTs//LiFePO4 pouch full cells; a high capacity of ~34 mAh/g at 10 C can be got with a Coulombic efficiency of 100% after 1000 cycles in pouch (MnS/Mn2SnS4)@N,S-ACTs//Na3V2(PO4)2O2F full cells.
2024, 35(11): 109353
doi: 10.1016/j.cclet.2023.109353
Abstract:
Sodium (Na) metal batteries have gained increasing attention more recently, owing to their high energy densities and cost efficiencies, but are severely handicapped by the unsatisfactory Coulombic efficiency (CE) and cycling stability stemming from dendrite growth on Na anodes. In this study, we developed a strategy of direct ink writing (DIW) 3D printing combined with electroless deposition to construct a hierarchical Cu grid coated with a dense nanoscale Ag interfacial layer as the host material for Na plating. The sodiophilic Ag interface contributes to a fall in the Na nucleation energy, hence enabling uniform Na deposition on each 3D-printed filament. The constructed 3D-printed structure can effectively moderate the electric-field distribution and lower the local current density for relieving Na inhomogeneous growth, as confirmed by finite element simulation and Na plating/stripping morphology evolution results. In particular, the unique 3D structure also promotes the lateral growth of Na, thus the volume change of Na metal was accommodated to stabilize the solid electrolyte interphase (SEI). As a result, the CE of the half-cell can reach 99.9% at the current density of 1 mA/cm2 after 300 cycles and the full-cell exhibits outstanding electrochemical performance (capacity retention of 91.0% after 500 cycles at 2 C).
Sodium (Na) metal batteries have gained increasing attention more recently, owing to their high energy densities and cost efficiencies, but are severely handicapped by the unsatisfactory Coulombic efficiency (CE) and cycling stability stemming from dendrite growth on Na anodes. In this study, we developed a strategy of direct ink writing (DIW) 3D printing combined with electroless deposition to construct a hierarchical Cu grid coated with a dense nanoscale Ag interfacial layer as the host material for Na plating. The sodiophilic Ag interface contributes to a fall in the Na nucleation energy, hence enabling uniform Na deposition on each 3D-printed filament. The constructed 3D-printed structure can effectively moderate the electric-field distribution and lower the local current density for relieving Na inhomogeneous growth, as confirmed by finite element simulation and Na plating/stripping morphology evolution results. In particular, the unique 3D structure also promotes the lateral growth of Na, thus the volume change of Na metal was accommodated to stabilize the solid electrolyte interphase (SEI). As a result, the CE of the half-cell can reach 99.9% at the current density of 1 mA/cm2 after 300 cycles and the full-cell exhibits outstanding electrochemical performance (capacity retention of 91.0% after 500 cycles at 2 C).
2024, 35(11): 109382
doi: 10.1016/j.cclet.2023.109382
Abstract:
Epoxy resin-reinforced graphite composites have found extensive application as bipolar plates in fuel cells for stationary power supplies, valued for their lightweight nature and exceptional durability. To enhance the interfacial properties between graphite and epoxy resin (EP), surface oxidation of graphite was carried out using diverse functional groups. Experimental assessments illustrated that the composites with graphite oxide resulted in heightened mechanical strength and toughness compared to pristine graphite, which could be attributed to the excellent interface connection. Moreover, these composites displayed remarkable conductivity while simultaneously retaining their mechanical attributes. Furthermore, molecular dynamics simulations outcomes unveiled that the inclusion of oxygen-containing functional groups on the graphite surface augmented the interfacial energy with EP, and the interface morphology between graphite and resin exhibited heightened stability throughout the stretching process. This simple and effective technique presents opportunities for improving composites interfaces, enabling high load transfer efficiency, and opens up a potential path for developing strong and tough composite bipolar plates for fuel cells.
Epoxy resin-reinforced graphite composites have found extensive application as bipolar plates in fuel cells for stationary power supplies, valued for their lightweight nature and exceptional durability. To enhance the interfacial properties between graphite and epoxy resin (EP), surface oxidation of graphite was carried out using diverse functional groups. Experimental assessments illustrated that the composites with graphite oxide resulted in heightened mechanical strength and toughness compared to pristine graphite, which could be attributed to the excellent interface connection. Moreover, these composites displayed remarkable conductivity while simultaneously retaining their mechanical attributes. Furthermore, molecular dynamics simulations outcomes unveiled that the inclusion of oxygen-containing functional groups on the graphite surface augmented the interfacial energy with EP, and the interface morphology between graphite and resin exhibited heightened stability throughout the stretching process. This simple and effective technique presents opportunities for improving composites interfaces, enabling high load transfer efficiency, and opens up a potential path for developing strong and tough composite bipolar plates for fuel cells.
2024, 35(11): 109389
doi: 10.1016/j.cclet.2023.109389
Abstract:
In order to solve the problem of poor conductivity of traditional LiFePO4 cathode binders, we developed sodium alginate-Congo red copolymers (SA-CR) as water-soluble electrically conductive and mechanically robust composite binder. Unlike most other electrically conductive polymer binders, the procedure is straightforward and low-cost to prepare SA-CR binder. Various SA -CR copolymers were prepared with different degree of compounding of CR to investigate the effect of CR on the electrochemical and physical properties of the prepared electrodes. The copolymer whose composition was filled with a mixture of SA and CR at a 3:1 mass ratio showed the best cell performance, due to the well-balanced electrical conductivity and mechanical properties. It exhibited a specific capacity of 118.8 mAh/g at the 100th cycle with 92.1% capacity retention, significantly better than the 108.5 mAh/g of conventional acetylene black electrodes. CR as a conduction-promoting agent in water-soluble composite binder favors the formation of continuous and homogenous conducting bridges throughout the electrode and increases the compaction density of electrode by reducing the conducting agent content of acetylene black and thus the improvement of electrode performance is realized.
In order to solve the problem of poor conductivity of traditional LiFePO4 cathode binders, we developed sodium alginate-Congo red copolymers (SA-CR) as water-soluble electrically conductive and mechanically robust composite binder. Unlike most other electrically conductive polymer binders, the procedure is straightforward and low-cost to prepare SA-CR binder. Various SA -CR copolymers were prepared with different degree of compounding of CR to investigate the effect of CR on the electrochemical and physical properties of the prepared electrodes. The copolymer whose composition was filled with a mixture of SA and CR at a 3:1 mass ratio showed the best cell performance, due to the well-balanced electrical conductivity and mechanical properties. It exhibited a specific capacity of 118.8 mAh/g at the 100th cycle with 92.1% capacity retention, significantly better than the 108.5 mAh/g of conventional acetylene black electrodes. CR as a conduction-promoting agent in water-soluble composite binder favors the formation of continuous and homogenous conducting bridges throughout the electrode and increases the compaction density of electrode by reducing the conducting agent content of acetylene black and thus the improvement of electrode performance is realized.
2024, 35(11): 109428
doi: 10.1016/j.cclet.2023.109428
Abstract:
SnO2 is a potential anode material with high theoretical capacity for lithium-ion batteries (LIBs), however, its applications have been limited by the severe volume expansion during charging-discharging process. In this work, an inverse opal TiO2/SnO2 composite with an interconnect network nanostructure was designed to confine SnO2 nanoparticles in the porous TiO2. Due to this nanoconfinement structure, the volume expansion in the process was effectively alleviated, therefore the safety performance and cycling stability of the battery were effectively improved. At the same time, with a large number of microporous structures in the framework, the appearance of pseudocapacitance improves the rate performance and reversible capacity. In terms of electrochemical kinetics, its framework provides the connected path for charge migration, effectively reducing the charge transfer impedance, meanwhile, quantities of micropores in its skeleton could provide a smoother channel for lithium ions, thus greatly improving the diffusion rate of LIBs. The design of this nanostructure provides a new idea for the research of SnO2-based anode with effectively enhanced electrochemical performance, which is promising anode for practical application.
SnO2 is a potential anode material with high theoretical capacity for lithium-ion batteries (LIBs), however, its applications have been limited by the severe volume expansion during charging-discharging process. In this work, an inverse opal TiO2/SnO2 composite with an interconnect network nanostructure was designed to confine SnO2 nanoparticles in the porous TiO2. Due to this nanoconfinement structure, the volume expansion in the process was effectively alleviated, therefore the safety performance and cycling stability of the battery were effectively improved. At the same time, with a large number of microporous structures in the framework, the appearance of pseudocapacitance improves the rate performance and reversible capacity. In terms of electrochemical kinetics, its framework provides the connected path for charge migration, effectively reducing the charge transfer impedance, meanwhile, quantities of micropores in its skeleton could provide a smoother channel for lithium ions, thus greatly improving the diffusion rate of LIBs. The design of this nanostructure provides a new idea for the research of SnO2-based anode with effectively enhanced electrochemical performance, which is promising anode for practical application.
2024, 35(11): 109435
doi: 10.1016/j.cclet.2023.109435
Abstract:
In electrochemical energy devices, the operating conditions always exert enormous influence on electrocatalysts' performances. Phosphoric acid (PA), acted as the proton carriers, can be adsorbed on Pt surface, block active sites and affect the electronic structure of Pt unfavorably, which severely restricts the performance of high-temperature proton exchange membrane fuel cells (HT-PEMFCs). Herein, simply basic organic compounds, such as dicyandiamide (DCD), melamine (Mel) and cyanuric acid (CA), are decorated on Pt surface (DCD-Pt/C, Mel-Pt/C and CA-Pt/C) to induce the adsorption transfer of proton carriers. The decoration can not only inject electrons to Pt and enhance oxygen reduction reaction (ORR) activity but also can induce PA to transfer from Pt surface to organic compounds, decontaminating active sites. In addition, the organic compounds with the larger conjugated system and the smaller electronegativity of ligating atoms would have a greater interaction with Pt, causing a larger decoration amount on Pt surface, which leads to more excellent ORR activity and resistance to PA blockage effect. Therefore, Mel-Pt/C shows a peak power density of 629 mW/cm2, exceeding commercial Pt/C (437 mW/cm2), DCD-Pt/C (539 mW/cm2) and CA-Pt/C (511 mW/cm2) with the same loading.
In electrochemical energy devices, the operating conditions always exert enormous influence on electrocatalysts' performances. Phosphoric acid (PA), acted as the proton carriers, can be adsorbed on Pt surface, block active sites and affect the electronic structure of Pt unfavorably, which severely restricts the performance of high-temperature proton exchange membrane fuel cells (HT-PEMFCs). Herein, simply basic organic compounds, such as dicyandiamide (DCD), melamine (Mel) and cyanuric acid (CA), are decorated on Pt surface (DCD-Pt/C, Mel-Pt/C and CA-Pt/C) to induce the adsorption transfer of proton carriers. The decoration can not only inject electrons to Pt and enhance oxygen reduction reaction (ORR) activity but also can induce PA to transfer from Pt surface to organic compounds, decontaminating active sites. In addition, the organic compounds with the larger conjugated system and the smaller electronegativity of ligating atoms would have a greater interaction with Pt, causing a larger decoration amount on Pt surface, which leads to more excellent ORR activity and resistance to PA blockage effect. Therefore, Mel-Pt/C shows a peak power density of 629 mW/cm2, exceeding commercial Pt/C (437 mW/cm2), DCD-Pt/C (539 mW/cm2) and CA-Pt/C (511 mW/cm2) with the same loading.
2024, 35(11): 109449
doi: 10.1016/j.cclet.2023.109449
Abstract:
3d transition metal chalcogenides have attracted much attention due to their unique magnetic properties. Although various Cr, V, and Fe-based chalcogenides have been fabricated recently, the limited Curie temperature (TC) still hinders their practical application. Based on the structural and magnetic advantages of MFe2O4 and Fe3Se4, we developed a one-pot solution synthesis method for the fabrication of NiFe2Se4 nanostructures with structural continuity, to facilitate the investigation of their magnetic properties. Notably, the morphology of NiFe2Se4 can be controlled from nano-rods to nano-platelets by controlling the growth direction. The coercivity (HC) of NiFe2Se4 with nano-cactus structure exhibits a maximum of 12.77 kOe at 5 K. The coercivity of ferrimagnetic NiFe2Se4 nano-platelets can be further adjusted to 1.52 kOe at room temperature. These results show that the magnetic properties of NiFe2Se4 can be significantly modified by controlling their morphologies. We also extend the method to the synthesis of CoFe2Se4 nano-cactus with an ultrahigh coercivity of 17.85 kOe at 5 K. Obviously, the synthesis strategy and their excellent magnetic properties of MFe2Se4 have sparked interest in ternary transition metal selenides as potential hard magnetic materials.
3d transition metal chalcogenides have attracted much attention due to their unique magnetic properties. Although various Cr, V, and Fe-based chalcogenides have been fabricated recently, the limited Curie temperature (TC) still hinders their practical application. Based on the structural and magnetic advantages of MFe2O4 and Fe3Se4, we developed a one-pot solution synthesis method for the fabrication of NiFe2Se4 nanostructures with structural continuity, to facilitate the investigation of their magnetic properties. Notably, the morphology of NiFe2Se4 can be controlled from nano-rods to nano-platelets by controlling the growth direction. The coercivity (HC) of NiFe2Se4 with nano-cactus structure exhibits a maximum of 12.77 kOe at 5 K. The coercivity of ferrimagnetic NiFe2Se4 nano-platelets can be further adjusted to 1.52 kOe at room temperature. These results show that the magnetic properties of NiFe2Se4 can be significantly modified by controlling their morphologies. We also extend the method to the synthesis of CoFe2Se4 nano-cactus with an ultrahigh coercivity of 17.85 kOe at 5 K. Obviously, the synthesis strategy and their excellent magnetic properties of MFe2Se4 have sparked interest in ternary transition metal selenides as potential hard magnetic materials.
2024, 35(11): 109462
doi: 10.1016/j.cclet.2023.109462
Abstract:
Rare earth ions (RE3+)-doped double perovskites have attracted tremendous attention for its fascinating optical properties. Nevertheless, RE3+ generally exhibits poor photoluminescence quantum yield (PLQY) for their parity-forbidden 4f-4f transition and the low doping concentration. Herein, we reported Sb3+/Sm3+-codoped rare earth-based double perovskite Cs2NaLuCl6 that enables efficient visible and near-infrared (NIR) emission, which stems from self-trapped exciton (STE) and Sm3+, respectively. Benefit from up to 72.89% energy transfer efficiency from STE to Sm3+ and high doping concentrations due to similar ionic activity between Sm3+ and Lu3+, thus eruptive PLQY of 74.58% in the visible light region and 23.12% in the NIR light region can be obtained. Moreover, Sb3+/Sm3+-codoped Cs2NaLuCl6 exhibits tunable emission characteristic in the visible light region under different excitation wavelengths, which can change from blue emission (254 nm excitation) to white emission (365 nm excitation). More particularly, only the NIR emission can be captured by the NIR camera when a 700 nm cutoff filter is added. The excellent stability and unique optical properties of Sb3+/Sm3+-codoped Cs2NaLuCl6 enable us to demonstrate its applications in NIR light-emitting diode, triple-mode fluorescence anti-counterfeiting and information encryption. These findings provide new inspiration for the application of rare earth-based double perovskite in optoelectronic devices.
Rare earth ions (RE3+)-doped double perovskites have attracted tremendous attention for its fascinating optical properties. Nevertheless, RE3+ generally exhibits poor photoluminescence quantum yield (PLQY) for their parity-forbidden 4f-4f transition and the low doping concentration. Herein, we reported Sb3+/Sm3+-codoped rare earth-based double perovskite Cs2NaLuCl6 that enables efficient visible and near-infrared (NIR) emission, which stems from self-trapped exciton (STE) and Sm3+, respectively. Benefit from up to 72.89% energy transfer efficiency from STE to Sm3+ and high doping concentrations due to similar ionic activity between Sm3+ and Lu3+, thus eruptive PLQY of 74.58% in the visible light region and 23.12% in the NIR light region can be obtained. Moreover, Sb3+/Sm3+-codoped Cs2NaLuCl6 exhibits tunable emission characteristic in the visible light region under different excitation wavelengths, which can change from blue emission (254 nm excitation) to white emission (365 nm excitation). More particularly, only the NIR emission can be captured by the NIR camera when a 700 nm cutoff filter is added. The excellent stability and unique optical properties of Sb3+/Sm3+-codoped Cs2NaLuCl6 enable us to demonstrate its applications in NIR light-emitting diode, triple-mode fluorescence anti-counterfeiting and information encryption. These findings provide new inspiration for the application of rare earth-based double perovskite in optoelectronic devices.
2024, 35(11): 109465
doi: 10.1016/j.cclet.2023.109465
Abstract:
Conventionally, organic radicals adhere to the Aufbau principle, the energy level of the singly occupied molecular orbital (SOMO) is not below the highest occupied molecular orbital (HOMO), but somewhat abnormal phenomena have appeared recently. In this study, we introduce a novel strategy by incorporating unique NHC-Au-X units into a tris(2,4,6-trichlorophenyl)methyl (TTM) system to create metal-involved open-shell complexes, denoted as TTM-NHC-Au-X (X = I, Br, or Cl). Density-functional theory calculations were used to predict an inversion in the energy of the SOMO and highest doubly occupied molecular orbital (HOMO) of TTM-NHC-Au-I, which is supported by experimental results. Organometallic radicals TTM-NHC-Au-X demonstrated distinct properties with different coordinated halides. The radical behaviors have been investigated by EPR, UV–vis spectroscopy and cyclic voltammetry, additional structural information provided by structurally comparing related the precursor complexes given by X-ray crystallography. TTM-NHC-Au-I with SOMOHOMO conversion (SHC) features a highly thermal decomposition temperature up to 305 ℃. Furthermore, the photostability of TTM-NHC-Au-I was found to be 75 and 23 times greater than that of TTM-NHC-Au-Br and TTM-NHC-Au-Cl, respectively. These findings provide valuable insights into the structural and electronic design principles governing the occurrence of SOMOHOMO conversion in open-shell systems.
Conventionally, organic radicals adhere to the Aufbau principle, the energy level of the singly occupied molecular orbital (SOMO) is not below the highest occupied molecular orbital (HOMO), but somewhat abnormal phenomena have appeared recently. In this study, we introduce a novel strategy by incorporating unique NHC-Au-X units into a tris(2,4,6-trichlorophenyl)methyl (TTM) system to create metal-involved open-shell complexes, denoted as TTM-NHC-Au-X (X = I, Br, or Cl). Density-functional theory calculations were used to predict an inversion in the energy of the SOMO and highest doubly occupied molecular orbital (HOMO) of TTM-NHC-Au-I, which is supported by experimental results. Organometallic radicals TTM-NHC-Au-X demonstrated distinct properties with different coordinated halides. The radical behaviors have been investigated by EPR, UV–vis spectroscopy and cyclic voltammetry, additional structural information provided by structurally comparing related the precursor complexes given by X-ray crystallography. TTM-NHC-Au-I with SOMOHOMO conversion (SHC) features a highly thermal decomposition temperature up to 305 ℃. Furthermore, the photostability of TTM-NHC-Au-I was found to be 75 and 23 times greater than that of TTM-NHC-Au-Br and TTM-NHC-Au-Cl, respectively. These findings provide valuable insights into the structural and electronic design principles governing the occurrence of SOMOHOMO conversion in open-shell systems.
2024, 35(11): 109466
doi: 10.1016/j.cclet.2023.109466
Abstract:
1-(4-(1,1-Dimethylethyl)phenyl)-3-(4-methoxyphenyl)-1,3-propanedione (known as Avobenzone/AVB), widely used throughout the world as a highly effective UVA absorber, can prevent the progression of photoaging in skin, and is also known for the disadvantage of having a reduced capability to absorb UVA when exposed to sunlight for long periods. To address this challenge, ZnTi-CO3-LDH with a two-dimensional layered structure was used to improve stability and synergistically enhance UV absorption of AVB. A novel AVB loaded ZnTi-CO3-LDH (AVB@ZnTi-LDH) material was synthesized by reconstruction method and the loading content (LC) was about 46.8% investigated by high-performance liquid chromatography (HPLC). A possible mechanism for the binding of AVB with the ZnTi-LDH surface was proposed. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations were used to confirm further the coordination between Zn on the layer and the oxygen atom of the carbonyl group of AVB. UV absorption and critical wavelength of AVB@ZnTi-LDH were superior to those of AVB and ZnTi-LDH precursors. Compared with pure AVB, the photodegradation rate was reduced from 15.06% to 4.06%. Especially in titanium dioxide, the decomposition rate was reduced from 29.75% to 7.92%. Furthermore, pure AVB often reacts with multivalent metal ions to induce an unpleasant color (light yellow to reddish brown), which is greatly mitigated with AVB@ZnTi-LDH. In this study, avobenzone was combined with hydrotalcite to prepare an organic-inorganic composite with excellent UV resistance and better stability, the composite has great promise for application in sunscreen cosmetics.
1-(4-(1,1-Dimethylethyl)phenyl)-3-(4-methoxyphenyl)-1,3-propanedione (known as Avobenzone/AVB), widely used throughout the world as a highly effective UVA absorber, can prevent the progression of photoaging in skin, and is also known for the disadvantage of having a reduced capability to absorb UVA when exposed to sunlight for long periods. To address this challenge, ZnTi-CO3-LDH with a two-dimensional layered structure was used to improve stability and synergistically enhance UV absorption of AVB. A novel AVB loaded ZnTi-CO3-LDH (AVB@ZnTi-LDH) material was synthesized by reconstruction method and the loading content (LC) was about 46.8% investigated by high-performance liquid chromatography (HPLC). A possible mechanism for the binding of AVB with the ZnTi-LDH surface was proposed. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations were used to confirm further the coordination between Zn on the layer and the oxygen atom of the carbonyl group of AVB. UV absorption and critical wavelength of AVB@ZnTi-LDH were superior to those of AVB and ZnTi-LDH precursors. Compared with pure AVB, the photodegradation rate was reduced from 15.06% to 4.06%. Especially in titanium dioxide, the decomposition rate was reduced from 29.75% to 7.92%. Furthermore, pure AVB often reacts with multivalent metal ions to induce an unpleasant color (light yellow to reddish brown), which is greatly mitigated with AVB@ZnTi-LDH. In this study, avobenzone was combined with hydrotalcite to prepare an organic-inorganic composite with excellent UV resistance and better stability, the composite has great promise for application in sunscreen cosmetics.
