Precise modulation of the active layer morphology to optimize exciton dissociation and charge collection efficiency is the research priority in organic solar cells(OSCs).In this work,two novel additives,TFFB as well a...Precise modulation of the active layer morphology to optimize exciton dissociation and charge collection efficiency is the research priority in organic solar cells(OSCs).In this work,two novel additives,TFFB as well as TCFB,are proposed and doped into acceptor using layer-by-layer deposition method to realize high-performance bilayer OSCs based on D18-Cl/Y6 system.The asymmetric additive TFFB was introduced to improve molecular polarity,facilitate molecular stacking and promote film crystallization.Compared to the control devices without additive-treated,power conversion efficiency(PCE)of D18-Cl/Y6(TFFB)OSCs was increased from 18.04%to 18.85%.Furthermore,TCFB with trichloromethyl instead of trifluoromethyl caused large quadrupole moment,which further enhanced the intermolecular interactions and induced the components distribution to form a better three-dimensional morphology structure.Corresponding D18-Cl/Y6(TCFB)devices achieved an excellent PCE of 19.15%,one of the highest PCE reported for binary OSCs to date.In addition,TCFB-treated devices exhibited favorable storage stability,remaining over 95%of the original efficiency after 2500 hours of placement.This study presents a simple and valid method that utilizing the role of quadrupole moment to optimize the hierarchical morphology and improve the charge dynamics process,finally realizing highly efficient and stable OSCs.展开更多
Weak intermolecular interactions in aniline-pyrrole dimer clusters have been studied by the dispersion-corrected density functional theory(DFT) calculations. Two distinct types of hydrogen bonds are demonstrated with ...Weak intermolecular interactions in aniline-pyrrole dimer clusters have been studied by the dispersion-corrected density functional theory(DFT) calculations. Two distinct types of hydrogen bonds are demonstrated with optimized geometric structures and largest interaction energy moduli. Comprehensive spectroscopic analysis is also addressed revealing the orientation-dependent interactions by noting the altered red-shifts of the infrared and Raman activities. Then we employ natural bond orbital(NBO)analysis and atom in molecules(AIM) theory to have determined the origin and relative energetic contributions of the weak interactions in these systems. NBO and AIM calculations confirm the V-shaped dimer cluster is dominated by N.H···N and C.H···π hydrogen bonds, while the J-aggregated isomer is stabilized by N.H···π, n→π* and weak π···π* stacking interactions.The noncovalent interactions are also demonstrated via energy decomposition analysis associated with electrostatic and dispersion contributions.展开更多
The title compound N,N′-4-aminomethyl-pyromellitic diimide （4-pmpmd） crystallizes in monoclinic, space group P21/c with a = 4.785（1）, b = 6.200（1）, c = 29.907（2） A, β = 93.583（11）°, V= 885.5（2） A^3,...The title compound N,N′-4-aminomethyl-pyromellitic diimide （4-pmpmd） crystallizes in monoclinic, space group P21/c with a = 4.785（1）, b = 6.200（1）, c = 29.907（2） A, β = 93.583（11）°, V= 885.5（2） A^3, Dc = 1.494 g/cm^3, Z= 2, C22H14N4O4, Mr = 398.37,/t（MoKα） = 0.106 mm^-1 and F（000） = 412, and its structure was refined to R = 0.0469 and wR = 0.1017 for 1194 observed reflections （F0 〉 4σ（F0））. The X-ray diffraction shows the existence of the staggered strong intermolecular C-H…O （DA） hydrogen bonds between adjacent molecules, the intermo- lecular C-H…π hydrogen bonds and the weak π…π stacking interactions, leading to the formation of multi-dimensional supramolecular network based on the Z-mode conformation of the title compound.展开更多
Comprehensive Summary Helically twisted molecular architectures are critical motifs in both biology and synthetic supramolecular chemistry,with unique functional properties derived from their chiral geometries.Althoug...Comprehensive Summary Helically twisted molecular architectures are critical motifs in both biology and synthetic supramolecular chemistry,with unique functional properties derived from their chiral geometries.Although lemniscular(figure-eight)macrocycles with a noncontact crossover point have attracted increasing interest,their metallosupramolecular analogs remain underexplored,largely because of synthetic challenges that hinder precise control.展开更多
