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2023 Volume 34 Issue 8
2023, 34(8): 107883
doi: 10.1016/j.cclet.2022.107883
Abstract:
Phase transition and phase separation of formamidinium-cesium (FA-Cs) perovskite during the fabrication and operation processes reduce the efficiency and stability of perovskite solar cells (PSCs). Here, we develop an in situ molecular self-assembly approach on perovskite surface using an amine nickel porphyrin (NiP). The NiP doped perovskite precursor solution was deposited on substrate by blade-coating under ambient condition. NiP molecules self-assemble into supramolecule bound on perovskite surface during the vacuum-assisted process. Such a modification controls the perovskite grain growth to generate the uniform perovskite film. The supramolecule can release the residual lattice strain to inhibit the phase transition of perovskite film, and promote the charge extraction and transport to suppress the phase separation of FA-Cs perovskite during long-term illumination condition. Consequently, the best efficiency of large-area NiP-based FA-Cs-PSCs with the active area of 1.0 cm2 is up to 20.3% (certified as 19.2%), which is close to the record efficiency (20.37%) by blade-coating. Unencapsulated NiP-doped device reveals the remarkably improved overall stabilities. This work affords a novel way to address the phase transition and phase separation in FA-Cs perovskite.
Phase transition and phase separation of formamidinium-cesium (FA-Cs) perovskite during the fabrication and operation processes reduce the efficiency and stability of perovskite solar cells (PSCs). Here, we develop an in situ molecular self-assembly approach on perovskite surface using an amine nickel porphyrin (NiP). The NiP doped perovskite precursor solution was deposited on substrate by blade-coating under ambient condition. NiP molecules self-assemble into supramolecule bound on perovskite surface during the vacuum-assisted process. Such a modification controls the perovskite grain growth to generate the uniform perovskite film. The supramolecule can release the residual lattice strain to inhibit the phase transition of perovskite film, and promote the charge extraction and transport to suppress the phase separation of FA-Cs perovskite during long-term illumination condition. Consequently, the best efficiency of large-area NiP-based FA-Cs-PSCs with the active area of 1.0 cm2 is up to 20.3% (certified as 19.2%), which is close to the record efficiency (20.37%) by blade-coating. Unencapsulated NiP-doped device reveals the remarkably improved overall stabilities. This work affords a novel way to address the phase transition and phase separation in FA-Cs perovskite.
2023, 34(8): 107884
doi: 10.1016/j.cclet.2022.107884
Abstract:
The key building blocks, tetrachlorinated terrylene diimides and the targeted sila-annulated terrylene diimides (Si-TDIs and 2Si-TDIs) were synthesized for the first time. Single-crystal analysis verified the almost planar molecular configurations of both Si-TDIs and 2Si-TDIs. They exhibited intriguing optical properties including red-shifted absorption and near-infrared emission properties with excellent fluorescence quantum yields, as well as precisely controlled HOMO/LUMO energy levels by Si-heteroannulation. The single-crystal organic field-effect transistors based on 2Si-TDI 5a featuring long and branched alkyl chains demonstrated well-balanced ambipolar transporting properties with electron/hole mobilities of 0.10/0.18 cm2 V−1 s−1.
The key building blocks, tetrachlorinated terrylene diimides and the targeted sila-annulated terrylene diimides (Si-TDIs and 2Si-TDIs) were synthesized for the first time. Single-crystal analysis verified the almost planar molecular configurations of both Si-TDIs and 2Si-TDIs. They exhibited intriguing optical properties including red-shifted absorption and near-infrared emission properties with excellent fluorescence quantum yields, as well as precisely controlled HOMO/LUMO energy levels by Si-heteroannulation. The single-crystal organic field-effect transistors based on 2Si-TDI 5a featuring long and branched alkyl chains demonstrated well-balanced ambipolar transporting properties with electron/hole mobilities of 0.10/0.18 cm2 V−1 s−1.
2023, 34(8): 107885
doi: 10.1016/j.cclet.2022.107885
Abstract:
Aqueous zinc ion batteries (AZIBs) have attracted much attention in recent years due to their high safety, low cost, and decent electrochemical performance. However, the traditional electrodes development process requires tedious synthesis and testing procedures, which reduces the efficiency of developing high-performance battery devices. Here, we proposed a high-throughput screening strategy based on first-principles calculations to aid the experimental development of high-performance spinel cathode materials for AZIBs. We obtained 14 spinel materials from 12,047 Mn/Zn-O based materials by examining their structures and whether they satisfy the basic properties of electrodes. Then their band structures and density of states, open circuit voltage and volume expansion rate, ionic diffusion coefficient and energy barrier were further evaluated by first-principles calculations, resulting in five potential candidates. One of the promising candidates identified, Mg2MnO4, was experimentally synthesized, characterized and integrated into an AZIB based cell to verify its performance as a cathode. The Mg2MnO4 cathode exhibits excellent cycling stability, which is consistent with the theoretically predicted low volume expansion. Moreover, at high current density, the Mg2MnO4 cathode still exhibits high reversible capacity and excellent rate performance, indicating that it is an excellent cathode material for AZIBs. Our work provides a new approach to accelerate the development of high-performance cathodes for AZIBs and other ion batteries.
Aqueous zinc ion batteries (AZIBs) have attracted much attention in recent years due to their high safety, low cost, and decent electrochemical performance. However, the traditional electrodes development process requires tedious synthesis and testing procedures, which reduces the efficiency of developing high-performance battery devices. Here, we proposed a high-throughput screening strategy based on first-principles calculations to aid the experimental development of high-performance spinel cathode materials for AZIBs. We obtained 14 spinel materials from 12,047 Mn/Zn-O based materials by examining their structures and whether they satisfy the basic properties of electrodes. Then their band structures and density of states, open circuit voltage and volume expansion rate, ionic diffusion coefficient and energy barrier were further evaluated by first-principles calculations, resulting in five potential candidates. One of the promising candidates identified, Mg2MnO4, was experimentally synthesized, characterized and integrated into an AZIB based cell to verify its performance as a cathode. The Mg2MnO4 cathode exhibits excellent cycling stability, which is consistent with the theoretically predicted low volume expansion. Moreover, at high current density, the Mg2MnO4 cathode still exhibits high reversible capacity and excellent rate performance, indicating that it is an excellent cathode material for AZIBs. Our work provides a new approach to accelerate the development of high-performance cathodes for AZIBs and other ion batteries.
2023, 34(8): 107896
doi: 10.1016/j.cclet.2022.107896
Abstract:
To understand the deformation mechanism of molecular crystals under mechanical forces will accelerate the molecular design and preparation of deformable crystals. Herein, the relationship between structural halogenation and molecular-level stacking, micro/nanoscale surface morphology, and macroscopic mechanical properties are investigated. Elastic crystals of halo-pyrimidinyl carbazoles (CzM-Cl, CzM-Br and CzM-Ⅰ) with lamellar structure and brittle crystal (CzM-F) were quantitatively analyzed by crystal energy framework (CEF) providing the inter/intralayer interaction energy (Inter/Intra-IE). It is revealed that the elastic crystals bend under external force as a result from stronger Intra-IE to prevent cleavage and weaker Inter-IE for the short-range movement of molecules on the slip plane. This research will provide an insight for the molecular design of flexible crystals and facilitate the development of next-generation smart crystal materials.
To understand the deformation mechanism of molecular crystals under mechanical forces will accelerate the molecular design and preparation of deformable crystals. Herein, the relationship between structural halogenation and molecular-level stacking, micro/nanoscale surface morphology, and macroscopic mechanical properties are investigated. Elastic crystals of halo-pyrimidinyl carbazoles (CzM-Cl, CzM-Br and CzM-Ⅰ) with lamellar structure and brittle crystal (CzM-F) were quantitatively analyzed by crystal energy framework (CEF) providing the inter/intralayer interaction energy (Inter/Intra-IE). It is revealed that the elastic crystals bend under external force as a result from stronger Intra-IE to prevent cleavage and weaker Inter-IE for the short-range movement of molecules on the slip plane. This research will provide an insight for the molecular design of flexible crystals and facilitate the development of next-generation smart crystal materials.
2023, 34(8): 107897
doi: 10.1016/j.cclet.2022.107897
Abstract:
Hydrocarbons are promising products for CO2 electroreduction (CRR) while is impeded by the low selectivity. Turning the curvature of the active site is an effective strategy to change the adsorption properties and further regulate the product distribution and reactivity. Herein, we have designed a novel V single atom catalyst (SAC) based on rolled two-dimensional (2D) BC3N2 substrate with different curvatures. The results have demonstrated that increased curvature can enhance the adsorption strength of CRR intermediates, which follows different mechanisms for systems with low and high curvature. This character eventually leads to the deviation away from the scaling line between Ead[CO]~Ead[COOH] based on transition metals for V@2D-BC3N2 systems. 3-3 system is screened as the optimal candidate for hydrocarbons production due to the enhanced binding ability of adsorbates, which can increase the reactivity for hydrocarbons production and hinder the production of H2 and HCOOH simultaneously.
Hydrocarbons are promising products for CO2 electroreduction (CRR) while is impeded by the low selectivity. Turning the curvature of the active site is an effective strategy to change the adsorption properties and further regulate the product distribution and reactivity. Herein, we have designed a novel V single atom catalyst (SAC) based on rolled two-dimensional (2D) BC3N2 substrate with different curvatures. The results have demonstrated that increased curvature can enhance the adsorption strength of CRR intermediates, which follows different mechanisms for systems with low and high curvature. This character eventually leads to the deviation away from the scaling line between Ead[CO]~Ead[COOH] based on transition metals for V@2D-BC3N2 systems. 3-3 system is screened as the optimal candidate for hydrocarbons production due to the enhanced binding ability of adsorbates, which can increase the reactivity for hydrocarbons production and hinder the production of H2 and HCOOH simultaneously.
2023, 34(8): 107898
doi: 10.1016/j.cclet.2022.107898
Abstract:
The oxalate-phosphate polyanion-mixed cathode materials are promising for sodium-ion batteries (SIBs) due to their unique open-framework structures and high voltage property. However, materials of this type generally contain crystal water molecules in the lattice frameworks, which may affect their energy storage properties. This work aims to disclose the impacts of crystal water on physiochemical and electrochemical properties of Na2(VO)2(HPO4)2(C2O4)·2H2O (NVPC-W). It shows that the water molecules can be eliminated by vacuum drying at 150 ℃. The elimination of water molecules does not change the crystal phase of the material, while the obtained Na2(VO)2(HPO4)2(C2O4) (NVPC) exhibits significant improvements in cycling stability, Coulombic efficiency, as well as rate performances. Kinetics analysis indicates that the existence of lattice water molecules hinders sodium-ion diffusion and promotes the degradation of electrodes. We believe the findings can help to develop high-performance cathode materials.
The oxalate-phosphate polyanion-mixed cathode materials are promising for sodium-ion batteries (SIBs) due to their unique open-framework structures and high voltage property. However, materials of this type generally contain crystal water molecules in the lattice frameworks, which may affect their energy storage properties. This work aims to disclose the impacts of crystal water on physiochemical and electrochemical properties of Na2(VO)2(HPO4)2(C2O4)·2H2O (NVPC-W). It shows that the water molecules can be eliminated by vacuum drying at 150 ℃. The elimination of water molecules does not change the crystal phase of the material, while the obtained Na2(VO)2(HPO4)2(C2O4) (NVPC) exhibits significant improvements in cycling stability, Coulombic efficiency, as well as rate performances. Kinetics analysis indicates that the existence of lattice water molecules hinders sodium-ion diffusion and promotes the degradation of electrodes. We believe the findings can help to develop high-performance cathode materials.
2023, 34(8): 107902
doi: 10.1016/j.cclet.2022.107902
Abstract:
Non-fused ring electron acceptors (NFREAs) have a broad application prospect in the commercialization of organic solar cells (OSCs) due to the advantages of simple synthesis and low cost. The selection of intermediate block cores of non-fused frameworks and the establishment of the relationship between molecular structure and device performance are crucial for the realization of high-performance OSCs. Herein, two A-D-A'-D-A type NFREAs namely CBTBO-4F and CBTBO-4Cl, constructed with a novel electron-deficient block unit N-(2-butyloctyl)-carbazole[3,4-c: 5,6-c]bis[1,2,5]thiadiazole (CBT) and bridging unit 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b: 3,4-b']dithiophene (DTC) coupling with different terminals (IC-2F/2Cl), were designed and synthesized. The two NFREAs feature broad and strong photoresponse from 500 nm to 900 nm due to the strong intramolecular charge transfer characteristics. Compared with CBTBO-4F, CBTBO-4Cl shows better molecular planarity, stronger crystallinity, more ordered molecular stacking, larger van der Waals surface, lower energy level and better active layer morphology, contributing to much better charge separation and transport behaviors in its based devices. As a result, the CBTBO-4Cl based device obtains a higher power conversion efficiency of 10.18% with an open-circuit voltage of 0.80 V and a short-circuit current density of 21.20 mA/cm2. These results not only demonstrate the great potential of CBT, a new building block of the benzothiazole family, in the construction of high-performance organic conjugated semiconductors, but also suggest that the terminal chlorination is an effective strategy to improve device performance.
Non-fused ring electron acceptors (NFREAs) have a broad application prospect in the commercialization of organic solar cells (OSCs) due to the advantages of simple synthesis and low cost. The selection of intermediate block cores of non-fused frameworks and the establishment of the relationship between molecular structure and device performance are crucial for the realization of high-performance OSCs. Herein, two A-D-A'-D-A type NFREAs namely CBTBO-4F and CBTBO-4Cl, constructed with a novel electron-deficient block unit N-(2-butyloctyl)-carbazole[3,4-c: 5,6-c]bis[1,2,5]thiadiazole (CBT) and bridging unit 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b: 3,4-b']dithiophene (DTC) coupling with different terminals (IC-2F/2Cl), were designed and synthesized. The two NFREAs feature broad and strong photoresponse from 500 nm to 900 nm due to the strong intramolecular charge transfer characteristics. Compared with CBTBO-4F, CBTBO-4Cl shows better molecular planarity, stronger crystallinity, more ordered molecular stacking, larger van der Waals surface, lower energy level and better active layer morphology, contributing to much better charge separation and transport behaviors in its based devices. As a result, the CBTBO-4Cl based device obtains a higher power conversion efficiency of 10.18% with an open-circuit voltage of 0.80 V and a short-circuit current density of 21.20 mA/cm2. These results not only demonstrate the great potential of CBT, a new building block of the benzothiazole family, in the construction of high-performance organic conjugated semiconductors, but also suggest that the terminal chlorination is an effective strategy to improve device performance.
2023, 34(8): 107910
doi: 10.1016/j.cclet.2022.107910
Abstract:
Among the emitters in powder dusting to visualize the latent fingerprints (LFPs), aggregation-induced emission luminogens (AIEgens) are well employed for their high brightness and resistance to photo-bleaching. However, the serious background interference and low resolution still limit their fast development. Therefore, to further enhance the signal-to-noise ratio in LFPs imaging, especially to improve the analysis for level 3 details, donor-acceptor (D-A) typed AIEgens of DTPA-2,3-P, DTPA-2,5-P and DTPA-2,6-P are designed here. It is observed that strong emission covering from 450 nm to 650 nm can be obtained for all these molecules, especially that a high PLQY value of 10.06% in solids is achieved in DTPA-2,3-P. This is much higher than that of the other two cases (0.80% and 0.51%). By utilizing the DTPA-2,3-P in powder dusting, fluorescence imaging of LFPs can be clearly captured on both smooth and rough substrates. Moreover, confocal laser scanning microscope (CLSM) enables us to achieve high-resolution LFPs imaging in both 2D and 3D views, providing more detailed information of fingerprints pores in width, distance, distribution, and shapes. The results here demonstrate that highly emissive AIEgen of DTPA-2,3-P could be an excellent candidate for the visualization of fingerprints, thus providing the potential application in criminal investigation in the future.
Among the emitters in powder dusting to visualize the latent fingerprints (LFPs), aggregation-induced emission luminogens (AIEgens) are well employed for their high brightness and resistance to photo-bleaching. However, the serious background interference and low resolution still limit their fast development. Therefore, to further enhance the signal-to-noise ratio in LFPs imaging, especially to improve the analysis for level 3 details, donor-acceptor (D-A) typed AIEgens of DTPA-2,3-P, DTPA-2,5-P and DTPA-2,6-P are designed here. It is observed that strong emission covering from 450 nm to 650 nm can be obtained for all these molecules, especially that a high PLQY value of 10.06% in solids is achieved in DTPA-2,3-P. This is much higher than that of the other two cases (0.80% and 0.51%). By utilizing the DTPA-2,3-P in powder dusting, fluorescence imaging of LFPs can be clearly captured on both smooth and rough substrates. Moreover, confocal laser scanning microscope (CLSM) enables us to achieve high-resolution LFPs imaging in both 2D and 3D views, providing more detailed information of fingerprints pores in width, distance, distribution, and shapes. The results here demonstrate that highly emissive AIEgen of DTPA-2,3-P could be an excellent candidate for the visualization of fingerprints, thus providing the potential application in criminal investigation in the future.
2023, 34(8): 107911
doi: 10.1016/j.cclet.2022.107911
Abstract:
To tackle undesirable shuttle reaction and sluggish reaction kinetics in lithium–sulfur (Li–S) batteries, we develop a porous and high-density oxygen-doped tantalum nitride nanostructure (nano-TaNO) as an efficient catalyst through delicate tailoring. Benefiting from well-defined interior and surface nanopore channels, the nano-TaNO favors abundant sulfur storage, easy electrolyte infiltration and good electrons/Li+ transport. More importantly, high-density O dopant in nano-TaNO not only provides high conductivity, but also promotes polysulfide adsorption/conversion via Li–O chemical interactions and the generation of S3*− radicals to activate additional evolution path from S8 to Li2S. Consequently, the nano-TaNO-based cathode exhibits excellent specific capacity and cyclability even under high sulfur loading condition. These interesting findings suggest the great potential of tantalum nitride and a high amount of anion doping engineering in manipulating intermediates and building high-performance Li−S rechargeable batteries.
To tackle undesirable shuttle reaction and sluggish reaction kinetics in lithium–sulfur (Li–S) batteries, we develop a porous and high-density oxygen-doped tantalum nitride nanostructure (nano-TaNO) as an efficient catalyst through delicate tailoring. Benefiting from well-defined interior and surface nanopore channels, the nano-TaNO favors abundant sulfur storage, easy electrolyte infiltration and good electrons/Li+ transport. More importantly, high-density O dopant in nano-TaNO not only provides high conductivity, but also promotes polysulfide adsorption/conversion via Li–O chemical interactions and the generation of S3*− radicals to activate additional evolution path from S8 to Li2S. Consequently, the nano-TaNO-based cathode exhibits excellent specific capacity and cyclability even under high sulfur loading condition. These interesting findings suggest the great potential of tantalum nitride and a high amount of anion doping engineering in manipulating intermediates and building high-performance Li−S rechargeable batteries.
2023, 34(8): 107916
doi: 10.1016/j.cclet.2022.107916
Abstract:
The liquid leakage and weak solar absorption capacity of organic phase change materials (PCMs) seriously hinder the efficient utilization of solar energy and thermal energy storage. To address these issues, we prepared nanoporous metal organic framework (Ni-MOF) for the vacuum infiltration of paraffin wax (PW), followed by the coating of solar-absorbing functional polydopamine (PDA) on the surface of PW@MOF for photothermal conversion and storage. As an efficient photon harvester, PDA coating endows PW@MOF/PDA composite PCMs with excellent photothermal conversion and storage properties due to the robust broadband solar absorption capability in the UV–vis region. Resultantly, our prepared PW@MOF/PDA composite PCMs exhibit a high photothermal conversion and storage efficiency of 91.2%, while that of PW@MOF composite PCMs is only zero. In addition, PW@MOF/PDA composite PCMs also exhibit excellent thermal stability, shape stability, energy storage stability, and photothermal conversion stability. More importantly, this coating strategy is universal by integrating different MOFs and solar absorbers, showing the potential to accelerate the major breakthroughs of high-efficiency MOF-based photothermal composite PCMs in solar energy utilization.
The liquid leakage and weak solar absorption capacity of organic phase change materials (PCMs) seriously hinder the efficient utilization of solar energy and thermal energy storage. To address these issues, we prepared nanoporous metal organic framework (Ni-MOF) for the vacuum infiltration of paraffin wax (PW), followed by the coating of solar-absorbing functional polydopamine (PDA) on the surface of PW@MOF for photothermal conversion and storage. As an efficient photon harvester, PDA coating endows PW@MOF/PDA composite PCMs with excellent photothermal conversion and storage properties due to the robust broadband solar absorption capability in the UV–vis region. Resultantly, our prepared PW@MOF/PDA composite PCMs exhibit a high photothermal conversion and storage efficiency of 91.2%, while that of PW@MOF composite PCMs is only zero. In addition, PW@MOF/PDA composite PCMs also exhibit excellent thermal stability, shape stability, energy storage stability, and photothermal conversion stability. More importantly, this coating strategy is universal by integrating different MOFs and solar absorbers, showing the potential to accelerate the major breakthroughs of high-efficiency MOF-based photothermal composite PCMs in solar energy utilization.
2023, 34(8): 107917
doi: 10.1016/j.cclet.2022.107917
Abstract:
Herein, we developed for the first time two carboxylic acid based intrinsic proton conductors (COOH-COF-1 and COOH-COF-2) via pre-assembly approach. The obtained COOH-COF-1 and COOH-COF-2 not only show outstanding chemical and thermal stabilities, but also exhibit superhigh intrinsic proton conductive behaviors. Especially, the intrinsic proton conductivity of COOH-COF-2 is up to 2.6 × 10−3 S/cm at 353 K and 98% RH, which is the highest value among all the reported acid functionalized COFs. This work lights up the way for the rational design of functional COFs with remarkably intrinsic proton conducting performance and related practical applications.
Herein, we developed for the first time two carboxylic acid based intrinsic proton conductors (COOH-COF-1 and COOH-COF-2) via pre-assembly approach. The obtained COOH-COF-1 and COOH-COF-2 not only show outstanding chemical and thermal stabilities, but also exhibit superhigh intrinsic proton conductive behaviors. Especially, the intrinsic proton conductivity of COOH-COF-2 is up to 2.6 × 10−3 S/cm at 353 K and 98% RH, which is the highest value among all the reported acid functionalized COFs. This work lights up the way for the rational design of functional COFs with remarkably intrinsic proton conducting performance and related practical applications.