2024, 35(11): 109468
doi: 10.1016/j.cclet.2023.109468
Abstract:
The complicated and diverse deep defects, voids, and grain boundary in the CZTSSe absorber are the main reasons for carrier recombination and efficiency degradation. The further improvement of the open-circuit voltage and fill factor so as to increase the efficiency of CZTSSe device is urgent. In this work, we obtained K-doped CZTSSe absorber by a simple solution method. The medium-sized K atoms, which combine the advantages of light and heavy alkali metals, are able to enter the grain interior as well as segregate at grain boundary. The K-Se liquid phase can improve the absorber crystallinity. We find that the accumulation of the wide bandgap compound K2Sn2S5 at grain boundary can increase the contact potential difference of grain boundary, form more effective hole barriers, and enhance the charge separation ability. At the same time, K doping passivates the interface as well as bulk defects and suppresses the non-radiative recombination. The improved crystallinity, enhanced charge transport capability and reduced defect density due to K doping result in a significant enhancement of the carrier lifetime, leading to 13.04% device efficiency. This study provides a new idea for simultaneous realization of grain boundary passivation and defect suppression in inorganic kesterite solar cells.
The complicated and diverse deep defects, voids, and grain boundary in the CZTSSe absorber are the main reasons for carrier recombination and efficiency degradation. The further improvement of the open-circuit voltage and fill factor so as to increase the efficiency of CZTSSe device is urgent. In this work, we obtained K-doped CZTSSe absorber by a simple solution method. The medium-sized K atoms, which combine the advantages of light and heavy alkali metals, are able to enter the grain interior as well as segregate at grain boundary. The K-Se liquid phase can improve the absorber crystallinity. We find that the accumulation of the wide bandgap compound K2Sn2S5 at grain boundary can increase the contact potential difference of grain boundary, form more effective hole barriers, and enhance the charge separation ability. At the same time, K doping passivates the interface as well as bulk defects and suppresses the non-radiative recombination. The improved crystallinity, enhanced charge transport capability and reduced defect density due to K doping result in a significant enhancement of the carrier lifetime, leading to 13.04% device efficiency. This study provides a new idea for simultaneous realization of grain boundary passivation and defect suppression in inorganic kesterite solar cells.
2024, 35(11): 109490
doi: 10.1016/j.cclet.2024.109490
Abstract:
Zeolitic imidazolate frameworks (ZIFs) are a series of materials composited by metal ions and organic ligands with high specific surface area, which might be great precursors to produce metal oxides by calcination for gas sensor application. However, Zn-ZIF (ZIF-8) is hard to transform as ZnO in air and keeping the unique framework simultaneously. In this work, Fe2+ was introduced into the metal node to replace a part of Zn2+ ions, and it could be oxidized as Fe3+ in the calcination to facilitate the oxidation process of the 2-methylimdazole ligands to give Fe-ZnO complex shell with high specific surface area (108 m2/g) and abundant oxygen vacancies (48%). The micro electro mechanical systems (MEMS) sensor based on the 6%-Fe-ZnO complex shell performed outstanding gas sensing properties to the low-concentration acetone vapor, including high response (ΔR/Rg = 11.2 to 5 ppm acetone), superior selectivity (Sacetone/Sethanol = 5.6) and fast response speed (τres = 2.6 s). This work not only provided the research of an exceptional acetone MEMS sensor, but also induced a strategy to produce metal oxide derived from ZIFs with complex structures for the universal synthesis methodology.
Zeolitic imidazolate frameworks (ZIFs) are a series of materials composited by metal ions and organic ligands with high specific surface area, which might be great precursors to produce metal oxides by calcination for gas sensor application. However, Zn-ZIF (ZIF-8) is hard to transform as ZnO in air and keeping the unique framework simultaneously. In this work, Fe2+ was introduced into the metal node to replace a part of Zn2+ ions, and it could be oxidized as Fe3+ in the calcination to facilitate the oxidation process of the 2-methylimdazole ligands to give Fe-ZnO complex shell with high specific surface area (108 m2/g) and abundant oxygen vacancies (48%). The micro electro mechanical systems (MEMS) sensor based on the 6%-Fe-ZnO complex shell performed outstanding gas sensing properties to the low-concentration acetone vapor, including high response (ΔR/Rg = 11.2 to 5 ppm acetone), superior selectivity (Sacetone/Sethanol = 5.6) and fast response speed (τres = 2.6 s). This work not only provided the research of an exceptional acetone MEMS sensor, but also induced a strategy to produce metal oxide derived from ZIFs with complex structures for the universal synthesis methodology.
2024, 35(11): 109493
doi: 10.1016/j.cclet.2024.109493
Abstract:
Multi-response metal cluster supercrystal materials, which can simultaneously display various such as color, photoluminescence, changes by bearing only one stimulus, have huge potential as stimuli-responsive intelligent material, but are rarely reported. Here, we report three Cu8 cluster supercrystals, Cu8-1, Cu8-2, and Cu8-3, with homologous cluster molecule units [Cu8(PNP)3(EPPTA)6](PF6)2 but distinct packing. These supercrystals display bright µs-long photoluminescence with a high quantum yield of up to 26.6% in solid-state at room temperature and aggregation-induced emission (AIE) characteristic. Superior thermal stability and blue-excitable bright yellow emission make Cu8-3 serve as a yellow phosphor for white light-emitting diode. Furthermore, upon being stimulated by solvent vapor and temperature, reversible supercrystal-to-supercrystal transformations can be witnessed accompanied by remarkable color and luminescence switching. This work not only provides a kind of Cu cluster supercrystal model but also motivates the further development of metal clusters in multi-response materials.
Multi-response metal cluster supercrystal materials, which can simultaneously display various such as color, photoluminescence, changes by bearing only one stimulus, have huge potential as stimuli-responsive intelligent material, but are rarely reported. Here, we report three Cu8 cluster supercrystals, Cu8-1, Cu8-2, and Cu8-3, with homologous cluster molecule units [Cu8(PNP)3(EPPTA)6](PF6)2 but distinct packing. These supercrystals display bright µs-long photoluminescence with a high quantum yield of up to 26.6% in solid-state at room temperature and aggregation-induced emission (AIE) characteristic. Superior thermal stability and blue-excitable bright yellow emission make Cu8-3 serve as a yellow phosphor for white light-emitting diode. Furthermore, upon being stimulated by solvent vapor and temperature, reversible supercrystal-to-supercrystal transformations can be witnessed accompanied by remarkable color and luminescence switching. This work not only provides a kind of Cu cluster supercrystal model but also motivates the further development of metal clusters in multi-response materials.
2024, 35(11): 109496
doi: 10.1016/j.cclet.2024.109496
Abstract:
Oxygen evolution reaction (OER), occurring at the anode of electrochemical water splitting requires a comprehensive understanding of oxygen electrocatalysis mechanism to optimize its efficiency. Atomically dispersed transition metal supported by nitrogen-doped carbon is featured with excellent catalytic performance. Herein, we report a Mg/Co bimetal site which utilizes Mg 3p electrons with strong binding of *OH (the first key reaction intermediates in the free energy diagram) to trigger the OER reaction and Co 3d itinerant character to regulate the binding strength of *O. Benefiting from the fine-tuned adsorption/desorption possesses, the optimized catalyst delivers superior OER activity with low overpotential, i.e., 310 mV at a current density of 10 mA/cm2 and 455 mV at 100 mA/cm2. Moreover, the current density is able to be maintained at 10 mA/cm2 for 10 h, consistent with the theoretical simulations for oxidization process, which demonstrates stable configurations after multiple *OH modification, revealing robust applicability in alkaline medium.
Oxygen evolution reaction (OER), occurring at the anode of electrochemical water splitting requires a comprehensive understanding of oxygen electrocatalysis mechanism to optimize its efficiency. Atomically dispersed transition metal supported by nitrogen-doped carbon is featured with excellent catalytic performance. Herein, we report a Mg/Co bimetal site which utilizes Mg 3p electrons with strong binding of *OH (the first key reaction intermediates in the free energy diagram) to trigger the OER reaction and Co 3d itinerant character to regulate the binding strength of *O. Benefiting from the fine-tuned adsorption/desorption possesses, the optimized catalyst delivers superior OER activity with low overpotential, i.e., 310 mV at a current density of 10 mA/cm2 and 455 mV at 100 mA/cm2. Moreover, the current density is able to be maintained at 10 mA/cm2 for 10 h, consistent with the theoretical simulations for oxidization process, which demonstrates stable configurations after multiple *OH modification, revealing robust applicability in alkaline medium.
2024, 35(11): 109501
doi: 10.1016/j.cclet.2024.109501
Abstract:
Spinel oxides, with the formula AB2O4 (A and B represent metal ions) perform superior electrocatalytic characteristic when A and B are transition metals like Co, Fe, Mn, etc. Abundant researches have been attached to the structure designments while methods are often energy-intensive and inefficient. Here, we devised a universal strategy to achieve rapid synthesis of nanocrystalline spinel materials with multiple components (Co3O4, Mn3O4, CoMn2O4 and CoFe2O4 are as examples), where phase formation is within 15 s. Under the Joule-heating shock, a crack-break process of microcosmic phase transformation is observed by in-situ transmission electron microscopy. The half-wave potential values of Co3O4—JH, Mn3O4—JH, CoMn2O4—JH and CoFe2O4—JH in the electrocatalytic oxygen reduction reaction were 0.77, 0.78, 0.79 and 0.76, respectively. This suggests that the Joule heating is a fast and efficient method for the preparation of spinel oxide electrocatalysts.
Spinel oxides, with the formula AB2O4 (A and B represent metal ions) perform superior electrocatalytic characteristic when A and B are transition metals like Co, Fe, Mn, etc. Abundant researches have been attached to the structure designments while methods are often energy-intensive and inefficient. Here, we devised a universal strategy to achieve rapid synthesis of nanocrystalline spinel materials with multiple components (Co3O4, Mn3O4, CoMn2O4 and CoFe2O4 are as examples), where phase formation is within 15 s. Under the Joule-heating shock, a crack-break process of microcosmic phase transformation is observed by in-situ transmission electron microscopy. The half-wave potential values of Co3O4—JH, Mn3O4—JH, CoMn2O4—JH and CoFe2O4—JH in the electrocatalytic oxygen reduction reaction were 0.77, 0.78, 0.79 and 0.76, respectively. This suggests that the Joule heating is a fast and efficient method for the preparation of spinel oxide electrocatalysts.
2024, 35(11): 109510
doi: 10.1016/j.cclet.2024.109510
Abstract:
Silicon (Si) is considered as one of the most promising anode materials for advanced lithium-ion batteries due to its high theoretical capacity, environmental friendliness, and widespread availability. However, great challenges such as volumetric expansion, limited ionic/electronic conductivity properties and complex manufacturing processes hinder its practical applications. Herein, a novel plasma-enhanced reduced graphene oxide fibers/Si (PrGOFs/Si) composite anode is first proposed by using wet-spinning technology followed by plasma-enhanced reduction method. The PrGOFs provide large space to accommodate the volume expansion of Si nanoparticles (SiNPs) by forming a flexible 3D conductive network. Compared to the conventional thermally reduced graphene oxide fibers/Si (TrGOFs/Si) sample, the PrGOFs/Si anodes demonstrate higher conductivity, specific surface area, and superior fabrication efficiency. Accordingly, the PrGOFs/Si anodes exhibit a reversible capacity of 698.3 mAh/g, and maintain a specific capacity of 602.5 mAh/g at a current density of 200 mA/g after 100 cycles, superior to conventional TrGOFs/Si counterparts. This research presents a novel strategy for the preparation of high-performance Si/carbon anodes for energy storage applications.
Silicon (Si) is considered as one of the most promising anode materials for advanced lithium-ion batteries due to its high theoretical capacity, environmental friendliness, and widespread availability. However, great challenges such as volumetric expansion, limited ionic/electronic conductivity properties and complex manufacturing processes hinder its practical applications. Herein, a novel plasma-enhanced reduced graphene oxide fibers/Si (PrGOFs/Si) composite anode is first proposed by using wet-spinning technology followed by plasma-enhanced reduction method. The PrGOFs provide large space to accommodate the volume expansion of Si nanoparticles (SiNPs) by forming a flexible 3D conductive network. Compared to the conventional thermally reduced graphene oxide fibers/Si (TrGOFs/Si) sample, the PrGOFs/Si anodes demonstrate higher conductivity, specific surface area, and superior fabrication efficiency. Accordingly, the PrGOFs/Si anodes exhibit a reversible capacity of 698.3 mAh/g, and maintain a specific capacity of 602.5 mAh/g at a current density of 200 mA/g after 100 cycles, superior to conventional TrGOFs/Si counterparts. This research presents a novel strategy for the preparation of high-performance Si/carbon anodes for energy storage applications.
2024, 35(11): 109561
doi: 10.1016/j.cclet.2024.109561
Abstract:
A novel approach was developed to fabricate a label-free electrochemical aptasensor for specific detection of mercury ions (Hg2+). This involved modifying polylysine (PLL)-coated black phosphorus-porous graphene (BP-PG) nanocomposites (PLL/BP-PG) onto the surface of glassy carbon electrodes (GCE), which were further modified with gold nanoparticles (AuNPs) to combine with a thiolated aptamer (Apt) capable of specifically recognizing Hg2+. BP-PG was synthesized using the solvothermal method and covalently bonded to form BP-PG nanosheets, resulting in significant enhanced electrochemical properties of the PLL/BP-PG composite. Furthermore, the PLL/BP-PG composite was improved environmental stability of BP and provided a considerable quantity of -NH2 for bonding to AuNPs firmly by assembling. The physical properties and electrochemical behavior of the substrate materials were investigated using various characterization techniques, and analytical parameters were optimized. It is shown that, the Apt/AuNPs/PLL/BP-PG/GCE had a linear response (R2 = 0.999) with good selectivity and high sensitivity over the Hg2+ range of 1–10,000 nmol/L. The proposed sensor has a detection limit of 0.045 nmol/L and can be employed for detecting of Hg2+. It also obtained satisfying results in river water, soil and vegetable samples.
A novel approach was developed to fabricate a label-free electrochemical aptasensor for specific detection of mercury ions (Hg2+). This involved modifying polylysine (PLL)-coated black phosphorus-porous graphene (BP-PG) nanocomposites (PLL/BP-PG) onto the surface of glassy carbon electrodes (GCE), which were further modified with gold nanoparticles (AuNPs) to combine with a thiolated aptamer (Apt) capable of specifically recognizing Hg2+. BP-PG was synthesized using the solvothermal method and covalently bonded to form BP-PG nanosheets, resulting in significant enhanced electrochemical properties of the PLL/BP-PG composite. Furthermore, the PLL/BP-PG composite was improved environmental stability of BP and provided a considerable quantity of -NH2 for bonding to AuNPs firmly by assembling. The physical properties and electrochemical behavior of the substrate materials were investigated using various characterization techniques, and analytical parameters were optimized. It is shown that, the Apt/AuNPs/PLL/BP-PG/GCE had a linear response (R2 = 0.999) with good selectivity and high sensitivity over the Hg2+ range of 1–10,000 nmol/L. The proposed sensor has a detection limit of 0.045 nmol/L and can be employed for detecting of Hg2+. It also obtained satisfying results in river water, soil and vegetable samples.
2024, 35(11): 109570
doi: 10.1016/j.cclet.2024.109570
Abstract:
Dual-specificity tyrosine-phosphorylation-regulated kinase 1A (DYRK1A) is the most promising target for diabetes treatment by promoting β-cell proliferation. The desmethylbellidifolin (DMB) as a DYRK1A inhibitor could facilitate β-cell proliferation in vivo and in vitro. However, DMB has the problem of weak binding affinity to DYRK1A, which means that continuous high concentration administration of DMB is effective for the diabetes. In order to solve this problem, we designed and synthesized a series of DMB-based proteolysis targeting chimeras (PROTACs) by taking advantage of the property of PROTAC that induce protein degradation in a cycle-catalytic manner. MDM2-based PROTAC X1–4P-MDM2 was identified as the most active PROTAC molecule. Mechanism research showed that X1–4P-MDM2 formed a ternary complex with DYRK1A and murine double minute 2 (MDM2), and induced the degradation of DYRK1A through the ubiquitin-proteasome system pathway. At a dose much lower than that of DMB, X1–4P-MDM2 still significantly enhanced β-cell proliferation by inhibiting transforming growth factor beta (TGF-β) and promoting the mitogen-activated protein kinases/extracellular signal-regulated kinase (MAPK/ERK) signaling pathway, which may provide a new strategy for the application of DMB in diabetes.
Dual-specificity tyrosine-phosphorylation-regulated kinase 1A (DYRK1A) is the most promising target for diabetes treatment by promoting β-cell proliferation. The desmethylbellidifolin (DMB) as a DYRK1A inhibitor could facilitate β-cell proliferation in vivo and in vitro. However, DMB has the problem of weak binding affinity to DYRK1A, which means that continuous high concentration administration of DMB is effective for the diabetes. In order to solve this problem, we designed and synthesized a series of DMB-based proteolysis targeting chimeras (PROTACs) by taking advantage of the property of PROTAC that induce protein degradation in a cycle-catalytic manner. MDM2-based PROTAC X1–4P-MDM2 was identified as the most active PROTAC molecule. Mechanism research showed that X1–4P-MDM2 formed a ternary complex with DYRK1A and murine double minute 2 (MDM2), and induced the degradation of DYRK1A through the ubiquitin-proteasome system pathway. At a dose much lower than that of DMB, X1–4P-MDM2 still significantly enhanced β-cell proliferation by inhibiting transforming growth factor beta (TGF-β) and promoting the mitogen-activated protein kinases/extracellular signal-regulated kinase (MAPK/ERK) signaling pathway, which may provide a new strategy for the application of DMB in diabetes.
2024, 35(11): 109574
doi: 10.1016/j.cclet.2024.109574
Abstract:
The development of enantioselective C-H macrocyclizations to efficiently access structurally diversified macrocycles is highly desirable, but remain a big challenge. Herein, we reported the first rhodium(Ⅲ)-catalyzed asymmetric intramolecular C-H macrocyclization, enabling the efficient synthesis of structurally diverse enantioenriched macrocycles. This robust enantioselective C-H macrocyclization has a broad functional group tolerance, excellent enantioselectivities (up to 98.5:1.5 e.r.) and a mild reaction condition, releasing CO2 as the single by-product. More significantly, the resulting unique enantioenriched 19-membered macrocycle 2f was found to demonstrate a potent in vitro anti-Zika virus (ZIKV) activity without obvious cytotoxicity. Further investigation revealed that the anti-ZIKV activity is presumably attributed to an autophagy inhibition in the early stage of viral infection by down-regulating the expression of autophagy related gene Atg12.
The development of enantioselective C-H macrocyclizations to efficiently access structurally diversified macrocycles is highly desirable, but remain a big challenge. Herein, we reported the first rhodium(Ⅲ)-catalyzed asymmetric intramolecular C-H macrocyclization, enabling the efficient synthesis of structurally diverse enantioenriched macrocycles. This robust enantioselective C-H macrocyclization has a broad functional group tolerance, excellent enantioselectivities (up to 98.5:1.5 e.r.) and a mild reaction condition, releasing CO2 as the single by-product. More significantly, the resulting unique enantioenriched 19-membered macrocycle 2f was found to demonstrate a potent in vitro anti-Zika virus (ZIKV) activity without obvious cytotoxicity. Further investigation revealed that the anti-ZIKV activity is presumably attributed to an autophagy inhibition in the early stage of viral infection by down-regulating the expression of autophagy related gene Atg12.
2024, 35(11): 109577
doi: 10.1016/j.cclet.2024.109577
Abstract:
For the first time, proteolysis-targeting chimeras (PROTAC) technology was utilized to achieve the isoform-selective degradation of class Ⅰ phosphoinositide 3-kinases (PI3Ks) in this study. Through screening and optimization, the PROTAC molecule ZM-PI05 was identified as a selective degrader of p110α in multiple breast cancer cells. More importantly, the degrader can down-regulate p85 regulatory subunit simultaneously, thereby inhibiting the non-enzymatic functions of PI3K that are independent on p110 catalytic subunits. Therefore, compared with PI3K inhibitor copanlisib, ZM-PI05 displayed the stronger anti-proliferative activity on breast cancer cells. In brief, a selective and efficient PROTAC molecule was developed to induce the degradation of p110α and concurrent reduction of p85 proteins, providing a tool compound for the biological study of PI3K-α by blocking its enzymatic and non-enzymatic functions.
For the first time, proteolysis-targeting chimeras (PROTAC) technology was utilized to achieve the isoform-selective degradation of class Ⅰ phosphoinositide 3-kinases (PI3Ks) in this study. Through screening and optimization, the PROTAC molecule ZM-PI05 was identified as a selective degrader of p110α in multiple breast cancer cells. More importantly, the degrader can down-regulate p85 regulatory subunit simultaneously, thereby inhibiting the non-enzymatic functions of PI3K that are independent on p110 catalytic subunits. Therefore, compared with PI3K inhibitor copanlisib, ZM-PI05 displayed the stronger anti-proliferative activity on breast cancer cells. In brief, a selective and efficient PROTAC molecule was developed to induce the degradation of p110α and concurrent reduction of p85 proteins, providing a tool compound for the biological study of PI3K-α by blocking its enzymatic and non-enzymatic functions.
2024, 35(11): 109578
doi: 10.1016/j.cclet.2024.109578
Abstract:
Enhancing the active tumor targeting ability and decreasing the clearance of reticuloendothelial system (RES) are important issues for drug delivery systems (DDSs) in cancer therapy. In recent years, cell membrane camouflage, as one of the biomimetic modification strategies, has shown huge potential. Many natural properties of source cells can be inherited, allowing the DDSs to successfully avoid phagocytosis by macrophages, prolong circulation time, and achieve homologous targeting to lesion tissue. In this study, a cancer cell membrane camouflaged nanoplatform based on gelatin with a typical core-shell structure was developed for cancer chemotherapy. Doxorubicin (DOX) loaded gelatin nanogel (NG@DOX) acted as the inner core, and 4T1 (mouse breast carcinoma cell) membrane was set as the outer shell (M-NG@DOX). The M-NG platform enhanced the ability of homologous targeting due to the surface protein of cell membrane being completely retained, which could promote the cell uptake of homotypic cells, avoid phagocytosis by RAW264.7 macrophages, and therefore increase accumulation in tumor tissue. Meanwhile, due to the better controlled drug release capability of M-NG@DOX, premature release of DOX in circulation could be reduced, minimizing side effects in common chemotherapy. As a result, the biomimetic nanoplatform in this study, obtained by a cancer cell membrane camouflaged drug delivery system, efficiently reached desirable tumor elimination, providing a significant strategy for effective targeted therapy and specific carcinoma therapy.