Self-assembly processes are ubiquitous in biological systems,playing essential roles in sustaining life activities.The exploration of self-assembled biomaterials(SABMs)holds great potential for advancing various field...Self-assembly processes are ubiquitous in biological systems,playing essential roles in sustaining life activities.The exploration of self-assembled biomaterials(SABMs)holds great potential for advancing various fields,particularly in biomedicine and materials science.Because of the unique reversibility and responsiveness to stimuli,dynamic covalent bonds(DCBs)and noncovalent bonds(NCBs)endow SABMs with self-healing properties,stimuli responsiveness and controllable degradation,making them highly versatile for a wide range of biomedical applications.In this article,recent advances and future trends for SABMs based on DCBs and NCBs are thoroughly reviewed.We begin by introducing the molecular principles and characteristics of DCBs and NCBs that govern the formation of SABMs.We also explore the responsive and functional features of these materials in detail.Finally,we summarize the perspectives and challenges associated with the development of SABMs in biomedical applications.We aim for this review to offer a comprehensive overview of SABMs,serving as a valuable resource for chemists and materials scientists striving to further advance the design of SABMs in biological applications.展开更多
Achieving high-performance perovskite solar modules(pero-SMs)over large areas under ambient conditions remains a significant barrier to the commercialization of perovskite photovoltaics.This challenge arises from the ...Achieving high-performance perovskite solar modules(pero-SMs)over large areas under ambient conditions remains a significant barrier to the commercialization of perovskite photovoltaics.This challenge arises from the strong solvent-perovskite coordination interactions in the hygroscopic perovskite precursor ink,which complicate the control of nucleation-growth kinetics and phase evolution during film formation in the presence of moisture,thereby hindering the formation of high-quality perovskite films.In this work,a“vip-solvent”additive strategy was developed by incorporating N,N-dimethylthioformamide(DMT)into the perovskite precursor ink to effectively modulate the coordination between the solvent and perovskite.It is demonstrated that DMT,structurally similar to the“main-solvent”system(DMF and DMSO),possesses lower coordination ability with Pb2+and forms non-covalent interactions with the primary solvents.These interactions weaken the solvent-perovskite coordination without sacrificing solubility,thereby stabilizing homogeneous nucleation and promoting direct crystallization from the sol-gel phase toα-FAPbI3.As a result,the ambient-printed FAPbI3 films exhibited high quality,with more compact grain stacking,smoother morphology,higher phase purity,and fewer defects.Consequently,the resulting perovskite solar cells(0.062 cm2)and pero-SMs(15.64 cm2)fabricated via blade coating under ambient conditions achieved remarkable power conversion efficiencies(PCEs)of 24.46%and 22.54%,respectively.展开更多
Ethane-selective adsorbents enable the direct production of high-purity C_(2)H_(4)in a single step,showcasing substantial research potential.In this work,we report the synthesis of two hydrogen-bonded organic framewor...Ethane-selective adsorbents enable the direct production of high-purity C_(2)H_(4)in a single step,showcasing substantial research potential.In this work,we report the synthesis of two hydrogen-bonded organic frameworks(HOFs),NKM-HOF-6 and NKM-HOF-7,featuring permanent microporosity.Upon treatment with hot acetone,NKM-HOF-6 undergoes a structural transformation into NKM-HOF-7,characterized by a transition from a 3D polycatenated framework to a 2D parallel displacement-stacked structure.This transformation leads to a reduction in the maximum pore size of NKM-HOF-7 and a decrease in the density of-CF_(3)groups within its channels,thereby enhancing its preferential