2023, 34(8): 107918
doi: 10.1016/j.cclet.2022.107918
Abstract:
Brookhart-type α-diimine nickel and palladium catalysts have been extensively studied over the past several decades; however, the heterogenization of these metal complexes has received much less attention. In this contribution, we installed a trifluoroborate potassium substituent on an α-diimine framework. The ionic nature of trifluoroborate potassium endowed the α-diimine nickel complex with a strong affinity for the SiO2 support, while its electron-donating nature enhanced the catalyst stability and polyethylene molecular weight. In the presence of only 100 equiv. of Et2AlCl cocatalyst, the SiO2-supported catalyst demonstrated significantly better performance than its homogeneous analog during ethylene polymerization, with extremely high activity (1.42–6.53 × 107 g mol−1 h−1) and high thermal stability. The heterogeneous system led to the formation of high-molecular-weight polyethylenes (Mn 142, 500–732, 800 g/mol), narrow polydispersities (2.18–3.00), tunable branching densities (21–64 per 1000 carbon atoms), and great mechanical properties. Moreover, the efficient copolymerization of ethylene with comonomers such as methyl 10-undecenoate, 6-chloro-1-hexene or 5-hexenylacetate was achieved. These superior properties enabled by the trifluoroborate potassium moiety may inspire its applications in other polymerization catalyst systems.
Brookhart-type α-diimine nickel and palladium catalysts have been extensively studied over the past several decades; however, the heterogenization of these metal complexes has received much less attention. In this contribution, we installed a trifluoroborate potassium substituent on an α-diimine framework. The ionic nature of trifluoroborate potassium endowed the α-diimine nickel complex with a strong affinity for the SiO2 support, while its electron-donating nature enhanced the catalyst stability and polyethylene molecular weight. In the presence of only 100 equiv. of Et2AlCl cocatalyst, the SiO2-supported catalyst demonstrated significantly better performance than its homogeneous analog during ethylene polymerization, with extremely high activity (1.42–6.53 × 107 g mol−1 h−1) and high thermal stability. The heterogeneous system led to the formation of high-molecular-weight polyethylenes (Mn 142, 500–732, 800 g/mol), narrow polydispersities (2.18–3.00), tunable branching densities (21–64 per 1000 carbon atoms), and great mechanical properties. Moreover, the efficient copolymerization of ethylene with comonomers such as methyl 10-undecenoate, 6-chloro-1-hexene or 5-hexenylacetate was achieved. These superior properties enabled by the trifluoroborate potassium moiety may inspire its applications in other polymerization catalyst systems.
2023, 34(8): 107919
doi: 10.1016/j.cclet.2022.107919
Abstract:
Opportunities coexist with challenges for the development of carbon-based cathodes with a high energy density applied for zinc ion hybrid capacitors (ZIHCs). In the present study, a facile and effective surface engineering approach is demonstrated to greatly improve the energy storage ability of commercial carbon paper (CP) in ZIHC. Benefiting from the introduced oxygen functional groups, larger surface area and improved surface wettability upon air calcination, the assembled aqueous ZIHC with the functionalized carbon paper (FCP) exhibits a much higher areal capacity of 0.22 mAh/cm2 at 1 mA/cm2, outperforming the counterpart with blank CP by over 5000 times. More importantly, a superior energy density and power density of 130.8 µWh/cm2 and 7460.5 µW/cm2, are respectively delivered. Furthermore, more than 90% of the initial capacity is retained over 10000 cycles. This surface engineering strategy to improve the energy storage capability is potentially applicable to developing a wide range of high-energy carbon electrode materials.
Opportunities coexist with challenges for the development of carbon-based cathodes with a high energy density applied for zinc ion hybrid capacitors (ZIHCs). In the present study, a facile and effective surface engineering approach is demonstrated to greatly improve the energy storage ability of commercial carbon paper (CP) in ZIHC. Benefiting from the introduced oxygen functional groups, larger surface area and improved surface wettability upon air calcination, the assembled aqueous ZIHC with the functionalized carbon paper (FCP) exhibits a much higher areal capacity of 0.22 mAh/cm2 at 1 mA/cm2, outperforming the counterpart with blank CP by over 5000 times. More importantly, a superior energy density and power density of 130.8 µWh/cm2 and 7460.5 µW/cm2, are respectively delivered. Furthermore, more than 90% of the initial capacity is retained over 10000 cycles. This surface engineering strategy to improve the energy storage capability is potentially applicable to developing a wide range of high-energy carbon electrode materials.
2023, 34(8): 107929
doi: 10.1016/j.cclet.2022.107929
Abstract:
Balancing cost and performance of porous carbon (PC) as anode for lithium-ion battery (LIBs) is the key to effectively promote commercial application. Herein, low-cost N-doped PC (NPC-Ts, T = 600, 750 and 900 ℃) were facilely prepared in batches via one-pot pyrolysis of agar with different carbonization temperature. The NPC-750 with specific surface area of 2914 m2/g and N content of 2.84% exhibits an ultrahigh reversible capacity of 1019 mAh/g at 0.1 A/g after 100 cycles and 837 mAh/g at 1 A/g after 500 cycles. Remarkably, the resulting LIBs exhibit an ultrafast charge-discharge feature with a remarkable capacity of 281 mAh/g at 10 A/g and a superlong cycle life with a capacity retention of 87% after 5000 cycles at 10 A/g. Coupling with LiFePO4 cathode, the fabricated lithium-ion full cells possess high capacity, excellent rate and cycling performances (125 mAh/g at 100 mA/g, capacity retention of 95%, after 220 cycles), highlighting the practicability of this NPC-750 as the anode materials.
Balancing cost and performance of porous carbon (PC) as anode for lithium-ion battery (LIBs) is the key to effectively promote commercial application. Herein, low-cost N-doped PC (NPC-Ts, T = 600, 750 and 900 ℃) were facilely prepared in batches via one-pot pyrolysis of agar with different carbonization temperature. The NPC-750 with specific surface area of 2914 m2/g and N content of 2.84% exhibits an ultrahigh reversible capacity of 1019 mAh/g at 0.1 A/g after 100 cycles and 837 mAh/g at 1 A/g after 500 cycles. Remarkably, the resulting LIBs exhibit an ultrafast charge-discharge feature with a remarkable capacity of 281 mAh/g at 10 A/g and a superlong cycle life with a capacity retention of 87% after 5000 cycles at 10 A/g. Coupling with LiFePO4 cathode, the fabricated lithium-ion full cells possess high capacity, excellent rate and cycling performances (125 mAh/g at 100 mA/g, capacity retention of 95%, after 220 cycles), highlighting the practicability of this NPC-750 as the anode materials.
2023, 34(8): 107930
doi: 10.1016/j.cclet.2022.107930
Abstract:
To achieve real-time monitoring of humidity in various applications, we prepared facile and ultra-thin CoAl layered double hydroxide (CoAl LDH) nanosheets to engineer quartz crystal microbalances (QCM). The characteristics of CoAl LDH were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectric spectroscopy (XPS), Brunauer–Emmett–Telle (BET), atomic force microscopy (AFM) and zeta potential. Due to their large specific surface area and abundant hydroxyl groups, CoAl LDH nanosheets exhibit good humidity sensing performance. In a range of 11.3% and 97.6% relative humidity (RH), the sensor behaved an ultrahigh sensitivity (127.8 Hz/%RH), fast response (9.1 s) and recovery time (3.1 s), low hysteresis (3.1%RH), good linearity (R2 = 0.9993), stability and selectivity. Besides, the sensor can recover the initial response frequency after being wetted by deionized water, revealing superior self-recovery ability under high humidity. Based on in-situ Fourier transform infrared spectroscopy (FT-IR), the adsorption mechanism of CoAl LDH toward water molecules was explored. The QCM sensor can distinguish different respiratory states of people and wetting degree of fingers, as well as monitor the humidity in vegetable packaging, suggesting excellent properties and a promising application in humidity sensing.
To achieve real-time monitoring of humidity in various applications, we prepared facile and ultra-thin CoAl layered double hydroxide (CoAl LDH) nanosheets to engineer quartz crystal microbalances (QCM). The characteristics of CoAl LDH were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectric spectroscopy (XPS), Brunauer–Emmett–Telle (BET), atomic force microscopy (AFM) and zeta potential. Due to their large specific surface area and abundant hydroxyl groups, CoAl LDH nanosheets exhibit good humidity sensing performance. In a range of 11.3% and 97.6% relative humidity (RH), the sensor behaved an ultrahigh sensitivity (127.8 Hz/%RH), fast response (9.1 s) and recovery time (3.1 s), low hysteresis (3.1%RH), good linearity (R2 = 0.9993), stability and selectivity. Besides, the sensor can recover the initial response frequency after being wetted by deionized water, revealing superior self-recovery ability under high humidity. Based on in-situ Fourier transform infrared spectroscopy (FT-IR), the adsorption mechanism of CoAl LDH toward water molecules was explored. The QCM sensor can distinguish different respiratory states of people and wetting degree of fingers, as well as monitor the humidity in vegetable packaging, suggesting excellent properties and a promising application in humidity sensing.
2023, 34(8): 107940
doi: 10.1016/j.cclet.2022.107940
Abstract:
Recently, a novel tetraarylimidazole derivative 2-(benzo[d]thiazol-2-yl)-4-(4,5-bis(4-methoxyphenyl)-1-phenyl-1H-imidazol-2-yl)-phenol (be called MHBT herein) was architectured by our research group showing the fascinating synergy of aggregation-induced emission (AIE) characteristic, excited-state intramolecular proton transfer (ESIPT) mechanism and intramolecular charge transfer (ICT) effect. Nevertheless, a detailed and reasonable interpretation of its mechanisms both in theory is urgently needed. Consequently, to unveil the working mechanism meticulously, herein, we tactfully applied density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods to illuminate the underlying mechanisms in different solvent conditions. After optimizing the structures, the geometric parameters of hydrogen bonds (HBs), the infrared (IR) vibrational spectrum, the reduced density gradient (RDG) isosurfaces were calculated in detail, vividly explaining how the enhancement of HBs behaved as the driving force to proceed ESIPT process. Simultaneously, the frontier molecular orbitals (FMOs) combined with the potential energy curves (PECs) were conducted to interpretate the role and character of ICT and ESIPT in molecule MHBT. Further, the PECs of MHBT for dihedral angles in different organic solvents were calculated to compare the dominant torsion degree, rationalizing the AIE phenomenon from the view of the restriction of intramolecular rotation process. This work may well underpin the understanding of the interaction between different mechanisms in fluorescent dyes and thereby provide meaningful guideline for the design and construction of ideal molecules
Recently, a novel tetraarylimidazole derivative 2-(benzo[d]thiazol-2-yl)-4-(4,5-bis(4-methoxyphenyl)-1-phenyl-1H-imidazol-2-yl)-phenol (be called MHBT herein) was architectured by our research group showing the fascinating synergy of aggregation-induced emission (AIE) characteristic, excited-state intramolecular proton transfer (ESIPT) mechanism and intramolecular charge transfer (ICT) effect. Nevertheless, a detailed and reasonable interpretation of its mechanisms both in theory is urgently needed. Consequently, to unveil the working mechanism meticulously, herein, we tactfully applied density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods to illuminate the underlying mechanisms in different solvent conditions. After optimizing the structures, the geometric parameters of hydrogen bonds (HBs), the infrared (IR) vibrational spectrum, the reduced density gradient (RDG) isosurfaces were calculated in detail, vividly explaining how the enhancement of HBs behaved as the driving force to proceed ESIPT process. Simultaneously, the frontier molecular orbitals (FMOs) combined with the potential energy curves (PECs) were conducted to interpretate the role and character of ICT and ESIPT in molecule MHBT. Further, the PECs of MHBT for dihedral angles in different organic solvents were calculated to compare the dominant torsion degree, rationalizing the AIE phenomenon from the view of the restriction of intramolecular rotation process. This work may well underpin the understanding of the interaction between different mechanisms in fluorescent dyes and thereby provide meaningful guideline for the design and construction of ideal molecules
2023, 34(8): 107946
doi: 10.1016/j.cclet.2022.107946
Abstract:
Silicon is recognized as the most advantageous next-generation anode material for LIBs in terms of its extremely high theoretical capacity and appropriate operating voltage. However, the application of Si anode is limited by huge volume expansion emerging with cycling, which in turn induces the collapse of the electrode structure, resulting in rapid capacity decay. Here, we report a strategy using self-swelling artificial laponite to prepare a laponite/MXene/CNT composite framework with both rigidity and flexibility, which can excellently address these challenges of Si anode. The self-swelling artificial laponite participates in the construction of hierarchical and porous structures, providing sufficient buffer space to mitigate the volume expansion of the LixSi alloying reaction. Meanwhile, tough and tightly cross-linked silicate nanosheets can improve the mechanical strength of the framework for strong structural stability. More importantly, the negative charge between the layers of artificial laponite can effectively promote fast Li-ion transport in the electrode. This free-standing silicon anode enables the preparation of high areal capacity electrodes to further enhance the energy density of LIBs and a higher reversible capacity of 2381.8 mAh/g at 0.1 C after 50 cycles with an initial coulombic of 85.6%. This work provides a simple and practical fabrication strategy for developing high-performance Si-based batteries, which can speed up their commercialization.
Silicon is recognized as the most advantageous next-generation anode material for LIBs in terms of its extremely high theoretical capacity and appropriate operating voltage. However, the application of Si anode is limited by huge volume expansion emerging with cycling, which in turn induces the collapse of the electrode structure, resulting in rapid capacity decay. Here, we report a strategy using self-swelling artificial laponite to prepare a laponite/MXene/CNT composite framework with both rigidity and flexibility, which can excellently address these challenges of Si anode. The self-swelling artificial laponite participates in the construction of hierarchical and porous structures, providing sufficient buffer space to mitigate the volume expansion of the LixSi alloying reaction. Meanwhile, tough and tightly cross-linked silicate nanosheets can improve the mechanical strength of the framework for strong structural stability. More importantly, the negative charge between the layers of artificial laponite can effectively promote fast Li-ion transport in the electrode. This free-standing silicon anode enables the preparation of high areal capacity electrodes to further enhance the energy density of LIBs and a higher reversible capacity of 2381.8 mAh/g at 0.1 C after 50 cycles with an initial coulombic of 85.6%. This work provides a simple and practical fabrication strategy for developing high-performance Si-based batteries, which can speed up their commercialization.
2023, 34(8): 107947
doi: 10.1016/j.cclet.2022.107947
Abstract:
For several decades, the promise of implementing of lithium (Li) metal anodes for Li batteries has been a "holy grail" for researchers. Herein, we have proposed a facile design of a MOF-derived Co3O4 nanoparticles modified nickel foam, i.e., Co3O4-NF, as a 3D host to achieve a uniform infusion of the molten Li. The molten Li was uniformly absorbed on the Co3O4-NF host only in 10 s due to its high Li lithiophilicity. The obtained Li-Co3O4-NF composite electrode shows high cycling stability in symmetric cells with low voltage hysteresis even at a high current density of 5 mA/cm2. The full cells of Li-Co3O4-NF/LiFePO4 can cycle for more than 500 cycles at 2C without obvious capacity decay. SEM after cycling and in situ optical microscope results suggest that the unique 3D host structure of the Li-Co3O4-NF anode plays key roles on suppressing the dendrite growth and decreasing the local current inhomogeneity. We believe this work might provide a new strategy for fabricating dendrite-free Li metal anodes and facilitate practical applications in Li batteries.
For several decades, the promise of implementing of lithium (Li) metal anodes for Li batteries has been a "holy grail" for researchers. Herein, we have proposed a facile design of a MOF-derived Co3O4 nanoparticles modified nickel foam, i.e., Co3O4-NF, as a 3D host to achieve a uniform infusion of the molten Li. The molten Li was uniformly absorbed on the Co3O4-NF host only in 10 s due to its high Li lithiophilicity. The obtained Li-Co3O4-NF composite electrode shows high cycling stability in symmetric cells with low voltage hysteresis even at a high current density of 5 mA/cm2. The full cells of Li-Co3O4-NF/LiFePO4 can cycle for more than 500 cycles at 2C without obvious capacity decay. SEM after cycling and in situ optical microscope results suggest that the unique 3D host structure of the Li-Co3O4-NF anode plays key roles on suppressing the dendrite growth and decreasing the local current inhomogeneity. We believe this work might provide a new strategy for fabricating dendrite-free Li metal anodes and facilitate practical applications in Li batteries.
2023, 34(8): 107964
doi: 10.1016/j.cclet.2022.107964
Abstract:
Co-crystal formation can improve the physicochemical properties of a compound, thus enhancing its druggability. Therefore, artificial intelligence-based co-crystal virtual screening in the early stage of drug development has attracted extensive attention from researchers. However, the complexity of developing and applying algorithms hinders it wide application. This study presents a data-driven co-crystal prediction method based on the XGBoost machine learning model of the scikit-learn package. The simplified molecular input line entry specification (SMILES) information of two compounds is simply inputted to determine whether a co-crystal can be formed. The data set includs the co-crystal records presented in the Cambridge Structural Database (CSD) and the records of no co-crystal formation from extant literature and experiments. RDKit molecular descriptors are adopted as the features of a compound in the data set. The developed model shows excellent performance in the proposed co-crystal training and validation sets with high accuracy, sensitivity, and F1 score. The prediction success rate of the model exceeds 90%. The model therefore provides a simple and feasible scheme for designing and screening co-crystal drugs efficiently and accurately.
Co-crystal formation can improve the physicochemical properties of a compound, thus enhancing its druggability. Therefore, artificial intelligence-based co-crystal virtual screening in the early stage of drug development has attracted extensive attention from researchers. However, the complexity of developing and applying algorithms hinders it wide application. This study presents a data-driven co-crystal prediction method based on the XGBoost machine learning model of the scikit-learn package. The simplified molecular input line entry specification (SMILES) information of two compounds is simply inputted to determine whether a co-crystal can be formed. The data set includs the co-crystal records presented in the Cambridge Structural Database (CSD) and the records of no co-crystal formation from extant literature and experiments. RDKit molecular descriptors are adopted as the features of a compound in the data set. The developed model shows excellent performance in the proposed co-crystal training and validation sets with high accuracy, sensitivity, and F1 score. The prediction success rate of the model exceeds 90%. The model therefore provides a simple and feasible scheme for designing and screening co-crystal drugs efficiently and accurately.
2023, 34(8): 107980
doi: 10.1016/j.cclet.2022.107980
Abstract:
Chiral organic-inorganic metal halide semiconductors (OIMHSs) have recently attracted numerous interests due to their unique chirality, structural tunability, and extensive physical properties. However, most reported chiral OIMHSs contain toxic lead, which will be a potential obstacle to their further applications. Herein, we successfully synthesized a novel chiral lead-free tin(Ⅳ)-based OIMHS [(R)-3-hydroxyquinuclidinium]2SnCl6 ([R-HQ]2SnCl6). It exhibits a wide band gap (Eg) of about 4.11 eV. Moreover, [R-HQ]2SnCl6 undergoes a phase transition around 330 K (Tc) and shows distinct dielectric switching characteristics with good repeatability. This work enriches the chiral lead-free OIMHS family and stimulates further exploration of chiral lead-free OIMHS switching materials
Chiral organic-inorganic metal halide semiconductors (OIMHSs) have recently attracted numerous interests due to their unique chirality, structural tunability, and extensive physical properties. However, most reported chiral OIMHSs contain toxic lead, which will be a potential obstacle to their further applications. Herein, we successfully synthesized a novel chiral lead-free tin(Ⅳ)-based OIMHS [(R)-3-hydroxyquinuclidinium]2SnCl6 ([R-HQ]2SnCl6). It exhibits a wide band gap (Eg) of about 4.11 eV. Moreover, [R-HQ]2SnCl6 undergoes a phase transition around 330 K (Tc) and shows distinct dielectric switching characteristics with good repeatability. This work enriches the chiral lead-free OIMHS family and stimulates further exploration of chiral lead-free OIMHS switching materials
2023, 34(8): 107981
doi: 10.1016/j.cclet.2022.107981
Abstract:
Recently, two-dimension (2D) materials have fueled considerable interest in the field of gas sensing to cope urgent demands at specific scenarios. Unfortunately, the susceptibility to ambient humidity, and/or fragile operation stability always frustrate their further practicability. To overcome these drawbacks, we proposed one novel flexible gas sensor based on bismuth selenide (Bi2Se3) nanoplates for sensitive NO2 detection at room temperature. The as-prepared Bi2Se3 sensor exhibited favorable sensing performance, including remarkable NO2 selectivity, high response of 120% and fast response time of 81 s toward 5 ppm NO2, an ultralow detection limit of 100 ppb, and nice stability. Besides, the excellent humidity tolerance and mechanical flexibility endowed Bi2Se3 sensors with admirable reliability under harsh working conditions. The first-principles calculation further revealed the insights of extraordinary NO2 selectivity and the underlying gas-sensing mechanism.
Recently, two-dimension (2D) materials have fueled considerable interest in the field of gas sensing to cope urgent demands at specific scenarios. Unfortunately, the susceptibility to ambient humidity, and/or fragile operation stability always frustrate their further practicability. To overcome these drawbacks, we proposed one novel flexible gas sensor based on bismuth selenide (Bi2Se3) nanoplates for sensitive NO2 detection at room temperature. The as-prepared Bi2Se3 sensor exhibited favorable sensing performance, including remarkable NO2 selectivity, high response of 120% and fast response time of 81 s toward 5 ppm NO2, an ultralow detection limit of 100 ppb, and nice stability. Besides, the excellent humidity tolerance and mechanical flexibility endowed Bi2Se3 sensors with admirable reliability under harsh working conditions. The first-principles calculation further revealed the insights of extraordinary NO2 selectivity and the underlying gas-sensing mechanism.
2023, 34(8): 107994
doi: 10.1016/j.cclet.2022.107994
Abstract:
Materials with facilely tunable spin configurations based on metal-radical coordination systems have potential applications for electronics and spintronics. Here, we report the ground state conversion of copper corrole radicals from singlet to triplet via the extension of the π-conjugation system by benzo-fusion at the β-position of corrole ligand. NMR spectroscopy, SQUID measurements and computational studies all support the ferromagnetic coupling between the Cu(Ⅱ) center and corrole π-radical of benzo-fused copper corrole 2-Cu, which is in sharp contrast with the antiferromagnetic coupling in regular non-extended copper corroles. The triplet 2-Cu is highly stable in air, and X-ray diffraction analysis revealed its unique highly planar corrole macrocycle. This work offers a promising strategy for creating high-spin systems in non-innocent metallocorroles.