Enhancing the active tumor targeting ability and decreasing the clearance of reticuloendothelial system (RES) are important issues for drug delivery systems (DDSs) in cancer therapy. In recent years, cell membrane camouflage, as one of the biomimetic modification strategies, has shown huge potential. Many natural properties of source cells can be inherited, allowing the DDSs to successfully avoid phagocytosis by macrophages, prolong circulation time, and achieve homologous targeting to lesion tissue. In this study, a cancer cell membrane camouflaged nanoplatform based on gelatin with a typical core-shell structure was developed for cancer chemotherapy. Doxorubicin (DOX) loaded gelatin nanogel (NG@DOX) acted as the inner core, and 4T1 (mouse breast carcinoma cell) membrane was set as the outer shell (M-NG@DOX). The M-NG platform enhanced the ability of homologous targeting due to the surface protein of cell membrane being completely retained, which could promote the cell uptake of homotypic cells, avoid phagocytosis by RAW264.7 macrophages, and therefore increase accumulation in tumor tissue. Meanwhile, due to the better controlled drug release capability of M-NG@DOX, premature release of DOX in circulation could be reduced, minimizing side effects in common chemotherapy. As a result, the biomimetic nanoplatform in this study, obtained by a cancer cell membrane camouflaged drug delivery system, efficiently reached desirable tumor elimination, providing a significant strategy for effective targeted therapy and specific carcinoma therapy.
2024, 35(11): 109592
doi: 10.1016/j.cclet.2024.109592
Abstract:
Melanoma treatment has been revolutionized with the development of targeted therapies and immunotherapies, which shows a positive influence on the patients. However, the long-term efficaciousness of such therapy is restricted by side effects, limited clinical effects as well as quick resistance to treatment. In this work, we prepared magnetocaloric carrier-free bimetallic hydrogels, named manganese-iron oxide nanocubes@polyethylene glycol-hydrogels (MFO@PEG-Gels), to realize ion-interferential cell cycle arrest for melanoma treatment. In detail, the tumor site was exposed to alternating magnetic field (AMF) after intratumorally injected MFO@PEG-Gels, which generated hyperthermia and promoted the sol-gel phase transition for MFO sustained release. Under the tumor microenvironment, hydrogen peroxide triggered MFO degradation to induce Mn2+ and Fe3+ release. On one hand, Mn2+ blocked G1/S phase through the activation of p27 pathway. On the other hand, Fe3+ could arrest the G2/M phase by upregulating the polo-like kinase 4 (PLK4) expression as well as inhibiting autolysosome formation to achieve the enhanced cell cycle arrest, thereby promoting the apoptosis of melanoma cells. In summary, this study proposed ion-interferential cell cycle arrest strategy by a multifunctional and injectable magnetic bimetallic hydrogel for melanoma treatment, which provided a secure and sustainable regimen for enhancing anti-tumor efficacy.
Melanoma treatment has been revolutionized with the development of targeted therapies and immunotherapies, which shows a positive influence on the patients. However, the long-term efficaciousness of such therapy is restricted by side effects, limited clinical effects as well as quick resistance to treatment. In this work, we prepared magnetocaloric carrier-free bimetallic hydrogels, named manganese-iron oxide nanocubes@polyethylene glycol-hydrogels (MFO@PEG-Gels), to realize ion-interferential cell cycle arrest for melanoma treatment. In detail, the tumor site was exposed to alternating magnetic field (AMF) after intratumorally injected MFO@PEG-Gels, which generated hyperthermia and promoted the sol-gel phase transition for MFO sustained release. Under the tumor microenvironment, hydrogen peroxide triggered MFO degradation to induce Mn2+ and Fe3+ release. On one hand, Mn2+ blocked G1/S phase through the activation of p27 pathway. On the other hand, Fe3+ could arrest the G2/M phase by upregulating the polo-like kinase 4 (PLK4) expression as well as inhibiting autolysosome formation to achieve the enhanced cell cycle arrest, thereby promoting the apoptosis of melanoma cells. In summary, this study proposed ion-interferential cell cycle arrest strategy by a multifunctional and injectable magnetic bimetallic hydrogel for melanoma treatment, which provided a secure and sustainable regimen for enhancing anti-tumor efficacy.
2024, 35(11): 109594
doi: 10.1016/j.cclet.2024.109594
Abstract:
α1-Adrenergic receptor (AR) blockers can be effective for the treatment of benign prostatic hyperplasia/lower urinary tract symptoms (BPH/LUTS), their usage is limited by cardiovascular-related side effects that are caused by the subtype nonselective nature or low selectivity of many current drugs. We previously reported that phenylpiperazine analogues with amide and propane linker were moderate α1D/1A adrenoceptor antagonists and exhibited better anti-BPH effect than lead compound naftopidil (NAF) in vivo, however, with modest α1D/1A-subtype selectivity. Herein, we replaced propane moiety with 2-hydroxypropanol linker and synthesized twenty-seven racemic derivatives with modified aromatic and hetero aromatic groups. Of these new compounds, quinoline surrogate 17 exhibited extremely weak antagonistic affinity on α1B in both cell-based calcium assay and tissue-based functional assay, so that elicited significant α1A/1B and α1D/1B selectivity. Intriguingly, the R enantiomer of 17 preferentially displayed superior anti-BPH effect in rat model compared with S-17, supporting ligand regulates the receptor in a highly stereospecific manner. Finally, the computer-aided modelling research was also performed in order to deeply understand the unique binding mode of R-17 in complex with α1A and the subtype receptor selectivity for R-17 was also rationalized in this study. Taken together, our work enriched the diversity of phenylpiperazines for the treatment of BPH/LUTS, and provided a basis for discovery of α1D/1A-selective ligands.
α1-Adrenergic receptor (AR) blockers can be effective for the treatment of benign prostatic hyperplasia/lower urinary tract symptoms (BPH/LUTS), their usage is limited by cardiovascular-related side effects that are caused by the subtype nonselective nature or low selectivity of many current drugs. We previously reported that phenylpiperazine analogues with amide and propane linker were moderate α1D/1A adrenoceptor antagonists and exhibited better anti-BPH effect than lead compound naftopidil (NAF) in vivo, however, with modest α1D/1A-subtype selectivity. Herein, we replaced propane moiety with 2-hydroxypropanol linker and synthesized twenty-seven racemic derivatives with modified aromatic and hetero aromatic groups. Of these new compounds, quinoline surrogate 17 exhibited extremely weak antagonistic affinity on α1B in both cell-based calcium assay and tissue-based functional assay, so that elicited significant α1A/1B and α1D/1B selectivity. Intriguingly, the R enantiomer of 17 preferentially displayed superior anti-BPH effect in rat model compared with S-17, supporting ligand regulates the receptor in a highly stereospecific manner. Finally, the computer-aided modelling research was also performed in order to deeply understand the unique binding mode of R-17 in complex with α1A and the subtype receptor selectivity for R-17 was also rationalized in this study. Taken together, our work enriched the diversity of phenylpiperazines for the treatment of BPH/LUTS, and provided a basis for discovery of α1D/1A-selective ligands.
2024, 35(11): 109601
doi: 10.1016/j.cclet.2024.109601
Abstract:
As a vital negative regulator of Wnt signaling pathway, human Notum (hNotum) plays a crucial regulatory role in the progression of many human diseases. Deciphering the relevance of hNotum to human diseases requires practical and reliable tools for visualizing hNotum activity in living systems. Herein, an enzyme-activatable fluorogenic tool (IR-783 octanoate) was rationally engineered for sensing and imaging hNotum activity in living systems by integrating computer-aided molecular design and biochemical assays. IR-783 octanoate showed good optical properties, excellent specificity and high binding-affinity towards hNotum (Km = 0.98 µmol/L). IR-783 octanoate could be well up-taken into the cancerous cells or tumors that over-expressed organic anion transporting polypeptides (OATPs), and then hydrolyzed by cellular hNotum to release free IR-783 ketone, which created brightly fluorescent signals around 646 nm. Further investigations showed that IR-783 octanoate achieved a good performance for in-situ functional imaging of hNotum in both living cells, cancerous tissues and organs. It was also found that some SW620 cells with multipolar spindles could be stained by IR-783 octanoate to emit extremely bright signals, suggesting that this agent could be used as a novel visualizing tool for tracing the cells undergoing abnormal cell mitoses. Collectively, this study devises a highly specific fluorogenic tool for in-situ functional imaging of hNotum in living systems, which offers a practical and reliable tool to dynamically track the changes in hNotum activity under various conditions.
As a vital negative regulator of Wnt signaling pathway, human Notum (hNotum) plays a crucial regulatory role in the progression of many human diseases. Deciphering the relevance of hNotum to human diseases requires practical and reliable tools for visualizing hNotum activity in living systems. Herein, an enzyme-activatable fluorogenic tool (IR-783 octanoate) was rationally engineered for sensing and imaging hNotum activity in living systems by integrating computer-aided molecular design and biochemical assays. IR-783 octanoate showed good optical properties, excellent specificity and high binding-affinity towards hNotum (Km = 0.98 µmol/L). IR-783 octanoate could be well up-taken into the cancerous cells or tumors that over-expressed organic anion transporting polypeptides (OATPs), and then hydrolyzed by cellular hNotum to release free IR-783 ketone, which created brightly fluorescent signals around 646 nm. Further investigations showed that IR-783 octanoate achieved a good performance for in-situ functional imaging of hNotum in both living cells, cancerous tissues and organs. It was also found that some SW620 cells with multipolar spindles could be stained by IR-783 octanoate to emit extremely bright signals, suggesting that this agent could be used as a novel visualizing tool for tracing the cells undergoing abnormal cell mitoses. Collectively, this study devises a highly specific fluorogenic tool for in-situ functional imaging of hNotum in living systems, which offers a practical and reliable tool to dynamically track the changes in hNotum activity under various conditions.
2024, 35(11): 109602
doi: 10.1016/j.cclet.2024.109602
Abstract:
Antibacterial agent of activatable photosensitizer not only has the advantages of traditional photosensitizers, such as good curative effect and low resistance, but also has better selectivity for bacteria and lower toxicity to normal tissues. Limited reports of activatable photosensitizer can be used to treat drug-resistant bacteria. In order to meet this challenge, we designed and synthesized an activatable photosensitizer (Ce-OHOA), which can not only selectively identify methicillin-resistant Staphylococcus aureus (MRSA) with high expression of β-lactamase by fluorescence imaging, but also kill MRSA with less than 10 times the concentration and 10 times the irradiation dose of CySG-2 reported. Ce-OHOA not only combines the dual functions of fluorescence diagnosis and photodynamic therapy, but also selectively acts on bacteria with high expression of β-lactamase and has little toxicity to normal cells. We expect that the study of this activating photosensitizer will provide a new solution for antibacterial photodynamic therapy (aPDT) of drug-resistant bacteria.
Antibacterial agent of activatable photosensitizer not only has the advantages of traditional photosensitizers, such as good curative effect and low resistance, but also has better selectivity for bacteria and lower toxicity to normal tissues. Limited reports of activatable photosensitizer can be used to treat drug-resistant bacteria. In order to meet this challenge, we designed and synthesized an activatable photosensitizer (Ce-OHOA), which can not only selectively identify methicillin-resistant Staphylococcus aureus (MRSA) with high expression of β-lactamase by fluorescence imaging, but also kill MRSA with less than 10 times the concentration and 10 times the irradiation dose of CySG-2 reported. Ce-OHOA not only combines the dual functions of fluorescence diagnosis and photodynamic therapy, but also selectively acts on bacteria with high expression of β-lactamase and has little toxicity to normal cells. We expect that the study of this activating photosensitizer will provide a new solution for antibacterial photodynamic therapy (aPDT) of drug-resistant bacteria.
2024, 35(11): 109603
doi: 10.1016/j.cclet.2024.109603
Abstract:
Non-alcoholic fatty liver disease (NAFLD) is prevalent worldwide as a chronic liver disease that not only gives rise to hepatic complications, but leads to other chronic diseases such as type 2 diabetes and atherosclerosis. The aberrant accumulation of lipid droplets (LDs) in hepatocytes is a prominent signature of NAFLD. However, conventional techniques lack the capability to effectively monitor the dynamic changes in LD levels during NAFLD with living organisms. Hence, it is imperative to develop LD-specific long-wavelength fluorescent probes with high imaging contrast for the in-situ diagnosis of NAFLD. In this study, we synthesized a new LD-selective long-wavelength fluorescent probe, denoted as LD-1, based on the twisted intramolecular charge transfer (TICT) mechanism. The probe exhibits a large Stokes shift and intensive fluorescence emission in nonpolar and viscous solutions. By self-assembling LD-1 with bovine serum albumin (BSA), a biocompatible, long-wavelength fluorescent probe hybrid, LD-1@BSA, was formed, allowing for LDs to be selectively imaged in hepatocytes. Moreover, LD-1@BSA successfully discriminates NAFLD cells before and after drug treatment, and achieves non-invasive and real-time monitoring of LD accumulation in a mouse model of NAFLD.
Non-alcoholic fatty liver disease (NAFLD) is prevalent worldwide as a chronic liver disease that not only gives rise to hepatic complications, but leads to other chronic diseases such as type 2 diabetes and atherosclerosis. The aberrant accumulation of lipid droplets (LDs) in hepatocytes is a prominent signature of NAFLD. However, conventional techniques lack the capability to effectively monitor the dynamic changes in LD levels during NAFLD with living organisms. Hence, it is imperative to develop LD-specific long-wavelength fluorescent probes with high imaging contrast for the in-situ diagnosis of NAFLD. In this study, we synthesized a new LD-selective long-wavelength fluorescent probe, denoted as LD-1, based on the twisted intramolecular charge transfer (TICT) mechanism. The probe exhibits a large Stokes shift and intensive fluorescence emission in nonpolar and viscous solutions. By self-assembling LD-1 with bovine serum albumin (BSA), a biocompatible, long-wavelength fluorescent probe hybrid, LD-1@BSA, was formed, allowing for LDs to be selectively imaged in hepatocytes. Moreover, LD-1@BSA successfully discriminates NAFLD cells before and after drug treatment, and achieves non-invasive and real-time monitoring of LD accumulation in a mouse model of NAFLD.
2024, 35(11): 109620
doi: 10.1016/j.cclet.2024.109620
Abstract:
Triple-negative breast cancer, due to its aggressive nature and lack of targeted treatment, faces serious challenges in breast cancer treatment. Conventional therapies, such as chemotherapy, are encumbered by a range of limitations, and there is an urgent need for more effective treatment strategies. Ferroptosis, as an iron-dependent form of cell death, has exhibited promising potential in cancer treatment. Combining ferroptosis with other cancer therapies offers new avenues for treatment. Tetrahedral DNA nanostructure (TDN), a novel DNA-based three-dimensional (3D) nanomaterial, is promising drug delivery vehicle and can be utilized for functionalizing inorganic nanomaterials. In this work, we have demonstrated the preparation of Fe3O4-PEI@TDN-DOX nanocomposites and elucidated their antitumor mechanism. The TDN facilitated the enhanced cellular uptake of polyetherimide (PEI)-modified Fe3O4, and the delivery of the chemotherapeutic drug doxorubicin (DOX) further augmented their anti-tumor effect. This novel strategy can destroy the tumor redox homeostasis and produce overwhelming lipid peroxides, consequently sensitizing the tumor to ferroptosis. The integration of ferroptosis with other cancer therapies opens up new possibilities for treatment. This research provides valuable mechanistic insights and practical strategies for leveraging nanotechnology to induce ferroptosis and amplify its impact on tumor cells.
Triple-negative breast cancer, due to its aggressive nature and lack of targeted treatment, faces serious challenges in breast cancer treatment. Conventional therapies, such as chemotherapy, are encumbered by a range of limitations, and there is an urgent need for more effective treatment strategies. Ferroptosis, as an iron-dependent form of cell death, has exhibited promising potential in cancer treatment. Combining ferroptosis with other cancer therapies offers new avenues for treatment. Tetrahedral DNA nanostructure (TDN), a novel DNA-based three-dimensional (3D) nanomaterial, is promising drug delivery vehicle and can be utilized for functionalizing inorganic nanomaterials. In this work, we have demonstrated the preparation of Fe3O4-PEI@TDN-DOX nanocomposites and elucidated their antitumor mechanism. The TDN facilitated the enhanced cellular uptake of polyetherimide (PEI)-modified Fe3O4, and the delivery of the chemotherapeutic drug doxorubicin (DOX) further augmented their anti-tumor effect. This novel strategy can destroy the tumor redox homeostasis and produce overwhelming lipid peroxides, consequently sensitizing the tumor to ferroptosis. The integration of ferroptosis with other cancer therapies opens up new possibilities for treatment. This research provides valuable mechanistic insights and practical strategies for leveraging nanotechnology to induce ferroptosis and amplify its impact on tumor cells.
2024, 35(11): 109624
doi: 10.1016/j.cclet.2024.109624
Abstract:
Endogenous metabolites play key functions in many important physiological and biochemical processes. The comprehensive in situ detection and direct imaging of metabolites in bio-tissues by matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI) is very important for understanding complex and diverse biological processes and has become an essential aspect of spatial omics. In this work, 4-aminoazobenzene (AAB) was successfully screened and optimized as a new negative ion (−)MALDI matrix to enhance the in situ detection and imaging of metabolites in tissues using MALDI-MSI. Obviously, AAB exhibited superior properties in terms of ultraviolet absorption, background ion interference, matrix morphology, and metabolite ionization efficiency. AAB was used for in situ detection and imaging of metabolites in rat brain and germinating Chinese yew seed tissue sections, where 264 and 339 metabolite ion signals were successfully detected and imaged using (-)MALDI-MS, respectively. In addition, high-resolution imaging of mouse eyeball section using MALDI-timsTOF MSI with spatial resolution of up to 10 µm was successfully carried out, showing that AAB is an efficient (-)MALDI matrix for capturing high-resolution images of metabolites in biological tissue sections.
Endogenous metabolites play key functions in many important physiological and biochemical processes. The comprehensive in situ detection and direct imaging of metabolites in bio-tissues by matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI) is very important for understanding complex and diverse biological processes and has become an essential aspect of spatial omics. In this work, 4-aminoazobenzene (AAB) was successfully screened and optimized as a new negative ion (−)MALDI matrix to enhance the in situ detection and imaging of metabolites in tissues using MALDI-MSI. Obviously, AAB exhibited superior properties in terms of ultraviolet absorption, background ion interference, matrix morphology, and metabolite ionization efficiency. AAB was used for in situ detection and imaging of metabolites in rat brain and germinating Chinese yew seed tissue sections, where 264 and 339 metabolite ion signals were successfully detected and imaged using (-)MALDI-MS, respectively. In addition, high-resolution imaging of mouse eyeball section using MALDI-timsTOF MSI with spatial resolution of up to 10 µm was successfully carried out, showing that AAB is an efficient (-)MALDI matrix for capturing high-resolution images of metabolites in biological tissue sections.
2024, 35(11): 109626
doi: 10.1016/j.cclet.2024.109626
Abstract:
Chemodynamic therapy (CDT) relying on the transformation of endogenous hydrogen peroxide (H2O2) into cytotoxic hydroxyl radicals (•OH) based on the catalysis of Fenton/Fenton-type reactions exhibits great potentiality for cancer treatment. However, the inadequate H2O2 supply and intricate redox homeostasis in tumor microenvironment (TME) severely impair the efficacy of CDT. Herein, we design self-assembled 1,2-distearoyl-sn-glycero-3-phosphoethanolamine conjugated polyethylene glycol (DSPE-PEG)-modified Fe(Ⅲ)-juglone nanoscale coordination polymers (FJP NCPs) as redox homeostasis disruptors for juglone-enhanced CDT. Responding to glutathione (GSH)-rich and acidic TME, the Fe2+/Fe3+-guided CDT and GSH consumption by Fe3+ are activated, resulting in •OH downstream and up-regulation of lipid peroxidation (LPO). In addition, the released juglone not only depletes GSH through Michael addition, but also elevates intracellular H2O2 level for achieving •OH further bursting. With the impressive efficiency of GSH exhaustion and reactive oxygen species (ROS) storm generation, ferroptosis and apoptosis are significantly enhanced by FJP NCPs in vivo. In brief, this facile and efficient design for versatile nanoscale coordination polymers presents a novel paradigm for effectively elevating CDT efficiency and tumor synergistic therapy.
Chemodynamic therapy (CDT) relying on the transformation of endogenous hydrogen peroxide (H2O2) into cytotoxic hydroxyl radicals (•OH) based on the catalysis of Fenton/Fenton-type reactions exhibits great potentiality for cancer treatment. However, the inadequate H2O2 supply and intricate redox homeostasis in tumor microenvironment (TME) severely impair the efficacy of CDT. Herein, we design self-assembled 1,2-distearoyl-sn-glycero-3-phosphoethanolamine conjugated polyethylene glycol (DSPE-PEG)-modified Fe(Ⅲ)-juglone nanoscale coordination polymers (FJP NCPs) as redox homeostasis disruptors for juglone-enhanced CDT. Responding to glutathione (GSH)-rich and acidic TME, the Fe2+/Fe3+-guided CDT and GSH consumption by Fe3+ are activated, resulting in •OH downstream and up-regulation of lipid peroxidation (LPO). In addition, the released juglone not only depletes GSH through Michael addition, but also elevates intracellular H2O2 level for achieving •OH further bursting. With the impressive efficiency of GSH exhaustion and reactive oxygen species (ROS) storm generation, ferroptosis and apoptosis are significantly enhanced by FJP NCPs in vivo. In brief, this facile and efficient design for versatile nanoscale coordination polymers presents a novel paradigm for effectively elevating CDT efficiency and tumor synergistic therapy.
2024, 35(11): 109627
doi: 10.1016/j.cclet.2024.109627
Abstract:
Chronic kidney disease (CKD) is an increasingly prevalent medical condition associated with high mortality and cardiovascular complications. The intricate interplay between kidney dysfunction and subsequent metabolic disturbances may provide insights into the underlying mechanisms driving CKD onset and progression. Herein, we proposed a large-scale plasma metabolite identification and quantification system that combines the strengths of targeted and untargeted metabolomics technologies, i.e., widely-targeted metabolomics (WT-Met) approach. WT-Met method enables large-scale identification and accurate quantification of thousands of metabolites. We collected plasma samples from 21 healthy controls and 62 CKD patients, categorized into different stages (22 in stages 1–3, 20 in stage 4, and 20 in stage 5). Using LC-MS-based WT-Met approach, we were able to effectively annotate and quantify a total of 1431 metabolites from the plasma samples. Focusing on the 539 endogenous metabolites, we identified 399 significantly altered metabolites and depicted their changing patterns from healthy controls to end-stage CKD. Furthermore, we employed machine-learning to identify the optimal combination of metabolites for predicting different stages of CKD. We generated a multiclass classifier consisting of 7 metabolites by machine-learning, which exhibited an average AUC of 0.99 for the test set. In general, amino acids, nucleotides, organic acids, and their metabolites emerged as the most significantly altered metabolites. However, their patterns of change varied across different stages of CKD. The 7-metabolite panel demonstrates promising potential as biomarker candidates for CKD. Further exploration of these metabolites can provide valuable insights into their roles in the etiology and progression of CKD.