affinity for C_(2)H_(6)over C_(2)H_(4).The adsorption capacity difference between C_(2)H_(6)and C_(2)H_(4)in NKM-HOF-7 is 11.1 cm^(3)·g^(-1),with an IAST selectivity of 1.77,surpassing the corresponding values for NKM-HOF-6(9.6 cm^(3)·g^(-1)and 1.56,respectively).Breakthrough experiments further reveal that NKM-HOF-7 achieves nearly twice the separation efficiency of NKM-HOF-6 for C_(2)H_(6)/C_(2)H_(4)(10/90,V/V)mixtures.Theoretical calculations attribute this enhanced C_(2)H_(6)affinity to the synergistic effects of optimized pore dimensions and functionalized pore surfaces in NKM-HOF-7.These findings provide critical insights for the rational design of highly efficient C_(2)H_(6)-selective adsorbents.展开更多
Theπ-πinteraction is acknowledged as the predominant factor to determine the molecular packing in organic photovoltaic materials,while other non-covalent intermolecular interactions especially theσ-πhyperconjugati...Theπ-πinteraction is acknowledged as the predominant factor to determine the molecular packing in organic photovoltaic materials,while other non-covalent intermolecular interactions especially theσ-πhyperconjugation are often ignored.Herein,a perylene diimide(PDI)derivative named FIDT-PDI is designed and synthesized to shed light into the effect of hyperconjugation on the molecular packing and further the photovoltaic performance.Dynamic NMR and 2D NOE NMR demonstrate the formation of intermolecularσ-πhyperconjugation between the C—H bond of the PDI moiety in one molecule and the phenyl sidechain in another molecule of FIDT-PDI.Benefiting from theσ-πhyperconjugation,FIDT-PDI with twisted backbone reversely exhibits more ordered packing and stronger crystallinity compared with another PDI derivative FIDTT-PDI which has better planarity,consequently achieving superior PCE and higher carrier mobility.This contribution is the first paradigm to unravel the structure-property relationship betweenσ-πhyper-conjugation of conjugated materials and corresponding photovoltaic performance.展开更多
Comprehensive Summary,The charge transport through peptides can imitate the corresponding processes in more complicated proteins,enabling us to develop high-performance bioelectronic devices and to understand the mech...Comprehensive Summary,The charge transport through peptides can imitate the corresponding processes in more complicated proteins,enabling us to develop high-performance bioelectronic devices and to understand the mechanisms of biomolecular recognition and information transfer.While charge transport modulation through individual peptides has been achieved via various covalent strategies,the intermolecular modulation is still very challenging,which may capture the charge transport between proteins.To tackle this challenge,we used well-defined self-assembled monolayers(SAMs)of oligopeptides as a model to imitate the interface of proteins and explored an interfacial amino acid strategy for charge transport modulation.We showed that non-covalently interfaced charged amino acids(e.g.,arginine)effectively attenuated the charge transport of glutamic acid terminated polyglycine peptide SAMs.By analyzing the relationship of the charge transport with the molecular frontier orbital relative to the Fermi energy level of the electrode,the molecule-electrodes coupling(Γ),and the trends in skewness and kurtosis with voltage and the dielectric constant(εr),we showed that the attenuation was from the decreasedΓand the reduced polarizability.We present an efficient strategy to modulate the charge transport of oligopeptide-SAM junctions by intermolecular interactions,which will advance our understanding of charge transport in biological systems and facilitate developing future electronics.展开更多
pH is an important stimuli-responsive signal because deprotonation-protonation process is crucial for many life functions.Photoacid is a kind of photoresponsive group that can release protons upon irradiation.This pro...pH is an important stimuli-responsive signal because deprotonation-protonation process is crucial for many life functions.Photoacid is a kind of photoresponsive group that can release protons upon irradiation.This property makes invasive pH control can be replaced by noninvasive light control.However,photoacid is rare.In this work,macrocyclic calixpyridinium was found to be used as a photoacid to release protons from acidic methylene under the irradiation of a 254 nm UV lamp.When the solution of calixpyridinium−disulfonated xantphos aggregates were irradiated by a 254 nm portable UV lamp,disulfonated xantphos was able to receive the protons released from calixpyridinium.This noninvasive photocontrolled proton transfer not only replaces an invasive pH regulation but also achieves a synergistic function.The deprotonation of calixpyridinium and the protonation of disulfonated xantphos can occur simultaneously to disrupt the aggregates.Moreover,the photoresponsive disassembly is reversible by heating.This photoresponsive material was further applied as a photocontrolled release model.In addition,a dissipative assembly was successfully designed based on this photoresponsive disassembly.This study supplies a generalized strategy to construct pH-responsive biocompatible materials with light-control properties by using macrocyclic calixpyridinium and its matched various vips in water.展开更多
One-step purification of ethylene(C_(2)H_(4))from acetylene/ethane/ethylene(C_(2)H_(2)/C_(2)H_(6)/C_(2)H_(4))ternary mixtures remains a challenging task in the chemical industry.While hydrogen-bonded organic framework...One-step purification of ethylene(C_(2)H_(4))from acetylene/ethane/ethylene(C_(2)H_(2)/C_(2)H_(6)/C_(2)H_(4))ternary mixtures remains a challenging task in the chemical industry.While hydrogen-bonded organic frameworks(HOFs)have shown promise for separating C_(2)hydrocarbons—typically favoring adsorption in the order of C_(2)H_(6)>C_(2)H_(4)>C_(2)H_(2)—existing materials have largely been limited to binary separations,particularly C_(2)H_(4)/C_(2)H_(6).Here,we report a robust HOF material,HOF-PTBA,that selectively adsorbs both C_(2)H_(2)and C_(2)H_(6),enabling one-step separation of high-purity C_(2)H_(4)from ternary C_(2)mixtures.HOF-PTBA exhibits the highest C_(2)H_(6)/C_(2)H_(4)and C_(2)H_(2)/C_(2)H_(4)adsorption ratios among all reported HOFs.Molecular simulations reveal that C_(2)H_(2)and C_(2)H_(6)form multiple strong interactions with the framework's pore walls,while C_(2)H_(4)exhibits only weak interactions,allowing it to pass through unbound.HOF-PTBA also demonstrates excellent stability under humid and acidic conditions,and can be synthesized via a simple solvent evaporation process,making it scalable and cost-effective.These features highlight its strong potential for practical application in industrial gas purification.展开更多
基金supported by the National Natural Science Foundation of China(NSFC Grant Nos.52130304,62222503 and 52073040)Sichuan Science and Technology Project(2023NSFSC1973,2024NSFSC0012,2024NSFSC1447,2025ZNSFSC1460 and 2025ZNSFSC0037)National Key R&D Program of China(2023YFB2604101).
文摘Precise modulation of the active layer morphology to optimize exciton dissociation and charge collection efficiency is the research priority in organic solar cells(OSCs).In this work,two novel additives,TFFB as well as TCFB,are proposed and doped into acceptor using layer-by-layer deposition method to realize high-performance bilayer OSCs based on D18-Cl/Y6 system.The asymmetric additive TFFB was introduced to improve molecular polarity,facilitate molecular stacking and promote film crystallization.Compared to the control devices without additive-treated,power conversion efficiency(PCE)of D18-Cl/Y6(TFFB)OSCs was increased from 18.04%to 18.85%.Furthermore,TCFB with trichloromethyl instead of trifluoromethyl caused large quadrupole moment,which further enhanced the intermolecular interactions and induced the components distribution to form a better three-dimensional morphology structure.Corresponding D18-Cl/Y6(TCFB)devices achieved an excellent PCE of 19.15%,one of the highest PCE reported for binary OSCs to date.In addition,TCFB-treated devices exhibited favorable storage stability,remaining over 95%of the original efficiency after 2500 hours of placement.This study presents a simple and valid method that utilizing the role of quadrupole moment to optimize the hierarchical morphology and improve the charge dynamics process,finally realizing highly efficient and stable OSCs.
基金supported by the National Project“Development of Advanced Scientific Instruments Based on Deep Ultraviolet Laser Source”(Y31M0112C1)the National Basic Research Program of China(2011CB808402)Z.Luo acknowledges the Young Professionals Programme in Institute of Chemistry,Chinese Academy of Sciences(ICCAS-Y3297B1261)
文摘Weak intermolecular interactions in aniline-pyrrole dimer clusters have been studied by the dispersion-corrected density functional theory(DFT) calculations. Two distinct types of hydrogen bonds are demonstrated with optimized geometric structures and largest interaction energy moduli. Comprehensive spectroscopic analysis is also addressed revealing the orientation-dependent interactions by noting the altered red-shifts of the infrared and Raman activities. Then we employ natural bond orbital(NBO)analysis and atom in molecules(AIM) theory to have determined the origin and relative energetic contributions of the weak interactions in these systems. NBO and AIM calculations confirm the V-shaped dimer cluster is dominated by N.H···N and C.H···π hydrogen bonds, while the J-aggregated isomer is stabilized by N.H···π, n→π* and weak π···π* stacking interactions.The noncovalent interactions are also demonstrated via energy decomposition analysis associated with electrostatic and dispersion contributions.
基金This work is financially supported by NNSF of China (No. 20303027)
文摘The title compound N,N′-4-aminomethyl-pyromellitic diimide （4-pmpmd） crystallizes in monoclinic, space group P21/c with a = 4.785（1）, b = 6.200（1）, c = 29.907（2） A, β = 93.583（11）°, V= 885.5（2） A^3, Dc = 1.494 g/cm^3, Z= 2, C22H14N4O4, Mr = 398.37,/t（MoKα） = 0.106 mm^-1 and F（000） = 412, and its structure was refined to R = 0.0469 and wR = 0.1017 for 1194 observed reflections （F0 〉 4σ（F0））. The X-ray diffraction shows the existence of the staggered strong intermolecular C-H…O （DA） hydrogen bonds between adjacent molecules, the intermo- lecular C-H…π hydrogen bonds and the weak π…π stacking interactions, leading to the formation of multi-dimensional supramolecular network based on the Z-mode conformation of the title compound.
基金support from the National Natural Science Foundation of China(22025107,92461302,22301040)the National Youth Top-notch Talent Support Program of China,the Shaanxi Postdoctoral Science Foundation Project(2023BSHYDZZ128)+1 种基金the Xi'an Key Laboratory of Functional Supramolecular Structure and Materialsthe FM&EM International Joint Laboratory of Northwest University.
文摘Comprehensive Summary Helically twisted molecular architectures are critical motifs in both biology and synthetic supramolecular chemistry,with unique functional properties derived from their chiral geometries.Although lemniscular(figure-eight)macrocycles with a noncontact crossover point have attracted increasing interest,their metallosupramolecular analogs remain underexplored,largely because of synthetic challenges that hinder precise control.
基金supported by the National Natural Science Foundation of China(Nos.22405212 and 22471219)the Shaanxi Fundamental Science Research Project for Chemistry&Biology(23JHZ002).
文摘Self-assembly processes are ubiquitous in biological systems,playing essential roles in sustaining life activities.The exploration of self-assembled biomaterials(SABMs)holds great potential for advancing various fields,particularly in biomedicine and materials science.Because of the unique reversibility and responsiveness to stimuli,dynamic covalent bonds(DCBs)and noncovalent bonds(NCBs)endow SABMs with self-healing properties,stimuli responsiveness and controllable degradation,making them highly versatile for a wide range of biomedical applications.In this article,recent advances and future trends for SABMs based on DCBs and NCBs are thoroughly reviewed.We begin by introducing the molecular principles and characteristics of DCBs and NCBs that govern the formation of SABMs.We also explore the responsive and functional features of these materials in detail.Finally,we summarize the perspectives and challenges associated with the development of SABMs in biomedical applications.We aim for this review to offer a comprehensive overview of SABMs,serving as a valuable resource for chemists and materials scientists striving to further advance the design of SABMs in biological applications.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFB4200302)the National Natural Science Foundation of China(Grant Nos.52325307,52273188,22075194)+1 种基金Department of Science and Technology of Jiangsu Province(No.BE2022023)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD),Collaborative Innovation Center of Suzhou Nano Science and Technology,and the Key Laboratory of Polymeric Materials Design and Synthesis for Biomedical Function,Soochow University.
文摘Achieving high-performance perovskite solar modules(pero-SMs)over large areas under ambient conditions remains a significant barrier to the commercialization of perovskite photovoltaics.This challenge arises from the strong solvent-perovskite coordination interactions in the hygroscopic perovskite precursor ink,which complicate the control of nucleation-growth kinetics and phase evolution during film formation in the presence of moisture,thereby hindering the formation of high-quality perovskite films.In this work,a“vip-solvent”additive strategy was developed by incorporating N,N-dimethylthioformamide(DMT)into the perovskite precursor ink to effectively modulate the coordination between the solvent and perovskite.It is demonstrated that DMT,structurally similar to the“main-solvent”system(DMF and DMSO),possesses lower coordination ability with Pb2+and forms non-covalent interactions with the primary solvents.These interactions weaken the solvent-perovskite coordination without sacrificing solubility,thereby stabilizing homogeneous nucleation and promoting direct crystallization from the sol-gel phase toα-FAPbI3.As a result,the ambient-printed FAPbI3 films exhibited high quality,with more compact grain stacking,smoother morphology,higher phase purity,and fewer defects.Consequently,the resulting perovskite solar cells(0.062 cm2)and pero-SMs(15.64 cm2)fabricated via blade coating under ambient conditions achieved remarkable power conversion efficiencies(PCEs)of 24.46%and 22.54%,respectively.
基金supported by the National Key Research and Development Program of China(2022YFA1502901)National Natural Science Foundation of China(22035003,22201137,and 22371137)Fundamental Research Funds for the Central Universities(63253171).
文摘Ethane-selective adsorbents enable the direct production of high-purity C_(2)H_(4)in a single step,showcasing substantial research potential.In this work,we report the synthesis of two hydrogen-bonded organic frameworks(HOFs),NKM-HOF-6 and NKM-HOF-7,featuring permanent microporosity.Upon treatment with hot acetone,NKM-HOF-6 undergoes a structural transformation into NKM-HOF-7,characterized by a transition from a 3D polycatenated framework to a 2D parallel displacement-stacked structure.This transformation leads to a reduction in the maximum pore size of NKM-HOF-7 and a decrease in the density of-CF_(3)groups within its channels,thereby enhancing its preferential affinity for C_(2)H_(6)over C_(2)H_(4).The adsorption capacity difference between C_(2)H_(6)and C_(2)H_(4)in NKM-HOF-7 is 11.1 cm^(3)·g^(-1),with an IAST selectivity of 1.77,surpassing the corresponding values for NKM-HOF-6(9.6 cm^(3)·g^(-1)and 1.56,respectively).Breakthrough experiments further reveal that NKM-HOF-7 achieves nearly twice the separation efficiency of NKM-HOF-6 for C_(2)H_(6)/C_(2)H_(4)(10/90,V/V)mixtures.Theoretical calculations attribute this enhanced C_(2)H_(6)affinity to the synergistic effects of optimized pore dimensions and functionalized pore surfaces in NKM-HOF-7.These findings provide critical insights for the rational design of highly efficient C_(2)H_(6)-selective adsorbents.
基金supported by the Natural Science Foundation of Shanghai (21ZR1435100)Shenzhen Science and Technology Innovation Commission (2021SZVUP075)the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University (SL2022MS015).
文摘Theπ-πinteraction is acknowledged as the predominant factor to determine the molecular packing in organic photovoltaic materials,while other non-covalent intermolecular interactions especially theσ-πhyperconjugation are often ignored.Herein,a perylene diimide(PDI)derivative named FIDT-PDI is designed and synthesized to shed light into the effect of hyperconjugation on the molecular packing and further the photovoltaic performance.Dynamic NMR and 2D NOE NMR demonstrate the formation of intermolecularσ-πhyperconjugation between the C—H bond of the PDI moiety in one molecule and the phenyl sidechain in another molecule of FIDT-PDI.Benefiting from theσ-πhyperconjugation,FIDT-PDI with twisted backbone reversely exhibits more ordered packing and stronger crystallinity compared with another PDI derivative FIDTT-PDI which has better planarity,consequently achieving superior PCE and higher carrier mobility.This contribution is the first paradigm to unravel the structure-property relationship betweenσ-πhyper-conjugation of conjugated materials and corresponding photovoltaic performance.
基金supported by financial support from the National Natural Science Foundation of China(21974102 and 21705019)the National Key R&D Program of China(2018YFA0703700).
文摘Comprehensive Summary,The charge transport through peptides can imitate the corresponding processes in more complicated proteins,enabling us to develop high-performance bioelectronic devices and to understand the mechanisms of biomolecular recognition and information transfer.While charge transport modulation through individual peptides has been achieved via various covalent strategies,the intermolecular modulation is still very challenging,which may capture the charge transport between proteins.To tackle this challenge,we used well-defined self-assembled monolayers(SAMs)of oligopeptides as a model to imitate the interface of proteins and explored an interfacial amino acid strategy for charge transport modulation.We showed that non-covalently interfaced charged amino acids(e.g.,arginine)effectively attenuated the charge transport of glutamic acid terminated polyglycine peptide SAMs.By analyzing the relationship of the charge transport with the molecular frontier orbital relative to the Fermi energy level of the electrode,the molecule-electrodes coupling(Γ),and the trends in skewness and kurtosis with voltage and the dielectric constant(εr),we showed that the attenuation was from the decreasedΓand the reduced polarizability.We present an efficient strategy to modulate the charge transport of oligopeptide-SAM junctions by intermolecular interactions,which will advance our understanding of charge transport in biological systems and facilitate developing future electronics.
基金We thank the Natural Science Foundation of Tianjin City(20JCYBJC00330)for financial support.
文摘pH is an important stimuli-responsive signal because deprotonation-protonation process is crucial for many life functions.Photoacid is a kind of photoresponsive group that can release protons upon irradiation.This property makes invasive pH control can be replaced by noninvasive light control.However,photoacid is rare.In this work,macrocyclic calixpyridinium was found to be used as a photoacid to release protons from acidic methylene under the irradiation of a 254 nm UV lamp.When the solution of calixpyridinium−disulfonated xantphos aggregates were irradiated by a 254 nm portable UV lamp,disulfonated xantphos was able to receive the protons released from calixpyridinium.This noninvasive photocontrolled proton transfer not only replaces an invasive pH regulation but also achieves a synergistic function.The deprotonation of calixpyridinium and the protonation of disulfonated xantphos can occur simultaneously to disrupt the aggregates.Moreover,the photoresponsive disassembly is reversible by heating.This photoresponsive material was further applied as a photocontrolled release model.In addition,a dissipative assembly was successfully designed based on this photoresponsive disassembly.This study supplies a generalized strategy to construct pH-responsive biocompatible materials with light-control properties by using macrocyclic calixpyridinium and its matched various vips in water.
基金support of the National Nature Science Foundation of China(22205163 and 22171210).
文摘One-step purification of ethylene(C_(2)H_(4))from acetylene/ethane/ethylene(C_(2)H_(2)/C_(2)H_(6)/C_(2)H_(4))ternary mixtures remains a challenging task in the chemical industry.While hydrogen-bonded organic frameworks(HOFs)have shown promise for separating C_(2)hydrocarbons—typically favoring adsorption in the order of C_(2)H_(6)>C_(2)H_(4)>C_(2)H_(2)—existing materials have largely been limited to binary separations,particularly C_(2)H_(4)/C_(2)H_(6).Here,we report a robust HOF material,HOF-PTBA,that selectively adsorbs both C_(2)H_(2)and C_(2)H_(6),enabling one-step separation of high-purity C_(2)H_(4)from ternary C_(2)mixtures.HOF-PTBA exhibits the highest C_(2)H_(6)/C_(2)H_(4)and C_(2)H_(2)/C_(2)H_(4)adsorption ratios among all reported HOFs.Molecular simulations reveal that C_(2)H_(2)and C_(2)H_(6)form multiple strong interactions with the framework's pore walls,while C_(2)H_(4)exhibits only weak interactions,allowing it to pass through unbound.HOF-PTBA also demonstrates excellent stability under humid and acidic conditions,and can be synthesized via a simple solvent evaporation process,making it scalable and cost-effective.These features highlight its strong potential for practical application in industrial gas purification.