Materials with facilely tunable spin configurations based on metal-radical coordination systems have potential applications for electronics and spintronics. Here, we report the ground state conversion of copper corrole radicals from singlet to triplet via the extension of the π-conjugation system by benzo-fusion at the β-position of corrole ligand. NMR spectroscopy, SQUID measurements and computational studies all support the ferromagnetic coupling between the Cu(Ⅱ) center and corrole π-radical of benzo-fused copper corrole 2-Cu, which is in sharp contrast with the antiferromagnetic coupling in regular non-extended copper corroles. The triplet 2-Cu is highly stable in air, and X-ray diffraction analysis revealed its unique highly planar corrole macrocycle. This work offers a promising strategy for creating high-spin systems in non-innocent metallocorroles.
2023, 34(8): 108004
doi: 10.1016/j.cclet.2022.108004
Abstract:
Phosphorus-doped mesoporous carbons (PMCs) were prepared using a self-doping and self-templating approach via direct pyrolysis of sodium phytate (C6H17NaO24P6). The one-pot method allows simultaneous carbonization and P doping, eliminating the need for pre-synthesis or post-activation treatment. The C6H17NaO24P6 is the source of both carbon and phosphorus, and the nano-Na4P2O7 particles produced during pyrolysis act as hard templates for the honeycomb mesoporous structure with high specific surface area (884–827 m2/g), large mesopore volume ratio (67%–75%) and rich phosphorus content (0.53–2.34 at%). As electrodes of supercapacitors in 6 mol/L KOH, the PMCs showed outstanding performance with a high capacitance of 202 F/g and excellent rate performance of 148 F/g at 30 A/g. In addition, the PMCs-based symmetrical supercapacitors can operate in an expanded working voltage of 0–1.6 V in 3 mol/L H2SO4 aqueous electrolytes with high-density energy of 11.8 Wh/kg.
Phosphorus-doped mesoporous carbons (PMCs) were prepared using a self-doping and self-templating approach via direct pyrolysis of sodium phytate (C6H17NaO24P6). The one-pot method allows simultaneous carbonization and P doping, eliminating the need for pre-synthesis or post-activation treatment. The C6H17NaO24P6 is the source of both carbon and phosphorus, and the nano-Na4P2O7 particles produced during pyrolysis act as hard templates for the honeycomb mesoporous structure with high specific surface area (884–827 m2/g), large mesopore volume ratio (67%–75%) and rich phosphorus content (0.53–2.34 at%). As electrodes of supercapacitors in 6 mol/L KOH, the PMCs showed outstanding performance with a high capacitance of 202 F/g and excellent rate performance of 148 F/g at 30 A/g. In addition, the PMCs-based symmetrical supercapacitors can operate in an expanded working voltage of 0–1.6 V in 3 mol/L H2SO4 aqueous electrolytes with high-density energy of 11.8 Wh/kg.
2023, 34(8): 108005
doi: 10.1016/j.cclet.2022.108005
Abstract:
The self-assembled behavior of an unsymmetric molecule (BCDTDA) with one imidazole group as center and benzoic acid group as functional group is studied, and the regulatory behaviors of coronene (COR) and three bipyridine derivatives (named BP, PEBP-C4 and PEBP-C8) on BCDTDA self-assembly structures are also investigated. Based on highly oriented pyrolytic graphite (HOPG) substrate, scanning tunneling microscopy (STM) is used to observe the variation of assembled behaviors at the solid-liquid interface. Because of the concentration effect, BCDTDA molecules can assemble into grids and Kagomés structures in the form of NH···O hydrogen bonded dimers. BCDTDA molecules still maintain dimeric structures in the regulation of COR and BP molecules to BCDTDA self-assembly. However, PEBP-C4 and PEBP-C8 destroy the structure of the dimers, and form a variety of co-assembled structures with BCDTDA. Different guest molecules coordinate the host molecules differently, which makes the experiment more meaningful. Combined with density functional theory (DFT) calculation, the discovery of molecular interactions provides a promising strategy for the construction of functional nanostructures and devices.
The self-assembled behavior of an unsymmetric molecule (BCDTDA) with one imidazole group as center and benzoic acid group as functional group is studied, and the regulatory behaviors of coronene (COR) and three bipyridine derivatives (named BP, PEBP-C4 and PEBP-C8) on BCDTDA self-assembly structures are also investigated. Based on highly oriented pyrolytic graphite (HOPG) substrate, scanning tunneling microscopy (STM) is used to observe the variation of assembled behaviors at the solid-liquid interface. Because of the concentration effect, BCDTDA molecules can assemble into grids and Kagomés structures in the form of NH···O hydrogen bonded dimers. BCDTDA molecules still maintain dimeric structures in the regulation of COR and BP molecules to BCDTDA self-assembly. However, PEBP-C4 and PEBP-C8 destroy the structure of the dimers, and form a variety of co-assembled structures with BCDTDA. Different guest molecules coordinate the host molecules differently, which makes the experiment more meaningful. Combined with density functional theory (DFT) calculation, the discovery of molecular interactions provides a promising strategy for the construction of functional nanostructures and devices.
2023, 34(8): 108006
doi: 10.1016/j.cclet.2022.108006
Abstract:
Herein, we discovered that the surface-confined condensation of boronic acid can happen spontaneously at room temperature, by comparing the kinetics of condensation of boronic acids with and without the negative sample bias, we found that the negative sample bias indeed accelerates the self-condensation reaction of boronic acid. Combining with in-situ STM images and ultraviolet photoemission spectrum (UPS) analysis, a reversible adsorption mechanism model was proposed and reasonably explains the reversible electric-field-induced phase transformation.
Herein, we discovered that the surface-confined condensation of boronic acid can happen spontaneously at room temperature, by comparing the kinetics of condensation of boronic acids with and without the negative sample bias, we found that the negative sample bias indeed accelerates the self-condensation reaction of boronic acid. Combining with in-situ STM images and ultraviolet photoemission spectrum (UPS) analysis, a reversible adsorption mechanism model was proposed and reasonably explains the reversible electric-field-induced phase transformation.
2023, 34(8): 108008
doi: 10.1016/j.cclet.2022.108008
Abstract:
Luminescent polymers have garnered considerable research attention for their excellent properties and wide range of applications in multi-responsive materials, bioimaging, and photoelectric devices. Thereout, various modulations of polymer structure are often the main approach to obtaining materials with different luminescent colors and functions. However, polymers with biodegradability, tunable color, and efficient emission simultaneously remain a challenge. Herein, we report a feasible strategy to achieve degradable and highly emissive polymers by exquisite combination and interplay of aggregation-induced emission (AIE) unit and environmental-friendly epoxide/CO2 copolymerization. A series of polycarbonates P-TEPxCNy (x = 0, 1, 2, 4, 30, 120; y = 0, 1) were prepared, with emission color changed from blue to yellow by controlling the proportion of two designed AIE-active monomers. Among them, Using P-TCN as emitting layer, high performance white light-emitting diode (WLED) device with an external quantum efficiency (EQE) of 26.09% and CIE coordinates of (0.32, 0.32) was achieved. In addition, the designed polymers can be used as selective sensors for nitroaromatic compounds in their nanoaggregate states.
Luminescent polymers have garnered considerable research attention for their excellent properties and wide range of applications in multi-responsive materials, bioimaging, and photoelectric devices. Thereout, various modulations of polymer structure are often the main approach to obtaining materials with different luminescent colors and functions. However, polymers with biodegradability, tunable color, and efficient emission simultaneously remain a challenge. Herein, we report a feasible strategy to achieve degradable and highly emissive polymers by exquisite combination and interplay of aggregation-induced emission (AIE) unit and environmental-friendly epoxide/CO2 copolymerization. A series of polycarbonates P-TEPxCNy (x = 0, 1, 2, 4, 30, 120; y = 0, 1) were prepared, with emission color changed from blue to yellow by controlling the proportion of two designed AIE-active monomers. Among them, Using P-TCN as emitting layer, high performance white light-emitting diode (WLED) device with an external quantum efficiency (EQE) of 26.09% and CIE coordinates of (0.32, 0.32) was achieved. In addition, the designed polymers can be used as selective sensors for nitroaromatic compounds in their nanoaggregate states.
Polymeric aluminum porphyrin: Controllable synthesis of ultra-low molecular weight CO2-based polyols
2023, 34(8): 108011
doi: 10.1016/j.cclet.2022.108011
Abstract:
Carbon dioxide-based polyols with ultra-low molecular weight (ULMW, Mn < 1000 g/mol) are emergent polyurethane precursors with economic and environmental benefits. However, the lack of effective proton-tolerant catalytic systems limits the development of this field. In this work, the polymeric aluminum porphyrin catalyst (PAPC) system was applied to the copolymerization of CO2 and propylene oxide, where sebacic acid, bisphenol A, poly(ethylene glycol), and water were used as chain transfer agents to achieve the controlled synthesis of CO2-polyols. The molecular weight of the resulting CO2-polyols could be facilely regulated in the range of 400–930 g/mol at low catalyst loadings, fully demonstrating its catalytic advantages of high activity, high product selectivity, and excellent proton tolerance of PAPC. Meanwhile, the catalytic efficiency of PAPC could reach up to 2.1–5.2 kg/g under organic CTA conditions, even reaching 1.9 kg/g using water as the CTA. The cPC content could be controlled within 1.0 wt% under the optimized conditions, indicating the excellent controllability of the PAPC system. ULMW CO2-polyols combines the advantages of low viscosity (~3000 mPa s at 25 ℃), low glass transition temperature (~−73 ℃), and high carbonate unit content (~40%), which is important for the development of high-performance polyurethanes.
Carbon dioxide-based polyols with ultra-low molecular weight (ULMW, Mn < 1000 g/mol) are emergent polyurethane precursors with economic and environmental benefits. However, the lack of effective proton-tolerant catalytic systems limits the development of this field. In this work, the polymeric aluminum porphyrin catalyst (PAPC) system was applied to the copolymerization of CO2 and propylene oxide, where sebacic acid, bisphenol A, poly(ethylene glycol), and water were used as chain transfer agents to achieve the controlled synthesis of CO2-polyols. The molecular weight of the resulting CO2-polyols could be facilely regulated in the range of 400–930 g/mol at low catalyst loadings, fully demonstrating its catalytic advantages of high activity, high product selectivity, and excellent proton tolerance of PAPC. Meanwhile, the catalytic efficiency of PAPC could reach up to 2.1–5.2 kg/g under organic CTA conditions, even reaching 1.9 kg/g using water as the CTA. The cPC content could be controlled within 1.0 wt% under the optimized conditions, indicating the excellent controllability of the PAPC system. ULMW CO2-polyols combines the advantages of low viscosity (~3000 mPa s at 25 ℃), low glass transition temperature (~−73 ℃), and high carbonate unit content (~40%), which is important for the development of high-performance polyurethanes.
2023, 34(8): 108018
doi: 10.1016/j.cclet.2022.108018
Abstract:
Single-atom nanozymes (SANs) have attracted extensive attention due to their characteristics of both single-atom catalysts (SACs) and enzymes. Using spin-polarized density functional theory (DFT) calculations combined with the hybrid solvation model, this work designed a series of carbon-supported Group Ⅷ transition metals TMS4-C SANs, similar to the TMS4 active center of formate dehydrogenase (FADH), aiming to develop highly efficient SANs for CO2 electroreduction. DFT calculations show that compared with TMN4-C, TMS4-C have FADH-like feature, which can selectively reduce CO2 to formic acid. Particularly, CoS4-C is the most promising SAN for CO2 reduction, with a low limiting potential of -0.07 V, which exceeds most reported catalysts. Two descriptors of TMX4-C (X = N, S) based on intrinsic and electronic structure properties were proposed to shed light on the origin activity of candidates. The findings presented here will provide new insights into the design of novel enzyme-like catalysts for electrochemical CO2 reduction.
Single-atom nanozymes (SANs) have attracted extensive attention due to their characteristics of both single-atom catalysts (SACs) and enzymes. Using spin-polarized density functional theory (DFT) calculations combined with the hybrid solvation model, this work designed a series of carbon-supported Group Ⅷ transition metals TMS4-C SANs, similar to the TMS4 active center of formate dehydrogenase (FADH), aiming to develop highly efficient SANs for CO2 electroreduction. DFT calculations show that compared with TMN4-C, TMS4-C have FADH-like feature, which can selectively reduce CO2 to formic acid. Particularly, CoS4-C is the most promising SAN for CO2 reduction, with a low limiting potential of -0.07 V, which exceeds most reported catalysts. Two descriptors of TMX4-C (X = N, S) based on intrinsic and electronic structure properties were proposed to shed light on the origin activity of candidates. The findings presented here will provide new insights into the design of novel enzyme-like catalysts for electrochemical CO2 reduction.
2023, 34(8): 108019
doi: 10.1016/j.cclet.2022.108019
Abstract:
The stability issue is one of the key factors hindering the commercial application of organic solar cells. All-polymer organic solar cell is one of the effective ways to solve the stability problem. In this work, we designed and synthesized two polymer donor materials PBDT and PDTBDT with different conjugation ranges, and demonstrated for the first time that extending the conjugation range of donor materials in all polymer solar cells can significantly improve device efficiency and stability. The experimental results of materials and devices show that PDTBDT with a larger conjugation range has stronger crystallinity and a more planar structure, which endows the active layer in its corresponding device with higher exciton dissociation probability, lower carrier recombination probability, more balanced charge transport properties and more favorable film morphology. As a result, the PDTBDT: PYF-T-o devices display an outstanding PCE of 13.38%, which is much higher than PBDT with smaller conjugation range based devices. Moreover, the PDTBDT: PYF-T-o device retains 0.86 of the initial PCE after over 500 h in the air atmosphere, exhibiting significantly improved stability. The improved stability is attributed to the enhanced moisture and air tolerance of active layer film thanks to the strong crystallinity of the donor material. These results demonstrate that the conjugation expansion strategy is one of the effective ways to obtain efficient and stable all-polymer organic solar cells.
The stability issue is one of the key factors hindering the commercial application of organic solar cells. All-polymer organic solar cell is one of the effective ways to solve the stability problem. In this work, we designed and synthesized two polymer donor materials PBDT and PDTBDT with different conjugation ranges, and demonstrated for the first time that extending the conjugation range of donor materials in all polymer solar cells can significantly improve device efficiency and stability. The experimental results of materials and devices show that PDTBDT with a larger conjugation range has stronger crystallinity and a more planar structure, which endows the active layer in its corresponding device with higher exciton dissociation probability, lower carrier recombination probability, more balanced charge transport properties and more favorable film morphology. As a result, the PDTBDT: PYF-T-o devices display an outstanding PCE of 13.38%, which is much higher than PBDT with smaller conjugation range based devices. Moreover, the PDTBDT: PYF-T-o device retains 0.86 of the initial PCE after over 500 h in the air atmosphere, exhibiting significantly improved stability. The improved stability is attributed to the enhanced moisture and air tolerance of active layer film thanks to the strong crystallinity of the donor material. These results demonstrate that the conjugation expansion strategy is one of the effective ways to obtain efficient and stable all-polymer organic solar cells.
2023, 34(8): 108020
doi: 10.1016/j.cclet.2022.108020
Abstract:
Membrane filtration is one of the effective approaches to harvest microalgae for industrial biofuel production. However, during the filtration process, microalgae cells and extracellular organic matter (EOM) will deposit on the membrane surface leading to reversible membrane fouling that can be removed by physical methods. When hydrophobic EOM is adsorbed on the membrane surface or inside pores, it will build up a gel layer, causing irreversible membrane fouling. Irreversible fouling can only be removed using chemical methods that will decrease membrane lifespan and increase operational costs. Here, we introduce a versatile superhydrophilic membrane with photo-Fenton self-cleaning property, which can prevent the reversible fouling and remove the irreversible fouling. Tannic acid (TA) and 3-aminopropyltriethoxysilane (APTES) were co-deposited on the polyvinylidene fluoride (PVDF) membrane via Schiff base and Michael addition reactions, and β-FeOOH nanorods were inlaid on the membrane surface by in situ mineralization. The water contact angle of the modified membrane is reduced from 120° to 0° Under 60 min visible light, the hydroxyl radical (·OH) generated by the photo-Fenton reaction degraded the irreversible fouling that blocked membrane pores. The irreversible fouling rates of modified membrane was reduced from 39.57% to 3.26%, compared with the original membrane. Microalgae harvesting results illustrated that the membrane has a high flux recovery rate (FRR) of 98.2%, showed excellent passive antifouling and active antifouling performance. We believe this work will spark a novel platform for optimizing energy-efficient microalgae harvesting separation membrane modules. In addition, this method of anti-fouling filtration for microorganisms can be extended to the industrial production of various bioenergy sources and will have very promising practical applications.
Membrane filtration is one of the effective approaches to harvest microalgae for industrial biofuel production. However, during the filtration process, microalgae cells and extracellular organic matter (EOM) will deposit on the membrane surface leading to reversible membrane fouling that can be removed by physical methods. When hydrophobic EOM is adsorbed on the membrane surface or inside pores, it will build up a gel layer, causing irreversible membrane fouling. Irreversible fouling can only be removed using chemical methods that will decrease membrane lifespan and increase operational costs. Here, we introduce a versatile superhydrophilic membrane with photo-Fenton self-cleaning property, which can prevent the reversible fouling and remove the irreversible fouling. Tannic acid (TA) and 3-aminopropyltriethoxysilane (APTES) were co-deposited on the polyvinylidene fluoride (PVDF) membrane via Schiff base and Michael addition reactions, and β-FeOOH nanorods were inlaid on the membrane surface by in situ mineralization. The water contact angle of the modified membrane is reduced from 120° to 0° Under 60 min visible light, the hydroxyl radical (·OH) generated by the photo-Fenton reaction degraded the irreversible fouling that blocked membrane pores. The irreversible fouling rates of modified membrane was reduced from 39.57% to 3.26%, compared with the original membrane. Microalgae harvesting results illustrated that the membrane has a high flux recovery rate (FRR) of 98.2%, showed excellent passive antifouling and active antifouling performance. We believe this work will spark a novel platform for optimizing energy-efficient microalgae harvesting separation membrane modules. In addition, this method of anti-fouling filtration for microorganisms can be extended to the industrial production of various bioenergy sources and will have very promising practical applications.
2023, 34(8): 108039
doi: 10.1016/j.cclet.2022.108039
Abstract:
Adsorptive separation of acetylene (C2H2) from carbon dioxide (CO2) is of great significance in petrochemical industry, but still remains as a daunting challenge by reason of their very similar molecular sizes/shapes and physical properties. Herein, we reported a new perchlorate-based hybrid ultramicroporous material ZJU-194 that features the unique flexible-robust network decorated with rich bare oxygen atoms. By integrating the refined pore space as well as specific binding sites, the activated ZJU-194 (ZJU-194a) enables a selective two-step gate-opening adsorption toward C2H2, but blocks off the further uptake of CO2. It thus exhibits a very high C2H2/CO2 selectivity (22.4) at ambient conditions, which is superior to most reported MOF materials. Its complete separation for 50/50 C2H2/CO2 mixtures is further evidenced by the dynamic breakthrough experiments.
Adsorptive separation of acetylene (C2H2) from carbon dioxide (CO2) is of great significance in petrochemical industry, but still remains as a daunting challenge by reason of their very similar molecular sizes/shapes and physical properties. Herein, we reported a new perchlorate-based hybrid ultramicroporous material ZJU-194 that features the unique flexible-robust network decorated with rich bare oxygen atoms. By integrating the refined pore space as well as specific binding sites, the activated ZJU-194 (ZJU-194a) enables a selective two-step gate-opening adsorption toward C2H2, but blocks off the further uptake of CO2. It thus exhibits a very high C2H2/CO2 selectivity (22.4) at ambient conditions, which is superior to most reported MOF materials. Its complete separation for 50/50 C2H2/CO2 mixtures is further evidenced by the dynamic breakthrough experiments.
2023, 34(8): 108044
doi: 10.1016/j.cclet.2022.108044
Abstract:
Chiral high-nuclearity lanthanide (4f) clusters have shown fantastic properties in various fields. However, their synthesis is still of great challenge. Herein, we report two pairs of enantiomers of high-nuclearity Dy-oxo clusters synthesized through in situ strategy. They are [Dy18(R/SHftp)4 (R/SH2btp)4(μ2-OH)8(μ3-OH)20(μ6-O)(NO3)4(μ-H2O)8]·[solvents] (1R and 1S) and [Dy9(R/SHftp)2 (R/SH2btp)2(OAc)6(μ3-OH)10(H2O)6](OAc)·[solvents] (2R and 2S), where R/SHftp2− and R/SH2btp3− represent in situ formed 2-formyl-6-[N-(threonine)iminomethyl]-4-methylphenol and 2,6-bis[N-(threonine)iminomethyl]-4-methylphenol anions, respectively. These in situ formed clusters were endowed with not only homochirality via introducing R/SHftp2− and R/SH2btp3− ligands, but also rich oxo-bridges by controlling the hydrolysis of DyⅢ ions. Different anions from DyⅢ salts further induced structural variation between two sets of clusters. 1R and 1S feature an unprecedent four-blade propeller shaped {Dy18} core, whose centered octahedral {Dy6} unit are surrounded by four triangular {Dy3} units. Strikingly, they represent the second largest chiral 4f cluster species so far. 2R and 2S display a sandglass-like {Dy9} skeleton that consist of two square pyramid {Dy5} units sharing a DyⅢ vertex. Magnetic investigation revealed possible antiferromagnetic interactions between the DyⅢ centers in these clusters.