Chronic kidney disease (CKD) is an increasingly prevalent medical condition associated with high mortality and cardiovascular complications. The intricate interplay between kidney dysfunction and subsequent metabolic disturbances may provide insights into the underlying mechanisms driving CKD onset and progression. Herein, we proposed a large-scale plasma metabolite identification and quantification system that combines the strengths of targeted and untargeted metabolomics technologies, i.e., widely-targeted metabolomics (WT-Met) approach. WT-Met method enables large-scale identification and accurate quantification of thousands of metabolites. We collected plasma samples from 21 healthy controls and 62 CKD patients, categorized into different stages (22 in stages 1–3, 20 in stage 4, and 20 in stage 5). Using LC-MS-based WT-Met approach, we were able to effectively annotate and quantify a total of 1431 metabolites from the plasma samples. Focusing on the 539 endogenous metabolites, we identified 399 significantly altered metabolites and depicted their changing patterns from healthy controls to end-stage CKD. Furthermore, we employed machine-learning to identify the optimal combination of metabolites for predicting different stages of CKD. We generated a multiclass classifier consisting of 7 metabolites by machine-learning, which exhibited an average AUC of 0.99 for the test set. In general, amino acids, nucleotides, organic acids, and their metabolites emerged as the most significantly altered metabolites. However, their patterns of change varied across different stages of CKD. The 7-metabolite panel demonstrates promising potential as biomarker candidates for CKD. Further exploration of these metabolites can provide valuable insights into their roles in the etiology and progression of CKD.
2024, 35(11): 109629
doi: 10.1016/j.cclet.2024.109629
Abstract:
The low drug bioavailability of eye drops challenges the therapy of ocular disorders with high efficacy. One of solutions is to extend the corneal retention and enhance the penetration of drug into cornea. Here we synthesize two fluorophore-conjugated peptide based analogs rich in positive charges (i.e., NBD-FFKK) and with a specific ligand (i.e., NBD-FFRGD), respectively, to visualize their performances in vitro and in vivo. The peptides both can self-assemble into supramolecular hydrogels with the microstructure of nanofibers. The in vitro experiments exhibit that two peptides are both uniformly distributed in cytoplasm, and the intracellular amount of peptide rich in positive charges is significantly larger than that of peptide with a specific ligand. The living corneal fluorescence shows that two peptides enter the corneal stroma within 15 min, and the peptide rich in positive charges is accumulated more extensively throughout the entire cornea, revealing that the supramolecular hydrogel eye drops penetrate the cornea more efficiently via electrostatic interaction than that via ligand-receptor interaction. This work, as a comparative study of supramolecular hydrogel eye drops on penetrating efficiency, indicates a possible direction for the design of eye drops with efficient corneal penetration.
The low drug bioavailability of eye drops challenges the therapy of ocular disorders with high efficacy. One of solutions is to extend the corneal retention and enhance the penetration of drug into cornea. Here we synthesize two fluorophore-conjugated peptide based analogs rich in positive charges (i.e., NBD-FFKK) and with a specific ligand (i.e., NBD-FFRGD), respectively, to visualize their performances in vitro and in vivo. The peptides both can self-assemble into supramolecular hydrogels with the microstructure of nanofibers. The in vitro experiments exhibit that two peptides are both uniformly distributed in cytoplasm, and the intracellular amount of peptide rich in positive charges is significantly larger than that of peptide with a specific ligand. The living corneal fluorescence shows that two peptides enter the corneal stroma within 15 min, and the peptide rich in positive charges is accumulated more extensively throughout the entire cornea, revealing that the supramolecular hydrogel eye drops penetrate the cornea more efficiently via electrostatic interaction than that via ligand-receptor interaction. This work, as a comparative study of supramolecular hydrogel eye drops on penetrating efficiency, indicates a possible direction for the design of eye drops with efficient corneal penetration.
2024, 35(11): 109633
doi: 10.1016/j.cclet.2024.109633
Abstract:
Nitrogen-doped carbon (N–C) materials have demonstrated exceptional performances in activating peroxymonosulfate (PMS) for environmental remediation. However, accommodating higher nitrogen contents remains challenging in N–C due to the thermodynamic instability of C–N skeleton. In this study, we proposed an innovative epitaxial growth approach to synthesize two-dimensional N–C nanosheets. Leveraging the abundant amino groups supplied by the polymer dots as growing sites, we successfully attained a high nitrogen level and spontaneously introduced abundant structural defects in the carbon framework. The resulting N–C nanosheets exhibited outstanding catalytic activity for the activation of PMS toward selective oxidation of diethyl 1,4-dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate (1,4-DHP) into diethyl 2,6-dimethylpyridine-3,5-dicarboxylate, which serves as a valuable intermediate in the synthesis of various pharmaceutical compounds. Comprehensive experimental and characterization investigations verified that the nitrogen sites and defects are the primary active sites for PMS activation and selective oxidation of 1,4-DHP. This work offered an efficient approach for the fabrication of high-nitrogen-loading carbon materials for catalytic oxidation reactions.
Nitrogen-doped carbon (N–C) materials have demonstrated exceptional performances in activating peroxymonosulfate (PMS) for environmental remediation. However, accommodating higher nitrogen contents remains challenging in N–C due to the thermodynamic instability of C–N skeleton. In this study, we proposed an innovative epitaxial growth approach to synthesize two-dimensional N–C nanosheets. Leveraging the abundant amino groups supplied by the polymer dots as growing sites, we successfully attained a high nitrogen level and spontaneously introduced abundant structural defects in the carbon framework. The resulting N–C nanosheets exhibited outstanding catalytic activity for the activation of PMS toward selective oxidation of diethyl 1,4-dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate (1,4-DHP) into diethyl 2,6-dimethylpyridine-3,5-dicarboxylate, which serves as a valuable intermediate in the synthesis of various pharmaceutical compounds. Comprehensive experimental and characterization investigations verified that the nitrogen sites and defects are the primary active sites for PMS activation and selective oxidation of 1,4-DHP. This work offered an efficient approach for the fabrication of high-nitrogen-loading carbon materials for catalytic oxidation reactions.
2024, 35(11): 109636
doi: 10.1016/j.cclet.2024.109636
Abstract:
Water-soluble inorganic ions (WSIIs) play a pivotal role in atmospheric chemical reactions, particularly influencing the formation of secondary particulate matter. A comprehensive grasp of the vertical distribution of atmospheric pollutants holds immense significance in understanding the diffusion and transportation of these pollutants. This study investigates the WSIIs of PM2.5 and size-segregated particles at the top (~2060 m a.s.l.) and foot of Mt. Hua during the winter of 2020. All the measured ions present significant higher concentrations (1.9~6.9 times) at the foot than the top. Cl− and K+ at the foot are more than 4 times of those at the top, whereas Ca2+ and Mg2+ are only 1.3–1.9 times higher. The particle size distribution of NO3−, SO42−, K+ and Cl− demonstrate a single peak distribution (0.7–1.1 µm) at the foot, but with a bimodal distribution (0.7–1.1 µm and 4.7–5.8 µm) at the top. These differences suggest that the aerosol at the alpine region is mainly transported via long-distance from Northwest/North China, but limited influenced by vertical transport through valley breeze. The changes of concentration and size distribution of WSIIs in dust event and non-dust period indicate that the effects of dust event on aerosols at ground surface were weaker than that of the free troposphere of Guanzhong Plain. Notably, our study underscores the dominant influence of NO3− in shaping the gas-particle distribution of ammonia within the winter free troposphere. Our results highlight the significant role of long-range transport on aerosols in the free troposphere in Guanzhong Plain, Northwest China.
Water-soluble inorganic ions (WSIIs) play a pivotal role in atmospheric chemical reactions, particularly influencing the formation of secondary particulate matter. A comprehensive grasp of the vertical distribution of atmospheric pollutants holds immense significance in understanding the diffusion and transportation of these pollutants. This study investigates the WSIIs of PM2.5 and size-segregated particles at the top (~2060 m a.s.l.) and foot of Mt. Hua during the winter of 2020. All the measured ions present significant higher concentrations (1.9~6.9 times) at the foot than the top. Cl− and K+ at the foot are more than 4 times of those at the top, whereas Ca2+ and Mg2+ are only 1.3–1.9 times higher. The particle size distribution of NO3−, SO42−, K+ and Cl− demonstrate a single peak distribution (0.7–1.1 µm) at the foot, but with a bimodal distribution (0.7–1.1 µm and 4.7–5.8 µm) at the top. These differences suggest that the aerosol at the alpine region is mainly transported via long-distance from Northwest/North China, but limited influenced by vertical transport through valley breeze. The changes of concentration and size distribution of WSIIs in dust event and non-dust period indicate that the effects of dust event on aerosols at ground surface were weaker than that of the free troposphere of Guanzhong Plain. Notably, our study underscores the dominant influence of NO3− in shaping the gas-particle distribution of ammonia within the winter free troposphere. Our results highlight the significant role of long-range transport on aerosols in the free troposphere in Guanzhong Plain, Northwest China.
2024, 35(11): 109639
doi: 10.1016/j.cclet.2024.109639
Abstract:
In this study, the environmentally friendly precursor, tartaric acid (TA), was employed for the generation of CO2 anion radical (CO2•−) in an advanced UV/TA/Fe3+ system to reduce the hazardous -N in wastewater. To optimize this process, various factors, including the dosage of Fe3+, TA, and pH, were systematically investigated for their impact on the reduction process. Under the conditions of 3 mmol/L Fe3+ dosage, 10 mmol/L TA dosage, and a pH of 2.5, -N was effectively removed from the water within 60 min, selectively transformed into N2, with a remarkable N2 selectivity of 91.2%. In the optimal conditions, the -N reduction mechanism in the UV/TA/Fe3+ system and the critical role of were illustrated. Finally, this study explored the reduction of real nitrified seawater using the UV/TA/Fe3+ system. The results demonstrated that the UV/TA/Fe3+ system could completely eliminate -N and achieve a N2 selectivity of up to 90%, with minimal interference from coexisting ions. This work holds promising implications for the environmentally benign treatment of nitrite-polluted wastewater.
In this study, the environmentally friendly precursor, tartaric acid (TA), was employed for the generation of CO2 anion radical (CO2•−) in an advanced UV/TA/Fe3+ system to reduce the hazardous -N in wastewater. To optimize this process, various factors, including the dosage of Fe3+, TA, and pH, were systematically investigated for their impact on the reduction process. Under the conditions of 3 mmol/L Fe3+ dosage, 10 mmol/L TA dosage, and a pH of 2.5, -N was effectively removed from the water within 60 min, selectively transformed into N2, with a remarkable N2 selectivity of 91.2%. In the optimal conditions, the -N reduction mechanism in the UV/TA/Fe3+ system and the critical role of were illustrated. Finally, this study explored the reduction of real nitrified seawater using the UV/TA/Fe3+ system. The results demonstrated that the UV/TA/Fe3+ system could completely eliminate -N and achieve a N2 selectivity of up to 90%, with minimal interference from coexisting ions. This work holds promising implications for the environmentally benign treatment of nitrite-polluted wastewater.
2024, 35(11): 109642
doi: 10.1016/j.cclet.2024.109642
Abstract:
Four novel compounds based on hexanuclear thorium cluster were synthesized and characterized. Compound 1 [Th6(HPyC)8(HCOO)4] is formed by replacing formate ligands of preassembled thorium cluster [Th6O4(OH)4(H2O)6(HCOO)12] with eight H2PyC (4-pyrazolecarboxylic acid) under solvothermal conditions. Each of the HPyC− ligands is coordinated with one Cu2+ to form the (4,8)-connected -net structure of compound 2 [(CuCl2)2Th6(HPyC)8(HCOO)4]. In compound 3 [(CuCl2)2Th6(HPyC)10(HCOO)4], ten of the formate ligands of preassembled Th6 cluster are replaced by HPyC− ligands. Compared with compound 2, the two extra HPyC− ligands in the equatorial plane of the Th6 cluster in compound 3 are not further connected to copper ions. Therefore, the topology structure of compound 3 is same with that of compound 2. Compound 4 [(Cu3Cl2)(CuCl2)Th6(PyC)3(HPyC)4(HCOO)5] contains three kinds of metal nodes, Th6 cluster, Cu3 cluster and mononuclear Cu2+, and exhibits a novel (5,7)-connected net structure, which was first discovered in actinide MOFs. Furthermore, considering the satisfactory stability of compound 4 and its unsaturated metal nodes and Lewis acid sites, the catalysis of cycloaddition of CO2 was further studied. We found that this thorium-copper heterometallic cluster organic framework can be used as a potential actinide functional material for catalyzing the efficient CO2 conversion to value-added products.
Four novel compounds based on hexanuclear thorium cluster were synthesized and characterized. Compound 1 [Th6(HPyC)8(HCOO)4] is formed by replacing formate ligands of preassembled thorium cluster [Th6O4(OH)4(H2O)6(HCOO)12] with eight H2PyC (4-pyrazolecarboxylic acid) under solvothermal conditions. Each of the HPyC− ligands is coordinated with one Cu2+ to form the (4,8)-connected -net structure of compound 2 [(CuCl2)2Th6(HPyC)8(HCOO)4]. In compound 3 [(CuCl2)2Th6(HPyC)10(HCOO)4], ten of the formate ligands of preassembled Th6 cluster are replaced by HPyC− ligands. Compared with compound 2, the two extra HPyC− ligands in the equatorial plane of the Th6 cluster in compound 3 are not further connected to copper ions. Therefore, the topology structure of compound 3 is same with that of compound 2. Compound 4 [(Cu3Cl2)(CuCl2)Th6(PyC)3(HPyC)4(HCOO)5] contains three kinds of metal nodes, Th6 cluster, Cu3 cluster and mononuclear Cu2+, and exhibits a novel (5,7)-connected net structure, which was first discovered in actinide MOFs. Furthermore, considering the satisfactory stability of compound 4 and its unsaturated metal nodes and Lewis acid sites, the catalysis of cycloaddition of CO2 was further studied. We found that this thorium-copper heterometallic cluster organic framework can be used as a potential actinide functional material for catalyzing the efficient CO2 conversion to value-added products.
2024, 35(11): 109649
doi: 10.1016/j.cclet.2024.109649
Abstract:
Constructing more stable self-assembled organic nanotubes has been one of the focuses of scientists in recent decades. Hexakis(m-phenylene ethynylene) (m-PE) benzene macrocycles can form stable tubular self-assemblies in nonpolar or weakly polar solvents through the π-π interaction of the main skeleton and the hydrogen bonding of the side chain amide. We covalently linked two macrocyclic units at the para position of the macrocycles using two oligo(β-alanine) linkers through an efficient synthetic route. UV–visible spectroscopy, fluorescence spectroscopy, and circular dichroism spectroscopy were employed to demonstrate that the incorporation of two peptide chains significantly enhances the stability of the self-assemblies. Meanwhile, the average open time of the ion channel formed by the macrocyclic dimer in the lipid bilayer was significantly better than that of the ion channel formed by a single macrocycle. This study shows that this strategy effectively improves the efficiency of self-assembly and the stability of its formed self-assemblies, providing a feasible strategy for constructing organic self-assembled nanotubes in highly polar solvents.
Constructing more stable self-assembled organic nanotubes has been one of the focuses of scientists in recent decades. Hexakis(m-phenylene ethynylene) (m-PE) benzene macrocycles can form stable tubular self-assemblies in nonpolar or weakly polar solvents through the π-π interaction of the main skeleton and the hydrogen bonding of the side chain amide. We covalently linked two macrocyclic units at the para position of the macrocycles using two oligo(β-alanine) linkers through an efficient synthetic route. UV–visible spectroscopy, fluorescence spectroscopy, and circular dichroism spectroscopy were employed to demonstrate that the incorporation of two peptide chains significantly enhances the stability of the self-assemblies. Meanwhile, the average open time of the ion channel formed by the macrocyclic dimer in the lipid bilayer was significantly better than that of the ion channel formed by a single macrocycle. This study shows that this strategy effectively improves the efficiency of self-assembly and the stability of its formed self-assemblies, providing a feasible strategy for constructing organic self-assembled nanotubes in highly polar solvents.
2024, 35(11): 109653
doi: 10.1016/j.cclet.2024.109653
Abstract:
Parkinson’s disease (PD) is an aging-associated neurodegenerative movement disorder with increasing morbidity and mortality rates. The current gold standard for diagnosing PD is clinical evaluation, which is often challenging and inaccurate. Metabolomics and lipidomics approaches have been extensively applied because of their potential in discovering valuable biomarkers for medical diagnostics. Here, we used comprehensive untargeted metabolomics and lipidomics methodologies based on liquid chromatography-mass spectrometry to evaluate metabolic abnormalities linked with PD. Two well-characterized cohorts of 288 plasma samples (143 PD patients and 145 control subjects in total) were used to examine metabolic alterations and identify diagnostic biomarkers. Unbiased multivariate and univariate studies were combined to identify the promising metabolic signatures, based on which the discriminant models for PD were established by integrating multiple machine learning algorithms. A 6-biomarker predictive model was constructed based on the omics profile in the discovery cohort, and the discriminant performance of the biomarker panel was evaluated with an accuracy over 81.6% both in the discovery cohort and validation cohort. The results indicated that PC (40:7), eicosatrienoic acid were negatively correlated with severity of PD, and pentalenic acid, PC (40:6p) and aspartic acid were positively correlated with severity of PD. In summary, we developed a multi-metabolite predictive model which can diagnose PD with over 81.6% accuracy based on this unique metabolic signature. Future clinical diagnosis of PD may benefit from the biomarker panel reported in this study.
Parkinson’s disease (PD) is an aging-associated neurodegenerative movement disorder with increasing morbidity and mortality rates. The current gold standard for diagnosing PD is clinical evaluation, which is often challenging and inaccurate. Metabolomics and lipidomics approaches have been extensively applied because of their potential in discovering valuable biomarkers for medical diagnostics. Here, we used comprehensive untargeted metabolomics and lipidomics methodologies based on liquid chromatography-mass spectrometry to evaluate metabolic abnormalities linked with PD. Two well-characterized cohorts of 288 plasma samples (143 PD patients and 145 control subjects in total) were used to examine metabolic alterations and identify diagnostic biomarkers. Unbiased multivariate and univariate studies were combined to identify the promising metabolic signatures, based on which the discriminant models for PD were established by integrating multiple machine learning algorithms. A 6-biomarker predictive model was constructed based on the omics profile in the discovery cohort, and the discriminant performance of the biomarker panel was evaluated with an accuracy over 81.6% both in the discovery cohort and validation cohort. The results indicated that PC (40:7), eicosatrienoic acid were negatively correlated with severity of PD, and pentalenic acid, PC (40:6p) and aspartic acid were positively correlated with severity of PD. In summary, we developed a multi-metabolite predictive model which can diagnose PD with over 81.6% accuracy based on this unique metabolic signature. Future clinical diagnosis of PD may benefit from the biomarker panel reported in this study.
2024, 35(11): 109656
doi: 10.1016/j.cclet.2024.109656
Abstract:
Regulation of cell fate requires the establishment and erasure of 5-methylcytosine (5mC) in genomic DNA. The formation of 5mC is achieved by DNA cytosine methyltransferases (DNMTs), whereas the removal of 5mC can be accomplished by various pathways. Aside from ten-eleven translocation (TET)-mediated oxidation of 5mC followed by thymine DNA glycosylase (TDG)-initiated base excision repair (BER), the direct deformylation of 5-formylcytosine (5fC) and decarboxylation of 5-carboxylcytosine (5caC) have also been discovered as the novel DNA demethylation pathways. Although these novel demethylation pathways have been identified in stem cells and somatic cells, their precise roles in regulating cell fate remain unclear. Here, we differentiate mouse embryonic stem cells (mESCs) into mouse embryoid bodies (mEBs), followed by further differentiation into mouse neural stem cells (mNSCs) and finally into mouse neurons (mNeurons). During this sequential differentiation process, we employ probe molecules, namely 2′-fluorinated 5-formylcytidine (F-5fC) and 2′-fluorinated 5-carboxyldeoxycytidine (F-5caC), for metabolic labeling. The results of mass spectrometry (MS) analysis demonstrate the deformylation and decarboxylation activities are progressively decreased and increased respectively during differentiation process, and this opposite demethylation tendency is not associated with DNMTs and TETs.
Regulation of cell fate requires the establishment and erasure of 5-methylcytosine (5mC) in genomic DNA. The formation of 5mC is achieved by DNA cytosine methyltransferases (DNMTs), whereas the removal of 5mC can be accomplished by various pathways. Aside from ten-eleven translocation (TET)-mediated oxidation of 5mC followed by thymine DNA glycosylase (TDG)-initiated base excision repair (BER), the direct deformylation of 5-formylcytosine (5fC) and decarboxylation of 5-carboxylcytosine (5caC) have also been discovered as the novel DNA demethylation pathways. Although these novel demethylation pathways have been identified in stem cells and somatic cells, their precise roles in regulating cell fate remain unclear. Here, we differentiate mouse embryonic stem cells (mESCs) into mouse embryoid bodies (mEBs), followed by further differentiation into mouse neural stem cells (mNSCs) and finally into mouse neurons (mNeurons). During this sequential differentiation process, we employ probe molecules, namely 2′-fluorinated 5-formylcytidine (F-5fC) and 2′-fluorinated 5-carboxyldeoxycytidine (F-5caC), for metabolic labeling. The results of mass spectrometry (MS) analysis demonstrate the deformylation and decarboxylation activities are progressively decreased and increased respectively during differentiation process, and this opposite demethylation tendency is not associated with DNMTs and TETs.
2024, 35(11): 109659
doi: 10.1016/j.cclet.2024.109659
Abstract:
A novel amine-modified pillar[5]arene bonded porous silica adsorbent (DETA-P5S) was designed to be applied to dynamic CO2 adsorption and selective separation of CO2 over N2 and CH4 gases mixture. The results demonstrated that reasonable introduction of DETA into the BE-P5 bonded silica support has significantly increased the adsorption capacity of CO2. The DETA-P5S has the optimal adsorption capacity of 9.1 mmol/g with 5 vol% CO2 at 40 ℃. The main reason of this increased capacity could be attributed to the enhanced CO2 diffusion into porous adsorbent for its better dispersion in the pores of amine-pillar[5]arene cavity and active site of DETA. Furthermore, the dynamic saturation adsorption capacities of DETA-P5S were 7.11 (0.37) and 6.18 (0.44) mmol/g for CO2/N2 and CO2/CH4, respectively, both the gas mixtures showed high separation selectivity. Simultaneously, the DETA-P5S can maintain outstanding CO2 adsorption capacity after fifteen regeneration cycles. Consequently, the designed DETA-P5S could serve as a promising adsorbent for CO2 capture and storage.
A novel amine-modified pillar[5]arene bonded porous silica adsorbent (DETA-P5S) was designed to be applied to dynamic CO2 adsorption and selective separation of CO2 over N2 and CH4 gases mixture. The results demonstrated that reasonable introduction of DETA into the BE-P5 bonded silica support has significantly increased the adsorption capacity of CO2. The DETA-P5S has the optimal adsorption capacity of 9.1 mmol/g with 5 vol% CO2 at 40 ℃. The main reason of this increased capacity could be attributed to the enhanced CO2 diffusion into porous adsorbent for its better dispersion in the pores of amine-pillar[5]arene cavity and active site of DETA. Furthermore, the dynamic saturation adsorption capacities of DETA-P5S were 7.11 (0.37) and 6.18 (0.44) mmol/g for CO2/N2 and CO2/CH4, respectively, both the gas mixtures showed high separation selectivity. Simultaneously, the DETA-P5S can maintain outstanding CO2 adsorption capacity after fifteen regeneration cycles. Consequently, the designed DETA-P5S could serve as a promising adsorbent for CO2 capture and storage.
2024, 35(11): 109664
doi: 10.1016/j.cclet.2024.109664
Abstract:
Label-free immunoassay is confronted with a great challenge that its insufficient sensitivity for low concentration analytes, which can be assigned to the low catalytic efficiency of modified materials towards electroactive molecules. Herein, a universal MOF nanozyme-induced catalytic amplification strategy was proposed for constructing highly sensitive label-free electrochemical immunoassay. Specifically, the synthesized CuFe-MOF nanozyme with superior peroxidase (POD)-like activity, regarding as a MOF nanozyme model, can catalyze hydrogen peroxide to produce hydroxyl radicals (•OH), which can efficiently oxidize electroactive probe (such as 1,2-phenylenediamine (o-PD)) accompanying with intense electrochemical signals. Modification of MOF nanozyme on the electrode and capture of antibodies for binding target antigens hinder the catalytic process of MOF nanozyme toward o-PD, resulting in a gradual decrease in electrochemical signal with increasing target antigen concentration, enabling quantitative label-free immunoassay. Thus, a highly sensitive label-free immunosensor using MOF nanozyme-induced catalytic amplification achieved effective detection of Immunoglobulin G (IgG) with a wide linear range of 0.001–50 ng/mL and low detection limit of 0.45 pg/mL. This work proposes a promising nanozyme-induced catalytic amplification strategy for the development of label-free electrochemical immunoassay.
Label-free immunoassay is confronted with a great challenge that its insufficient sensitivity for low concentration analytes, which can be assigned to the low catalytic efficiency of modified materials towards electroactive molecules. Herein, a universal MOF nanozyme-induced catalytic amplification strategy was proposed for constructing highly sensitive label-free electrochemical immunoassay. Specifically, the synthesized CuFe-MOF nanozyme with superior peroxidase (POD)-like activity, regarding as a MOF nanozyme model, can catalyze hydrogen peroxide to produce hydroxyl radicals (•OH), which can efficiently oxidize electroactive probe (such as 1,2-phenylenediamine (o-PD)) accompanying with intense electrochemical signals. Modification of MOF nanozyme on the electrode and capture of antibodies for binding target antigens hinder the catalytic process of MOF nanozyme toward o-PD, resulting in a gradual decrease in electrochemical signal with increasing target antigen concentration, enabling quantitative label-free immunoassay. Thus, a highly sensitive label-free immunosensor using MOF nanozyme-induced catalytic amplification achieved effective detection of Immunoglobulin G (IgG) with a wide linear range of 0.001–50 ng/mL and low detection limit of 0.45 pg/mL. This work proposes a promising nanozyme-induced catalytic amplification strategy for the development of label-free electrochemical immunoassay.
2024, 35(11): 109667
doi: 10.1016/j.cclet.2024.109667
Abstract:
Nanographenes (NGs) with twisted backbones are emerging as new candidates for chiroptical materials. In this work, we describe a new strategy for synthesizing a [10]twistacene-embedded NG which exhibits a rare flag-hinge-like geometry. By neatly creating steric crowding on the [6]helicene breaches of the NG skeleton, the synthesis only provided homochiral isomers without generating the "meso‑" isomer. The formed NGs showed high luminescence with quantum yield up to 52%, and promising circularly polarized luminescence (CPL) performance with |glum| up to 5.0 × 10−3. Besides, these NGs also showed outstanding CPL brightness (BCPL) up to 305 L mol−1 cm−1 among chiral NGs.
Nanographenes (NGs) with twisted backbones are emerging as new candidates for chiroptical materials. In this work, we describe a new strategy for synthesizing a [10]twistacene-embedded NG which exhibits a rare flag-hinge-like geometry. By neatly creating steric crowding on the [6]helicene breaches of the NG skeleton, the synthesis only provided homochiral isomers without generating the "meso‑" isomer. The formed NGs showed high luminescence with quantum yield up to 52%, and promising circularly polarized luminescence (CPL) performance with |glum| up to 5.0 × 10−3. Besides, these NGs also showed outstanding CPL brightness (BCPL) up to 305 L mol−1 cm−1 among chiral NGs.
2024, 35(11): 109670
doi: 10.1016/j.cclet.2024.109670
Abstract:
Small peptides have attracted increasing attention for their unique features and diverse biological functions. Achieving rapid separation and accurate quantification, however, remains a challenge because of their low abundance and the co-existence of numerous structural isomers. In this study, we developed a novel approach using isotope chemical labeling for ultrasensitive determination of di/tripeptides in biological samples. We successfully synthesized a novel derivatization reagent, 4-(2-(ethoxymethylene)-3-oxobutanamido)-N,N,N-trimethylbenzenaminium iodide (EOTMBA) as well as its deuterium-labeled isotope reagent (d3-EOTMBA). A total of 97 small peptides, including 89 dipeptides and 8 tripeptides, could be completely derivatized in methanol within 1.5 h at 60 ℃. After EOTMBA labeling, analysis of these di/tripeptides were achieved within 22 min by LC-MS/MS analysis. The method demonstrated 86.3%–113% accuracy and the limit of quantification ranged from 0.25 fmol/L to 5 nmol/L. Using this method, we achieved ultrasensitive and accurate quantification of di/tripeptides in 147 plasma, 49 urine and 46 bile samples obtained from healthy individuals and patients with biliary tract diseases. The identified differential di/tripeptide biomarker panels showed promising diagnostic performance for patients with biliary tract cancer with area under the receiver operating curve values from 0.870 to 0.996. Furthermore, this method was successfully applied to quantify di/tripeptides in the extract of an animal-derived traditional Chinese medicine, Eupolyphaga sinensis Walker. These findings highlight the possible application of the analytical method in clinics and for the purposes of quality control of traditional Chinese medicines.
Small peptides have attracted increasing attention for their unique features and diverse biological functions. Achieving rapid separation and accurate quantification, however, remains a challenge because of their low abundance and the co-existence of numerous structural isomers. In this study, we developed a novel approach using isotope chemical labeling for ultrasensitive determination of di/tripeptides in biological samples. We successfully synthesized a novel derivatization reagent, 4-(2-(ethoxymethylene)-3-oxobutanamido)-N,N,N-trimethylbenzenaminium iodide (EOTMBA) as well as its deuterium-labeled isotope reagent (d3-EOTMBA). A total of 97 small peptides, including 89 dipeptides and 8 tripeptides, could be completely derivatized in methanol within 1.5 h at 60 ℃. After EOTMBA labeling, analysis of these di/tripeptides were achieved within 22 min by LC-MS/MS analysis. The method demonstrated 86.3%–113% accuracy and the limit of quantification ranged from 0.25 fmol/L to 5 nmol/L. Using this method, we achieved ultrasensitive and accurate quantification of di/tripeptides in 147 plasma, 49 urine and 46 bile samples obtained from healthy individuals and patients with biliary tract diseases. The identified differential di/tripeptide biomarker panels showed promising diagnostic performance for patients with biliary tract cancer with area under the receiver operating curve values from 0.870 to 0.996. Furthermore, this method was successfully applied to quantify di/tripeptides in the extract of an animal-derived traditional Chinese medicine, Eupolyphaga sinensis Walker. These findings highlight the possible application of the analytical method in clinics and for the purposes of quality control of traditional Chinese medicines.
2024, 35(11): 109679
doi: 10.1016/j.cclet.2024.109679
Abstract:
Efficient activation of molecular oxygen (O2) is considered a promising technique for the removal of antibiotics. However, how to effectively regulate electrons distribution to promote O2 activation remains a challenge at present. In this study, phosphorus and sodium co-doped carbon nitride (PNaCN) were designed to rearrange the electrons distribution to activate O2 for the degradation of tetracycline. The generation of •O2−was innovatively observed via in-situ O2 fitting Fourier transform infrared (FTIR) spectroscopy, demonstrating the outstanding O2 activation ability of PNa5. Density functional theory (DFT) further confirmed that the rational co-doping led to the rearrangement of local electrons, resulting in electron-rich Na sites and electron-deficient P sites. These sites exhibited greater susceptibility to O2 adsorption and charge transfer. Besides, the degradation rate of tetracycline was increased by 2.44 times using co-doped CN. This study provides a new inspiration for enhancing O2 activation by inducing electrons rearrangement.
Efficient activation of molecular oxygen (O2) is considered a promising technique for the removal of antibiotics. However, how to effectively regulate electrons distribution to promote O2 activation remains a challenge at present. In this study, phosphorus and sodium co-doped carbon nitride (PNaCN) were designed to rearrange the electrons distribution to activate O2 for the degradation of tetracycline. The generation of •O2−was innovatively observed via in-situ O2 fitting Fourier transform infrared (FTIR) spectroscopy, demonstrating the outstanding O2 activation ability of PNa5. Density functional theory (DFT) further confirmed that the rational co-doping led to the rearrangement of local electrons, resulting in electron-rich Na sites and electron-deficient P sites. These sites exhibited greater susceptibility to O2 adsorption and charge transfer. Besides, the degradation rate of tetracycline was increased by 2.44 times using co-doped CN. This study provides a new inspiration for enhancing O2 activation by inducing electrons rearrangement.
2024, 35(11): 109683
doi: 10.1016/j.cclet.2024.109683
Abstract:
The new reactions between o-hydroxyphenyl enaminones and Langlois reagent (CF3SO2Na) for the tunable synthesis of 3-(trifluoromethylthio) chromones and 3-trifluoromethylsulfinyl chromones are reported herein. Both type of reactions proceed under transition metal-free conditions. In addition, the conditions for the synthesis of 3-trifluoromethylsulfinyl chromones have also been found to be applicable for the synthesis of 3-alkyl/arylsulfinyl chromones.
The new reactions between o-hydroxyphenyl enaminones and Langlois reagent (CF3SO2Na) for the tunable synthesis of 3-(trifluoromethylthio) chromones and 3-trifluoromethylsulfinyl chromones are reported herein. Both type of reactions proceed under transition metal-free conditions. In addition, the conditions for the synthesis of 3-trifluoromethylsulfinyl chromones have also been found to be applicable for the synthesis of 3-alkyl/arylsulfinyl chromones.
2024, 35(11): 109685
doi: 10.1016/j.cclet.2024.109685
Abstract:
A new 1,4-amidocyanation of 1,3-enynes with N-amidopyridin-1-ium salts and TMSCN using a copper and photoredox synergetic catalysis for producing α-amido allenyl nitriles is developed. Employing N-amidopyridin-1-ium salts as the amidyl radical precursors, the reaction enables the formation of two new bonds, one C(sp3)-N bond and one C(sp2)-C(sp) bond, in a single reaction step. This reaction represents a mild, general route to the construction of the α-amido allenyl nitrile architectures, which characterizes a broad scope, a good functional group compatibility and an excellent selectivity.
A new 1,4-amidocyanation of 1,3-enynes with N-amidopyridin-1-ium salts and TMSCN using a copper and photoredox synergetic catalysis for producing α-amido allenyl nitriles is developed. Employing N-amidopyridin-1-ium salts as the amidyl radical precursors, the reaction enables the formation of two new bonds, one C(sp3)-N bond and one C(sp2)-C(sp) bond, in a single reaction step. This reaction represents a mild, general route to the construction of the α-amido allenyl nitrile architectures, which characterizes a broad scope, a good functional group compatibility and an excellent selectivity.
2024, 35(11): 109700
doi: 10.1016/j.cclet.2024.109700
Abstract:
Heterojunction engineering is recognized as a promising strategy to modulate the photocatalytic properties of semiconductors. Herein, lead-free Cs2CuBr4 perovskite quantum dots (PQDs) were confined in a mesoporous CuO framework and a p-n type S-scheme heterojunction of Cs2CuBr4/CuO (CCB/CuO) photocatalyst was fabricated. Experimental characterizations confirmed the effective confinement of the Cs2CuBr4 PQDs in the mesoporous CuO framework, which enabled intimate contact in the interface of CCB/CuO heterojunction, thus facilitating the interfacial charge migration and separation between p-type CuO and n-type Cs2CuBr4. Owing to the outstanding charge transport property and CO2 adsorption capacity, the developed CCB/CuO heterojunction exhibited remarkably enhanced photocatalytic CO2 conversion efficiency with an electron consumption rate (Relectron) of 281.1 µmol g−1 h−1, which was approximately 2.8 times higher than that of pristine Cs2CuBr4. These findings provide some insights into the rational engineering design of lead-free perovskite-based heterostructures for efficient photocatalytic CO2 conversion.
Heterojunction engineering is recognized as a promising strategy to modulate the photocatalytic properties of semiconductors. Herein, lead-free Cs2CuBr4 perovskite quantum dots (PQDs) were confined in a mesoporous CuO framework and a p-n type S-scheme heterojunction of Cs2CuBr4/CuO (CCB/CuO) photocatalyst was fabricated. Experimental characterizations confirmed the effective confinement of the Cs2CuBr4 PQDs in the mesoporous CuO framework, which enabled intimate contact in the interface of CCB/CuO heterojunction, thus facilitating the interfacial charge migration and separation between p-type CuO and n-type Cs2CuBr4. Owing to the outstanding charge transport property and CO2 adsorption capacity, the developed CCB/CuO heterojunction exhibited remarkably enhanced photocatalytic CO2 conversion efficiency with an electron consumption rate (Relectron) of 281.1 µmol g−1 h−1, which was approximately 2.8 times higher than that of pristine Cs2CuBr4. These findings provide some insights into the rational engineering design of lead-free perovskite-based heterostructures for efficient photocatalytic CO2 conversion.
2024, 35(11): 109732
doi: 10.1016/j.cclet.2024.109732
Abstract:
Developing applicable methods to forge linkages between sp3 and sp2-hydridized carbons is of great significance in drug discovery. We show here a new, Ni-catalyzed reductive cross-coupling reaction that forms Csp3−Csp2 bonds from aryl iodides and cyclic sulfonium salts. Notably, Csp3−Csp2 bonds can be forged selectively at the iodine-bearing carbon of bromo(iodo)arenes which is usually recognized as a huge challenge under the catalytic reductive cross-coupling (CRCC) conditions. Experimental and computational mechanistic studies support LNiⅠAr as an active species, while the untraditional anti-Markovnikov selective alkylation of asymmetric sulfonium salts is determined by the oxidative S-substitution of sulfonium salts with LNiⅠAr. This protocol further expands the range of alkyl electrophiles under the CRCC conditions and provides a new strategy for the construction of Csp3−Csp2 bonds.
Developing applicable methods to forge linkages between sp3 and sp2-hydridized carbons is of great significance in drug discovery. We show here a new, Ni-catalyzed reductive cross-coupling reaction that forms Csp3−Csp2 bonds from aryl iodides and cyclic sulfonium salts. Notably, Csp3−Csp2 bonds can be forged selectively at the iodine-bearing carbon of bromo(iodo)arenes which is usually recognized as a huge challenge under the catalytic reductive cross-coupling (CRCC) conditions. Experimental and computational mechanistic studies support LNiⅠAr as an active species, while the untraditional anti-Markovnikov selective alkylation of asymmetric sulfonium salts is determined by the oxidative S-substitution of sulfonium salts with LNiⅠAr. This protocol further expands the range of alkyl electrophiles under the CRCC conditions and provides a new strategy for the construction of Csp3−Csp2 bonds.
2024, 35(11): 109750
doi: 10.1016/j.cclet.2024.109750
Abstract:
Roxarsone (ROX) is a commonly used antibacterial and growth-promoting additive to animal feed. The development of an effective method for detecting ROX and its conversion products is of importance because of their potential harm to human health and ecosystem. Herein, we report the designed synthesis of a novel one-dimensional covalent organic framework (1D COF), named EP-COF, and its application as a fluorescent probe for ROX sensing. EP-COF is constructed based on imine linkages, exhibiting high crystallinity, strong fluorescence emission, and good dispersibility in water. It displays a remarkable capability to efficiently detect ROX, with an impressive detection limit of 4.5 nmol/L. Moreover, EP-COF also offers advantages of excellent selectivity, and high structural stability. This work not only presents a promising approach for the detection of harmful substances like ROX, but also serves as a valuable reference for exploring application of 1D COFs in chemical sensing.
Roxarsone (ROX) is a commonly used antibacterial and growth-promoting additive to animal feed. The development of an effective method for detecting ROX and its conversion products is of importance because of their potential harm to human health and ecosystem. Herein, we report the designed synthesis of a novel one-dimensional covalent organic framework (1D COF), named EP-COF, and its application as a fluorescent probe for ROX sensing. EP-COF is constructed based on imine linkages, exhibiting high crystallinity, strong fluorescence emission, and good dispersibility in water. It displays a remarkable capability to efficiently detect ROX, with an impressive detection limit of 4.5 nmol/L. Moreover, EP-COF also offers advantages of excellent selectivity, and high structural stability. This work not only presents a promising approach for the detection of harmful substances like ROX, but also serves as a valuable reference for exploring application of 1D COFs in chemical sensing.
2024, 35(11): 109757
doi: 10.1016/j.cclet.2024.109757
Abstract:
The supramolecular Förster resonance energy transfer (FRET) is seen as a promising approach for organic photocatalysis using dyes as catalysts, because it combines the high efficiency of energy transfer with the dynamic responsiveness based on non-covalent interactions. Here we propose a supramolecular FRET photocatalysis strategy for α-oxyamination reaction based on supramolecular confinement effect. The well-designed benzothiadiazole-based cationic monomer as energy donor and the dyes of Nile Red as acceptor are doped into the amphiphilic surfactants of sodium dodecyl sulfate (SDS). Benefitting from the supramolecular confinement space provided by SDS in aqueous environment, the FRET process between the monomer and Nile Red is effectively achieved (exciton migration rate: 3.99 × 1014 L mol‒1 s‒1). On this basis, the supramolecular FRET system is used as an efficient energy source to catalyze α-oxyamination reactions between a series of 1,3-dicarbonyl compounds and 2,2,6,6-tetramethylpiperidine-1-oxyl under white LED light, showing a yield as high as 94% and a turnover frequency value of 3.92 h‒1. This photocatalytic result shows a great enhancement compared to that of Nile Red alone.
The supramolecular Förster resonance energy transfer (FRET) is seen as a promising approach for organic photocatalysis using dyes as catalysts, because it combines the high efficiency of energy transfer with the dynamic responsiveness based on non-covalent interactions. Here we propose a supramolecular FRET photocatalysis strategy for α-oxyamination reaction based on supramolecular confinement effect. The well-designed benzothiadiazole-based cationic monomer as energy donor and the dyes of Nile Red as acceptor are doped into the amphiphilic surfactants of sodium dodecyl sulfate (SDS). Benefitting from the supramolecular confinement space provided by SDS in aqueous environment, the FRET process between the monomer and Nile Red is effectively achieved (exciton migration rate: 3.99 × 1014 L mol‒1 s‒1). On this basis, the supramolecular FRET system is used as an efficient energy source to catalyze α-oxyamination reactions between a series of 1,3-dicarbonyl compounds and 2,2,6,6-tetramethylpiperidine-1-oxyl under white LED light, showing a yield as high as 94% and a turnover frequency value of 3.92 h‒1. This photocatalytic result shows a great enhancement compared to that of Nile Red alone.
2024, 35(11): 109759
doi: 10.1016/j.cclet.2024.109759
Abstract:
Antibiotic resistance poses a critical threat to human healthcare, largely driven by bacterial biofilms. These biofilms resist the immune system and antibiotics, rendering enclosed microbial cells 10–1000 times more antibiotic-resistant than planktonic cells, leading to severe infections. Therefore, there is an urgent need to develop innovative tools for investigating biofilm regulators and devising novel antibacterial strategies. In this study, we developed Cy-NEO-PA, a near-infrared (NIR) fluorescent probe responsive to penicillin G acylase (PGA), with bacteria-targeting ability. This probe was designed to visualize the influence of environmental factors on biofilm formation in Acinetobacter baumannii (A. baumannii). Our findings demonstrated that glucose suppressed PGA production, leading to enhanced biofilm formation, whereas phenylacetic acid (PAA) stimulated PGA production and inhibited biofilm formation in A. baumannii. These observations highlight the remarkable capability of Cy-NEO-PA to accurately measure PGA dynamics, shedding light on the critical role of PGA in biofilm development. Additionally, Cy-NEO-PA exhibited excellent biocompatibility, potent reactive oxygen species (ROS) generation, efficient photothermal conversion, and bacteria-targeting abilities, making it a promising agent for combating bacterial infections and promoting wound healing through photothermal (PTT)/photodynamic (PDT) therapy. These discoveries emphasize the significant role of PGA in antibacterial therapy and offer valuable insights for the design of effective strategies targeting PGA to combat biofilm-associated infections.
Antibiotic resistance poses a critical threat to human healthcare, largely driven by bacterial biofilms. These biofilms resist the immune system and antibiotics, rendering enclosed microbial cells 10–1000 times more antibiotic-resistant than planktonic cells, leading to severe infections. Therefore, there is an urgent need to develop innovative tools for investigating biofilm regulators and devising novel antibacterial strategies. In this study, we developed Cy-NEO-PA, a near-infrared (NIR) fluorescent probe responsive to penicillin G acylase (PGA), with bacteria-targeting ability. This probe was designed to visualize the influence of environmental factors on biofilm formation in Acinetobacter baumannii (A. baumannii). Our findings demonstrated that glucose suppressed PGA production, leading to enhanced biofilm formation, whereas phenylacetic acid (PAA) stimulated PGA production and inhibited biofilm formation in A. baumannii. These observations highlight the remarkable capability of Cy-NEO-PA to accurately measure PGA dynamics, shedding light on the critical role of PGA in biofilm development. Additionally, Cy-NEO-PA exhibited excellent biocompatibility, potent reactive oxygen species (ROS) generation, efficient photothermal conversion, and bacteria-targeting abilities, making it a promising agent for combating bacterial infections and promoting wound healing through photothermal (PTT)/photodynamic (PDT) therapy. These discoveries emphasize the significant role of PGA in antibacterial therapy and offer valuable insights for the design of effective strategies targeting PGA to combat biofilm-associated infections.
2024, 35(11): 109791
doi: 10.1016/j.cclet.2024.109791
Abstract:
Reported here is the synthesis of a new macrocycle bearing anionic carboxylate groups with water-soluble aggregation-induced emission (AIE). The water-soluble macrocycle without typical AIE luminogens is constructed based on the building block of benzothiadiazole. It exhibits a remarkable AIE effect. This water-soluble macrocycle can selectively bind different types of biogenic amines in aqueous media with the tightest binding towards spermine. The fluorescence enhancement induced by supramolecular encapsulation is used to detect spermine.
Reported here is the synthesis of a new macrocycle bearing anionic carboxylate groups with water-soluble aggregation-induced emission (AIE). The water-soluble macrocycle without typical AIE luminogens is constructed based on the building block of benzothiadiazole. It exhibits a remarkable AIE effect. This water-soluble macrocycle can selectively bind different types of biogenic amines in aqueous media with the tightest binding towards spermine. The fluorescence enhancement induced by supramolecular encapsulation is used to detect spermine.
2024, 35(11): 109812
doi: 10.1016/j.cclet.2024.109812
Abstract:
The construction of enzyme reactors based on metal-organic frameworks (MOFs) as the immobilized matrix is a proven strategy that has achieved the widespread application of enzymes across industries. Although many MOFs and a variety of strategies have been developed, a formidable challenge remains in maintaining the high enzyme activity with excellent recyclability and tolerance for harsh conditions. Herein, using degradable redox stimuli-responsive liposomes as the templates with microporous MOFs (M-MOFs) as the hosts for enzyme encapsulation, a series of enzyme reactors (enzyme@M-MOFs) was designed and created. Based on the premise of enhancing enzyme protection in the harsh environment, this strategy provided a high degree-of-freedom space via removal of liposomes that improved the conformational freedom of the enzymes, promoted the mass transfer of substrates and products, and greatly boosted the catalytic activity. Importantly, the strategy had good universality and was applied to various liposomes, M-MOFs and enzymes. Additionally, the co-encapsulation of different enzymes with synergistic functions was performed using the M-MOFs platform. This study solved the problems of the conformation limitation of enzymes and mass transfer resistance of substrates and products using the proposed enzyme@M-MOFs, providing a new approach for the construction of biological cascade reaction devices based on MOFs materials.
The construction of enzyme reactors based on metal-organic frameworks (MOFs) as the immobilized matrix is a proven strategy that has achieved the widespread application of enzymes across industries. Although many MOFs and a variety of strategies have been developed, a formidable challenge remains in maintaining the high enzyme activity with excellent recyclability and tolerance for harsh conditions. Herein, using degradable redox stimuli-responsive liposomes as the templates with microporous MOFs (M-MOFs) as the hosts for enzyme encapsulation, a series of enzyme reactors (enzyme@M-MOFs) was designed and created. Based on the premise of enhancing enzyme protection in the harsh environment, this strategy provided a high degree-of-freedom space via removal of liposomes that improved the conformational freedom of the enzymes, promoted the mass transfer of substrates and products, and greatly boosted the catalytic activity. Importantly, the strategy had good universality and was applied to various liposomes, M-MOFs and enzymes. Additionally, the co-encapsulation of different enzymes with synergistic functions was performed using the M-MOFs platform. This study solved the problems of the conformation limitation of enzymes and mass transfer resistance of substrates and products using the proposed enzyme@M-MOFs, providing a new approach for the construction of biological cascade reaction devices based on MOFs materials.
2024, 35(11): 109849
doi: 10.1016/j.cclet.2024.109849
Abstract:
The device configuration with mesoporous titanium dioxide (m-TiO2) has garnered considerable attention as a promising solution for high-stable perovskite and dye-sensitized solar cells, although its application in organic solar cells remains unexplored. In this communication, we have incorporated this structure into both bulk-heterojunction (BHJ) and single-component organic solar cells (SCOSCs). Surprisingly, mesoporous OSCs (M-OSCs) demonstrate a deteriorative efficiency in BHJ-type cells, whereas this configuration succeeds in SCOSCs, exhibiting competitive performance with planar OSCs (P-OSCs). This pioneering study has resulted in a competitive power conversion efficiency of 9.67% for m-TiO2-based cells, marking a significant milestone in the advancement of OSCs. Importantly, profiting from the better ultraviolet resistance of m-TiO2 than zinc oxide, this M-OSC exhibits superior photostability than that of P-OSCs when subjected to continuous one-sun (AM1.5G) illumination. In its entirety, this research not only introduces the concept of M-OSCs for the first time but also unveils a novel device architecture poised to address the long-term stability concerns within the realm of OSCs.
The device configuration with mesoporous titanium dioxide (m-TiO2) has garnered considerable attention as a promising solution for high-stable perovskite and dye-sensitized solar cells, although its application in organic solar cells remains unexplored. In this communication, we have incorporated this structure into both bulk-heterojunction (BHJ) and single-component organic solar cells (SCOSCs). Surprisingly, mesoporous OSCs (M-OSCs) demonstrate a deteriorative efficiency in BHJ-type cells, whereas this configuration succeeds in SCOSCs, exhibiting competitive performance with planar OSCs (P-OSCs). This pioneering study has resulted in a competitive power conversion efficiency of 9.67% for m-TiO2-based cells, marking a significant milestone in the advancement of OSCs. Importantly, profiting from the better ultraviolet resistance of m-TiO2 than zinc oxide, this M-OSC exhibits superior photostability than that of P-OSCs when subjected to continuous one-sun (AM1.5G) illumination. In its entirety, this research not only introduces the concept of M-OSCs for the first time but also unveils a novel device architecture poised to address the long-term stability concerns within the realm of OSCs.
2024, 35(11): 109850
doi: 10.1016/j.cclet.2024.109850
Abstract:
The design and synthesis of organic high-temperature reversible thermochromic materials is one of the difficult issues in the field of organic chromic materials. In this paper, four diacetylene monomers named DBA-PCDA, TBA-PCDA, DBE-PCDA and TBE-PCDA, each containing multiple diacetylene units, were synthesized from 10,12-pentacosadiynoic acid (PCDA) through the amidation or esterification reactions, using 4,4′-diaminobiphenyl, 1,3,5-tris(4-aminophenyl)benzene, 4,4′-dihydroxybiphenyl, and 1,3,5-tris(4-hydroxyphenyl)benzene as bridging units. The effects of functional groups that can form hydrogen bond and π-π interactions on the solid-state polymerization properties of monomers and the thermochromic properties of the corresponding PDAs were investigated. The results show that only DBA-PCDA and TBA-PCDA, which contain functional groups that can form hydrogen bonding interactions, can be polymerized under 254-nm UV irradiation. The corresponding poly(DBA-PCDA) exhibits reversible thermochromic property even heated up to 200 ℃, showing a potential application in the field of high-temperature thermal indicator above 100 ℃. This work provides a new perspective to the development of PDA with high-temperature reversible thermochromic property.
The design and synthesis of organic high-temperature reversible thermochromic materials is one of the difficult issues in the field of organic chromic materials. In this paper, four diacetylene monomers named DBA-PCDA, TBA-PCDA, DBE-PCDA and TBE-PCDA, each containing multiple diacetylene units, were synthesized from 10,12-pentacosadiynoic acid (PCDA) through the amidation or esterification reactions, using 4,4′-diaminobiphenyl, 1,3,5-tris(4-aminophenyl)benzene, 4,4′-dihydroxybiphenyl, and 1,3,5-tris(4-hydroxyphenyl)benzene as bridging units. The effects of functional groups that can form hydrogen bond and π-π interactions on the solid-state polymerization properties of monomers and the thermochromic properties of the corresponding PDAs were investigated. The results show that only DBA-PCDA and TBA-PCDA, which contain functional groups that can form hydrogen bonding interactions, can be polymerized under 254-nm UV irradiation. The corresponding poly(DBA-PCDA) exhibits reversible thermochromic property even heated up to 200 ℃, showing a potential application in the field of high-temperature thermal indicator above 100 ℃. This work provides a new perspective to the development of PDA with high-temperature reversible thermochromic property.
2024, 35(11): 109864
doi: 10.1016/j.cclet.2024.109864
Abstract:
In the exploration of circularly polarized luminescence (CPL) materials, doping cholesteric liquid crystals (CLCs) with achiral dyes is a common strategy. Conjugated polymers are favored as achiral dyes for their superior luminescent properties. In this study, a series of oligomers (M1-M3) and the conjugated polymer F8BT were synthesized to systematically assess the impact of the length of the conjugated backbone on CPL signals of CLCs doped with conjugated polymers. As the length rose from M1 to M3, CPL intensity concurrently increased (glum increased from 0.35 to 0.84), attributable to enhanced dichroism (order parameter, SF increased from 0.20 to 0.56). In contrast, F8BT polymer resulted in diminished CPL intensity (|glum| = 0.64) due to the reduced compatibility. Achieving a balance between dichroism and compatibility is crucial for optimizing CPL in conjugated polymer-doped CLCs. The guiding principle established here may have broad applicability in other CPL assemblies, offering a strategic avenue to engineer high-performance CPL materials with conjugated polymer.
In the exploration of circularly polarized luminescence (CPL) materials, doping cholesteric liquid crystals (CLCs) with achiral dyes is a common strategy. Conjugated polymers are favored as achiral dyes for their superior luminescent properties. In this study, a series of oligomers (M1-M3) and the conjugated polymer F8BT were synthesized to systematically assess the impact of the length of the conjugated backbone on CPL signals of CLCs doped with conjugated polymers. As the length rose from M1 to M3, CPL intensity concurrently increased (glum increased from 0.35 to 0.84), attributable to enhanced dichroism (order parameter, SF increased from 0.20 to 0.56). In contrast, F8BT polymer resulted in diminished CPL intensity (|glum| = 0.64) due to the reduced compatibility. Achieving a balance between dichroism and compatibility is crucial for optimizing CPL in conjugated polymer-doped CLCs. The guiding principle established here may have broad applicability in other CPL assemblies, offering a strategic avenue to engineer high-performance CPL materials with conjugated polymer.
2024, 35(11): 109879
doi: 10.1016/j.cclet.2024.109879
Abstract:
Metal-catalyzed alkene arylalkoxylation is a powerful complexity-building strategy for the synthesis of oxygen heterocycles from simple γ-unsaturated alcohols, but only a few examples of catalytic enantioselective methods exist. Herein, an efficient palladium-catalyzed enantioselective arylalkoxylation of γ-hydroxyalkenes with aryl halides is reported. The salient features of this transformation include a remarkable broad substrate scope, mild reaction conditions, and good functional group tolerance, delivering a series of chiral tetrahydrofurans containing a tertiary or quaternary stereocenter in good yields with up to 95% ee. The Xu10 ligand with a suitable side-arm was responsible for the high reactivity and good enantioselectivity of this transformation.
Metal-catalyzed alkene arylalkoxylation is a powerful complexity-building strategy for the synthesis of oxygen heterocycles from simple γ-unsaturated alcohols, but only a few examples of catalytic enantioselective methods exist. Herein, an efficient palladium-catalyzed enantioselective arylalkoxylation of γ-hydroxyalkenes with aryl halides is reported. The salient features of this transformation include a remarkable broad substrate scope, mild reaction conditions, and good functional group tolerance, delivering a series of chiral tetrahydrofurans containing a tertiary or quaternary stereocenter in good yields with up to 95% ee. The Xu10 ligand with a suitable side-arm was responsible for the high reactivity and good enantioselectivity of this transformation.
2024, 35(11): 109887
doi: 10.1016/j.cclet.2024.109887
Abstract:
Highly active transition metal nitrides are desirable for electrocatalytic reactions, but their long-term stability is still unsatisfactory and thus limiting commercial applications. Herein, for the first time, we report a unique and universal room-temperature urea plasma method for controllable synthesis of N-doped carbon coated metal (Fe, Co, Ni, etc.) nitrides arrays electrocatalysts. The preformed metal oxides arrays can be successfully converted into metal nitrides arrays with preserved nanostructures and a thin layer of N-doped carbon (N-C) via one-step urea plasma. Typically, as a representative case, N-C@CoN nanowire arrays are illustrated and corresponding formation mechanism by plasma is proposed. Notably, the designed N-C@CoN catalysts deliver excellent electrocatalytic activity and long-term stability both in oxygen evolution reaction (OER) and urea oxidation reaction (UOR). For OER, a low overpotential (264 mV at 10 mA/cm2) and high stability (>50 h at 20 mA/cm2) are acquired. For UOR, a current density of 100 mA/cm2 is achieved at only 1.39 V and maintain over 100 h. Theoretical calculations reveal that the synergetic coupling effect of CoN and N-C can significantly facilitate the charge-transfer process, optimize adsorbed intermediates binding strength and further greatly decrease the energy barrier. This strategy provides a novel method for fabrication of N-C@ metal nitrides as highly active and stable catalysts.
Highly active transition metal nitrides are desirable for electrocatalytic reactions, but their long-term stability is still unsatisfactory and thus limiting commercial applications. Herein, for the first time, we report a unique and universal room-temperature urea plasma method for controllable synthesis of N-doped carbon coated metal (Fe, Co, Ni, etc.) nitrides arrays electrocatalysts. The preformed metal oxides arrays can be successfully converted into metal nitrides arrays with preserved nanostructures and a thin layer of N-doped carbon (N-C) via one-step urea plasma. Typically, as a representative case, N-C@CoN nanowire arrays are illustrated and corresponding formation mechanism by plasma is proposed. Notably, the designed N-C@CoN catalysts deliver excellent electrocatalytic activity and long-term stability both in oxygen evolution reaction (OER) and urea oxidation reaction (UOR). For OER, a low overpotential (264 mV at 10 mA/cm2) and high stability (>50 h at 20 mA/cm2) are acquired. For UOR, a current density of 100 mA/cm2 is achieved at only 1.39 V and maintain over 100 h. Theoretical calculations reveal that the synergetic coupling effect of CoN and N-C can significantly facilitate the charge-transfer process, optimize adsorbed intermediates binding strength and further greatly decrease the energy barrier. This strategy provides a novel method for fabrication of N-C@ metal nitrides as highly active and stable catalysts.
2024, 35(11): 109927
doi: 10.1016/j.cclet.2024.109927
Abstract:
A series of novel crown aldoxime ethers were synthesized, demonstrating notable thermal and hydrolysis stability. The showcased acid-catalyzed and photo-induced cis/trans isomerization, which enables orthogonal control over both guest complexation and the chiroptical effects of these crown aldoxime ethers, manifesting a regulation of complexation through isomerization at binding heteroatoms.
A series of novel crown aldoxime ethers were synthesized, demonstrating notable thermal and hydrolysis stability. The showcased acid-catalyzed and photo-induced cis/trans isomerization, which enables orthogonal control over both guest complexation and the chiroptical effects of these crown aldoxime ethers, manifesting a regulation of complexation through isomerization at binding heteroatoms.
2024, 35(11): 109929
doi: 10.1016/j.cclet.2024.109929
Abstract:
Stimulus-responsive room-temperature phosphorescence (RTP) materials have gained significant attention for their important optoelectronic application prospects. However, the fabrication strategy and underlying mechanism of stimulus-responsive RTP materials remain less explored. Herein, we present a reliable strategy for achieving pH-responsive RTP materials by integrating poly(vinyl alcohol) (PVA) with carboxylic acid or amino group functionalized terpyridine (Tpy) derivatives. The resulting Tpy derivatives-based RTP materials displayed reversible changes in emission color, intensity, and lifetime of both prompt and delayed emission. Notably, the RTP emission undergoes a significant diminish upon exposure to acid due to the protonation of Tpy units. Taking advantage of the decent RTP emission and pH-responsiveness of these RTP films, a spatial-time-resolved anti-counterfeiting application is demonstrated as a proof-of-concept for largely enhancing the security level. This study not only provides new prospects for developing smart RTP materials but also promotes the advancement of optical anti-counterfeiting applications.
Stimulus-responsive room-temperature phosphorescence (RTP) materials have gained significant attention for their important optoelectronic application prospects. However, the fabrication strategy and underlying mechanism of stimulus-responsive RTP materials remain less explored. Herein, we present a reliable strategy for achieving pH-responsive RTP materials by integrating poly(vinyl alcohol) (PVA) with carboxylic acid or amino group functionalized terpyridine (Tpy) derivatives. The resulting Tpy derivatives-based RTP materials displayed reversible changes in emission color, intensity, and lifetime of both prompt and delayed emission. Notably, the RTP emission undergoes a significant diminish upon exposure to acid due to the protonation of Tpy units. Taking advantage of the decent RTP emission and pH-responsiveness of these RTP films, a spatial-time-resolved anti-counterfeiting application is demonstrated as a proof-of-concept for largely enhancing the security level. This study not only provides new prospects for developing smart RTP materials but also promotes the advancement of optical anti-counterfeiting applications.
2024, 35(11): 109966
doi: 10.1016/j.cclet.2024.109966
Abstract:
Shape-persistent arylene ethynylene molecular cages have been investigated as transmembrane channels for ions and small molecules. The molecular cages were obtained starting from tetrayne monomers through alkyne metathesis cyclooligomerization. We found these porphyrin-based rigid molecular cages can insert into the lipid bilayer and efficiently transport ions and small molecules (e.g., calcein). Our study reveals longer hydrophobic alkyl chains on the cage molecule promote the channeling efficiency, while shorter and/or more polar side chains impair such activity. Kinetic analysis shows linear correlation between the rate of proton transport and the concentration of the cage, suggesting the active species is likely a monomeric cage. We found that C70-encapsulated cages are nearly inactive for transmembrane ion transportation, indicating that ions are likely transported through the internal cavity of the cage. Discrete shape-persistent organic cages represent highly stable synthetic ion channels or pores, which could have interesting applications in biomimetic signaling and drug delivery.
Shape-persistent arylene ethynylene molecular cages have been investigated as transmembrane channels for ions and small molecules. The molecular cages were obtained starting from tetrayne monomers through alkyne metathesis cyclooligomerization. We found these porphyrin-based rigid molecular cages can insert into the lipid bilayer and efficiently transport ions and small molecules (e.g., calcein). Our study reveals longer hydrophobic alkyl chains on the cage molecule promote the channeling efficiency, while shorter and/or more polar side chains impair such activity. Kinetic analysis shows linear correlation between the rate of proton transport and the concentration of the cage, suggesting the active species is likely a monomeric cage. We found that C70-encapsulated cages are nearly inactive for transmembrane ion transportation, indicating that ions are likely transported through the internal cavity of the cage. Discrete shape-persistent organic cages represent highly stable synthetic ion channels or pores, which could have interesting applications in biomimetic signaling and drug delivery.
2024, 35(11): 110005
doi: 10.1016/j.cclet.2024.110005
Abstract:
The electrocatalytic reduction of nitrate (NO3–) not only facilitates the environmentally sustainable production of ammonia (NH3) but also purifies water by removing NO3–, thereby transforming waste into valuable resources. The process of converting NO3– to NH3 is complex, involving eight electron transfers and multiple intermediates, making the choice of electrocatalyst critical. In this study, we report a cobalt selenide (CoSe2) nanowire array on carbon cloth (CoSe2/CC) as an effective electrocatalyst for the NO3– to NH3 conversion. In an alkaline medium with 0.1 mol/L NO3–, CoSe2/CC demonstrates exceptional NH3 Faradaic efficiency of 97.6% and a high NH3 yield of 517.7 µmol h–1 cm–2 at –0.6 V versus the reversible hydrogen electrode. Furthermore, insights into the reaction mechanism of CoSe2 in the electrocatalytic NO3– reduction are elucidated through density functional theory calculations.
The electrocatalytic reduction of nitrate (NO3–) not only facilitates the environmentally sustainable production of ammonia (NH3) but also purifies water by removing NO3–, thereby transforming waste into valuable resources. The process of converting NO3– to NH3 is complex, involving eight electron transfers and multiple intermediates, making the choice of electrocatalyst critical. In this study, we report a cobalt selenide (CoSe2) nanowire array on carbon cloth (CoSe2/CC) as an effective electrocatalyst for the NO3– to NH3 conversion. In an alkaline medium with 0.1 mol/L NO3–, CoSe2/CC demonstrates exceptional NH3 Faradaic efficiency of 97.6% and a high NH3 yield of 517.7 µmol h–1 cm–2 at –0.6 V versus the reversible hydrogen electrode. Furthermore, insights into the reaction mechanism of CoSe2 in the electrocatalytic NO3– reduction are elucidated through density functional theory calculations.
2024, 35(11): 110024
doi: 10.1016/j.cclet.2024.110024
Abstract:
A photocatalyst-free visible-light-promoted three-component reaction of thianthrenium salts, isothiocyanates, and amines is presented, which affords a rapid and efficient approach to S-arylisothioureas under mild conditions. This developed method exhibits the advantages of readily available raw materials, broad substrate scope, good functional tolerance, and operational simplicity. It is worth mentioning that the byproduct thianthrene can be recycled in quantity, ultimately maximizing the atomic economy of the reaction and avoiding chemical waste. Mechanism investigations support the strategy involving a photoinduced EDA complex.
A photocatalyst-free visible-light-promoted three-component reaction of thianthrenium salts, isothiocyanates, and amines is presented, which affords a rapid and efficient approach to S-arylisothioureas under mild conditions. This developed method exhibits the advantages of readily available raw materials, broad substrate scope, good functional tolerance, and operational simplicity. It is worth mentioning that the byproduct thianthrene can be recycled in quantity, ultimately maximizing the atomic economy of the reaction and avoiding chemical waste. Mechanism investigations support the strategy involving a photoinduced EDA complex.
2024, 35(11): 110050
doi: 10.1016/j.cclet.2024.110050
Abstract:
Benzo[4,5]imidazo[1,2-a]pyrimidine-based derivatives play crucial roles in medicines, pesticides, tracers and photoelectric materials. However, their synthesis approach still needs to be optimized, and their fluorescent properties in intracellular microenvironment are unclear. Here, a Cu(Ⅱ)-catalyzed cascade coupling cyclization reaction was successfully developed to synthesize benzo[4,5]imidazo[1,2-a]pyrimidine scaffold with mild reaction conditions, broad substrate scopes and high yields. After a system study, we found that compound 4aa displayed an optimal viscosity-specific response with remarkable fluorescence enhancement (102-fold) for glycerol at 490 nm. Particularly, 4aa possessed excellent structure-inherent targeting (SIT) capability for lysosome (P = 0.95) with high pH stability and large Stokes shift. Importantly, 4aa was validated for its effectiveness in diagnosing lysosomal storage disorders (LSD) in living cells. The 4aa also showed its potential to map the micro-viscosity and its metabolism process in zebrafish. This work not only affords an efficient protocol to fabricate benzo[4,5]imidazo[1,2-a]pyrimidine derivatives, reveals this skeleton has excellent SIT features for lysosome, but also manifests that 4aa can serve as a practical tool to monitor lysosomal viscosity and diagnose LSD.
Benzo[4,5]imidazo[1,2-a]pyrimidine-based derivatives play crucial roles in medicines, pesticides, tracers and photoelectric materials. However, their synthesis approach still needs to be optimized, and their fluorescent properties in intracellular microenvironment are unclear. Here, a Cu(Ⅱ)-catalyzed cascade coupling cyclization reaction was successfully developed to synthesize benzo[4,5]imidazo[1,2-a]pyrimidine scaffold with mild reaction conditions, broad substrate scopes and high yields. After a system study, we found that compound 4aa displayed an optimal viscosity-specific response with remarkable fluorescence enhancement (102-fold) for glycerol at 490 nm. Particularly, 4aa possessed excellent structure-inherent targeting (SIT) capability for lysosome (P = 0.95) with high pH stability and large Stokes shift. Importantly, 4aa was validated for its effectiveness in diagnosing lysosomal storage disorders (LSD) in living cells. The 4aa also showed its potential to map the micro-viscosity and its metabolism process in zebrafish. This work not only affords an efficient protocol to fabricate benzo[4,5]imidazo[1,2-a]pyrimidine derivatives, reveals this skeleton has excellent SIT features for lysosome, but also manifests that 4aa can serve as a practical tool to monitor lysosomal viscosity and diagnose LSD.
2024, 35(11): 110111
doi: 10.1016/j.cclet.2024.110111
Abstract:
As a key biomarker for noninvasive diagnosis of diabetes, the selective detection of trace acetone in exhaled gas using a portable and low-cost device remains a great challenge. Semiconductor metal oxide (SMO) based gas sensors have drawn signification attention due to their potential in miniaturization, user-friendliness, high cost-effectiveness and selective real-time detection for noninvasive clinical diagnosis. Herein, we propose a one-pot solvent evaporation induced tricomponent co-assembly strategy to design a novel ordered mesoporous SMO of silica-implanted WO3 (SiO2/WO3) as sensing materials for trace acetone detection. The controlled co-assembly of silicon and tungsten precursors and amphiphilic diblock copolymer poly(ethylene oxide)-block-polystyrene (PEO-b-PS), and the subsequent thermal treatment enable the local lattice disorder of WO3 induced by the amorphous silica and the formation of ordered mesoporous SiO2/WO3 hybrid walls with a unique metastable ε-phase WO3 framework. The obtained mesoporous SiO2/WO3 composites possess highly crystalline framework with large uniform pore size (12.0–13.3 nm), high surface area (99–113 m2/g) and pore volume (0.17–0.23 cm3/g). Typically, the as-fabricated gas sensor based on mesoporous 2.5%SiO2/WO3 exhibits rapid response/recovery rate (5/17 s), superior sensitivity (Rair/Rgas = 105 for 50 ppm acetone), as well as high selectivity towards acetone. The limit of detection is as low as 0.25 ppm, which is considerably lower than the thresh value of acetone concentration (>1.1 ppm) in the exhaled breath of diabetic patients, demonstrating its great prospect in real-time monitoring in diabetes diagnosis. Moreover, the mesoporous 2.5%SiO2/WO3 sensor is integrated into a wireless sensing module connected to a smart phone, providing a convenient real-time detection of acetone.
As a key biomarker for noninvasive diagnosis of diabetes, the selective detection of trace acetone in exhaled gas using a portable and low-cost device remains a great challenge. Semiconductor metal oxide (SMO) based gas sensors have drawn signification attention due to their potential in miniaturization, user-friendliness, high cost-effectiveness and selective real-time detection for noninvasive clinical diagnosis. Herein, we propose a one-pot solvent evaporation induced tricomponent co-assembly strategy to design a novel ordered mesoporous SMO of silica-implanted WO3 (SiO2/WO3) as sensing materials for trace acetone detection. The controlled co-assembly of silicon and tungsten precursors and amphiphilic diblock copolymer poly(ethylene oxide)-block-polystyrene (PEO-b-PS), and the subsequent thermal treatment enable the local lattice disorder of WO3 induced by the amorphous silica and the formation of ordered mesoporous SiO2/WO3 hybrid walls with a unique metastable ε-phase WO3 framework. The obtained mesoporous SiO2/WO3 composites possess highly crystalline framework with large uniform pore size (12.0–13.3 nm), high surface area (99–113 m2/g) and pore volume (0.17–0.23 cm3/g). Typically, the as-fabricated gas sensor based on mesoporous 2.5%SiO2/WO3 exhibits rapid response/recovery rate (5/17 s), superior sensitivity (Rair/Rgas = 105 for 50 ppm acetone), as well as high selectivity towards acetone. The limit of detection is as low as 0.25 ppm, which is considerably lower than the thresh value of acetone concentration (>1.1 ppm) in the exhaled breath of diabetic patients, demonstrating its great prospect in real-time monitoring in diabetes diagnosis. Moreover, the mesoporous 2.5%SiO2/WO3 sensor is integrated into a wireless sensing module connected to a smart phone, providing a convenient real-time detection of acetone.
2024, 35(11): 110112
doi: 10.1016/j.cclet.2024.110112
Abstract:
A facile visible-light-induced 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) catalyzed four-component reaction of alkenes, quinoxalin-2(1H)-ones, P4S10 and alcohols has been developed at room temperature. This tandem reaction provides an efficient strategy for the construction of various phosphorodithioate-containing quinoxalin-2(1H)-ones with moderate to good yields by using air (dioxygen) as the green oxidant. Experimental studies revealed a radical process was involved in this photochemical reaction.
A facile visible-light-induced 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) catalyzed four-component reaction of alkenes, quinoxalin-2(1H)-ones, P4S10 and alcohols has been developed at room temperature. This tandem reaction provides an efficient strategy for the construction of various phosphorodithioate-containing quinoxalin-2(1H)-ones with moderate to good yields by using air (dioxygen) as the green oxidant. Experimental studies revealed a radical process was involved in this photochemical reaction.
2024, 35(11): 110254
doi: 10.1016/j.cclet.2024.110254
Abstract:
Defects can strongly affect the lattice, strain, and electronic structures of nanomaterials photocatalysts, like a double-edged sword of both positive significance and negative influence on photocatalytic performances. To date, most studies into defects only partially elucidated their beneficial or detrimental roles in photocatalysis. However, a quantitative understanding of the photocatalytic performances modulated by defect concentration still needs to be discovered. Here, a series of TiO2−X mesoporous spheres (MS) with different oxygen vacancy concentrations for photocatalytic applications were prepared by high-temperature chemical reduction. The link between oxygen vacancy concentration and photocatalytic performance was successfully established. The localization of carriers dominated by the Stark effect is first enhanced and then weakened with increasing oxygen vacancy concentration, which is a crucial factor in explaining the double-edged sword role of defect concentration in photocatalysis. As the reduction temperature rises to 300 ℃, carrier localization dominated by the quantum-confined Stark effect maximizes the separation ability of photo generated electron hole pairs, thus exhibiting the best catalytic performance for photocatalytic hydrogen production and the degradation of organic pollutants, as demonstrated by a hydrogen evolution rate of 523.7 µmol g-1 h-1 and a ninefold higher RhB photodegradation rate compared to TiO2 MS. The work offers excellent flexibility for precisely constructing high-performance photocatalysts by understanding vacancy engineering.
Defects can strongly affect the lattice, strain, and electronic structures of nanomaterials photocatalysts, like a double-edged sword of both positive significance and negative influence on photocatalytic performances. To date, most studies into defects only partially elucidated their beneficial or detrimental roles in photocatalysis. However, a quantitative understanding of the photocatalytic performances modulated by defect concentration still needs to be discovered. Here, a series of TiO2−X mesoporous spheres (MS) with different oxygen vacancy concentrations for photocatalytic applications were prepared by high-temperature chemical reduction. The link between oxygen vacancy concentration and photocatalytic performance was successfully established. The localization of carriers dominated by the Stark effect is first enhanced and then weakened with increasing oxygen vacancy concentration, which is a crucial factor in explaining the double-edged sword role of defect concentration in photocatalysis. As the reduction temperature rises to 300 ℃, carrier localization dominated by the quantum-confined Stark effect maximizes the separation ability of photo generated electron hole pairs, thus exhibiting the best catalytic performance for photocatalytic hydrogen production and the degradation of organic pollutants, as demonstrated by a hydrogen evolution rate of 523.7 µmol g-1 h-1 and a ninefold higher RhB photodegradation rate compared to TiO2 MS. The work offers excellent flexibility for precisely constructing high-performance photocatalysts by understanding vacancy engineering.
2024, 35(11): 109381
doi: 10.1016/j.cclet.2023.109381
Abstract:
Nanozymes are the paradigm for bridging inorganic nanomaterials with biology and environment for taking the spontaneous responsibilities to outplay natural enzymes. Metal-organic frameworks (MOFs) are mesoporous materials of inorganic-organic coordination, bearing ampoules of active/target sites and having the tendency to mimic natural enzymes. Thus MOF-based nanozymes (NZs) could be recognized for their tremendous potential for bio-catalysis. However, MOFs are of four types namely: modified MOFs, pristine MOFs, MOF-derived materials and MOFs comprised of natural enzymes. The MOFs-based NZ modulated via ultrasound, light, and heat revealed diversified applications. This article is concentrated on different methods for the preparation of MOF-based NZ for mimicking the responses of catalases, multi-functional enzymes, oxidases, superoxide dismutase, hydrolases, and peroxidases, progress and challenges of MOFs/MOF-based materials for exploiting their recent and futuristic approaches in biomedical sector.
Nanozymes are the paradigm for bridging inorganic nanomaterials with biology and environment for taking the spontaneous responsibilities to outplay natural enzymes. Metal-organic frameworks (MOFs) are mesoporous materials of inorganic-organic coordination, bearing ampoules of active/target sites and having the tendency to mimic natural enzymes. Thus MOF-based nanozymes (NZs) could be recognized for their tremendous potential for bio-catalysis. However, MOFs are of four types namely: modified MOFs, pristine MOFs, MOF-derived materials and MOFs comprised of natural enzymes. The MOFs-based NZ modulated via ultrasound, light, and heat revealed diversified applications. This article is concentrated on different methods for the preparation of MOF-based NZ for mimicking the responses of catalases, multi-functional enzymes, oxidases, superoxide dismutase, hydrolases, and peroxidases, progress and challenges of MOFs/MOF-based materials for exploiting their recent and futuristic approaches in biomedical sector.
2024, 35(11): 109461
doi: 10.1016/j.cclet.2023.109461
Abstract:
Lithium–sulfur (Li–S) batteries are considered one of the most promising next-generation secondary batteries owing to their ultrahigh theoretical energy density. However, practical applications are hindered by the shuttle effect of soluble lithium polysulfides (LiPSs) and sluggish redox kinetics, which result in low active material utilization and poor cycling stability. Various copper-based materials have been used to inhibit the shuttle effect of LiPSs, owing to the strong anchoring effect caused by the lithiophilic/sulphilic sites and the accelerated conversion kinetics caused by excellent catalytic activity. This study briefly introduces the working principles of Li–S batteries, followed by a summary of the synthetic methods for copper-based materials. Moreover, the recent research progress in the utilization of various copper-based materials in cathodes and separators of Li–S batteries, including copper oxides, copper sulfides, copper phosphides, copper selenides, copper-based metal-organic frameworks (MOFs), and copper single-atom, are systematically summarized. Subsequently, three strategies to improve the electrochemical performance of copper-based materials through defect engineering, morphology regulation, and synergistic effect of different components are presented. Finally, our perspectives on the future development of copper-based materials are presented, highlighting the major challenges in the rational design and synthesis of high-performance Li–S batteries.
Lithium–sulfur (Li–S) batteries are considered one of the most promising next-generation secondary batteries owing to their ultrahigh theoretical energy density. However, practical applications are hindered by the shuttle effect of soluble lithium polysulfides (LiPSs) and sluggish redox kinetics, which result in low active material utilization and poor cycling stability. Various copper-based materials have been used to inhibit the shuttle effect of LiPSs, owing to the strong anchoring effect caused by the lithiophilic/sulphilic sites and the accelerated conversion kinetics caused by excellent catalytic activity. This study briefly introduces the working principles of Li–S batteries, followed by a summary of the synthetic methods for copper-based materials. Moreover, the recent research progress in the utilization of various copper-based materials in cathodes and separators of Li–S batteries, including copper oxides, copper sulfides, copper phosphides, copper selenides, copper-based metal-organic frameworks (MOFs), and copper single-atom, are systematically summarized. Subsequently, three strategies to improve the electrochemical performance of copper-based materials through defect engineering, morphology regulation, and synergistic effect of different components are presented. Finally, our perspectives on the future development of copper-based materials are presented, highlighting the major challenges in the rational design and synthesis of high-performance Li–S batteries.
2024, 35(11): 109500
doi: 10.1016/j.cclet.2024.109500
Abstract:
Metal batteries have attracted considerable attention from researchers because of their low reduction voltage and high specific capacity. However, the reduction in the capacity and lifespan of batteries caused by the dendrite growth of metal anode limits the development of metal batteries. Metal-organic frameworks (MOFs) can be used to protect metal anodes owing to their advantages of ideal specific surface area, tunable porosity, and physiochemical stability in electrolytes. Therefore, MOFs have been extensively investigated in metal batteries. The introduction of MOFs to the metal anode interface can greatly improve the performance of batteries. In this review, the synthesis methods of typical MOFs and their derivatives, their protective mechanism on the metal anode, including Li, Na, K, Zn, and Mg, and their effects on the performance of metal batteries were elucidated. This review would help to design and apply MOFs to the anode interface in metal batteries.
Metal batteries have attracted considerable attention from researchers because of their low reduction voltage and high specific capacity. However, the reduction in the capacity and lifespan of batteries caused by the dendrite growth of metal anode limits the development of metal batteries. Metal-organic frameworks (MOFs) can be used to protect metal anodes owing to their advantages of ideal specific surface area, tunable porosity, and physiochemical stability in electrolytes. Therefore, MOFs have been extensively investigated in metal batteries. The introduction of MOFs to the metal anode interface can greatly improve the performance of batteries. In this review, the synthesis methods of typical MOFs and their derivatives, their protective mechanism on the metal anode, including Li, Na, K, Zn, and Mg, and their effects on the performance of metal batteries were elucidated. This review would help to design and apply MOFs to the anode interface in metal batteries.
2024, 35(11): 109515
doi: 10.1016/j.cclet.2024.109515
Abstract:
The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) are the two half reactions that make up the over water splitting reaction. Increasing oxygen evolution reaction rate wound immensely raise the efficiency of over water splitting reaction because it is the rate limiting reaction in water splitting reaction. The key to improve OER performance is the development and utilization of advanced catalysts. As one of the most potential catalysts for HER, it has gradually attracted the attention of researchers in the aspect of catalytic OER. It is very necessary to review the research progress of Transition metal dichalcogenides (TMDs) in catalytic OER to promote the research process in the field. In this review, we comprehensively and systematically summarized the strategies to improve TMDs electrocatalytic OER. First of all, structural regulation of TMDs-based electrocatalyst was summarized in detail, mainly including size engineering, defect engineering, doping engineering, phase engineering and heterojunction engineering. Once more, magnetic field regulation as a representative of external field regulation to improve TMDs electrocatalytic OER performance was discussed in depth. Last but not least, the strategies to improve TMDs electrocatalytic OER is prospected and some views on the development of this field are also put forward, which are expected to enhance the catalytic efficiency of TMDs for OER.
The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) are the two half reactions that make up the over water splitting reaction. Increasing oxygen evolution reaction rate wound immensely raise the efficiency of over water splitting reaction because it is the rate limiting reaction in water splitting reaction. The key to improve OER performance is the development and utilization of advanced catalysts. As one of the most potential catalysts for HER, it has gradually attracted the attention of researchers in the aspect of catalytic OER. It is very necessary to review the research progress of Transition metal dichalcogenides (TMDs) in catalytic OER to promote the research process in the field. In this review, we comprehensively and systematically summarized the strategies to improve TMDs electrocatalytic OER. First of all, structural regulation of TMDs-based electrocatalyst was summarized in detail, mainly including size engineering, defect engineering, doping engineering, phase engineering and heterojunction engineering. Once more, magnetic field regulation as a representative of external field regulation to improve TMDs electrocatalytic OER performance was discussed in depth. Last but not least, the strategies to improve TMDs electrocatalytic OER is prospected and some views on the development of this field are also put forward, which are expected to enhance the catalytic efficiency of TMDs for OER.
2024, 35(11): 109562
doi: 10.1016/j.cclet.2024.109562
Abstract:
Nanoparticles that employ stimuli-responsive polymeric delivery carriers have emerged as intelligent nanoplatforms with great potential in cancer theranostics, mainly including cancer diagnosis, controlled/triggered drug delivery, and real-time monitoring of therapeutic response. Particularly, tumor microenvironment (TME)-responsive polymeric nanocarriers in response to weak acidity, hypoxia, reactive oxygen species (ROS), glutathione (GSH), or tumor enzymes in the TME show great promise in facilitating tumor accumulation, enhancing tumor penetration, prolonging tumor retention, and achieving controlled drug release, thereby improving the efficiency of tumor therapy. Besides, the combination of chemotherapy and phototherapy presents a promising endeavor for the treatment of tumors, which allows for the integration of the advantages of each treatment modality, addressing the shortcomings of the two methods, and amplifying the efficacy of tumor treatment while reducing adverse reactions. This review focuses on the latest progress in the development of TME-responsive polymeric nanoparticles for synergetic chemo-photo therapy, and discusses the critical challenges and future considerations involved in the fabrication of TME-responsive nanocarriers.
Nanoparticles that employ stimuli-responsive polymeric delivery carriers have emerged as intelligent nanoplatforms with great potential in cancer theranostics, mainly including cancer diagnosis, controlled/triggered drug delivery, and real-time monitoring of therapeutic response. Particularly, tumor microenvironment (TME)-responsive polymeric nanocarriers in response to weak acidity, hypoxia, reactive oxygen species (ROS), glutathione (GSH), or tumor enzymes in the TME show great promise in facilitating tumor accumulation, enhancing tumor penetration, prolonging tumor retention, and achieving controlled drug release, thereby improving the efficiency of tumor therapy. Besides, the combination of chemotherapy and phototherapy presents a promising endeavor for the treatment of tumors, which allows for the integration of the advantages of each treatment modality, addressing the shortcomings of the two methods, and amplifying the efficacy of tumor treatment while reducing adverse reactions. This review focuses on the latest progress in the development of TME-responsive polymeric nanoparticles for synergetic chemo-photo therapy, and discusses the critical challenges and future considerations involved in the fabrication of TME-responsive nanocarriers.
2024, 35(11): 109564
doi: 10.1016/j.cclet.2024.109564
Abstract:
Skin wound healing is an important aspect of regenerative medicine. Metal-organic frameworks (MOFs) have attracted considerable attention as promising nanomaterials for skin wound healing due to their remarkable versatility, tunable pore size, surface area, targeted delivery of various therapeutic agents, and controlled release properties. The combination of these materials with biocompatible and synthetic polymers can help improve their performance in wound regeneration. This review examines the potential of MOF-polymer composites in skin wound healing. Physical and biological chemical properties and methods of making MOFs and their composites have been investigated. In the final section of this review, challenges and future prospects for the development of MOF-polymer composites are stated.
Skin wound healing is an important aspect of regenerative medicine. Metal-organic frameworks (MOFs) have attracted considerable attention as promising nanomaterials for skin wound healing due to their remarkable versatility, tunable pore size, surface area, targeted delivery of various therapeutic agents, and controlled release properties. The combination of these materials with biocompatible and synthetic polymers can help improve their performance in wound regeneration. This review examines the potential of MOF-polymer composites in skin wound healing. Physical and biological chemical properties and methods of making MOFs and their composites have been investigated. In the final section of this review, challenges and future prospects for the development of MOF-polymer composites are stated.
2024, 35(11): 109576
doi: 10.1016/j.cclet.2024.109576
Abstract:
With the increasing demand for personalized and precise treatment, the rapid advancement of synthetic biology technology has inevitably led to the development of nanobiology-based drug delivery systems. Synthetic biology-based drug delivery systems are being increasingly used in the treatment of various diseases. On one hand, synthetic biology technology enables the clever combination of chassis cells, bacteria, and their derivatives with nanomaterials, forming nano-artificial hybrid systems. These systems effectively integrate the functions of both materials, leading to further breakthroughs and optimization of biological functions. On the other hand, synthetic biology strategies guide the self-assembly of modular nanocomponents with biocatalytic or intelligent response functions, resulting in the mimicry of living cell features such as compartmentalization of enzymatic reactions and responsiveness to external stimuli. This provides novel design ideas for the construction of artificial cells. This paper aims to explore the construction and application of biogenic drug delivery systems based on whole cells, cell membrane-encapsulated nanoparticles, exosomes, bacteria, bacterial outer membrane vesicles and artificial cells, taking into account recent advances in this field. The advantages and limitations of current synthetic biology-based nanodrug delivery systems for clinical translation are discussed, and the future prospects of nanotechnology for intelligent drug diagnostic and therapeutic systems are envisioned.
With the increasing demand for personalized and precise treatment, the rapid advancement of synthetic biology technology has inevitably led to the development of nanobiology-based drug delivery systems. Synthetic biology-based drug delivery systems are being increasingly used in the treatment of various diseases. On one hand, synthetic biology technology enables the clever combination of chassis cells, bacteria, and their derivatives with nanomaterials, forming nano-artificial hybrid systems. These systems effectively integrate the functions of both materials, leading to further breakthroughs and optimization of biological functions. On the other hand, synthetic biology strategies guide the self-assembly of modular nanocomponents with biocatalytic or intelligent response functions, resulting in the mimicry of living cell features such as compartmentalization of enzymatic reactions and responsiveness to external stimuli. This provides novel design ideas for the construction of artificial cells. This paper aims to explore the construction and application of biogenic drug delivery systems based on whole cells, cell membrane-encapsulated nanoparticles, exosomes, bacteria, bacterial outer membrane vesicles and artificial cells, taking into account recent advances in this field. The advantages and limitations of current synthetic biology-based nanodrug delivery systems for clinical translation are discussed, and the future prospects of nanotechnology for intelligent drug diagnostic and therapeutic systems are envisioned.
2024, 35(11): 109584
doi: 10.1016/j.cclet.2024.109584
Abstract:
Developing natural nano-platforms with high biocompatibility and natural targeting ability represents great significance for drug delivery. High-density lipoprotein (HDL), a natural lipid-protein complex, plays important roles in physiological activities, particularly in reverse cholesterol transport (RCT) and be closely associated with atherosclerotic cardiovascular diseases. Recent studies have demonstrated that HDLs have the potential to serve as ideal drug carriers. Recombinant HDLs (rHDLs) have been used to encapsulate substances such as small interfering RNA (siRNA), drugs, and contrast agents, fully utilizing the biocompatibility and targeting ability of rHDL in the body and providing new strategies for drug delivery and disease treatment. In this review, we discussed in detail the basic principles of HDL as a drug delivery system, the mechanisms of targeted drug delivery, and several methods for preparing HDL nanoparticles. Afterward, we comprehensively reviewed the applications of HDL as a drug carrier in cardiovascular diseases, cancer treatment (such as glioblastoma, breast cancer, hepatocellular carcinoma and urologic cancers) and some other fields. Finally, we reviewed the therapeutic effects and safety of HDL nanoparticles in clinical studies. Through a review and summary of these research advances, we aim to fully understand the potential of HDL as a drug carrier in clinical applications, providing valuable references and guidance for future research and expedites the translational application of HDL as drug carriers.
Developing natural nano-platforms with high biocompatibility and natural targeting ability represents great significance for drug delivery. High-density lipoprotein (HDL), a natural lipid-protein complex, plays important roles in physiological activities, particularly in reverse cholesterol transport (RCT) and be closely associated with atherosclerotic cardiovascular diseases. Recent studies have demonstrated that HDLs have the potential to serve as ideal drug carriers. Recombinant HDLs (rHDLs) have been used to encapsulate substances such as small interfering RNA (siRNA), drugs, and contrast agents, fully utilizing the biocompatibility and targeting ability of rHDL in the body and providing new strategies for drug delivery and disease treatment. In this review, we discussed in detail the basic principles of HDL as a drug delivery system, the mechanisms of targeted drug delivery, and several methods for preparing HDL nanoparticles. Afterward, we comprehensively reviewed the applications of HDL as a drug carrier in cardiovascular diseases, cancer treatment (such as glioblastoma, breast cancer, hepatocellular carcinoma and urologic cancers) and some other fields. Finally, we reviewed the therapeutic effects and safety of HDL nanoparticles in clinical studies. Through a review and summary of these research advances, we aim to fully understand the potential of HDL as a drug carrier in clinical applications, providing valuable references and guidance for future research and expedites the translational application of HDL as drug carriers.
2024, 35(11): 109585
doi: 10.1016/j.cclet.2024.109585
Abstract:
Adenosine triphosphate (ATP), known as a common metabolic product in organism, is not only importance to provide energy in various cellular activities but also is widely explored in the bio-inspired synthetic supramolecular area which becomes a fascinating topic with the rapid development of biology, chemistry and materials science. In this review, the recent advances about ATP interacted with functional small organic compounds and metal coordinated complexes are summarized. The design principles, its function as an active supramolecular matrix, the associated non-covalent binding modes and assembly induced properties including the optical properties, morphologies are presented in details. Besides, their applications for metal ion detecting, enzyme activity monitoring and drug delivery are described due to their excellently dynamic assembly properties, adjustability, and response to stimuli. Finally, an overview of the existing challenges and future prospects of ATP-induced supramolecular systems are also discussed.
Adenosine triphosphate (ATP), known as a common metabolic product in organism, is not only importance to provide energy in various cellular activities but also is widely explored in the bio-inspired synthetic supramolecular area which becomes a fascinating topic with the rapid development of biology, chemistry and materials science. In this review, the recent advances about ATP interacted with functional small organic compounds and metal coordinated complexes are summarized. The design principles, its function as an active supramolecular matrix, the associated non-covalent binding modes and assembly induced properties including the optical properties, morphologies are presented in details. Besides, their applications for metal ion detecting, enzyme activity monitoring and drug delivery are described due to their excellently dynamic assembly properties, adjustability, and response to stimuli. Finally, an overview of the existing challenges and future prospects of ATP-induced supramolecular systems are also discussed.
2024, 35(11): 109591
doi: 10.1016/j.cclet.2024.109591
Abstract:
This article reviews the latest research advances of tetrahedral framework nucleic acid (tFNA)-based systems in their fabrication, modification, and the potential applications in biomedicine. TFNA arises from the synthesis of four single-stranded DNA chains. Each chain contains brief sequences that complement those found in the other three, culminating in the creation of a pyramid-shaped nanostructure of approximately 10 nanometers in size. The first generation of tFNA demonstrates inherent compatibility with biological systems and the ability to permeate cell membrane effectively. These attributes translate into remarkable capabilities for regulating various cellular biological processes, fostering tissue regeneration, and modulating immune responses. The subsequent evolution of tFNA introduces enhanced adaptability and a relatively higher degree of biological stability. This advancement encompasses structural modifications, such as the addition of functional domains at the vertices or side arms, integration of low molecular weight pharmaceuticals, and the implementation of diverse strategies aimed at reversing multi-drug resistance in tumor cells or microorganisms. These augmentations empower tFNA-based systems to be utilized in different scenarios, thus broadening their potential applications in various biomedical fields.
This article reviews the latest research advances of tetrahedral framework nucleic acid (tFNA)-based systems in their fabrication, modification, and the potential applications in biomedicine. TFNA arises from the synthesis of four single-stranded DNA chains. Each chain contains brief sequences that complement those found in the other three, culminating in the creation of a pyramid-shaped nanostructure of approximately 10 nanometers in size. The first generation of tFNA demonstrates inherent compatibility with biological systems and the ability to permeate cell membrane effectively. These attributes translate into remarkable capabilities for regulating various cellular biological processes, fostering tissue regeneration, and modulating immune responses. The subsequent evolution of tFNA introduces enhanced adaptability and a relatively higher degree of biological stability. This advancement encompasses structural modifications, such as the addition of functional domains at the vertices or side arms, integration of low molecular weight pharmaceuticals, and the implementation of diverse strategies aimed at reversing multi-drug resistance in tumor cells or microorganisms. These augmentations empower tFNA-based systems to be utilized in different scenarios, thus broadening their potential applications in various biomedical fields.
2024, 35(11): 109622
doi: 10.1016/j.cclet.2024.109622
Abstract:
Electrochemiluminescence has been developed as a robust analytical technique owing to its intrinsic advantages, such as near-zero background signal noise, wide dynamic ranges, high sensitivity and low cost and simple equipment. ECL luminophore as the critical component to generate light signals plays significant roles in this robust analytical system. Compared with traditional ECL luminophores, near infrared (NIR) ECL luminophores have attracted significant attentions recently due to their negligible autofluorescence, lower background interference and deep tissue penetration. Although substantial progresses have been achieved in exploring novel NIR ECL luminophores and elucidating their roles in addressing diverse challenges, there is still scarce of comprehensive reviews on the development of NIR ECL luminophores so far. In this review, the recent advancements on NIR ECL materials, including inorganic metal complexes, organic small molecules, metal nanoclusters, quantum dots and lanthanide-based materials, have been thoroughly summarized and discussed. In addition, we also provide a comprehensive overview of the challenges and prospects that lie ahead for the future development of NIR ECL luminophores in the future.
Electrochemiluminescence has been developed as a robust analytical technique owing to its intrinsic advantages, such as near-zero background signal noise, wide dynamic ranges, high sensitivity and low cost and simple equipment. ECL luminophore as the critical component to generate light signals plays significant roles in this robust analytical system. Compared with traditional ECL luminophores, near infrared (NIR) ECL luminophores have attracted significant attentions recently due to their negligible autofluorescence, lower background interference and deep tissue penetration. Although substantial progresses have been achieved in exploring novel NIR ECL luminophores and elucidating their roles in addressing diverse challenges, there is still scarce of comprehensive reviews on the development of NIR ECL luminophores so far. In this review, the recent advancements on NIR ECL materials, including inorganic metal complexes, organic small molecules, metal nanoclusters, quantum dots and lanthanide-based materials, have been thoroughly summarized and discussed. In addition, we also provide a comprehensive overview of the challenges and prospects that lie ahead for the future development of NIR ECL luminophores in the future.
2024, 35(11): 109637
doi: 10.1016/j.cclet.2024.109637
Abstract:
Reactive oxygen species (ROS) are essential in various pathological and physiological processes. Developing nanosystems that generate ROS in a controlled manner is of great interest for nanomedicine. DNA nanotechnology offers a promising approach to constructing programmable ROS-generating platforms. By incorporating photosensitizers or metal ions, DNA nanostructures can be designed to produce ROS in a spatially and temporally desired fashion. DNA-based ROS-generating nanosystems hold great potential in intracellular homeostasis regulation, drug release, and cancer therapy. This review summarizes recent advances in developing DNA-based ROS-generating nanosystems, highlights their emerging biomedical applications, and discusses the opportunities and challenges for further applications. DNA nanotechnology provides a versatile toolkit to construct biocompatible ROS-generating platforms for next-generation nanomedicines.
Reactive oxygen species (ROS) are essential in various pathological and physiological processes. Developing nanosystems that generate ROS in a controlled manner is of great interest for nanomedicine. DNA nanotechnology offers a promising approach to constructing programmable ROS-generating platforms. By incorporating photosensitizers or metal ions, DNA nanostructures can be designed to produce ROS in a spatially and temporally desired fashion. DNA-based ROS-generating nanosystems hold great potential in intracellular homeostasis regulation, drug release, and cancer therapy. This review summarizes recent advances in developing DNA-based ROS-generating nanosystems, highlights their emerging biomedical applications, and discusses the opportunities and challenges for further applications. DNA nanotechnology provides a versatile toolkit to construct biocompatible ROS-generating platforms for next-generation nanomedicines.
2024, 35(11): 109647
doi: 10.1016/j.cclet.2024.109647
Abstract:
Aliphatic C(sp3)–H moieties are ubiquitous in numerous organic compounds. Direct functionalization of inert C(sp3)–H bonds is a powerful and straightforward approach for the efficient construction of diverse carbon–carbon or carbon–heteroatom bonds. Chelating group directed metal-catalyzed remote functionalization of readily available alkenes has emerged as an appealing strategy for rapidly accessing various value-added aliphatic molecules. With the aid of directing groups, various α-, β- and γ-functionalized alkanes could be synthesized smoothly with excellent regioselectivity. The preferred formation of a stable five- or six-membered metallacycle intermediate terminates the chain-walking at a specific methylene site, which serves as the driving force for excellent site-selective migratory functionalization. This review herein is aimed at summarizing the recent progress on the metal-catalyzed regiodivergent functionalization of unactivated alkenes by merging alkene isomerization and cross-coupling with the assistance of directing auxiliary. Last but not least, the current situations and future directions in this field are highlighted and discussed.
Aliphatic C(sp3)–H moieties are ubiquitous in numerous organic compounds. Direct functionalization of inert C(sp3)–H bonds is a powerful and straightforward approach for the efficient construction of diverse carbon–carbon or carbon–heteroatom bonds. Chelating group directed metal-catalyzed remote functionalization of readily available alkenes has emerged as an appealing strategy for rapidly accessing various value-added aliphatic molecules. With the aid of directing groups, various α-, β- and γ-functionalized alkanes could be synthesized smoothly with excellent regioselectivity. The preferred formation of a stable five- or six-membered metallacycle intermediate terminates the chain-walking at a specific methylene site, which serves as the driving force for excellent site-selective migratory functionalization. This review herein is aimed at summarizing the recent progress on the metal-catalyzed regiodivergent functionalization of unactivated alkenes by merging alkene isomerization and cross-coupling with the assistance of directing auxiliary. Last but not least, the current situations and future directions in this field are highlighted and discussed.
2024, 35(11): 109651
doi: 10.1016/j.cclet.2024.109651
Abstract:
Microbial fabrication of metal nanoparticles (MNPs) has received significant attention due to the advantages of low toxicity, energy efficiency and ecological safety. Diverse groups of MNPs can be synthesized intracellularly or extracellularly by various wild-type microorganisms, including bacteria, fungi, algae and viruses. Synthetic biology approaches, represented by genetic engineering, have been applied to overcome the shortcomings in productivity, stability, and controllability of biosynthetic MNPs. Scanning electron microscope (SEM), transmission electron microscope (TEM) and other characterization techniques assist in deciphering their unique properties. In addition, biosynthetic MNPs have been widely explored for the utilization in environmental remediation and contaminant detection. And machine learning contains a great potential for designing targeted MNPs and predicting their toxicity. This review provides a comprehensive overview of the research progress in the microbial synthesis of MNPs. An outlook on the current challenges and future prospects in the biologically controllable synthesis and engineering environmental applications of MNPs is also provided in this review.
Microbial fabrication of metal nanoparticles (MNPs) has received significant attention due to the advantages of low toxicity, energy efficiency and ecological safety. Diverse groups of MNPs can be synthesized intracellularly or extracellularly by various wild-type microorganisms, including bacteria, fungi, algae and viruses. Synthetic biology approaches, represented by genetic engineering, have been applied to overcome the shortcomings in productivity, stability, and controllability of biosynthetic MNPs. Scanning electron microscope (SEM), transmission electron microscope (TEM) and other characterization techniques assist in deciphering their unique properties. In addition, biosynthetic MNPs have been widely explored for the utilization in environmental remediation and contaminant detection. And machine learning contains a great potential for designing targeted MNPs and predicting their toxicity. This review provides a comprehensive overview of the research progress in the microbial synthesis of MNPs. An outlook on the current challenges and future prospects in the biologically controllable synthesis and engineering environmental applications of MNPs is also provided in this review.
2024, 35(11): 109693
doi: 10.1016/j.cclet.2024.109693
Abstract:
Gas adsorption remains an attractive area of research. The hierarchical structure can reduce diffusion limitations and facilitate molecular transport, while acid sites can be used as adsorption sites. These make zeolites widely used in the field of gas adsorption. How to obtain zeolite adsorbents with better adsorption properties by modulating the hierarchical structure and acid sites is a pressing issue nowadays. This review highlights the strategies to modulate the hierarchical structure as well as the acid sites; and then explains how these strategies are achieved. The mechanism of zeolite adsorption on gases is then described in terms of these two properties. Lastly, the adsorption properties of zeolites for certain gases under specific conditions are summarised. An outlook of zeolite hierarchical structures and acid site modulation strategies is given.
Gas adsorption remains an attractive area of research. The hierarchical structure can reduce diffusion limitations and facilitate molecular transport, while acid sites can be used as adsorption sites. These make zeolites widely used in the field of gas adsorption. How to obtain zeolite adsorbents with better adsorption properties by modulating the hierarchical structure and acid sites is a pressing issue nowadays. This review highlights the strategies to modulate the hierarchical structure as well as the acid sites; and then explains how these strategies are achieved. The mechanism of zeolite adsorption on gases is then described in terms of these two properties. Lastly, the adsorption properties of zeolites for certain gases under specific conditions are summarised. An outlook of zeolite hierarchical structures and acid site modulation strategies is given.
2024, 35(11): 109780
doi: 10.1016/j.cclet.2024.109780
Abstract:
This review profiles twelve fluorine-containing drugs approved by the US Food and Drug Administration (FDA) for the clinic in 2023. These small molecule drugs represent such therapeutic areas as cancer, neuromuscular disorder, immunodeficiency, virology, and infectious diseases. Medicinal chemistry discovery, biological activity, and synthetic routes have been discussed for each drug. Also, new trends in structural positioning, functionality, and degree of fluorination are discussed. Besides fluorination, the importance of amino acid residues and chirality in the design of new pharmaceuticals is highlighted.
This review profiles twelve fluorine-containing drugs approved by the US Food and Drug Administration (FDA) for the clinic in 2023. These small molecule drugs represent such therapeutic areas as cancer, neuromuscular disorder, immunodeficiency, virology, and infectious diseases. Medicinal chemistry discovery, biological activity, and synthetic routes have been discussed for each drug. Also, new trends in structural positioning, functionality, and degree of fluorination are discussed. Besides fluorination, the importance of amino acid residues and chirality in the design of new pharmaceuticals is highlighted.
2024, 35(11): 109852
doi: 10.1016/j.cclet.2024.109852
Abstract:
Rechargeable magnesium ion batteries (RMBs) are investigated as lithium-ion batteries (LIBs) alternatives owing to their favorable merits of high energy density, abundance and low expenditure of Mg, as well as especially non-toxic safety and low risk of dendrite formation in anodes, which endows them to be more easily assembled in electric-power vehicles for the extended application of civilian-military fields. Nevertheless, the high charge density, strong polarization effect, and slow diffusion kinetics of Mg2+ remain a large obstacle and thus enormous efforts have to be paid to mend the gap with commercial demand for cathode materials. At present, RMBs cathode materials mainly contain transition metal sulfides/oxides, polyanionic compounds and Prussian blue analogs, and several methods such as nano structuring, doping regulation and coating modification have been applied to materials design for better performance. In this paper, the current research status of RMBs cathode materials at home & abroad is arranged and summarized along with challenges of development in the future focusing on synthesis of RMBs cathode materials with high energy density as well as satisfactory cycling performance. And this analysis aims to provide reference and basis for researchers working on RMBs technology advancement.
Rechargeable magnesium ion batteries (RMBs) are investigated as lithium-ion batteries (LIBs) alternatives owing to their favorable merits of high energy density, abundance and low expenditure of Mg, as well as especially non-toxic safety and low risk of dendrite formation in anodes, which endows them to be more easily assembled in electric-power vehicles for the extended application of civilian-military fields. Nevertheless, the high charge density, strong polarization effect, and slow diffusion kinetics of Mg2+ remain a large obstacle and thus enormous efforts have to be paid to mend the gap with commercial demand for cathode materials. At present, RMBs cathode materials mainly contain transition metal sulfides/oxides, polyanionic compounds and Prussian blue analogs, and several methods such as nano structuring, doping regulation and coating modification have been applied to materials design for better performance. In this paper, the current research status of RMBs cathode materials at home & abroad is arranged and summarized along with challenges of development in the future focusing on synthesis of RMBs cathode materials with high energy density as well as satisfactory cycling performance. And this analysis aims to provide reference and basis for researchers working on RMBs technology advancement.
2024, 35(11): 109893
doi: 10.1016/j.cclet.2024.109893
Abstract:
In 2023, The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important results in the five research directions. First, for controllable catalytic polymerization, a new silicon-centered organoboron binary catalyst was developed for copolymerization of epoxides, and a series of cooperative organocatalysts were proposed for ring-opening copolymerization of chalcogen-rich monomers. Second, with respect to microstructure and rheology, axially encoded metafiber demonstrated its capacity for integrating multiple electronics, while artificial nacre materials showed improved strength and toughness due to interlayer entanglement. Third, concerning separating functional polymers, interfacial polymerization was monitored via aggregation-induced emission, and vacuum filtration was applied to assist interfacial polymerization. Fourth, in terms of biomedical functional polymers, we designed antibacterial materials such as a novel quaternary ammonium salt that enables polyethylene terephthalate recycling and its antibacterial function, nanozyme-armed phage proved its efficiency in combating bacterial infection, and also transition metal nanoparticles showed capacities in antibacterial treatments. We also made achievements in biomedical materials, including polymeric microneedles for minimally invasive implantation and functionalization of cardiac patches, as well as ROS-responsive/scavenging prodrug/miRNA balloon coating to promote drug delivery efficiency. Besides, methods and mechanisms of RNA labeling has been developed. Fifth, about photo-electro-magnetic functional polymers, through-space conjugation was successfully manipulated by altering subunit packing modes, room-temperature phosphorescent hydrogels were synthesized via polymerization-induced crystallization of dopant molecules, and single crystals of both fullerene and non-fullerene acceptors were grown in crystallized organogel, with their photodetection performance further explored. The related works are reviewed in this paper.
In 2023, The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important results in the five research directions. First, for controllable catalytic polymerization, a new silicon-centered organoboron binary catalyst was developed for copolymerization of epoxides, and a series of cooperative organocatalysts were proposed for ring-opening copolymerization of chalcogen-rich monomers. Second, with respect to microstructure and rheology, axially encoded metafiber demonstrated its capacity for integrating multiple electronics, while artificial nacre materials showed improved strength and toughness due to interlayer entanglement. Third, concerning separating functional polymers, interfacial polymerization was monitored via aggregation-induced emission, and vacuum filtration was applied to assist interfacial polymerization. Fourth, in terms of biomedical functional polymers, we designed antibacterial materials such as a novel quaternary ammonium salt that enables polyethylene terephthalate recycling and its antibacterial function, nanozyme-armed phage proved its efficiency in combating bacterial infection, and also transition metal nanoparticles showed capacities in antibacterial treatments. We also made achievements in biomedical materials, including polymeric microneedles for minimally invasive implantation and functionalization of cardiac patches, as well as ROS-responsive/scavenging prodrug/miRNA balloon coating to promote drug delivery efficiency. Besides, methods and mechanisms of RNA labeling has been developed. Fifth, about photo-electro-magnetic functional polymers, through-space conjugation was successfully manipulated by altering subunit packing modes, room-temperature phosphorescent hydrogels were synthesized via polymerization-induced crystallization of dopant molecules, and single crystals of both fullerene and non-fullerene acceptors were grown in crystallized organogel, with their photodetection performance further explored. The related works are reviewed in this paper.
2024, 35(11): 110134
doi: 10.1016/j.cclet.2024.110134
Abstract:
