Very recently, the local coordination environment of active sites has been found to strongly influence their performance in electrocatalytic CO_(2) reduction by tuning the intrinsic kinetics of CO_(2) activation and i...Very recently, the local coordination environment of active sites has been found to strongly influence their performance in electrocatalytic CO_(2) reduction by tuning the intrinsic kinetics of CO_(2) activation and intermediate stabilization. It is imperative to elucidate the mechanism for such an influence towards the rational design of efficient catalysts;however, the complex interactions between the multiple factors involved in the system make it challenging to establish a clear structure–performance relationship. In this work, we chose ion-intercalated silver(I)-based coordination networks(AgCNs) with a well-defined structure as a model platform, which enables us to understand the regulation mechanism of counterions as the counterions are the only tuning factor involved in such a system. We prepared two isostructural Ag CNs with different intercalation ions or counterions of BF_(4)^(-) and ClO_(4)^(-)(named as AgCNs-BF_(4) and AgCNs-ClO_(4)) and found that the former has a more competitive CO_(2) electroreduction performance than the latter. AgCNs-BF_(4) achieves the highest Faradaic efficiency for CO_(2) to CO of 87.1% at-1.0 V(vs. RHE) with a higher partial current density, while AgCNs-ClO_(4) exhibits only 77.2% at the same applied potential.Spectroscopic characterizations and theoretical calculation reveal that the presence of BF_(4)^(-)is more favorable for stabilizing the COOH^(*) intermediate by weakening hydrogen bonds, which accounts for the superior activity of Ag CNs-BF_(4).展开更多
Langevin dynamics simulations are employed to explore the effects of chain stiffness and electrostatic interaction(EI) on the conformational behavior of a circular semiflexible polyelectrolyte(CSPE) in presence of tri...Langevin dynamics simulations are employed to explore the effects of chain stiffness and electrostatic interaction(EI) on the conformational behavior of a circular semiflexible polyelectrolyte(CSPE) in presence of trivalent counterions.We investigate the effect of bending energy b and the dimensionless Bjerrum length A on the conformational behavior of the CSPE with a fixed chain length.The competition among the EIs,chain stiffness and entropy of the system leads to rich conformations for the CSPE.As the b is less than or equal to 50,The shape of the CSPE changes from a oblate ring to a rod at small A,then to a toroid at intermediate A,and finally to a globule at very large A.However,the globular conformation is not observed for large b.In addition,we find that the number of torus ring increases with A increase,while decreases with b increase.This study should be helpful in gaining insight into the conformational behaviour of charged biopolymer.展开更多
This paper proved that octodecyl propylenediamine could form vesicles in pure water and aqueous solution of CuCl2 or Cu（NO3）2. The structure and morphology of vesicles were different when the copper （Ⅱ） salt was ...This paper proved that octodecyl propylenediamine could form vesicles in pure water and aqueous solution of CuCl2 or Cu（NO3）2. The structure and morphology of vesicles were different when the copper （Ⅱ） salt was added to the solution. The results showed that both the counterions and the ligands had strong influence on the configuration of coordinated structures and packing model in bilayer membrane of vesicles.展开更多
This study investigates the effect of counterions on the chiral recognition of 1,1'-Binaphthyl-2,2'-diamine (BNA) and 1,1'-Binaphthyl-2,2'-diyl hydrogenphosphate (BNP) enantiomers when using an amino a...This study investigates the effect of counterions on the chiral recognition of 1,1'-Binaphthyl-2,2'-diamine (BNA) and 1,1'-Binaphthyl-2,2'-diyl hydrogenphosphate (BNP) enantiomers when using an amino acid-based surfactant undecanoyl L-leucine (und-Leu) as the chiral pseudostationary phase in capillary electrophoresis. The effects of using two different counterions (sodium and lysine) on the chiral recognition of binaphthyl derivatives were compared at varying pH conditions. The enantiomeric separation of BNA and BNP enantiomers via capillary electrophoresis, using und-Leu as the chiral recognition medium, significantly improved the enantiomeric resolution in capillary electrophoresis at pH 7 when using Lysine counterions as compared to using sodium as the counterion. More specifically, at a surfactant concentration of 45 mM, at pH 7, a significant increase in chiral selectivity was observed when lysine was used as the counterion compared to sodium. The enantiomeric resolution of BNA and BNP increased by 6-fold and 1.1-fold, respectively, in capillary electrophoresis experiments when lysine was utilized as the counterion compared to using sodium. Furthermore, the retention factor of BNA and BNP enantiomers also increased approximately 3.5-fold and 4-fold, respectively, in the presence of lysine counterions as compared to using sodium counterions. When running buffer in capillary electrophoresis was increased to pH 11, the resolution and retention factors were nearly identical when comparing the effects of the sodium and lysine counterions. This signifies the important role of lysine’s positive net charge on chiral recognition. This study provides insight into the potential advantages of using cationic, pH-dependent counterions such as lysine to significantly improve the chiral recognition of binaphthyl derivatives when using chiral anionic surfactants as the pseudostationary phase in capillary electrophoresis.展开更多
Experimental, theoretical and computational studies revealed that the characteristic time scales involved in counterion dynamics in polyelectrolytes systems might span several orders of magnitude ranging from subnanos...Experimental, theoretical and computational studies revealed that the characteristic time scales involved in counterion dynamics in polyelectrolytes systems might span several orders of magnitude ranging from subnanosecond times to time scales corresponding to acoustic-like phonon mode frequencies, with an structural organization of counterions in charge density waves (CDWs). These facts raise the possibility of observing Magnetic Resonance (MR) signals due to the movement of counterions in polyelectrolytes. In case that this signal is detected in macroions or other biological systems, like micelles, vesicles, organeles, etc. with rotational symmetry, this method opens a new tool to measure with precission the counterions velocity.展开更多
DNA is one of most important biological polyelectrolytes, which is negatively charged in physiological condition. Most of Its charge is neutralized by attracting cations in solution. In some conditions, the effective ...DNA is one of most important biological polyelectrolytes, which is negatively charged in physiological condition. Most of Its charge is neutralized by attracting cations in solution. In some conditions, the effective charge of DNA switches its sign from negative to positive, implying charge inversion of DNA. The underlying microscopic mechanism of the counterintuitive phenomenon is still not fully understood although specific chemical affinity and electrostatic ion correlation are considered as two possible driving forces. In this review, we present some recent experimental progress in the modulation and control of DNA charge by single molecular techniques. It has been shown that DNA charge inversion can be modulated bidirectionly by decreasing or increasing the dielectric constant of solution to make the electrophoretic mobility of DNA increase from a negative value to a positive value. In this meanwhile, charge inversion and condensation of DNA in solution of trivalent and quadrivalent counterions are significantly influenced by pH value of the solution. When mixing quadrivalent counterion with mono-, di-and tri-valent counterions in solution, suppression and promotion of DNA charge inversion can be observed. In addition, hydrophobic effect can play an important role in DNA charge inversiton and compaction. We show that the organic monovalent ions of tetraphenyl chloride arsenic （Ph4As＋） can induce DNA compaction and even invert its electrophoretic mobility. Thus, hydrophobic effect can be the main driving force of DNA charge inversion and compaction by the organic monovalent ion.展开更多
We have prepared polyion complex （PIC） hydrogel consisting of poly（3-（methacryloylami no）propyl-trimethylamonium chloride） and poly（sodium p-styrenesulfonate） polyelectrolytes via a two-step polymerization pro...We have prepared polyion complex （PIC） hydrogel consisting of poly（3-（methacryloylami no）propyl-trimethylamonium chloride） and poly（sodium p-styrenesulfonate） polyelectrolytes via a two-step polymerization procedure and have investigated specific ion effects on the self- healing of the PIC hydrogel. Our study demonstrates that the mechanical properties of the PIC hydrogel are strongly dependent on the type of the ions doped in the hydrogel. The ion-specific effects can be used to modulate the self-healing efficiency of the PIC hydrogel. As the doped anions change from kosmotrops to chaotropes, the self-healing efficiency of the PIC hydrogel increases. A more chaotropic anion has a stronger ability to break the ionic bonds formed within the hydrogel, leading to a higher efficiency during the healing.展开更多
基金supported by financial support in part by NSFC (91961106, 51902253, 21725102)Anhui Provincial Natural Science Foundation (Grant 2108085MB46)+1 种基金Key Project of Youth Elite Support Plan in Universities of Anhui Province (Grant gxyqZD2021121)Shaanxi Provincial Natural Science Foundation (2020JQ-778)。
文摘Very recently, the local coordination environment of active sites has been found to strongly influence their performance in electrocatalytic CO_(2) reduction by tuning the intrinsic kinetics of CO_(2) activation and intermediate stabilization. It is imperative to elucidate the mechanism for such an influence towards the rational design of efficient catalysts;however, the complex interactions between the multiple factors involved in the system make it challenging to establish a clear structure–performance relationship. In this work, we chose ion-intercalated silver(I)-based coordination networks(AgCNs) with a well-defined structure as a model platform, which enables us to understand the regulation mechanism of counterions as the counterions are the only tuning factor involved in such a system. We prepared two isostructural Ag CNs with different intercalation ions or counterions of BF_(4)^(-) and ClO_(4)^(-)(named as AgCNs-BF_(4) and AgCNs-ClO_(4)) and found that the former has a more competitive CO_(2) electroreduction performance than the latter. AgCNs-BF_(4) achieves the highest Faradaic efficiency for CO_(2) to CO of 87.1% at-1.0 V(vs. RHE) with a higher partial current density, while AgCNs-ClO_(4) exhibits only 77.2% at the same applied potential.Spectroscopic characterizations and theoretical calculation reveal that the presence of BF_(4)^(-)is more favorable for stabilizing the COOH^(*) intermediate by weakening hydrogen bonds, which accounts for the superior activity of Ag CNs-BF_(4).
基金financially supported by the National Natural Science Foundation of China (Nos. 21863003, 22173080, 21873082, 21674096 and 61762048)the Jiangxi Provincial Natural Science Foundation (No.20202BABL203015)。
文摘Langevin dynamics simulations are employed to explore the effects of chain stiffness and electrostatic interaction(EI) on the conformational behavior of a circular semiflexible polyelectrolyte(CSPE) in presence of trivalent counterions.We investigate the effect of bending energy b and the dimensionless Bjerrum length A on the conformational behavior of the CSPE with a fixed chain length.The competition among the EIs,chain stiffness and entropy of the system leads to rich conformations for the CSPE.As the b is less than or equal to 50,The shape of the CSPE changes from a oblate ring to a rod at small A,then to a toroid at intermediate A,and finally to a globule at very large A.However,the globular conformation is not observed for large b.In addition,we find that the number of torus ring increases with A increase,while decreases with b increase.This study should be helpful in gaining insight into the conformational behaviour of charged biopolymer.
文摘This paper proved that octodecyl propylenediamine could form vesicles in pure water and aqueous solution of CuCl2 or Cu（NO3）2. The structure and morphology of vesicles were different when the copper （Ⅱ） salt was added to the solution. The results showed that both the counterions and the ligands had strong influence on the configuration of coordinated structures and packing model in bilayer membrane of vesicles.
文摘This study investigates the effect of counterions on the chiral recognition of 1,1'-Binaphthyl-2,2'-diamine (BNA) and 1,1'-Binaphthyl-2,2'-diyl hydrogenphosphate (BNP) enantiomers when using an amino acid-based surfactant undecanoyl L-leucine (und-Leu) as the chiral pseudostationary phase in capillary electrophoresis. The effects of using two different counterions (sodium and lysine) on the chiral recognition of binaphthyl derivatives were compared at varying pH conditions. The enantiomeric separation of BNA and BNP enantiomers via capillary electrophoresis, using und-Leu as the chiral recognition medium, significantly improved the enantiomeric resolution in capillary electrophoresis at pH 7 when using Lysine counterions as compared to using sodium as the counterion. More specifically, at a surfactant concentration of 45 mM, at pH 7, a significant increase in chiral selectivity was observed when lysine was used as the counterion compared to sodium. The enantiomeric resolution of BNA and BNP increased by 6-fold and 1.1-fold, respectively, in capillary electrophoresis experiments when lysine was utilized as the counterion compared to using sodium. Furthermore, the retention factor of BNA and BNP enantiomers also increased approximately 3.5-fold and 4-fold, respectively, in the presence of lysine counterions as compared to using sodium counterions. When running buffer in capillary electrophoresis was increased to pH 11, the resolution and retention factors were nearly identical when comparing the effects of the sodium and lysine counterions. This signifies the important role of lysine’s positive net charge on chiral recognition. This study provides insight into the potential advantages of using cationic, pH-dependent counterions such as lysine to significantly improve the chiral recognition of binaphthyl derivatives when using chiral anionic surfactants as the pseudostationary phase in capillary electrophoresis.
文摘Experimental, theoretical and computational studies revealed that the characteristic time scales involved in counterion dynamics in polyelectrolytes systems might span several orders of magnitude ranging from subnanosecond times to time scales corresponding to acoustic-like phonon mode frequencies, with an structural organization of counterions in charge density waves (CDWs). These facts raise the possibility of observing Magnetic Resonance (MR) signals due to the movement of counterions in polyelectrolytes. In case that this signal is detected in macroions or other biological systems, like micelles, vesicles, organeles, etc. with rotational symmetry, this method opens a new tool to measure with precission the counterions velocity.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11274245,10974146,and 11304232)the Natural Science Foundation of Zhejiang Provice,China(Grant No.LY17A040006)the Wenzhou Science and Technology Project,China(Grant No.S20160011)
文摘DNA is one of most important biological polyelectrolytes, which is negatively charged in physiological condition. Most of Its charge is neutralized by attracting cations in solution. In some conditions, the effective charge of DNA switches its sign from negative to positive, implying charge inversion of DNA. The underlying microscopic mechanism of the counterintuitive phenomenon is still not fully understood although specific chemical affinity and electrostatic ion correlation are considered as two possible driving forces. In this review, we present some recent experimental progress in the modulation and control of DNA charge by single molecular techniques. It has been shown that DNA charge inversion can be modulated bidirectionly by decreasing or increasing the dielectric constant of solution to make the electrophoretic mobility of DNA increase from a negative value to a positive value. In this meanwhile, charge inversion and condensation of DNA in solution of trivalent and quadrivalent counterions are significantly influenced by pH value of the solution. When mixing quadrivalent counterion with mono-, di-and tri-valent counterions in solution, suppression and promotion of DNA charge inversion can be observed. In addition, hydrophobic effect can play an important role in DNA charge inversiton and compaction. We show that the organic monovalent ions of tetraphenyl chloride arsenic （Ph4As＋） can induce DNA compaction and even invert its electrophoretic mobility. Thus, hydrophobic effect can be the main driving force of DNA charge inversion and compaction by the organic monovalent ion.
文摘We have prepared polyion complex （PIC） hydrogel consisting of poly（3-（methacryloylami no）propyl-trimethylamonium chloride） and poly（sodium p-styrenesulfonate） polyelectrolytes via a two-step polymerization procedure and have investigated specific ion effects on the self- healing of the PIC hydrogel. Our study demonstrates that the mechanical properties of the PIC hydrogel are strongly dependent on the type of the ions doped in the hydrogel. The ion-specific effects can be used to modulate the self-healing efficiency of the PIC hydrogel. As the doped anions change from kosmotrops to chaotropes, the self-healing efficiency of the PIC hydrogel increases. A more chaotropic anion has a stronger ability to break the ionic bonds formed within the hydrogel, leading to a higher efficiency during the healing.