Chiral high-nuclearity lanthanide (4f) clusters have shown fantastic properties in various fields. However, their synthesis is still of great challenge. Herein, we report two pairs of enantiomers of high-nuclearity Dy-oxo clusters synthesized through in situ strategy. They are [Dy18(R/SHftp)4 (R/SH2btp)4(μ2-OH)8(μ3-OH)20(μ6-O)(NO3)4(μ-H2O)8]·[solvents] (1R and 1S) and [Dy9(R/SHftp)2 (R/SH2btp)2(OAc)6(μ3-OH)10(H2O)6](OAc)·[solvents] (2R and 2S), where R/SHftp2− and R/SH2btp3− represent in situ formed 2-formyl-6-[N-(threonine)iminomethyl]-4-methylphenol and 2,6-bis[N-(threonine)iminomethyl]-4-methylphenol anions, respectively. These in situ formed clusters were endowed with not only homochirality via introducing R/SHftp2− and R/SH2btp3− ligands, but also rich oxo-bridges by controlling the hydrolysis of DyⅢ ions. Different anions from DyⅢ salts further induced structural variation between two sets of clusters. 1R and 1S feature an unprecedent four-blade propeller shaped {Dy18} core, whose centered octahedral {Dy6} unit are surrounded by four triangular {Dy3} units. Strikingly, they represent the second largest chiral 4f cluster species so far. 2R and 2S display a sandglass-like {Dy9} skeleton that consist of two square pyramid {Dy5} units sharing a DyⅢ vertex. Magnetic investigation revealed possible antiferromagnetic interactions between the DyⅢ centers in these clusters.
2023, 34(8): 108051
doi: 10.1016/j.cclet.2022.108051
Abstract:
Ferroelectric semiconductors have sparked growing attention in the field of optoelectronics, due to their unique ferroelectric photovoltaic effect. Recently, substantial efforts have been devoted to the development of ferroelectric semiconductors, including inorganic oxides, organic-inorganic hybrids, and metal-free perovskites. Nevertheless, reports of ferroelectric semiconductors with a bandgap of less than 2 eV have been scarce. Here, in combination with the incorporation of triiodide (I3−) and the introduction of chiral cations, we successfully constructed a pair of enantiomeric organic-inorganic hybrid ferroelectric semiconductors, (S-1,2-DAP·I)4·I3·BiI6 and (R-1,2-DAP·I)4·I3·BiI6 (R/S-1,2-DAP = (R/S)-(–)-1,2-diaminopropane), which possess high-temperature multiaxial ferroelectric phase transition with an Aizu notation of 422F2(s) at 405 K, a narrow bandgap of 1.56 eV comparable to that of CH3NH3PbI3 (~1.5 eV), and an impressive piezoelectric response (piezoelectric coefficient, d22 of 35 pC/N) on par with PVDF (polyvinylidene fluoride, 30 pC/N). With intriguing attributes, (S-1,2-DAP·I)4·I3·BiI6 and (R-1,2-DAP·I)4·I3·BiI6 exhibit great potential for application of self-power polarized-light detection and piezoelectric sensors.
Ferroelectric semiconductors have sparked growing attention in the field of optoelectronics, due to their unique ferroelectric photovoltaic effect. Recently, substantial efforts have been devoted to the development of ferroelectric semiconductors, including inorganic oxides, organic-inorganic hybrids, and metal-free perovskites. Nevertheless, reports of ferroelectric semiconductors with a bandgap of less than 2 eV have been scarce. Here, in combination with the incorporation of triiodide (I3−) and the introduction of chiral cations, we successfully constructed a pair of enantiomeric organic-inorganic hybrid ferroelectric semiconductors, (S-1,2-DAP·I)4·I3·BiI6 and (R-1,2-DAP·I)4·I3·BiI6 (R/S-1,2-DAP = (R/S)-(–)-1,2-diaminopropane), which possess high-temperature multiaxial ferroelectric phase transition with an Aizu notation of 422F2(s) at 405 K, a narrow bandgap of 1.56 eV comparable to that of CH3NH3PbI3 (~1.5 eV), and an impressive piezoelectric response (piezoelectric coefficient, d22 of 35 pC/N) on par with PVDF (polyvinylidene fluoride, 30 pC/N). With intriguing attributes, (S-1,2-DAP·I)4·I3·BiI6 and (R-1,2-DAP·I)4·I3·BiI6 exhibit great potential for application of self-power polarized-light detection and piezoelectric sensors.
2023, 34(8): 108055
doi: 10.1016/j.cclet.2022.108055
Abstract:
The combination of cyclopentadiene, β-diketonate and tripyrazoylborate ligands with dysprosium ion afforded five mononuclear compounds: [(Cp)2Dy(Tp*)] (1Dy), [(Cp)Dy(Tp*)Cl(THF)] (2Dy), [(Cp)Dy(Tp)Cl(THF)] (3Dy), [(DBM)Dy(Tp)Cl(THF)] (4Dy), [{(Tp)Dy(DBM)2(H2O)}·THF] (5Dy) (Cp = cyclopentadiene; Tp* = hydrotris(3,5-dimethyl-1-pyrazolyl)borate; Tp = hydrotris(1-pyrazolyl)borate; DBM = dibenzoylmethanoate). Magnetic study revealed that 1Dy and 3Dy exhibited typical butterfly-type hysteresis. AC susceptibility study combined with ab initio calculations indicated that the magnetic relaxation behaviors of 1Dy–4Dy were governed by the Orbach and Raman processes under applied DC field. Moreover, 3Dy showed two-step magnetic relaxation, which was attributed to the static disordering of the coordinated THF molecule. Magnetic anisotropy analysis indicated that it was the relative strength of the interactions between DyIII and surrounding ligands that determined the orientation of the magnetic easy axis.
The combination of cyclopentadiene, β-diketonate and tripyrazoylborate ligands with dysprosium ion afforded five mononuclear compounds: [(Cp)2Dy(Tp*)] (1Dy), [(Cp)Dy(Tp*)Cl(THF)] (2Dy), [(Cp)Dy(Tp)Cl(THF)] (3Dy), [(DBM)Dy(Tp)Cl(THF)] (4Dy), [{(Tp)Dy(DBM)2(H2O)}·THF] (5Dy) (Cp = cyclopentadiene; Tp* = hydrotris(3,5-dimethyl-1-pyrazolyl)borate; Tp = hydrotris(1-pyrazolyl)borate; DBM = dibenzoylmethanoate). Magnetic study revealed that 1Dy and 3Dy exhibited typical butterfly-type hysteresis. AC susceptibility study combined with ab initio calculations indicated that the magnetic relaxation behaviors of 1Dy–4Dy were governed by the Orbach and Raman processes under applied DC field. Moreover, 3Dy showed two-step magnetic relaxation, which was attributed to the static disordering of the coordinated THF molecule. Magnetic anisotropy analysis indicated that it was the relative strength of the interactions between DyIII and surrounding ligands that determined the orientation of the magnetic easy axis.
2023, 34(8): 108056
doi: 10.1016/j.cclet.2022.108056
Abstract:
Nitrogen-doped carbon catalysts with hierarchical porous structure are promising oxygen evolution reaction (OER) catalysts due to the faster mass transfer and better charge carrying ability. Herein, an exquisite high nitrogen-containing ligand was designed and readily synthesized from the low-cost biomolecule adenine. Accordingly, three new MOFs (TJU-103, TJU-104 and TJU-105) were prepared using the Co(Ⅱ) or Mn(Ⅱ) ions as metal nodes. Through rationally controlling pyrolysis condition, in virtue of the high nitrogen content in well-defined periodic structure of the pristine MOFs, TJU-104–900 among the derived MOFs with hierarchical porous structure, i.e., N-doped graphitic carbon encapsulating homogeneously distributed cobalt nanoparticles, could be conveniently obtained. Thanks to the synergistic effect of the hierarchical structure and well dispersed active components (i.e., C=O, Co‒Nx, graphitic C and N, pyridinic N), it could exhibit an overpotential of 280 mV@10 mA/cm2 on carbon cloth for OER activity. This work provides the inspiration for fabrication of nitrogen-doped carbon/metal electrocatalysts from cost-effective and abundant biomolecules, which is promising for practical OER application.
Nitrogen-doped carbon catalysts with hierarchical porous structure are promising oxygen evolution reaction (OER) catalysts due to the faster mass transfer and better charge carrying ability. Herein, an exquisite high nitrogen-containing ligand was designed and readily synthesized from the low-cost biomolecule adenine. Accordingly, three new MOFs (TJU-103, TJU-104 and TJU-105) were prepared using the Co(Ⅱ) or Mn(Ⅱ) ions as metal nodes. Through rationally controlling pyrolysis condition, in virtue of the high nitrogen content in well-defined periodic structure of the pristine MOFs, TJU-104–900 among the derived MOFs with hierarchical porous structure, i.e., N-doped graphitic carbon encapsulating homogeneously distributed cobalt nanoparticles, could be conveniently obtained. Thanks to the synergistic effect of the hierarchical structure and well dispersed active components (i.e., C=O, Co‒Nx, graphitic C and N, pyridinic N), it could exhibit an overpotential of 280 mV@10 mA/cm2 on carbon cloth for OER activity. This work provides the inspiration for fabrication of nitrogen-doped carbon/metal electrocatalysts from cost-effective and abundant biomolecules, which is promising for practical OER application.
2023, 34(8): 108057
doi: 10.1016/j.cclet.2022.108057
Abstract:
Plastic and elastic behaviors of organic crystals have profound influence on the processability of pharmaceutical substances. Analogous to metals, the identifications of molecular slip planes in organic crystals are regarded as a strategy for harnessing plasticity. In this work, we experimentally characterized the form Ⅱ anhydrous theophylline (THPa) and its monohydrate (THPm) for their distinct plastic and elastic behaviors. Extensive DFT calculations were performed to model the effects of increasing lattice strains on molecular packing. We discovered that the energy barrier associated with the strain-induced molecular rearrangement would link to the plasticity of THPa, and possibly other simple aromatic compounds. Meanwhile, water molecules in THPm disrupt the stacking architecture from THPm and effectively undermine the general mechanism for plasticity. Hydrate formation would therefore be an alternative strategy to engineer the mechanical property of organic crystalline materials.
Plastic and elastic behaviors of organic crystals have profound influence on the processability of pharmaceutical substances. Analogous to metals, the identifications of molecular slip planes in organic crystals are regarded as a strategy for harnessing plasticity. In this work, we experimentally characterized the form Ⅱ anhydrous theophylline (THPa) and its monohydrate (THPm) for their distinct plastic and elastic behaviors. Extensive DFT calculations were performed to model the effects of increasing lattice strains on molecular packing. We discovered that the energy barrier associated with the strain-induced molecular rearrangement would link to the plasticity of THPa, and possibly other simple aromatic compounds. Meanwhile, water molecules in THPm disrupt the stacking architecture from THPm and effectively undermine the general mechanism for plasticity. Hydrate formation would therefore be an alternative strategy to engineer the mechanical property of organic crystalline materials.
2023, 34(8): 108058
doi: 10.1016/j.cclet.2022.108058
Abstract:
Food waste (FW) has been recognized as essential reservoir for resource recovery via anaerobic fermentation, which could also bring the potential risk of antibiotic resistance genes (ARGs) dissemination. Although the structural deficiency of FW could be stimulated by enzymatic pretreatment to enhance fermentation efficiency, the influences of enzymatic pretreatment on ARGs fate and microbial metabolic pathways involved in ARGs dissemination have rarely been reported. This work proved that enzymatic pretreatment could effectively decrease the total abundance of ARGs (reduced by 13.8%-24.5%) during long-term FW fermentation. It was found that enzymatic pretreatment significantly reduced the ARGs belonging to the efflux pump, which might be ascribed to its ability to increase membrane permeability. Furthermore, enzymatic pretreatment was in favor of reducing microbial diversity and various potential ARGs host (e.g., Methanosarcina, Clostridium, Prevotella, Parabacteroides). Also, this pretreatment remarkably up-regulated the genetic expressions involved in ABC transporter (e.g., eryF and mntA) and down-regulated the genetic expressions that participated in DNA replication, two-component systems (e.g., uphA and cckA), and quorum sensing (e.g., rpfF and lsrG), thereby decreasing ARGs transmission. This study would expand the insight of the influences of pretreatment method on ARGs fate during FW fermentation, and offer practical guidance on the sustainable management of FW.
Food waste (FW) has been recognized as essential reservoir for resource recovery via anaerobic fermentation, which could also bring the potential risk of antibiotic resistance genes (ARGs) dissemination. Although the structural deficiency of FW could be stimulated by enzymatic pretreatment to enhance fermentation efficiency, the influences of enzymatic pretreatment on ARGs fate and microbial metabolic pathways involved in ARGs dissemination have rarely been reported. This work proved that enzymatic pretreatment could effectively decrease the total abundance of ARGs (reduced by 13.8%-24.5%) during long-term FW fermentation. It was found that enzymatic pretreatment significantly reduced the ARGs belonging to the efflux pump, which might be ascribed to its ability to increase membrane permeability. Furthermore, enzymatic pretreatment was in favor of reducing microbial diversity and various potential ARGs host (e.g., Methanosarcina, Clostridium, Prevotella, Parabacteroides). Also, this pretreatment remarkably up-regulated the genetic expressions involved in ABC transporter (e.g., eryF and mntA) and down-regulated the genetic expressions that participated in DNA replication, two-component systems (e.g., uphA and cckA), and quorum sensing (e.g., rpfF and lsrG), thereby decreasing ARGs transmission. This study would expand the insight of the influences of pretreatment method on ARGs fate during FW fermentation, and offer practical guidance on the sustainable management of FW.
2023, 34(8): 108059
doi: 10.1016/j.cclet.2022.108059
Abstract:
Rapid detection of foodborne pathogens is crucial to prevent the outbreaks of foodborne diseases. In this work, we proposed a novel microfluidic biosensor based on magnetorheological elastomer (MRE) and smartphone. First, micropump and microvalves were constructed by deforming the MRE under magnetic actuation and integrated into the microfluidic biosensor for fluidic control. Then, the micropump was used to deliver immune porous gold@platinum nanocatalysts (Au@PtNCs), bacterial sample, and immunomagnetic nanoparticles (MNPs) into a micromixer, where they were mixed, incubated and magnetically separated to obtain the Au@PtNC-bacteria-MNP complexes. After 3, 3′, 5, 5′-tetramethylbenzidine and hydrogen peroxide were injected and catalyzed by the Au@PtNCs, smartphone was used to measure the color of the catalysate for quantitative analysis of target bacteria. Under optimal conditions, this biosensor could detect Salmonella typhimurium quantitatively and automatically in 1 h with a linear detection range of 8.0 × 101 CFU/mL to 8.0 × 104 CFU/mL and a detection limit of 62 CFU/mL. The microfluidic biosensor was compact in size, simple to use, and efficient for detection, and might be used for in-field screening of foodborne pathogens to prevent food poisoning.
Rapid detection of foodborne pathogens is crucial to prevent the outbreaks of foodborne diseases. In this work, we proposed a novel microfluidic biosensor based on magnetorheological elastomer (MRE) and smartphone. First, micropump and microvalves were constructed by deforming the MRE under magnetic actuation and integrated into the microfluidic biosensor for fluidic control. Then, the micropump was used to deliver immune porous gold@platinum nanocatalysts (Au@PtNCs), bacterial sample, and immunomagnetic nanoparticles (MNPs) into a micromixer, where they were mixed, incubated and magnetically separated to obtain the Au@PtNC-bacteria-MNP complexes. After 3, 3′, 5, 5′-tetramethylbenzidine and hydrogen peroxide were injected and catalyzed by the Au@PtNCs, smartphone was used to measure the color of the catalysate for quantitative analysis of target bacteria. Under optimal conditions, this biosensor could detect Salmonella typhimurium quantitatively and automatically in 1 h with a linear detection range of 8.0 × 101 CFU/mL to 8.0 × 104 CFU/mL and a detection limit of 62 CFU/mL. The microfluidic biosensor was compact in size, simple to use, and efficient for detection, and might be used for in-field screening of foodborne pathogens to prevent food poisoning.
2023, 34(8): 108061
doi: 10.1016/j.cclet.2022.108061
Abstract:
In this study, a continuous-flow procedure containing four steps has been developed to synthesize Pigment Red 53 and modify its crystal structure. This process avoided the problems of conveying highly insoluble reaction intermediates by removing intermediate operating steps. After optimization, the overall yield of Pigment Red 53:1 reached 97.1% in the total residence time of 80 s by this diazotization-coupling-laking-crystal transition process. From batch to continuous flow, the purity of products increased from 97.1% to 98.2% and the median diameter of pigment particles decreased from 14 µm to 1.9 µm. This process achieved a similar crystal transition effect in 18 s as in batch, producing α, δ and ν crystals of Pigment Red 53:2 as expected. In conclusion, this continuous-flow procedure displays advantages in both synthesis and crystal transition, indicating another potential use for industrial application.
In this study, a continuous-flow procedure containing four steps has been developed to synthesize Pigment Red 53 and modify its crystal structure. This process avoided the problems of conveying highly insoluble reaction intermediates by removing intermediate operating steps. After optimization, the overall yield of Pigment Red 53:1 reached 97.1% in the total residence time of 80 s by this diazotization-coupling-laking-crystal transition process. From batch to continuous flow, the purity of products increased from 97.1% to 98.2% and the median diameter of pigment particles decreased from 14 µm to 1.9 µm. This process achieved a similar crystal transition effect in 18 s as in batch, producing α, δ and ν crystals of Pigment Red 53:2 as expected. In conclusion, this continuous-flow procedure displays advantages in both synthesis and crystal transition, indicating another potential use for industrial application.
2023, 34(8): 108063
doi: 10.1016/j.cclet.2022.108063
Abstract:
Small molecule activators could equally provide powerful tools as inhibitors do for interrogating cellular signal transduction. However, targeted protein activation is chemically challenging. Developing activators against Src homology region 2 domain-containing phosphatase-1 (SHP-1) to block STAT3 pathway represents a promising strategy for DLBCL therapy. Here we reported a new class of thieno[2,3-b]quinoline-procaine hybrid molecules as SHP-1 allosteric activators. The representative hybrid compound 3b displayed SHP-1 activating effect with EC50 of 5.48 ± 0.28 µmol/L. Further investigations confirmed that 3b allosterically interacted with SHP-1, switched it from close to open conformation, blocked SHP-1/p-STAT3 pathway, induced apoptosis and inhibited ABC-DLBCL cell proliferation in vitro, and delayed tumor growth in the xenograft model of SU-DHL-2. Overall, this work offered a novel paradigm to develop SHP-1 allosteric activators through chemical space evolution of PTPs inhibitors, and firstly validated the therapeutic strategy that directly activating SHP-1 alone could be a potential therapy against ABC-DLBCL via blocking STAT3 pathway.
Small molecule activators could equally provide powerful tools as inhibitors do for interrogating cellular signal transduction. However, targeted protein activation is chemically challenging. Developing activators against Src homology region 2 domain-containing phosphatase-1 (SHP-1) to block STAT3 pathway represents a promising strategy for DLBCL therapy. Here we reported a new class of thieno[2,3-b]quinoline-procaine hybrid molecules as SHP-1 allosteric activators. The representative hybrid compound 3b displayed SHP-1 activating effect with EC50 of 5.48 ± 0.28 µmol/L. Further investigations confirmed that 3b allosterically interacted with SHP-1, switched it from close to open conformation, blocked SHP-1/p-STAT3 pathway, induced apoptosis and inhibited ABC-DLBCL cell proliferation in vitro, and delayed tumor growth in the xenograft model of SU-DHL-2. Overall, this work offered a novel paradigm to develop SHP-1 allosteric activators through chemical space evolution of PTPs inhibitors, and firstly validated the therapeutic strategy that directly activating SHP-1 alone could be a potential therapy against ABC-DLBCL via blocking STAT3 pathway.
2023, 34(8): 108064
doi: 10.1016/j.cclet.2022.108064
Abstract:
Precise and spatiotemporal control over the pesticide remains to be a challenge. More efficient controlled release systems (CRSs) have been developed to support the precise delivery of active ingredients. Herein, we incorporated the photoremovable protecting groups (PRPGs) into phenamacril (PHE) and obtained two photo-responsive fungicides of NV-PHE and DEACM-PHE. The 4,5-dimethoxy-o-nitrobenzyl (NV) or 7-diethylaminocoumarin (DEACM)-caged PHE could release the active molecule PHE after irradiation of UV light and blue light, respectively. Optical properties and in-vitro/vivo fungicidal activities of NV-PHE and DEACM-PHE demonstrated the feasibility for light controlled release of PHE. DEACM-PHE could release 98% PHE by illumination of blue light. The irradiated DEACM-PHE could preserve the similar bioactivity of PHE, and significantly improve the in-vitro/vivo fungicidal activities compared to the non-irradiated DEACM-PHE. The optical controlled release of PHE from DEACM-PHE enabled the precise and spatiotemporal delivery of PHE, diversifying the development of CRSs for pesticide, and providing environment-friendly agricultural applications with high pesticide efficiency.
Precise and spatiotemporal control over the pesticide remains to be a challenge. More efficient controlled release systems (CRSs) have been developed to support the precise delivery of active ingredients. Herein, we incorporated the photoremovable protecting groups (PRPGs) into phenamacril (PHE) and obtained two photo-responsive fungicides of NV-PHE and DEACM-PHE. The 4,5-dimethoxy-o-nitrobenzyl (NV) or 7-diethylaminocoumarin (DEACM)-caged PHE could release the active molecule PHE after irradiation of UV light and blue light, respectively. Optical properties and in-vitro/vivo fungicidal activities of NV-PHE and DEACM-PHE demonstrated the feasibility for light controlled release of PHE. DEACM-PHE could release 98% PHE by illumination of blue light. The irradiated DEACM-PHE could preserve the similar bioactivity of PHE, and significantly improve the in-vitro/vivo fungicidal activities compared to the non-irradiated DEACM-PHE. The optical controlled release of PHE from DEACM-PHE enabled the precise and spatiotemporal delivery of PHE, diversifying the development of CRSs for pesticide, and providing environment-friendly agricultural applications with high pesticide efficiency.
2023, 34(8): 108067
doi: 10.1016/j.cclet.2022.108067
Abstract:
Unraveling the catalytic reaction mechanism is a long-term challenge for developing efficient catalysts. The blooming bimetallic catalyst have enabled to activate inert bonds and realize complex C-C formation. Herein, we theoretically discover a dual-phosphinito bridged hetero-bimetallic species that verified by NMR experiments. Our results indicate only dual-phosphinito Ni-Al model can be an active catalyst in asymmetric cycloadditions via C-C activation and C-H activation, which can well rationalize the experimental observations for both reactivity and stereo-selectivity. An unprecedented tandem redox dehydrogenation mechanism was revealed to control the formation of this active species overriding the inherent basicity. Synergistic Lewis acid and eg orbital interactions, including dz2 orbital reoccupation and dx2-y2 orbital recombination, were disclosed to understand both thermodynamic and kinetic advance of dual-bridged model, displaying feasible redox properties.
Unraveling the catalytic reaction mechanism is a long-term challenge for developing efficient catalysts. The blooming bimetallic catalyst have enabled to activate inert bonds and realize complex C-C formation. Herein, we theoretically discover a dual-phosphinito bridged hetero-bimetallic species that verified by NMR experiments. Our results indicate only dual-phosphinito Ni-Al model can be an active catalyst in asymmetric cycloadditions via C-C activation and C-H activation, which can well rationalize the experimental observations for both reactivity and stereo-selectivity. An unprecedented tandem redox dehydrogenation mechanism was revealed to control the formation of this active species overriding the inherent basicity. Synergistic Lewis acid and eg orbital interactions, including dz2 orbital reoccupation and dx2-y2 orbital recombination, were disclosed to understand both thermodynamic and kinetic advance of dual-bridged model, displaying feasible redox properties.
2023, 34(8): 108069
doi: 10.1016/j.cclet.2022.108069
Abstract:
Small-molecule hydrogels based on amino acid derivatives have promising applications in many biological fields, including cell culture, drug delivery, and tissue engineering. Although these hydrogels have been widely reported to have low cytotoxicity, biocompatibility, and tunable bioactivity, problems such as harsh preparation conditions and complex material design hinder their application. Herein, by adjusting pH to induce non-covalent interactions between small-molecule tryptophan derivatives (N-[(phenylmethoxy)carbonyl]-L-tryptophan, Mw: 338.35), we developed a self-assembled three-dimensional network hydrogel that can be rapidly formed in seconds. And the supramolecular self-assembly mechanism of the hydrogels was also investigated in detail through experimental characterizations and density functional theory calculation. As-prepared hydrogels also exhibit reversible pH-stimulated response and self-healing properties. This study details a research process for the simple and rapid preparation of tryptophan derivative-based hydrogels, which provides more reference ideas for the future development of materials based on other amino acid derivatives.
Small-molecule hydrogels based on amino acid derivatives have promising applications in many biological fields, including cell culture, drug delivery, and tissue engineering. Although these hydrogels have been widely reported to have low cytotoxicity, biocompatibility, and tunable bioactivity, problems such as harsh preparation conditions and complex material design hinder their application. Herein, by adjusting pH to induce non-covalent interactions between small-molecule tryptophan derivatives (N-[(phenylmethoxy)carbonyl]-L-tryptophan, Mw: 338.35), we developed a self-assembled three-dimensional network hydrogel that can be rapidly formed in seconds. And the supramolecular self-assembly mechanism of the hydrogels was also investigated in detail through experimental characterizations and density functional theory calculation. As-prepared hydrogels also exhibit reversible pH-stimulated response and self-healing properties. This study details a research process for the simple and rapid preparation of tryptophan derivative-based hydrogels, which provides more reference ideas for the future development of materials based on other amino acid derivatives.
2023, 34(8): 108070
doi: 10.1016/j.cclet.2022.108070
Abstract:
Carbon dots (CDs) with room-temperature phosphorescence (RTP) have attracted dramatically growing interest in optical functional materials. However, the photoluminescence mechanism of CDs is still a vital and challenging topic. In this work, we prepared CD-based RTP materials via melting boric acid with various lengths of alkyl amine compounds as precursors. The spatial effect on the structure and the RTP properties of CDs were systematically investigated. With the increase in carbon chain length, the interplanar spacing of the carbon core expands and crosslink-enhanced emission weakens, resulting in a decrease in the phosphorescence intensity and lifetimes. Meanwhile, based on triplet-to-singlet resonance energy transfer, we employed intense and long-lived phosphorescence CDs as the donor and short-lived fluorescent dyes as the acceptor to achieve long-lived multicolor afterglow. By the triplet-to-singlet resonance energy transfer, the afterglow color can change from green to orange. The afterglow lifetimes are more than 0.9 s. Thanks to the outstanding afterglow properties, the composites were used for time-resolved and multiple-color advanced anticounterfeiting. This work will promote the design of multicolor and long-lived afterglow materials and expand their applications.
Carbon dots (CDs) with room-temperature phosphorescence (RTP) have attracted dramatically growing interest in optical functional materials. However, the photoluminescence mechanism of CDs is still a vital and challenging topic. In this work, we prepared CD-based RTP materials via melting boric acid with various lengths of alkyl amine compounds as precursors. The spatial effect on the structure and the RTP properties of CDs were systematically investigated. With the increase in carbon chain length, the interplanar spacing of the carbon core expands and crosslink-enhanced emission weakens, resulting in a decrease in the phosphorescence intensity and lifetimes. Meanwhile, based on triplet-to-singlet resonance energy transfer, we employed intense and long-lived phosphorescence CDs as the donor and short-lived fluorescent dyes as the acceptor to achieve long-lived multicolor afterglow. By the triplet-to-singlet resonance energy transfer, the afterglow color can change from green to orange. The afterglow lifetimes are more than 0.9 s. Thanks to the outstanding afterglow properties, the composites were used for time-resolved and multiple-color advanced anticounterfeiting. This work will promote the design of multicolor and long-lived afterglow materials and expand their applications.
2023, 34(8): 108074
doi: 10.1016/j.cclet.2022.108074
Abstract:
Shortcut nitrification-denitrification (SCND) is widely concerned because of its low energy consumption and high nitrogen removal efficiency. However, the current difficulty lies in the stable maintenance of SCND performance, which leads to the challenge of large-scale application of this new denitrification technology. In this study, the nitrogen removal pathway from complete nitrification-denitrification (CND) to SCND was rapidly realized under high free ammonia (FA), high pH and low dissolved oxygen (DO) conditions. The variations of specific oxygen uptake rate (SOUR) of activated sludge in both processes were investigated by an online SOUR monitoring device. Different curves of SOUR from CND to SCND process were observed, and the ammonia peak obtained based on SOUR monitoring could be used to control aeration time accurately in SCND process. Accordingly, the SOUR ratio of ammonia oxidizing bacteria (AOB) to nitrite oxidizing bacteria (NOB) (SOURAOB/SOURNOB) was increased from 1.40 to 2.93. 16S rRNA Miseq high throughput sequencing revealed the dynamics of AOB and NOB, and the ratio of relative abundance (AOB/NOB) was increased from 1.03 to 3.12. Besides, SOURAOB/SOURNOB displayed significant correlations to ammonia removal rate (P < 0.05), ammonia oxidation rate / nitrite oxidation rate (P < 0.05), nitrite accumulation rate (P < 0.05) and the relative abundance of AOB/NOB (P < 0.05). Thus, a strategy for evaluation the SCND process stability based on online SOUR monitoring is proposed, which provides a theoretical basis for optimizing the SCND performance.
Shortcut nitrification-denitrification (SCND) is widely concerned because of its low energy consumption and high nitrogen removal efficiency. However, the current difficulty lies in the stable maintenance of SCND performance, which leads to the challenge of large-scale application of this new denitrification technology. In this study, the nitrogen removal pathway from complete nitrification-denitrification (CND) to SCND was rapidly realized under high free ammonia (FA), high pH and low dissolved oxygen (DO) conditions. The variations of specific oxygen uptake rate (SOUR) of activated sludge in both processes were investigated by an online SOUR monitoring device. Different curves of SOUR from CND to SCND process were observed, and the ammonia peak obtained based on SOUR monitoring could be used to control aeration time accurately in SCND process. Accordingly, the SOUR ratio of ammonia oxidizing bacteria (AOB) to nitrite oxidizing bacteria (NOB) (SOURAOB/SOURNOB) was increased from 1.40 to 2.93. 16S rRNA Miseq high throughput sequencing revealed the dynamics of AOB and NOB, and the ratio of relative abundance (AOB/NOB) was increased from 1.03 to 3.12. Besides, SOURAOB/SOURNOB displayed significant correlations to ammonia removal rate (P < 0.05), ammonia oxidation rate / nitrite oxidation rate (P < 0.05), nitrite accumulation rate (P < 0.05) and the relative abundance of AOB/NOB (P < 0.05). Thus, a strategy for evaluation the SCND process stability based on online SOUR monitoring is proposed, which provides a theoretical basis for optimizing the SCND performance.
2023, 34(8): 108076
doi: 10.1016/j.cclet.2022.108076
Abstract:
Owing to their unique design and development, high safety and low-cost efficient cathode is still at the forefront of research for rechargeable zinc-ion batteries. However, the suitable cathode operating with ultrahigh capacity with a dendrite-free anode reaction mechanism remains challenging. In this, the first archetype of a high-rate and morphologically stabled cathode material is constructed from novel cauliflower-like nano-ZnV2S4 for aqueous zinc-ion batteries. Thus, nano-ZnV2S4 was prepared with an anion exchange reaction using ZnV2(OH)8 cauliflower-like nanostructured array as a template interestingly no morphological and shape changes were detected. The as-prepared nano-ZnV2S4 electrode reveals a specific discharge capacity of 348.2 mAh/g during 0.5 A/g with enhanced rate capability and excellent capacity retention of 89.2% at 4 A/g current density even after completing 1000 cycles.
Owing to their unique design and development, high safety and low-cost efficient cathode is still at the forefront of research for rechargeable zinc-ion batteries. However, the suitable cathode operating with ultrahigh capacity with a dendrite-free anode reaction mechanism remains challenging. In this, the first archetype of a high-rate and morphologically stabled cathode material is constructed from novel cauliflower-like nano-ZnV2S4 for aqueous zinc-ion batteries. Thus, nano-ZnV2S4 was prepared with an anion exchange reaction using ZnV2(OH)8 cauliflower-like nanostructured array as a template interestingly no morphological and shape changes were detected. The as-prepared nano-ZnV2S4 electrode reveals a specific discharge capacity of 348.2 mAh/g during 0.5 A/g with enhanced rate capability and excellent capacity retention of 89.2% at 4 A/g current density even after completing 1000 cycles.
2023, 34(8): 108078
doi: 10.1016/j.cclet.2022.108078
Abstract:
π-Electron coupling of pendant conjugated segment in π-stacked semiconducting polymers always causes the formation of defect trapped sites and further quenched high-band excitons, which is harmful to the performance and stability of deep-blue polymer light-emitting diodes (PLEDs). Herein, considerate of “defect” carbazole (Cz) electromers in poly(N-vinylcarbazole) (PVK), a series of fluorene units are introduced into pendant segments (PVCz-DMeF, PVCz-FMeNPh and PVCz-DFMeNPh) to suppress the strong π-electron coupling of pendant Cz units and enhance radiative transition toward fabricating sable PLEDs. Compared to PVCz-FMeNPh and PVCz-DFMeNPh, PVCz-DMeF spin-coated films show a relatively efficient deep-blue emission, completely similar to its single pendant chromophore, confirmed an extremely weak charge-transfer and electron coupling between adjacent pendant segments. Therefore, PLEDs based on PVCz-DMeF present stable and deep-blue emission with a high color purity (0.17, 0.08), associated with extremely weak defect emission at 600~700 nm (induced by carbazole electromers). Finally, PLEDs based on PVCz-DMeF/F8BT blended films (1:1) also present the high maximum luminance (Lmax) of 6261 cd/m2 and current efficiency (CEmax) of 2.03 cd/A, confirmed slightly trapped sites formation. Therefore, precisely control the arrangement and packing model of pendant units in π-stacked polymer is an essential prerequisite for building efficient and stable emitter for optoelectronic devices.
π-Electron coupling of pendant conjugated segment in π-stacked semiconducting polymers always causes the formation of defect trapped sites and further quenched high-band excitons, which is harmful to the performance and stability of deep-blue polymer light-emitting diodes (PLEDs). Herein, considerate of “defect” carbazole (Cz) electromers in poly(N-vinylcarbazole) (PVK), a series of fluorene units are introduced into pendant segments (PVCz-DMeF, PVCz-FMeNPh and PVCz-DFMeNPh) to suppress the strong π-electron coupling of pendant Cz units and enhance radiative transition toward fabricating sable PLEDs. Compared to PVCz-FMeNPh and PVCz-DFMeNPh, PVCz-DMeF spin-coated films show a relatively efficient deep-blue emission, completely similar to its single pendant chromophore, confirmed an extremely weak charge-transfer and electron coupling between adjacent pendant segments. Therefore, PLEDs based on PVCz-DMeF present stable and deep-blue emission with a high color purity (0.17, 0.08), associated with extremely weak defect emission at 600~700 nm (induced by carbazole electromers). Finally, PLEDs based on PVCz-DMeF/F8BT blended films (1:1) also present the high maximum luminance (Lmax) of 6261 cd/m2 and current efficiency (CEmax) of 2.03 cd/A, confirmed slightly trapped sites formation. Therefore, precisely control the arrangement and packing model of pendant units in π-stacked polymer is an essential prerequisite for building efficient and stable emitter for optoelectronic devices.
2023, 34(8): 108079
doi: 10.1016/j.cclet.2022.108079
Abstract:
Current clinical treatments cannot effectively delay the progression of osteoarthritis (OA). Consequently, joint replacement surgery is required for late-stage OA when patients cannot tolerate pain and joint dysfunction. Therefore, the prevention of OA progression in the early and middle stages is an urgent clinical problem. In a previous study, we demonstrated that NDRG3-mediated hypoxic response might be closely related to the development and progression of OA. In this study, an injectable thermosensitive hydrogel was established by cross-linking Pluronic F-127 and hyaluronic acid (HA) for the sustained release of hypoxia-induced exosomes (HExos) derived from adipose-derived mesenchymal stem cells. We demonstrated that for OA at the early and middle stages, the HExos-loaded HP hydrogel could maintain the chondrocyte phenotype by enhancing chondrocyte autophagy, reducing chondrocyte apoptosis, and promoting chondrocyte activity and proliferation through the NDRG3-mediated hypoxic response. This novel composite hydrogel, which could activate the NDRG3-mediated hypoxic response, may provide new ideas and a theoretical basis for the treatment of early- and mid-stage OA.
Current clinical treatments cannot effectively delay the progression of osteoarthritis (OA). Consequently, joint replacement surgery is required for late-stage OA when patients cannot tolerate pain and joint dysfunction. Therefore, the prevention of OA progression in the early and middle stages is an urgent clinical problem. In a previous study, we demonstrated that NDRG3-mediated hypoxic response might be closely related to the development and progression of OA. In this study, an injectable thermosensitive hydrogel was established by cross-linking Pluronic F-127 and hyaluronic acid (HA) for the sustained release of hypoxia-induced exosomes (HExos) derived from adipose-derived mesenchymal stem cells. We demonstrated that for OA at the early and middle stages, the HExos-loaded HP hydrogel could maintain the chondrocyte phenotype by enhancing chondrocyte autophagy, reducing chondrocyte apoptosis, and promoting chondrocyte activity and proliferation through the NDRG3-mediated hypoxic response. This novel composite hydrogel, which could activate the NDRG3-mediated hypoxic response, may provide new ideas and a theoretical basis for the treatment of early- and mid-stage OA.
2023, 34(8): 108080
doi: 10.1016/j.cclet.2022.108080
Abstract:
Due to the high local concentration of substrates in confined space, porous solid Brønsted acids have been extensively explored for efficient acid-catalyzed reaction. However, the porous structures with strong Brønsted acids lack long-term stability due to chemical hydrolysis. Moreover, the products inhibition effect in confined rigid cavities severely obstructs subsequent catalysis. Here, tubular Brønsted acid catalyst with unique recognition of protons was presented by self-assembly of pH-responsive aromatic amphiphiles. The responsive assembly could mechanically transfer hydrogen ions from low-concentration acidic solution into tubular defined pores, thereby producing effective catalytic activity for Mannich reactions in mildly acidic solution. Notably, the tubular catalyst unfolded into flat sheets upon addition of triethylamine for efficient release of products, which could be recovered by subsequent acidification and the catalytic activity still remained. Therefore, the porous Brønsted acid with reversible assembly provides a new strategy for mass synthesis through increasing conversion times.
Due to the high local concentration of substrates in confined space, porous solid Brønsted acids have been extensively explored for efficient acid-catalyzed reaction. However, the porous structures with strong Brønsted acids lack long-term stability due to chemical hydrolysis. Moreover, the products inhibition effect in confined rigid cavities severely obstructs subsequent catalysis. Here, tubular Brønsted acid catalyst with unique recognition of protons was presented by self-assembly of pH-responsive aromatic amphiphiles. The responsive assembly could mechanically transfer hydrogen ions from low-concentration acidic solution into tubular defined pores, thereby producing effective catalytic activity for Mannich reactions in mildly acidic solution. Notably, the tubular catalyst unfolded into flat sheets upon addition of triethylamine for efficient release of products, which could be recovered by subsequent acidification and the catalytic activity still remained. Therefore, the porous Brønsted acid with reversible assembly provides a new strategy for mass synthesis through increasing conversion times.
2023, 34(8): 108081
doi: 10.1016/j.cclet.2022.108081
Abstract:
In this work, we have designed and synthesized a cyano-substituted p-phenylenevinylene derivative (PPTA), which can self-assemble into positively charged nanoparticles in an aqueous solution with a deep green fluorescence. An anionic polyelectrolyte material guar gum modified by carboxylic acid (GP5A) was chosen to build an artificial light-harvesting system (LHS) through self-assembly with PPTA, in which two acceptors Eosin Y (EY) and Nile red (NiR) were loaded into the PPTA-GP5A assemblies through electrostatic interaction and Van der Waals force. By adjusting the molar ratio of PPTA-GP5A/EY at 1:0.004, the one-step artificial LHS can exhibit high energy transfer efficiency (38.9%) and antenna effect (AE) (4.6). Subsequently, with the addition of NiR, the and AE of the two-step sequential artificial LHS were calculated to be 71.9% and 13.5, respectively. Moreover, the two-step artificial LHS constructed by the polyelectrolyte material GP5A can be used as a nanoreactor to photocatalyst alkylation of C-H bonds of phenyl vinyl sulfone (PVS) and tetrahydrofuran (THF) in water with a yield of 42%. Therefore, we have constructed an artificial LHS with two-step energy transfer based on polyelectrolytes through the electrostatic interaction to improve energy transfer efficiency, which can also be used as a nanoreactor for photocatalysis.
In this work, we have designed and synthesized a cyano-substituted p-phenylenevinylene derivative (PPTA), which can self-assemble into positively charged nanoparticles in an aqueous solution with a deep green fluorescence. An anionic polyelectrolyte material guar gum modified by carboxylic acid (GP5A) was chosen to build an artificial light-harvesting system (LHS) through self-assembly with PPTA, in which two acceptors Eosin Y (EY) and Nile red (NiR) were loaded into the PPTA-GP5A assemblies through electrostatic interaction and Van der Waals force. By adjusting the molar ratio of PPTA-GP5A/EY at 1:0.004, the one-step artificial LHS can exhibit high energy transfer efficiency (38.9%) and antenna effect (AE) (4.6). Subsequently, with the addition of NiR, the and AE of the two-step sequential artificial LHS were calculated to be 71.9% and 13.5, respectively. Moreover, the two-step artificial LHS constructed by the polyelectrolyte material GP5A can be used as a nanoreactor to photocatalyst alkylation of C-H bonds of phenyl vinyl sulfone (PVS) and tetrahydrofuran (THF) in water with a yield of 42%. Therefore, we have constructed an artificial LHS with two-step energy transfer based on polyelectrolytes through the electrostatic interaction to improve energy transfer efficiency, which can also be used as a nanoreactor for photocatalysis.
2023, 34(8): 108082
doi: 10.1016/j.cclet.2022.108082
Abstract:
Hydrazine hydrate (DH) is an important fine chemical intermediate and as fuel for rockets, however, it also has serious toxic for humans and environment. Developing novel materials and methods for sensitive detection of DH in water and air is an important task. In order to effectively detect DH, a novel conductive supramolecular polymer metallogel (PQ-Ag) has been constructed by the coordination of bis-5-hydroxyquinoline functionalized pillar[5]arene (PQ5) with Ag+. The metallogel PQ-Ag could realize the multi-channel sensitive detection of DH through naked-eye, fluorescence, and electrochemical methods. The lowest limit of detection (LOD) is 0.1 mg/m3 in air and 2.68 × 10−8 mol/L in water, which is lower than the standard of the US Environmental Protection Agency (EPA) for DH of maximum allowable concentration in drinking water. More importantly, an electronic device for DH detection based on the metallogel PQ-Ag was designed and prepared, which can realize conveniently and efficiently multi-channel detection and alert of DH through sound and light alarms not only in water but also in air.
Hydrazine hydrate (DH) is an important fine chemical intermediate and as fuel for rockets, however, it also has serious toxic for humans and environment. Developing novel materials and methods for sensitive detection of DH in water and air is an important task. In order to effectively detect DH, a novel conductive supramolecular polymer metallogel (PQ-Ag) has been constructed by the coordination of bis-5-hydroxyquinoline functionalized pillar[5]arene (PQ5) with Ag+. The metallogel PQ-Ag could realize the multi-channel sensitive detection of DH through naked-eye, fluorescence, and electrochemical methods. The lowest limit of detection (LOD) is 0.1 mg/m3 in air and 2.68 × 10−8 mol/L in water, which is lower than the standard of the US Environmental Protection Agency (EPA) for DH of maximum allowable concentration in drinking water. More importantly, an electronic device for DH detection based on the metallogel PQ-Ag was designed and prepared, which can realize conveniently and efficiently multi-channel detection and alert of DH through sound and light alarms not only in water but also in air.
2023, 34(8): 108087
doi: 10.1016/j.cclet.2022.108087
Abstract:
Despite the 1,2-difunctionalization reactions of styrenes have been well developed, the 1,1-regioselective addition reaction remains challenging. We disclose herein a palladium-catalyzed, highly 1,1-regioselective alkenylboration of styrenes by using alkenyl triflates and a diboron reagent as the coupling partners. A wide scope of styrenes derivatives and alkenyl triflates participate this reaction to provide the corresponding allyl boronates with high regioisomeric ratios. The success of this reaction is ascribed to the application of 1,10-phenanthroline-derivated ligand and the addition of ammonium chloride salt. Moreover, acrylate esters can also selectively afford the 1,1-alkenylboration products under the same reaction conditions.
Despite the 1,2-difunctionalization reactions of styrenes have been well developed, the 1,1-regioselective addition reaction remains challenging. We disclose herein a palladium-catalyzed, highly 1,1-regioselective alkenylboration of styrenes by using alkenyl triflates and a diboron reagent as the coupling partners. A wide scope of styrenes derivatives and alkenyl triflates participate this reaction to provide the corresponding allyl boronates with high regioisomeric ratios. The success of this reaction is ascribed to the application of 1,10-phenanthroline-derivated ligand and the addition of ammonium chloride salt. Moreover, acrylate esters can also selectively afford the 1,1-alkenylboration products under the same reaction conditions.
2023, 34(8): 108088
doi: 10.1016/j.cclet.2022.108088
Abstract:
Synthesis and functionalization of novel macrocyclic host molecules are important topics in supramolecular chemistry. In this work, the first amphiphilic [2]biphenyl-extended pillar[6]arene (AM-[2]BP-ExP6) was designed and synthesized with poly(ethylene glycol) chains as the hydrophilic tails and a rigid cavity as the hydrophobic core. Due to its amphiphilic nature, AM-[2]BP-ExP6 could self-assemble to stable fibers in water. What's more, AM-[2]BP-ExP6 could associate with quaternary ammonium modified tetraphenylethylene guest (QTPE) to form a 2:1 host-guest complex, accompanied by significant enhanced fluorescence. Interestingly, different like AM-[2]BP-ExP6, AM-[2]BP-ExP6⊃QTPE host-guest complex self-assembled into fluorescent particles with diameter about 310 nm, the obtained fluorescent particles can be further employed in living cell imaging.
Synthesis and functionalization of novel macrocyclic host molecules are important topics in supramolecular chemistry. In this work, the first amphiphilic [2]biphenyl-extended pillar[6]arene (AM-[2]BP-ExP6) was designed and synthesized with poly(ethylene glycol) chains as the hydrophilic tails and a rigid cavity as the hydrophobic core. Due to its amphiphilic nature, AM-[2]BP-ExP6 could self-assemble to stable fibers in water. What's more, AM-[2]BP-ExP6 could associate with quaternary ammonium modified tetraphenylethylene guest (QTPE) to form a 2:1 host-guest complex, accompanied by significant enhanced fluorescence. Interestingly, different like AM-[2]BP-ExP6, AM-[2]BP-ExP6⊃QTPE host-guest complex self-assembled into fluorescent particles with diameter about 310 nm, the obtained fluorescent particles can be further employed in living cell imaging.
2023, 34(8): 108090
doi: 10.1016/j.cclet.2022.108090
Abstract:
Electrochemical oxidation of aqueous tris(1,3-dichloro-2-propyl) phosphate (TDCPP) by using Ti/SnO2-Sb/La-PbO2 as anode was investigated for the first time, and the degradation mechanisms and toxicity changes of the degradation intermediates were further determined. Results suggested that electrochemical degradation of TDCPP followed pseudo-first-order kinetics, and the reaction rate constant (k) was 0.0332 min−1 at the applied current density of 10 mA/cm2 and Na2SO4 concentration of 10 mmol/L. There was better TDCPP degradation performance at higher current density. Free hydroxy radical (·OH) was proved to play dominant role in TDCPP oxidation via quenching experiment, with a relative contribution rate of 60.1%. A total of five intermediates (M1, C6H11Cl4O4P; M2, C3H7Cl2O4P; M3, C9H16Cl5O5P; M4, C9H14Cl5O6P; M5, C6H10Cl3O6P) were identified, and the intermediates were further degraded prolonging with the reaction time. Flow cytometer results suggested that the toxicity of TDCPP and degradation intermediates significantly reduced, and the detoxification efficiency was achieved at 78.1% at 180 min. ECOSAR predictive model was used to assess the relative toxicity of TDCPP and the degradation intermediates. The EC50 to green algae was 3.59 mg/L for TDCPP, and the values raised to 84, 574, 54.6, 391, and 8920 mg/L for M1, M2, M3, M4, and M5, respectively, indicating that the degradation intermediates are less toxic or not toxic. Electrochemical advanced oxidation process is a valid technology to degrade TDCPP and pose a good detoxification effect.
Electrochemical oxidation of aqueous tris(1,3-dichloro-2-propyl) phosphate (TDCPP) by using Ti/SnO2-Sb/La-PbO2 as anode was investigated for the first time, and the degradation mechanisms and toxicity changes of the degradation intermediates were further determined. Results suggested that electrochemical degradation of TDCPP followed pseudo-first-order kinetics, and the reaction rate constant (k) was 0.0332 min−1 at the applied current density of 10 mA/cm2 and Na2SO4 concentration of 10 mmol/L. There was better TDCPP degradation performance at higher current density. Free hydroxy radical (·OH) was proved to play dominant role in TDCPP oxidation via quenching experiment, with a relative contribution rate of 60.1%. A total of five intermediates (M1, C6H11Cl4O4P; M2, C3H7Cl2O4P; M3, C9H16Cl5O5P; M4, C9H14Cl5O6P; M5, C6H10Cl3O6P) were identified, and the intermediates were further degraded prolonging with the reaction time. Flow cytometer results suggested that the toxicity of TDCPP and degradation intermediates significantly reduced, and the detoxification efficiency was achieved at 78.1% at 180 min. ECOSAR predictive model was used to assess the relative toxicity of TDCPP and the degradation intermediates. The EC50 to green algae was 3.59 mg/L for TDCPP, and the values raised to 84, 574, 54.6, 391, and 8920 mg/L for M1, M2, M3, M4, and M5, respectively, indicating that the degradation intermediates are less toxic or not toxic. Electrochemical advanced oxidation process is a valid technology to degrade TDCPP and pose a good detoxification effect.
2023, 34(8): 108092
doi: 10.1016/j.cclet.2022.108092
Abstract:
Nucleic acid detection (NAD) based on real-time polymerase chain reaction (real-time PCR) is gold standard for infectious disease detection. Magnetic nanoparticles (MNPs) are widely used for nucleic acid extraction (NAE) because of their excellent properties. Microfluidic technology makes automated NAD possible. However, most of the NAD microfluidic chips are too complex to be applied to point-of-care (POC) testing. In this paper, a simple-structure cartridge was developed for POC detection of infectious diseases. This self-contained cartridge can be divided into a magnetic-controlled NAE part, a valve-piston combined fluidic control part and a PCR chip, which is able to extract nucleic acid from up to 500 µL of liquid samples by MNPs and finish the detection process from “sample in” to “answer out” automatically. Performance tests of the cartridges show that it met the demands of automated NAD. Results of on-cartridge detection of hepatitis B virus (HBV) demonstrated that this system has good uniformity and no cross-contamination between different cartridges, and the limit of detection (LOD) of this system for HBV in serum is 50 IU/mL. Multiplex detections of severe acute respiratory syndrome coronaviruses 2 (SARS-CoV-2) with a concentration of 500 copies/mL were carried out on the system and 100% positive detection rate was achieved.
Nucleic acid detection (NAD) based on real-time polymerase chain reaction (real-time PCR) is gold standard for infectious disease detection. Magnetic nanoparticles (MNPs) are widely used for nucleic acid extraction (NAE) because of their excellent properties. Microfluidic technology makes automated NAD possible. However, most of the NAD microfluidic chips are too complex to be applied to point-of-care (POC) testing. In this paper, a simple-structure cartridge was developed for POC detection of infectious diseases. This self-contained cartridge can be divided into a magnetic-controlled NAE part, a valve-piston combined fluidic control part and a PCR chip, which is able to extract nucleic acid from up to 500 µL of liquid samples by MNPs and finish the detection process from “sample in” to “answer out” automatically. Performance tests of the cartridges show that it met the demands of automated NAD. Results of on-cartridge detection of hepatitis B virus (HBV) demonstrated that this system has good uniformity and no cross-contamination between different cartridges, and the limit of detection (LOD) of this system for HBV in serum is 50 IU/mL. Multiplex detections of severe acute respiratory syndrome coronaviruses 2 (SARS-CoV-2) with a concentration of 500 copies/mL were carried out on the system and 100% positive detection rate was achieved.
2023, 34(8): 108093
doi: 10.1016/j.cclet.2022.108093
Abstract:
Adenosine triphosphate (ATP) plays an important role in various biological processes and the ATP level is closely associated with many diseases. Herein, we designed a novel dual-emissive fluorescence nanoplatform for ATP sensing based on red emissive europium metal-organic framework (Eu-MOF) and blue emissive gold nanoclusters (AuNCs). The presence of ATP causes the decomposition of Eu-MOF owing to strong affinity of Eu3+ with ATP. As a result, the red emission of Eu-MOF decreases while the blue emission of AuNCs remains unchanged. The distinct red/blue emission intensity change enables the establishment of a ratiometric fluorescent and visual sensor of ATP. Moreover, a fluorescent paper-based sensor was fabricated with the ratiometric ATP probes, which enabled easy-to-use and visual detection of ATP in serum samples with a smartphone.
Adenosine triphosphate (ATP) plays an important role in various biological processes and the ATP level is closely associated with many diseases. Herein, we designed a novel dual-emissive fluorescence nanoplatform for ATP sensing based on red emissive europium metal-organic framework (Eu-MOF) and blue emissive gold nanoclusters (AuNCs). The presence of ATP causes the decomposition of Eu-MOF owing to strong affinity of Eu3+ with ATP. As a result, the red emission of Eu-MOF decreases while the blue emission of AuNCs remains unchanged. The distinct red/blue emission intensity change enables the establishment of a ratiometric fluorescent and visual sensor of ATP. Moreover, a fluorescent paper-based sensor was fabricated with the ratiometric ATP probes, which enabled easy-to-use and visual detection of ATP in serum samples with a smartphone.
2023, 34(8): 108099
doi: 10.1016/j.cclet.2022.108099
Abstract:
Rosmarinic acid (RA) is promising as a natural and nontoxic food additive. However, many analysis methods for RA generally depend on large instruments and single signals for quantitative detection. A new up-conversion fluorescence, colorimetric and photothermal multi-modal sensing strategy is developed for the quantification of RA. β-cyclodextrin (CD) modified citric acid (Cit) wrapped NaYF4:Yb/Er-Cit-CD (Y:Yb/Er-Cit-CD) up-conversion nanocomposite has been synthesized, which emits green fluorescence at 550 nm under 980 nm near-infrared (NIR) excitation. In the presence of oxidized 3, 3′, 5, 5′-tetramethylbenzidine (oxTMB), the green fluorescence is significantly quenched attributed to the fluorescence inner filter effect (IFE) between oxTMB and Y:Yb/Er-Cit-CD. When RA is intervened, blue oxTMB is reduced to colorless 3, 3′, 5, 5′-tetramethylbenzidine (TMB) inducing the recovery of up-conversion fluorescence. At the same time, colorimetric and photothermal signals readout can be easily achieved thanks to the color indication and photothermal effect of the oxTMB. The constructed Y:Yb/Er-Cit-CD/oxTMB sensor displays high sensitivity, visibility and simplicity for RA, and the limits of detection (LOD) for fluorescence, colorimetric and photothermal were 0.004 µmol/L, 0.036 µmol/L and 0.043 µmol/L, respectively. This sensing system is successfully performed for the detection of RA in food samples.
Rosmarinic acid (RA) is promising as a natural and nontoxic food additive. However, many analysis methods for RA generally depend on large instruments and single signals for quantitative detection. A new up-conversion fluorescence, colorimetric and photothermal multi-modal sensing strategy is developed for the quantification of RA. β-cyclodextrin (CD) modified citric acid (Cit) wrapped NaYF4:Yb/Er-Cit-CD (Y:Yb/Er-Cit-CD) up-conversion nanocomposite has been synthesized, which emits green fluorescence at 550 nm under 980 nm near-infrared (NIR) excitation. In the presence of oxidized 3, 3′, 5, 5′-tetramethylbenzidine (oxTMB), the green fluorescence is significantly quenched attributed to the fluorescence inner filter effect (IFE) between oxTMB and Y:Yb/Er-Cit-CD. When RA is intervened, blue oxTMB is reduced to colorless 3, 3′, 5, 5′-tetramethylbenzidine (TMB) inducing the recovery of up-conversion fluorescence. At the same time, colorimetric and photothermal signals readout can be easily achieved thanks to the color indication and photothermal effect of the oxTMB. The constructed Y:Yb/Er-Cit-CD/oxTMB sensor displays high sensitivity, visibility and simplicity for RA, and the limits of detection (LOD) for fluorescence, colorimetric and photothermal were 0.004 µmol/L, 0.036 µmol/L and 0.043 µmol/L, respectively. This sensing system is successfully performed for the detection of RA in food samples.
2023, 34(8): 108102
doi: 10.1016/j.cclet.2022.108102
Abstract:
The threat to public health from bacterial infections has led to an urgent need to develop simpler, faster and more reliable bacterial detection methods. In this work, we developed a universal dual-recognition based sandwich fluorescence resonance energy transfer (FRET) sensor by using specific aptamer-modified quantum dots (Aptamer-QDs) as energy donor and lectin concanavalin A (Con A) modified gold nanoparticles (Con A-AuNPs) as energy acceptor to achieve rapid and sensitive detection of Escherichia coli (E. coli) within 0.5 h. In the presence of the target E. coli, the energy donor of Aptamer-QDs and acceptor of Con A-AuNPs were close to each other, causing changes of FRET signals. Based on the constructed FRET sensor, a linear detection range of from 102 cfu/mL to 2 × 108 cfu/mL with the detection limit of 45 cfu/mL for E. coli was achieved. Furthermore, the FRET sensor was applied to detect E. coli in the milk and orange juice with the detection limit of 300 cfu/mL and 200 cfu/mL, respectively and recovery rate from 83.1% to 112.5%. The strategy holds great promise in pathogenic bacteria detection due to its rapid and sensitivity.
The threat to public health from bacterial infections has led to an urgent need to develop simpler, faster and more reliable bacterial detection methods. In this work, we developed a universal dual-recognition based sandwich fluorescence resonance energy transfer (FRET) sensor by using specific aptamer-modified quantum dots (Aptamer-QDs) as energy donor and lectin concanavalin A (Con A) modified gold nanoparticles (Con A-AuNPs) as energy acceptor to achieve rapid and sensitive detection of Escherichia coli (E. coli) within 0.5 h. In the presence of the target E. coli, the energy donor of Aptamer-QDs and acceptor of Con A-AuNPs were close to each other, causing changes of FRET signals. Based on the constructed FRET sensor, a linear detection range of from 102 cfu/mL to 2 × 108 cfu/mL with the detection limit of 45 cfu/mL for E. coli was achieved. Furthermore, the FRET sensor was applied to detect E. coli in the milk and orange juice with the detection limit of 300 cfu/mL and 200 cfu/mL, respectively and recovery rate from 83.1% to 112.5%. The strategy holds great promise in pathogenic bacteria detection due to its rapid and sensitivity.
2023, 34(8): 108104
doi: 10.1016/j.cclet.2022.108104
Abstract:
In clinic, the combination of intravenous pembrolizumab (PD-1 monoclonal antibody) with oral Lenvatinib (LEN) exhibited an enhanced synergistic benefit for cancer therapy. However, the clinical outcomes were always limited by the problems of inconsistent pharmacokinetic profiles of two drugs, lower drug accumulation in tumor and obvious side effects during the combination therapy. Here, in situ-forming thermosensitive hydrogels based on PLGA-PEG-PLGA triblock copolymers were prepared for local administration of anti-PD1 and LEN (P&L@Gel) to improve therapeutic efficacy and safety. After peritumoral or surgical resection site injection, the significant increased concentrations of both drugs in tumor were observed with the local sustained release of P&L@Gel. In comparison with the group of intraperitoneal anti-PD1 plus oral LEN (P-ip&L-po), significantly higher tumor inhibition efficiency on CT26 tumor models could be obtained in P&L@Gel group, even at the dose of one-eighth of the former, same tumor-inhibition effects could be achieved. The enhanced antitumor efficacy of P&L@Gel group was probably associated with the 2.2 folds of increased level of CD8+ T cells and the polarization of tumor associated macrophage from M2 to M1 along with the increased drug accumulation. Moreover, compared with the obvious side effects of P-ip&L-po group, no significant changes of PLT, ALT and UA in blood, as well as IL-1α and IL-1β in mice paws were observed between P&L@Gel group and untreated group. These results suggested that local administration of anti-PD1 and LEN with thermosensitive hydrogel could offer a potential strategy for tumors or tumor postoperative adjuvant treatment.
In clinic, the combination of intravenous pembrolizumab (PD-1 monoclonal antibody) with oral Lenvatinib (LEN) exhibited an enhanced synergistic benefit for cancer therapy. However, the clinical outcomes were always limited by the problems of inconsistent pharmacokinetic profiles of two drugs, lower drug accumulation in tumor and obvious side effects during the combination therapy. Here, in situ-forming thermosensitive hydrogels based on PLGA-PEG-PLGA triblock copolymers were prepared for local administration of anti-PD1 and LEN (P&L@Gel) to improve therapeutic efficacy and safety. After peritumoral or surgical resection site injection, the significant increased concentrations of both drugs in tumor were observed with the local sustained release of P&L@Gel. In comparison with the group of intraperitoneal anti-PD1 plus oral LEN (P-ip&L-po), significantly higher tumor inhibition efficiency on CT26 tumor models could be obtained in P&L@Gel group, even at the dose of one-eighth of the former, same tumor-inhibition effects could be achieved. The enhanced antitumor efficacy of P&L@Gel group was probably associated with the 2.2 folds of increased level of CD8+ T cells and the polarization of tumor associated macrophage from M2 to M1 along with the increased drug accumulation. Moreover, compared with the obvious side effects of P-ip&L-po group, no significant changes of PLT, ALT and UA in blood, as well as IL-1α and IL-1β in mice paws were observed between P&L@Gel group and untreated group. These results suggested that local administration of anti-PD1 and LEN with thermosensitive hydrogel could offer a potential strategy for tumors or tumor postoperative adjuvant treatment.
2023, 34(8): 108106
doi: 10.1016/j.cclet.2022.108106
Abstract:
Nature chooses phosphorylation as a key modification to modulate and program the functions of proteins. Various phosphorylated peptides (PPs) have been widely identified and investigated by biologists, but the possibility that PPs could become a building unit for artificial materials is neglected. Here we report for the first time a supramolecular assembly of PPs with the assistance of dysprosium ions (Dy3+). Dy3+ bridges multiple phosphate groups in double-phosphorylated peptides (di-PPs), and braid these peptide chains into nanofibers. The assembly occurs inside nanochannels and blocks the channels, leading to prominent "ON–OFF" switching in transmembrane ionic current. The di-PPs' assembling process could be dynamically regulated by the addition or deletion of phosphate groups under the control of kinases or phosphatases. This study proves the huge potential of PPs being utilized as materials via self-assembling, which will promote the design of novel bio-inspired artificial materials and devices.
Nature chooses phosphorylation as a key modification to modulate and program the functions of proteins. Various phosphorylated peptides (PPs) have been widely identified and investigated by biologists, but the possibility that PPs could become a building unit for artificial materials is neglected. Here we report for the first time a supramolecular assembly of PPs with the assistance of dysprosium ions (Dy3+). Dy3+ bridges multiple phosphate groups in double-phosphorylated peptides (di-PPs), and braid these peptide chains into nanofibers. The assembly occurs inside nanochannels and blocks the channels, leading to prominent "ON–OFF" switching in transmembrane ionic current. The di-PPs' assembling process could be dynamically regulated by the addition or deletion of phosphate groups under the control of kinases or phosphatases. This study proves the huge potential of PPs being utilized as materials via self-assembling, which will promote the design of novel bio-inspired artificial materials and devices.
2023, 34(8): 108108
doi: 10.1016/j.cclet.2022.108108
Abstract:
Photoresponsive supramolecular systems have merited extensive attention for their applications in materials science and life science. Here, we synthesized a water-soluble stiff-stilbene molecular photoswitch, exhibiting outstanding photoisomerization reaction between its (E)- and (Z)-configurations upon irradiation at distinct light. The photoswitch can assemble with cucurbit[7]uril (CB[7]) to form a superior fluorescent supramolecular complex (compared to the only guest) with excellent water solubility, which manifested dramatic photoluminescence enhancement caused by restriction of intramolecular rotation and remained good photochromic characteristics. Furthermore, introduction of CB[7] influence photoreaction quantum yield (Φ) of the stiff-stilbene, leading to reduction of ΦE→Z and increase of ΦZ→E of the stiff-stilbene. Importantly, the photoadjustable supramolecular assembly can act as a fluorescence switch, and the phototunable guest further selectively modulate G-quadruplex structure of Tel22 upon light irradiation or with addition of CB[7]. The study provides a new simple way for accurately regulating photochromic properties of molecular switches and developing smart materials with potential applications in controlled modulation of G-quadruplex, targeted biological imaging and so on.
Photoresponsive supramolecular systems have merited extensive attention for their applications in materials science and life science. Here, we synthesized a water-soluble stiff-stilbene molecular photoswitch, exhibiting outstanding photoisomerization reaction between its (E)- and (Z)-configurations upon irradiation at distinct light. The photoswitch can assemble with cucurbit[7]uril (CB[7]) to form a superior fluorescent supramolecular complex (compared to the only guest) with excellent water solubility, which manifested dramatic photoluminescence enhancement caused by restriction of intramolecular rotation and remained good photochromic characteristics. Furthermore, introduction of CB[7] influence photoreaction quantum yield (Φ) of the stiff-stilbene, leading to reduction of ΦE→Z and increase of ΦZ→E of the stiff-stilbene. Importantly, the photoadjustable supramolecular assembly can act as a fluorescence switch, and the phototunable guest further selectively modulate G-quadruplex structure of Tel22 upon light irradiation or with addition of CB[7]. The study provides a new simple way for accurately regulating photochromic properties of molecular switches and developing smart materials with potential applications in controlled modulation of G-quadruplex, targeted biological imaging and so on.
2023, 34(8): 108110
doi: 10.1016/j.cclet.2022.108110
Abstract:
Residual antibiotics in food pose a serious long-term threat to human health. Therefore, an on-site visualization method for antibiotic detection is required. However, the requirements of traditional antibiotic testing methods in terms of operator proficiency and equipment cost hinder the rapid point-of-care-testing detection of suspected samples. Herein, we reported an integrated microfluidic device combining a microfluidic chip containing cruciform valves with immunochromatographic strips for the rapid detection of multiple antibiotics in milk. The rapid qualitative and quantitative analysis of four types of antibiotics (sulfonamides, β-lactams, streptomycin, and tetracyclines) was performed using mobile phone photography and mobile phone application analysis. The detection time was maintained at 10 min. The limits of detection (LODs) for the four antibiotics were 0.15, 0.12, 0.25, and 0.29 ng/mL, respectively, and the selectivity for the different antibiotics was observed even in a highly complex matrix. This device successfully integrated separation and real-time detection onto a chip and might provide a promising perspective for the detection of multiple antibiotics in milk.
Residual antibiotics in food pose a serious long-term threat to human health. Therefore, an on-site visualization method for antibiotic detection is required. However, the requirements of traditional antibiotic testing methods in terms of operator proficiency and equipment cost hinder the rapid point-of-care-testing detection of suspected samples. Herein, we reported an integrated microfluidic device combining a microfluidic chip containing cruciform valves with immunochromatographic strips for the rapid detection of multiple antibiotics in milk. The rapid qualitative and quantitative analysis of four types of antibiotics (sulfonamides, β-lactams, streptomycin, and tetracyclines) was performed using mobile phone photography and mobile phone application analysis. The detection time was maintained at 10 min. The limits of detection (LODs) for the four antibiotics were 0.15, 0.12, 0.25, and 0.29 ng/mL, respectively, and the selectivity for the different antibiotics was observed even in a highly complex matrix. This device successfully integrated separation and real-time detection onto a chip and might provide a promising perspective for the detection of multiple antibiotics in milk.
2023, 34(8): 108120
doi: 10.1016/j.cclet.2022.108120
Abstract:
Electrochemical reduction of CO2 (CO2RR) to value-added chemicals is an attractive strategy for greenhouse gas mitigation and carbon recycle. Carbon material is one of most promising electrocatalysts but its product selectivity is limited by few modulating approaches for active sites. Herein, the predominant pyridinic N-B sites (accounting for 80% to all N species) are fabricated in hierarchically porous structure of graphene nanoribbons/amorphous carbon. The graphene nanoribbons and porous structure can accelerate electron and ion/gas transport during CO2RR, respectively. This carbon electrocatalyst exhibits excellent selectivity toward CO2 reduction to CH4 with the faradaic efficiency of 68% at -0.50 V vs. RHE. As demonstrated by density functional theory, a proper adsorbed energy of *CO and *CH2O are generated on the pyridinic N-B site resulting into high CH4 selectivity. Therefore, this study provides a novel method to modulate active sites of carbon-based electrocatalyst to obtain high CH4 selectivity.
Electrochemical reduction of CO2 (CO2RR) to value-added chemicals is an attractive strategy for greenhouse gas mitigation and carbon recycle. Carbon material is one of most promising electrocatalysts but its product selectivity is limited by few modulating approaches for active sites. Herein, the predominant pyridinic N-B sites (accounting for 80% to all N species) are fabricated in hierarchically porous structure of graphene nanoribbons/amorphous carbon. The graphene nanoribbons and porous structure can accelerate electron and ion/gas transport during CO2RR, respectively. This carbon electrocatalyst exhibits excellent selectivity toward CO2 reduction to CH4 with the faradaic efficiency of 68% at -0.50 V vs. RHE. As demonstrated by density functional theory, a proper adsorbed energy of *CO and *CH2O are generated on the pyridinic N-B site resulting into high CH4 selectivity. Therefore, this study provides a novel method to modulate active sites of carbon-based electrocatalyst to obtain high CH4 selectivity.
2023, 34(8): 108122
doi: 10.1016/j.cclet.2022.108122
Abstract:
By considering the exceptional properties of supramolecular, noble metals (NM) and magnetic nanoparticles (NPs), we successfully synthesized a novel magnetic, metals and supramolecular composite. Briefly, the Fe3O4@SiO2 core-shell spheres were first modified with gold (Au) and palladium (Pd) NPs and then with mono-6-thio-β-cyclodextrin (SH-β-CD). The synthesized Fe3O4@SiO2-Au-Pd@SH-β-CD nanocomposite shows a good magnetic response (42.3 emu/g). The nanocomposite showed good performance for the reductive degradation of rhodamine B (RhB) and 4-nitrophenol (4-NP). The calculated rate constant (k) values for the reduction of 4-NP and RhB were 0.062± 0.02 s−1 and 0.027± 0.01 s−1, respectively. The high catalytical performance was supposed to be due to the host-guest interaction of β-CD and also due to the NM synergic effect. The nanocomposite structural and chemical morphology was investigated by various spectroscopic techniques. Furthermore, the catalyst was recycled six times and it maintains morphology, chemical nature, and high magnetic behavior, as demonstrated by FTIR and TEM analysis of the recycled catalyst. These results demonstrate a very efficient, cost-effective, and recyclable catalyst in the field of catalysis technology development.
By considering the exceptional properties of supramolecular, noble metals (NM) and magnetic nanoparticles (NPs), we successfully synthesized a novel magnetic, metals and supramolecular composite. Briefly, the Fe3O4@SiO2 core-shell spheres were first modified with gold (Au) and palladium (Pd) NPs and then with mono-6-thio-β-cyclodextrin (SH-β-CD). The synthesized Fe3O4@SiO2-Au-Pd@SH-β-CD nanocomposite shows a good magnetic response (42.3 emu/g). The nanocomposite showed good performance for the reductive degradation of rhodamine B (RhB) and 4-nitrophenol (4-NP). The calculated rate constant (k) values for the reduction of 4-NP and RhB were 0.062± 0.02 s−1 and 0.027± 0.01 s−1, respectively. The high catalytical performance was supposed to be due to the host-guest interaction of β-CD and also due to the NM synergic effect. The nanocomposite structural and chemical morphology was investigated by various spectroscopic techniques. Furthermore, the catalyst was recycled six times and it maintains morphology, chemical nature, and high magnetic behavior, as demonstrated by FTIR and TEM analysis of the recycled catalyst. These results demonstrate a very efficient, cost-effective, and recyclable catalyst in the field of catalysis technology development.
2023, 34(8): 108125
doi: 10.1016/j.cclet.2022.108125
Abstract:
As a representative of chronic wounds, the long-term high levels of oxidative stress and blood sugar in chronic diabetic wounds lead to serious complications, making them the biggest challenge in the research on wound healing. Many edible natural biomaterials rich in terpenes, phenols, and flavonoids can act as efficient antioxidants. In this study, okra extract was selected as the main component of a wound dressing. The okra extracts obtained via different methods comprehensively maintained the bioactivity of multiple molecules. The robust antioxidant properties of okra significantly reduced intracellular reactive oxygen species production, thereby accelerating the wound healing process. The results showed that okra extracts and their hydrogel dressings increased cell migration, angiogenesis, and re-epithelization of the chronic wound area, considerably promoting wound remodeling in diabetic rats. Therefore, okra-based hydrogels are promising candidates for skin regeneration and wider tissue engineering applications.
As a representative of chronic wounds, the long-term high levels of oxidative stress and blood sugar in chronic diabetic wounds lead to serious complications, making them the biggest challenge in the research on wound healing. Many edible natural biomaterials rich in terpenes, phenols, and flavonoids can act as efficient antioxidants. In this study, okra extract was selected as the main component of a wound dressing. The okra extracts obtained via different methods comprehensively maintained the bioactivity of multiple molecules. The robust antioxidant properties of okra significantly reduced intracellular reactive oxygen species production, thereby accelerating the wound healing process. The results showed that okra extracts and their hydrogel dressings increased cell migration, angiogenesis, and re-epithelization of the chronic wound area, considerably promoting wound remodeling in diabetic rats. Therefore, okra-based hydrogels are promising candidates for skin regeneration and wider tissue engineering applications.
2023, 34(8): 108126
doi: 10.1016/j.cclet.2022.108126
Abstract:
Spatial configuration has a significant effect on chemical self-assembly. However, the importance of spatial configuration in supramolecular adhesive materials has been frequently ignored. In this study, the effects of the spatial configuration on cohesion and adhesion were investigated. Owing to the diversities of the chemical structures and assembly patterns, 1,2-disubstituted cyclohexane derivatives were used in this combined experimental and theoretical investigation. The self-sorting assembly of enantiopure isomers improved cohesion but had a negative effect on adhesion. In contrast, racemic mixtures displayed stronger adhesion effects. Moreover, it was proven that the cis-configuration was more favorable for supramolecular adhesion than the trans-counterpart. In addition, the influence of the spatial configuration of 1,2-disubstituted cyclohexane derivatives could be effectively mitigated by hydrogen bond donors or acceptors. The addition of natural acids yielded three-dimensional polymeric networks, in which the spatial configuration was not the decisive factor for supramolecular adhesion.
Spatial configuration has a significant effect on chemical self-assembly. However, the importance of spatial configuration in supramolecular adhesive materials has been frequently ignored. In this study, the effects of the spatial configuration on cohesion and adhesion were investigated. Owing to the diversities of the chemical structures and assembly patterns, 1,2-disubstituted cyclohexane derivatives were used in this combined experimental and theoretical investigation. The self-sorting assembly of enantiopure isomers improved cohesion but had a negative effect on adhesion. In contrast, racemic mixtures displayed stronger adhesion effects. Moreover, it was proven that the cis-configuration was more favorable for supramolecular adhesion than the trans-counterpart. In addition, the influence of the spatial configuration of 1,2-disubstituted cyclohexane derivatives could be effectively mitigated by hydrogen bond donors or acceptors. The addition of natural acids yielded three-dimensional polymeric networks, in which the spatial configuration was not the decisive factor for supramolecular adhesion.
2023, 34(8): 108129
doi: 10.1016/j.cclet.2023.108129
Abstract:
Exosomes offer ideal biomarkers for liquid biopsies. However, high-efficient capture of exosomes has been proven to be extreme challenging. Here, we report a soluble pH-responsive host-guest-based nanosystem (pH-HGN) for homogeneous isolation of exosomes around physiological pH. The pH-HGN consists of two specifically functionalized modules. First, a pH-responsive module, poly-dimethylaminoethyl methacrylate, provides homogeneous capture circumstances and sharp pH-triggered self-assembly separation in aqueous solution to improve capture efficiency and reduce nonspecific adsorption. Second, a host-guest module, poly-acrylamide azobenzene and β-cyclodextrin linked with exosomes-specific antibody, could act as the "cleavable bridge" to specific capture and subsequent rapid release of captured exosomes through host-guest interaction between β-cyclodextrin and AAAB moieties. The pH-HGN offered high capture efficiencies for exosomes from two different cell lines, which were 90.2% ± 0.28% and 87.0% ± 4.6% for H1299 and MCF-7 cell-derived exosomes, respectively. The purity of isolated exosomes was (1.49 ± 0.71) × 1011 particles/μg, which was 4.1 times higher compared with the gold standard ultracentrifugation (UC) method. Furthermore, the isolated exosomes via the pH-HGN can preserve well integrity and biological activity. The developed pH-HGN was further successfully applied to differentiate lung cancer patients from healthy persons. These findings indicated that pH-HGN is a promising strategy in exosomes-based research and downstream applications.
Exosomes offer ideal biomarkers for liquid biopsies. However, high-efficient capture of exosomes has been proven to be extreme challenging. Here, we report a soluble pH-responsive host-guest-based nanosystem (pH-HGN) for homogeneous isolation of exosomes around physiological pH. The pH-HGN consists of two specifically functionalized modules. First, a pH-responsive module, poly-dimethylaminoethyl methacrylate, provides homogeneous capture circumstances and sharp pH-triggered self-assembly separation in aqueous solution to improve capture efficiency and reduce nonspecific adsorption. Second, a host-guest module, poly-acrylamide azobenzene and β-cyclodextrin linked with exosomes-specific antibody, could act as the "cleavable bridge" to specific capture and subsequent rapid release of captured exosomes through host-guest interaction between β-cyclodextrin and AAAB moieties. The pH-HGN offered high capture efficiencies for exosomes from two different cell lines, which were 90.2% ± 0.28% and 87.0% ± 4.6% for H1299 and MCF-7 cell-derived exosomes, respectively. The purity of isolated exosomes was (1.49 ± 0.71) × 1011 particles/μg, which was 4.1 times higher compared with the gold standard ultracentrifugation (UC) method. Furthermore, the isolated exosomes via the pH-HGN can preserve well integrity and biological activity. The developed pH-HGN was further successfully applied to differentiate lung cancer patients from healthy persons. These findings indicated that pH-HGN is a promising strategy in exosomes-based research and downstream applications.
2023, 34(8): 108132
doi: 10.1016/j.cclet.2023.108132
Abstract:
DNA-encoded chemical libraries technology has become a novel approach to finding hit compounds in early drug discovery. The chemical space in a DEL would be expanded to realize its full potential, especially when integrating privileged scaffold dihydroquinazoline that has demonstrated a variety of diverse bioactivities. Driven by the requirement of parallel combinatorial synthesis, we here report a facile synthesis of on-DNA dihydroquinazolinone from aldehyde and anthranilamide. This DNA-compatible reaction was promoted by antimony trichloride, which has been proven to accelerate the reaction and improve conversions. Notably, the broad substrate scope of aldehydes and anthranilamides was explored under the mild reaction condition to achieve moderate-to-excellent conversion yields. We further applied the reaction into on-DNA macrocyclization, obtaining macrocycles embedded dihydroquinazolinone scaffold in synthetically useful conversion yields.
DNA-encoded chemical libraries technology has become a novel approach to finding hit compounds in early drug discovery. The chemical space in a DEL would be expanded to realize its full potential, especially when integrating privileged scaffold dihydroquinazoline that has demonstrated a variety of diverse bioactivities. Driven by the requirement of parallel combinatorial synthesis, we here report a facile synthesis of on-DNA dihydroquinazolinone from aldehyde and anthranilamide. This DNA-compatible reaction was promoted by antimony trichloride, which has been proven to accelerate the reaction and improve conversions. Notably, the broad substrate scope of aldehydes and anthranilamides was explored under the mild reaction condition to achieve moderate-to-excellent conversion yields. We further applied the reaction into on-DNA macrocyclization, obtaining macrocycles embedded dihydroquinazolinone scaffold in synthetically useful conversion yields.
2023, 34(8): 108164
doi: 10.1016/j.cclet.2023.108164
Abstract:
The organic carbon source coating LiFexMn1-xPO4 suffers from the problem of non-uniform carbon cladding. Too thick carbon cladding layer instead hinders the de-embedding of lithium ions. In this paper, we choose cornstalk as the carbon source, then LiFe0.5Mn0.5PO4@cornstalk-C (LFMP@C-C) with 3D anchoring structure is prepared by the solvothermal method. The results show that the LFMP with cornstalk as the carbon source has better performance compared to the sucrose-coated LFMP material (LFMP@C). The discharge capacity of LFMP@C-C is 116 mAh/g for the first cycle at 1 C and the capacity retention rate is 94.0% after 500 cycles, and the discharge capacity of LFMP@C-C is more than 17.17% higher than that of LFMP@C.
The organic carbon source coating LiFexMn1-xPO4 suffers from the problem of non-uniform carbon cladding. Too thick carbon cladding layer instead hinders the de-embedding of lithium ions. In this paper, we choose cornstalk as the carbon source, then LiFe0.5Mn0.5PO4@cornstalk-C (LFMP@C-C) with 3D anchoring structure is prepared by the solvothermal method. The results show that the LFMP with cornstalk as the carbon source has better performance compared to the sucrose-coated LFMP material (LFMP@C). The discharge capacity of LFMP@C-C is 116 mAh/g for the first cycle at 1 C and the capacity retention rate is 94.0% after 500 cycles, and the discharge capacity of LFMP@C-C is more than 17.17% higher than that of LFMP@C.
2023, 34(8): 108507
doi: 10.1016/j.cclet.2023.108507
Abstract:
Thiophenol (PhSH) is an important raw material for organic synthesis, while its high toxicity to organisms makes it an environmental pollutant. Therefore, it is crucial to accurately detect PhSH and explore its metabolic process in the living system. Herein, a near-infrared (NIR) fluorescent probe TEM-FB was developed for sensing PhSH with a turn-on fluorescent signal at 719 nm and a large Stokes shift (198 nm) based on generating the intramolecular charge transfer (ICT) process. TEM-FB shows high specificity and significant sensitivity towards PhSH (detection limit: 10 nmol/L) via the aromatic nucleophilic substitution mechanism. Furthermore, it was successfully applied to image PhSH in multiple cell lines and in zebrafish. Notably, we revealed the oxidative stress process caused by PhSH and demonstrated that the hydrogen peroxide (H2O2) in cells would alleviate the poisonousness from exogenous PhSH for the first time. This work provides a promising bioimaging tool for monitoring PhSH in living systems and visualizing the process of oxidative stress induced by PhSH.
Thiophenol (PhSH) is an important raw material for organic synthesis, while its high toxicity to organisms makes it an environmental pollutant. Therefore, it is crucial to accurately detect PhSH and explore its metabolic process in the living system. Herein, a near-infrared (NIR) fluorescent probe TEM-FB was developed for sensing PhSH with a turn-on fluorescent signal at 719 nm and a large Stokes shift (198 nm) based on generating the intramolecular charge transfer (ICT) process. TEM-FB shows high specificity and significant sensitivity towards PhSH (detection limit: 10 nmol/L) via the aromatic nucleophilic substitution mechanism. Furthermore, it was successfully applied to image PhSH in multiple cell lines and in zebrafish. Notably, we revealed the oxidative stress process caused by PhSH and demonstrated that the hydrogen peroxide (H2O2) in cells would alleviate the poisonousness from exogenous PhSH for the first time. This work provides a promising bioimaging tool for monitoring PhSH in living systems and visualizing the process of oxidative stress induced by PhSH.
2023, 34(8): 108512
doi: 10.1016/j.cclet.2023.108512
Abstract:
High-performance and low-cost gas sensors are highly desirable and involved in industrial production and environmental detection. The combination of highly conductive MXene and metal oxide materials is a promising strategy to further improve the sensing performances. In this study, the hollow SnO2 nanospheres and few-layer MXene are assembled rationally via facile electrostatic synthesis processes, then the SnO2/Ti3C2Tx nanocomposites were obtained. Compared with that based on either pure SnO2 nanoparticles or hollow nanospheres of SnO2, the SnO2/Ti3C2Tx composite-based sensor exhibits much better sensing performances such as higher response (36.979), faster response time (5 s), and much improved selectivity as well as stability (15 days) to 100 ppm C2H5OH at low working temperature (200 ℃). The improved sensing performances are mainly attributed to the large specific surface area and significantly increased oxygen vacancy concentration, which provides a large number of active sites for gas adsorption and surface catalytic reaction. In addition, the heterostructure interfaces between SnO2 hollow spheres and MXene layers are beneficial to gas sensing behaviors due to the synergistic effect.
High-performance and low-cost gas sensors are highly desirable and involved in industrial production and environmental detection. The combination of highly conductive MXene and metal oxide materials is a promising strategy to further improve the sensing performances. In this study, the hollow SnO2 nanospheres and few-layer MXene are assembled rationally via facile electrostatic synthesis processes, then the SnO2/Ti3C2Tx nanocomposites were obtained. Compared with that based on either pure SnO2 nanoparticles or hollow nanospheres of SnO2, the SnO2/Ti3C2Tx composite-based sensor exhibits much better sensing performances such as higher response (36.979), faster response time (5 s), and much improved selectivity as well as stability (15 days) to 100 ppm C2H5OH at low working temperature (200 ℃). The improved sensing performances are mainly attributed to the large specific surface area and significantly increased oxygen vacancy concentration, which provides a large number of active sites for gas adsorption and surface catalytic reaction. In addition, the heterostructure interfaces between SnO2 hollow spheres and MXene layers are beneficial to gas sensing behaviors due to the synergistic effect.
2023, 34(8): 108572
doi: 10.1016/j.cclet.2023.108572
Abstract:
Ammonium vanadate compounds featuring large capacity, superior rate capability and light weight are regarded as promising cathode materials for aqueous zinc ion batteries (AZIBs). However, the controllable synthesis of desired ammonium vanadates remains a challenge. Herein, various ammonium vanadate compounds were successfully prepared by taking advantage of ethylene glycol (EG) regulated polyol-reduction strategy and solvent effect via hydrothermal reaction. The morphology and crystalline phase of resultant products show an evolution from dendritic (NH4)2V6O16 to rod-like NH4V4O10 and finally to lamellar (NH4)2V4O9 as increasing the amount of EG. Specifically, the NH4V4O10 product exhibits a high initial capacity of 427.5 mAh/g at 0.1 A/g and stable cycling with a capacity retention of 90.4% after 5000 cycles at 10 A/g. The relatively excellent electrochemical performances of NH4V4O10 can be ascribed to the stable open-framework layered structure, favorable (001) interplanar spacing, and peculiar rod-like morphology, which are beneficial to the highly reversible Zn2+ storage behaviors. This work offers a unique way for the rational design of high-performance cathode materials for AZIBs.
Ammonium vanadate compounds featuring large capacity, superior rate capability and light weight are regarded as promising cathode materials for aqueous zinc ion batteries (AZIBs). However, the controllable synthesis of desired ammonium vanadates remains a challenge. Herein, various ammonium vanadate compounds were successfully prepared by taking advantage of ethylene glycol (EG) regulated polyol-reduction strategy and solvent effect via hydrothermal reaction. The morphology and crystalline phase of resultant products show an evolution from dendritic (NH4)2V6O16 to rod-like NH4V4O10 and finally to lamellar (NH4)2V4O9 as increasing the amount of EG. Specifically, the NH4V4O10 product exhibits a high initial capacity of 427.5 mAh/g at 0.1 A/g and stable cycling with a capacity retention of 90.4% after 5000 cycles at 10 A/g. The relatively excellent electrochemical performances of NH4V4O10 can be ascribed to the stable open-framework layered structure, favorable (001) interplanar spacing, and peculiar rod-like morphology, which are beneficial to the highly reversible Zn2+ storage behaviors. This work offers a unique way for the rational design of high-performance cathode materials for AZIBs.
2023, 34(8): 107968
doi: 10.1016/j.cclet.2022.107968
Abstract:
Benefitting from the development of non-fullerene acceptors (NFAs), remarkable advances have been achieved with the power conversion efficiency (PCE) exceeding 19% over the last few years. However, the major achievement comes from fused ring electron acceptors (FREAs) with complex structures, leading to high cost. Hence, it is urgent to design new materials to resolve the cost issues concerning basic commercial requirements of organic solar cells. Recently, great progress has been made in fully non-fused ring electron acceptors (NFREAs) with only single-aromatic ring in the electron-donating core, which might achieve a fine balance between the efficiency and cost, thus accelerating the commercial application of organic solar cells. Therefore, this article summarizes the recent advances of fully NFREAs with efficiency over 10%, which may provide a guidance for developing the cost-effective solar cells.
Benefitting from the development of non-fullerene acceptors (NFAs), remarkable advances have been achieved with the power conversion efficiency (PCE) exceeding 19% over the last few years. However, the major achievement comes from fused ring electron acceptors (FREAs) with complex structures, leading to high cost. Hence, it is urgent to design new materials to resolve the cost issues concerning basic commercial requirements of organic solar cells. Recently, great progress has been made in fully non-fused ring electron acceptors (NFREAs) with only single-aromatic ring in the electron-donating core, which might achieve a fine balance between the efficiency and cost, thus accelerating the commercial application of organic solar cells. Therefore, this article summarizes the recent advances of fully NFREAs with efficiency over 10%, which may provide a guidance for developing the cost-effective solar cells.
2023, 34(8): 107996
doi: 10.1016/j.cclet.2022.107996
Abstract:
The rapid evolution of portable and wearable electronic devices has fueled the development of smart functional textiles that are able to conduct electricity, sense body movements, or store energy. One main challenge inhibiting the further development of functional textile-based electronics is the lack of robust functional fibers with suitable electrical, electrochemical and sensing functionalities. MXenes, an emerging family of two-dimensional (2D) materials, have shown to be promising candidates for producing functional fibers due to their exceptional electrical and electrochemical properties combined with solution processability. The unique ability of MXenes to readily form liquid crystal phases in various solvents has allowed them to generate additive-free fibers using a wet spinning process. In this work, we review the recent exciting developments in the fabrication of neat MXenes fibers and present a critical evaluation of practical challenges in MXenes processing that influence the macroscale material properties and the performance of the subsequent devices. We also provide our assessment for the future opportunities and challenges in producing MXene fibers to help pave the way for their widespread use in advanced wearable applications.
The rapid evolution of portable and wearable electronic devices has fueled the development of smart functional textiles that are able to conduct electricity, sense body movements, or store energy. One main challenge inhibiting the further development of functional textile-based electronics is the lack of robust functional fibers with suitable electrical, electrochemical and sensing functionalities. MXenes, an emerging family of two-dimensional (2D) materials, have shown to be promising candidates for producing functional fibers due to their exceptional electrical and electrochemical properties combined with solution processability. The unique ability of MXenes to readily form liquid crystal phases in various solvents has allowed them to generate additive-free fibers using a wet spinning process. In this work, we review the recent exciting developments in the fabrication of neat MXenes fibers and present a critical evaluation of practical challenges in MXenes processing that influence the macroscale material properties and the performance of the subsequent devices. We also provide our assessment for the future opportunities and challenges in producing MXene fibers to help pave the way for their widespread use in advanced wearable applications.
2023, 34(8): 107999
doi: 10.1016/j.cclet.2022.107999
Abstract:
Molecular oxygen within Polyoxometalates (POMs) based compounds are ideal oxidants with high atom economy and its use results in the production of water as the only byproduct. Significant progress has been made in the development of catalytic methods for aerobic alcohol oxidation to have aldehydes and ketones with POMs based compounds. They are alternative to the use of traditional hypervalent iodine catalyst systems which are with molecular oxygen as a terminal oxidant. Further, POMs based catalysts can be applied to catalytic reactions with different modes of energization such as thermocatalysis, photocatalysis and electrocatalysis. This review summarizes the frontier advances in polyoxometalates for catalytic alcohol selective oxidation in thermocatalytic, electrocatalytic, and photocatalytic applications. The three advantages of POM catalysts in terms of performance, economy, and environmental protection are highlighted. These include the use of sol-gel and electrostatic assembly methods to increase the reaction surface area, reduce the use of precious metals, and improve the stability of POMs catalysts. The field of selective alcohol oxidation is advanced. Finally, the challenges of preparing more efficient and "green" catalysts are presented.
Molecular oxygen within Polyoxometalates (POMs) based compounds are ideal oxidants with high atom economy and its use results in the production of water as the only byproduct. Significant progress has been made in the development of catalytic methods for aerobic alcohol oxidation to have aldehydes and ketones with POMs based compounds. They are alternative to the use of traditional hypervalent iodine catalyst systems which are with molecular oxygen as a terminal oxidant. Further, POMs based catalysts can be applied to catalytic reactions with different modes of energization such as thermocatalysis, photocatalysis and electrocatalysis. This review summarizes the frontier advances in polyoxometalates for catalytic alcohol selective oxidation in thermocatalytic, electrocatalytic, and photocatalytic applications. The three advantages of POM catalysts in terms of performance, economy, and environmental protection are highlighted. These include the use of sol-gel and electrostatic assembly methods to increase the reaction surface area, reduce the use of precious metals, and improve the stability of POMs catalysts. The field of selective alcohol oxidation is advanced. Finally, the challenges of preparing more efficient and "green" catalysts are presented.
2023, 34(8): 108049
doi: 10.1016/j.cclet.2022.108049
Abstract:
The unique structural features represented by micro-nanoneedle tip structure reflect wonderful physical and chemical properties. The tip effect includes the concentration of energy such as electrons, photons and magnetism in the tip region, which has promising applications in the fields of energy conversion, water capture, environmental restoration and so on. In this review, a comprehensive and systematic summary of the latest advances in the application of the tip effect in different fields is provided. Utilizing advanced Finite Difference Time Domain simulation, we further propose our understanding of the fundamental mechanism of the tip effect induced by micro-nanostructure. However, we need to forge the present study to further reveal the essential law of the tip effect from the perspective of theoretical calculations. This review would provide a solid foundation for further development and application of the tip effect.
The unique structural features represented by micro-nanoneedle tip structure reflect wonderful physical and chemical properties. The tip effect includes the concentration of energy such as electrons, photons and magnetism in the tip region, which has promising applications in the fields of energy conversion, water capture, environmental restoration and so on. In this review, a comprehensive and systematic summary of the latest advances in the application of the tip effect in different fields is provided. Utilizing advanced Finite Difference Time Domain simulation, we further propose our understanding of the fundamental mechanism of the tip effect induced by micro-nanostructure. However, we need to forge the present study to further reveal the essential law of the tip effect from the perspective of theoretical calculations. This review would provide a solid foundation for further development and application of the tip effect.
2023, 34(8): 108050
doi: 10.1016/j.cclet.2022.108050
Abstract:
Single atom catalysts (SACs) have become the frontier research fields in catalysis. The M1-Nx-Cy based SACs, wherein single metal atoms (M1) are stabilized by N-doped carbonaceous materials, have provided new opportunities for catalysis due to their high reactivity, maximized atomic utilization, and high selectivity. In this review, the fabrication methods of M1-Nx-Cy based SACs via support anchoring strategy and coordination design strategy are summarized to help the readers understand the interaction mechanism of single atoms and support. Then, characterization technologies for identifying single metal atoms are presented. Besides, the environmental applications including management of harmful gases, water purification are discussed. Finally, future opportunities and challenges for preparation strategies, mechanisms and applications are concluded. We conclude this review by emphasizing the fact that M1-Nx-Cy based SACs has the potential to become an important candidate for solving current and future environmental pollution problems.
Single atom catalysts (SACs) have become the frontier research fields in catalysis. The M1-Nx-Cy based SACs, wherein single metal atoms (M1) are stabilized by N-doped carbonaceous materials, have provided new opportunities for catalysis due to their high reactivity, maximized atomic utilization, and high selectivity. In this review, the fabrication methods of M1-Nx-Cy based SACs via support anchoring strategy and coordination design strategy are summarized to help the readers understand the interaction mechanism of single atoms and support. Then, characterization technologies for identifying single metal atoms are presented. Besides, the environmental applications including management of harmful gases, water purification are discussed. Finally, future opportunities and challenges for preparation strategies, mechanisms and applications are concluded. We conclude this review by emphasizing the fact that M1-Nx-Cy based SACs has the potential to become an important candidate for solving current and future environmental pollution problems.
2023, 34(8): 108060
doi: 10.1016/j.cclet.2022.108060
Abstract:
Dentin hypersensitivity (DH) associated with dentinal tubule exposure is one of the most common causes of toothache with a rapid onset and short duration. Medication, filling repair, laser irradiation, crown therapy, and desensitizing toothpaste are standard clinical treatment strategies, but unsatisfactory treatment modalities are marked by long-term administration, poor dentinal tubule closure, microleakage, and the development of secondary caries. To improve the treatment efficiency of DH, numerous organic or inorganic biomaterials have been developed to relieve toothache and reverse the instability of desensitization. Biomaterials are expected to participate in dental remineralization to achieve desensitization. This review discusses various biomaterials for DH therapy based on different desensitization mechanisms, including dentinal tubule closure and dental nerve blockade, and presents a perspective on the underlying future of dentin regeneration medicine for DH therapy.
Dentin hypersensitivity (DH) associated with dentinal tubule exposure is one of the most common causes of toothache with a rapid onset and short duration. Medication, filling repair, laser irradiation, crown therapy, and desensitizing toothpaste are standard clinical treatment strategies, but unsatisfactory treatment modalities are marked by long-term administration, poor dentinal tubule closure, microleakage, and the development of secondary caries. To improve the treatment efficiency of DH, numerous organic or inorganic biomaterials have been developed to relieve toothache and reverse the instability of desensitization. Biomaterials are expected to participate in dental remineralization to achieve desensitization. This review discusses various biomaterials for DH therapy based on different desensitization mechanisms, including dentinal tubule closure and dental nerve blockade, and presents a perspective on the underlying future of dentin regeneration medicine for DH therapy.
2023, 34(8): 108075
doi: 10.1016/j.cclet.2022.108075
Abstract:
Anthropogenic carbon dioxide (CO2) emission from the combustion of fossil fuels aggravates the global greenhouse effect. The implementation of CO2 capture and transformation technologies have recently received great attention for providing a pathway in dealing with global climate change. Among these technologies, electrochemical CO2 capture technology has attracted wide attention because of its environmental friendliness and flexible operating processes. Bipolar membranes (BPMs) are considered as one of the key components in electrochemical devices, especially for electrochemical CO2 reduction and electrodialysis devices. BPMs create an alkaline environment for CO2 capture and a stable pH environment for electrocatalysis on a single electrode. The key to CO2 capture in these devices is to understand the water dissociation mechanism occurring in BPMs, which could be used for optimizing the operating conditions for CO2 capture and transformation. In this paper, the references and technologies of electrochemical CO2 capture based on BPMs are reviewed in detail, thus the challenges and opportunities are also discussed for the development of more efficient, sustainable and practical CO2 capture and transformation based on BPMs.
Anthropogenic carbon dioxide (CO2) emission from the combustion of fossil fuels aggravates the global greenhouse effect. The implementation of CO2 capture and transformation technologies have recently received great attention for providing a pathway in dealing with global climate change. Among these technologies, electrochemical CO2 capture technology has attracted wide attention because of its environmental friendliness and flexible operating processes. Bipolar membranes (BPMs) are considered as one of the key components in electrochemical devices, especially for electrochemical CO2 reduction and electrodialysis devices. BPMs create an alkaline environment for CO2 capture and a stable pH environment for electrocatalysis on a single electrode. The key to CO2 capture in these devices is to understand the water dissociation mechanism occurring in BPMs, which could be used for optimizing the operating conditions for CO2 capture and transformation. In this paper, the references and technologies of electrochemical CO2 capture based on BPMs are reviewed in detail, thus the challenges and opportunities are also discussed for the development of more efficient, sustainable and practical CO2 capture and transformation based on BPMs.
2023, 34(8): 108077
doi: 10.1016/j.cclet.2022.108077
Abstract:
Circularly polarized light (CPL) is an inherently chiral entity and is regarded as one of the possible deterministic signals that led to the evolution of homochirality in earth. Thus, CPL as an external physical field has been widely used in a technique known as absolute asymmetric synthesis, because a product enriched in one enantiomer is formed from racemic precursor molecules without the intervention of a chiral catalyst. In this review, we retrospect the historical research of CPL-induced absolute asymmetric synthesis, including chiral organic molecules, helical polymers, supramolecular assemblies, noble metal nanostructures. However, based on these results, we concluded that the chiral photon-matter interaction is very faint due to the arrangement of molecular bonds giving rise to chiral features, is over a smaller distance than the helical pitch of CPL, leading extremely small enantiomeric excess for product. Therefore, we highlight the recently emerged technology called superchiral field, in which the superchiral far-field and near-field could enhance the dissymmetry of optical field and near-field, respectively. In sum, we hope this review could bring some enlightenment to researchers and further improve the enantioselectivity of CPL-induced absolute asymmetric synthesis.
Circularly polarized light (CPL) is an inherently chiral entity and is regarded as one of the possible deterministic signals that led to the evolution of homochirality in earth. Thus, CPL as an external physical field has been widely used in a technique known as absolute asymmetric synthesis, because a product enriched in one enantiomer is formed from racemic precursor molecules without the intervention of a chiral catalyst. In this review, we retrospect the historical research of CPL-induced absolute asymmetric synthesis, including chiral organic molecules, helical polymers, supramolecular assemblies, noble metal nanostructures. However, based on these results, we concluded that the chiral photon-matter interaction is very faint due to the arrangement of molecular bonds giving rise to chiral features, is over a smaller distance than the helical pitch of CPL, leading extremely small enantiomeric excess for product. Therefore, we highlight the recently emerged technology called superchiral field, in which the superchiral far-field and near-field could enhance the dissymmetry of optical field and near-field, respectively. In sum, we hope this review could bring some enlightenment to researchers and further improve the enantioselectivity of CPL-induced absolute asymmetric synthesis.
2023, 34(8): 108098
doi: 10.1016/j.cclet.2022.108098
Abstract:
Cancer immunotherapy harnesses the immune system to attack tumors and has received extensive attention in recent years. Cancer vaccines as an important branch of immunotherapy are designed for delivering tumor antigens to antigen-presenting cells (APCs) to stimulate a strong immune response to against tumors, representing a potentially therapeutic and prophylactic effect with the long-term anti-cancer benefits. Nevertheless, the disappointing outcomes of their clinical use might be attributed to dilemma in antigen selection, immunogenicity, lymph nodes (LNs) targeting ability, lysosomal escape ability, immune evasion, etc. Nanotechnology, aiming to overcome these barriers, has been utilized in cancer vaccine development for decades. Numerous preclinical and clinical studies demonstrate positive results in nanomaterials-based cancer vaccines with considerable improvement in the vaccine efficacy. In this review, we systematically introduced the characteristics of nanovaccines and highlighted the different types of nanomaterials used for cancer vaccine design. In addition, the opportunities and challenges of the emerging nanotechnology-based cancer vaccines were discussed.
Cancer immunotherapy harnesses the immune system to attack tumors and has received extensive attention in recent years. Cancer vaccines as an important branch of immunotherapy are designed for delivering tumor antigens to antigen-presenting cells (APCs) to stimulate a strong immune response to against tumors, representing a potentially therapeutic and prophylactic effect with the long-term anti-cancer benefits. Nevertheless, the disappointing outcomes of their clinical use might be attributed to dilemma in antigen selection, immunogenicity, lymph nodes (LNs) targeting ability, lysosomal escape ability, immune evasion, etc. Nanotechnology, aiming to overcome these barriers, has been utilized in cancer vaccine development for decades. Numerous preclinical and clinical studies demonstrate positive results in nanomaterials-based cancer vaccines with considerable improvement in the vaccine efficacy. In this review, we systematically introduced the characteristics of nanovaccines and highlighted the different types of nanomaterials used for cancer vaccine design. In addition, the opportunities and challenges of the emerging nanotechnology-based cancer vaccines were discussed.
2023, 34(8): 108105
doi: 10.1016/j.cclet.2022.108105
Abstract:
1,4-Enyne units are ubiquitous skeletons in biologically active molecules and natural products. Especially, they represent versatile building blocks for abundant downstream derivatizations via controllable modifications of both alkene and alkyne units independently. Recently, great efforts have been made to establish efficient protocols to achieve optically active 1,4-enynes. Considering the enormous application potential of enantioenriched 1,4-enyne units but no related review on this topic has been described, here we aim to provide a comprehensive summary on the catalytic methods established for enantioselective constructions of these intriguing skeletons. According to the reaction types, this review is divided into five parts, including asymmetric allylic substitution, asymmetric propargylic substitution, asymmetric alkynylallylic substitution, asymmetric hydroalkynylation and asymmetric 1,2-addition of alkynes to conjugated imines or ketones.
1,4-Enyne units are ubiquitous skeletons in biologically active molecules and natural products. Especially, they represent versatile building blocks for abundant downstream derivatizations via controllable modifications of both alkene and alkyne units independently. Recently, great efforts have been made to establish efficient protocols to achieve optically active 1,4-enynes. Considering the enormous application potential of enantioenriched 1,4-enyne units but no related review on this topic has been described, here we aim to provide a comprehensive summary on the catalytic methods established for enantioselective constructions of these intriguing skeletons. According to the reaction types, this review is divided into five parts, including asymmetric allylic substitution, asymmetric propargylic substitution, asymmetric alkynylallylic substitution, asymmetric hydroalkynylation and asymmetric 1,2-addition of alkynes to conjugated imines or ketones.
2023, 34(8): 108123
doi: 10.1016/j.cclet.2022.108123
Abstract:
Derivatives of piperazine, which is one of the most important heterocycles, are often used as linkers to connect active substructures that show promising bioactivities, especially in the field of agrochemicals. From 2000 to 2022, many piperazine-containing compounds were found to exhibit excellent activities against fungi, bacteria, insects, plant viruses, and weeds and have also been used as plant growth regulators. Currently, the development of novel pesticides to prevent the invasion of crop pathogens and ensure the quality and yields of crops is still needed. We herein investigated and summarized the role that piperazine plays in the discovery of pesticides to provide a comprehensive summary of the broad activities of piperazine derivatives in agricultural applications and offer a potential reference for novel pesticide design using piperazine-containing compounds. Moreover, structure–activity relationships (SARs) analyses of bioactive piperazine-containing compounds are also discussed for a deeper understanding.
Derivatives of piperazine, which is one of the most important heterocycles, are often used as linkers to connect active substructures that show promising bioactivities, especially in the field of agrochemicals. From 2000 to 2022, many piperazine-containing compounds were found to exhibit excellent activities against fungi, bacteria, insects, plant viruses, and weeds and have also been used as plant growth regulators. Currently, the development of novel pesticides to prevent the invasion of crop pathogens and ensure the quality and yields of crops is still needed. We herein investigated and summarized the role that piperazine plays in the discovery of pesticides to provide a comprehensive summary of the broad activities of piperazine derivatives in agricultural applications and offer a potential reference for novel pesticide design using piperazine-containing compounds. Moreover, structure–activity relationships (SARs) analyses of bioactive piperazine-containing compounds are also discussed for a deeper understanding.
2023, 34(8): 108124
doi: 10.1016/j.cclet.2022.108124
Abstract:
The design and synthesis of photoactive macrocyclic molecules continue to attract attention because such species play important roles in supramolecular chemistry as well as photoelectronic applications. Donor-acceptor (D-A) conjugated macrocycles are an emerging class of photoactive molecules due to their D-A conjugated structural characteristics and tunable optical properties. In addition, the well-defined cavities in such D-A macrocycles endow them with versatile host-guest properties. In this review, we provide a comprehensive summary of D-A conjugated macrocycle chemistry, detailing recent progress in the area of synthetic methods, optical properties, host-guest chemistry and applications of the underlying chemistry to chemical sensors, bioimaging and photoelectronic devices. Our objective is to provide not only a review of the fundamental findings, but also to outline future research directions where D-A conjugated macrocycles and their constructs may have a role to play.
The design and synthesis of photoactive macrocyclic molecules continue to attract attention because such species play important roles in supramolecular chemistry as well as photoelectronic applications. Donor-acceptor (D-A) conjugated macrocycles are an emerging class of photoactive molecules due to their D-A conjugated structural characteristics and tunable optical properties. In addition, the well-defined cavities in such D-A macrocycles endow them with versatile host-guest properties. In this review, we provide a comprehensive summary of D-A conjugated macrocycle chemistry, detailing recent progress in the area of synthetic methods, optical properties, host-guest chemistry and applications of the underlying chemistry to chemical sensors, bioimaging and photoelectronic devices. Our objective is to provide not only a review of the fundamental findings, but also to outline future research directions where D-A conjugated macrocycles and their constructs may have a role to play.
2023, 34(8): 108278
doi: 10.1016/j.cclet.2023.108278
Abstract:
Metal-based catalysts with different site sizes (e.g., metal nanoparticles (NPs) and single atom catalysts (SACs)) demonstrated outstanding catalytic activities in versatile Fenton-like reactions. However, the surface/structural instability is a critical issue, which will result in rapid passivation in Fenton-like reaction and fail in long-term operation. The catalytic stability of the catalysts with different metal sizes considering versatile peroxides (H2O2, peroxymonosulfate (PMS), and peroxodisulfate (PDS)) should be analyzed. In addition, strategies for catalyst regeneration and recyclability improvement are also important to realize the metal-based catalysts for practical applications. In this review, catalytic stability of catalysts with different metal sizes in the backgrounds of versatile peroxides and water matrixes in Fenton-like reactions were first evaluated. Regeneration of metal catalytic sites with different methods were also reviewed. Finally, major challenges and development of methods concerning the stability and regeneration of metal catalytic sites with different sizes were discussed to understand the future researches of metal catalytic sites in Fenton-like reactions.
Metal-based catalysts with different site sizes (e.g., metal nanoparticles (NPs) and single atom catalysts (SACs)) demonstrated outstanding catalytic activities in versatile Fenton-like reactions. However, the surface/structural instability is a critical issue, which will result in rapid passivation in Fenton-like reaction and fail in long-term operation. The catalytic stability of the catalysts with different metal sizes considering versatile peroxides (H2O2, peroxymonosulfate (PMS), and peroxodisulfate (PDS)) should be analyzed. In addition, strategies for catalyst regeneration and recyclability improvement are also important to realize the metal-based catalysts for practical applications. In this review, catalytic stability of catalysts with different metal sizes in the backgrounds of versatile peroxides and water matrixes in Fenton-like reactions were first evaluated. Regeneration of metal catalytic sites with different methods were also reviewed. Finally, major challenges and development of methods concerning the stability and regeneration of metal catalytic sites with different sizes were discussed to understand the future researches of metal catalytic sites in Fenton-like reactions.
2023, 34(8): 108185
doi: 10.1016/j.cclet.2023.108185
Abstract:
2023, 34(8): 108221
doi: 10.1016/j.cclet.2023.108221
Abstract:
