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
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
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
Polymer-grafted ion exchange adsorbents were of great interest for the development of high-performance protein chromatography in biopharmaceutical and related fields.In this work,protein retention was systematically i...Polymer-grafted ion exchange adsorbents were of great interest for the development of high-performance protein chromatography in biopharmaceutical and related fields.In this work,protein retention was systematically investigated in ion exchange chromatography packed respectively with dextran-grafted cation exchange adsorbents containing sulphopropyl(SP)ligand,SP Sepharose XL and Capto S,and non-grafted cation exchange adsorbent,SP Sepharose FF,using five proteins.With an increase of buffer p Hs,retention factors of proteins decreased among all the adsorbents,demonstrating the dominant role of electrostatic interaction for protein binding on cation exchange adsorbents.The evidences further revealed that the scattered positive charges on the surface of protein molecules,rather than net charge of protein molecule,determined protein retention on cation exchange adsorbent.Likely,counterions including NH4^+,K^+,Na^+and Mg^2+exhibited distinct influence on protein retention.It was well ascribed to solvent-mediated indirect ion-macromolecule interactions and direct ion-macromolecule interactions.Compared with SP Sepharose FF,polymer structure in dextran-grafted cation exchange adsorbents ultimately brought about different ligand distributions and smaller pore sizes,thereby regulating protein retention in cation exchange chromatography.By comparing the retention of myoglobin andβ-lactoglobulin B in SP Sepharose XL and Capto S,we reasonably speculated that the enhancement of nonelectrostatic interaction caused by reducing the space arm length was a major reason for an increasing retention factor of myoglobin in Capto S.The results in this research help us understand adsorption mechanism of protein in polymer-grafted adsorbents and give scientific guidance for the development of chromatographic materials.展开更多
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
The effects of variant counterions with ionic strength of 0.05, 0.10, 0.20 and 0.25 mol·kg^-1 on the stability and particle size of silica sols have been studied using the traditional methods of Ubbelohde viscosi...The effects of variant counterions with ionic strength of 0.05, 0.10, 0.20 and 0.25 mol·kg^-1 on the stability and particle size of silica sols have been studied using the traditional methods of Ubbelohde viscosity measurement, TEM and titration respectively, finding that the stability and particle size of the silica sols are all concerned with the acidic, positively electric properties and the sizes of the counterions, as well as the attraction between the counterions and surface silicon hydroxyl groups of the silica sols. The small positively charged counterions lead to the decrease in particle sizes, making the silica sol the most stable. But the larger weakly acidic counterions can restrict the particle sizes of the silica sols and easily make the sols coagulate. It was also found that there existed a linear relationship between log r and log η, which has not ever been reported. The effect of temperature on the stability and particle sizes was also discussed.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
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
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
The removal of phosphate from aqueous solution by Donnan dialysis with anion-exchange membrane was investigated.The results show that phosphate could be removed from aqueous solution without supplying external high pr...The removal of phosphate from aqueous solution by Donnan dialysis with anion-exchange membrane was investigated.The results show that phosphate could be removed from aqueous solution without supplying external high pressure or electrical potential.Under the conditions of influent phosphate of 2.0 mg/L,counterion(Cl-)concentration of 0.1 mol/L,stirring speed of 500 r/min and phase temperature of 298 K,the removal of phosphate achieves 70.0%.Decreasing counterion concentration has little influence on the removal of phosphate,but phosphate amount in anion-exchange membrane increases significantly.With the increase of stirring speed and phase temperature,the removal efficiency of phosphate greatly is improved.Existing forms of phosphate in aqueous solution affected transport of phosphate and only strong acidic pH of feed solution(pH=3.0)decreases the removal of phosphate.Transport of phosphate is also accompanied by change of pH value of feed solution.In consequence,it might be a promise potential process for phosphate advanced wastewater treatment,especially in the area where high salted nature water can be utilized.展开更多
Laccase is a promising oxidase with environmental applications, such as lignin degradation and chlorophenol detoxification. Laccase immobilization can significantly improve physiochemical stability and reusability com...Laccase is a promising oxidase with environmental applications, such as lignin degradation and chlorophenol detoxification. Laccase immobilization can significantly improve physiochemical stability and reusability compared to the free enzymes. In this work, anion effect was investigated in entrapment of Cu-alginate matrix with five types of anions, including perchlorate （ClO4）, nitrate （NO3）, sulfate （SO42 ）, chloride （Cl）, and acetate （CH3CO2-）. Accordingly, chloride inhibition and acetate activation were detected in the o-tolidine kinetic experiments, while effects of the other three anions were much smaller. Such counteranion effects were also observed in the laccase-catalyzed biodegradation of 2,4- dichlorophenol. The results indicated that counteranions in the enzyme immobilization process are crucial for catalytic capacity, probably due to the competition with the carboxylate groups in alginate. Our results also imply that these anions might coordinate the copper cations in laccase.展开更多
The wettability of the membrane surface has shown obvious influent on the separation performance of the membrane.In this work,a hydrophilic PDA-[PDDA/TiO2]+Cl-membrane was prepared by a one-step codeposition of poly(d...The wettability of the membrane surface has shown obvious influent on the separation performance of the membrane.In this work,a hydrophilic PDA-[PDDA/TiO2]+Cl-membrane was prepared by a one-step codeposition of poly(diallyldimethylammonium chloride)(PDDA)polyelectrolyte solution containing positively charged TiO2@PDDA nanoparticles with the assistance of dopamine(DA).Such positively charged membrane can be transformed into a hydrophobic membrane PDA-[PDDA/TiO2]+PFO-via the counterion exchange between Cl-and PFO-(perfluorooctanoate).The transformation between hydrophilicity and hydrophobicity is reversible.For both hydrophilic and hydrophobic membranes,the nanofiltration performances were respectively investigated by the aqueous solution and ethanol solution of dyes including methyl blue(MB),Congo red(CR)and Evans blue(EB),and as well metal salt aqueous solution.The consecutive running stability and anti-fouling performance of both hydrophilic and hydrophobic membranes were explored.The results revealed that both membranes showed high nanofiltration performances for retention of dyes in(non)aqueous solution.For the hydrophilic membrane,the rejection of salts in a sequence is MgSO4>Na2SO4>MgCl2>NaCl.Moreover,both of the hydrophilic and hydrophobic membranes showed high stability and antifouling property.展开更多
Understanding the relationship between structure and properties is critical to the development of solidstate luminescence materials with desired characteristics and performance optimization. In this work, we elaborate...Understanding the relationship between structure and properties is critical to the development of solidstate luminescence materials with desired characteristics and performance optimization. In this work, we elaborately designed and synthesized a pair of mononuclear iridium(Ⅲ) complexes with similar structures but different degrees of cationization. [Ir2-f][2PF_(6)] with two counterions is obtained by simple Nmethylation of the ancillary ligand of [Ir1-f][PF_(6)] which is a classic cationic iridium(Ⅲ) complex. Such a tiny modification results in tremendously different optical properties in dilute solutions and powders.[Ir1-f][PF_(6)] exhibits weak light in solution but enhanced emission in solid-state as well as poly(methyl methacrylate) matrix, indicative of its aggregation-induced emission(AIE) activity. On the sharp contrary, [Ir2-f][2PF_(6)] is an aggregation-caused quenching(ACQ) emitter showing strong emission in the isolated state but nearly nonemissive in aggregation states. Benefiting from the appealing characteristics of mechanochromic luminescence and AIE behavior, [Ir1-f][PF_(6)] has been successfully applied in reversible re-writable data recording and cell imaging. These results might provide deep insights into AIE and ACQ phenomenon of iridium(Ⅲ) complexes and facilitate the development of phosphorescent materials with promising properties.展开更多
We present the results of molecular dynamics simulations of net positively charged fullerene nanoparticles in salt- free and salt-added solution. The aggregation of fullerene （C60）-like nanoparticle and counterion a...We present the results of molecular dynamics simulations of net positively charged fullerene nanoparticles in salt- free and salt-added solution. The aggregation of fullerene （C60）-like nanoparticle and counterion are studied in detail as a function of temperatures and a finite salt concentration. Our simulations show that the strong conformation changes as temperature changes. The net positively-charged nanoparticles do not repel each other but are condensed under proper temperatures. If salts are added, the aggregated nanoparticles will be disaggregated due to the Debye screening effect.展开更多
DNA condensation is an important process in many fields including life sciences, polymer physics, and applied technology. In the nucleus, DNA is condensed into chromosomes. In polymer physics, DNA is treated as a semi...DNA condensation is an important process in many fields including life sciences, polymer physics, and applied technology. In the nucleus, DNA is condensed into chromosomes. In polymer physics, DNA is treated as a semi-flexible molecule and a polyelectrolyte. Many agents, including multi-valent cations, surfactants, and neutral poor solvents, can cause DNA condensation, also referred to as coil–globule transition. Moreover, DNA condensation has been used for extraction and gene delivery in applied technology. Many physical theories have been presented to elucidate the mechanism underlying DNA condensation, including the counterion correlation theory, the electrostatic zipper theory, and the hydration force theory. Recently several single-molecule studies have focused on DNA condensation, shedding new light on old concepts. In this document, the multi-field concepts and theories related to DNA condensation are introduced and clarified as well as the advances and considerations of single-molecule DNA condensation experiments are introduced.展开更多
The counterion-mediated hydrogen bonding(CMHB)is related to the hydrogen bonding between bound counterions and polyelectrolyte chains in polyelectrolyte systems,where the counterions can both electrostatically bind to...The counterion-mediated hydrogen bonding(CMHB)is related to the hydrogen bonding between bound counterions and polyelectrolyte chains in polyelectrolyte systems,where the counterions can both electrostatically bind to the charged groups of polyelectrolyte chains and act as hydrogen bond donors or acceptors to form hydrogen bonds with the hydrogen bond sites associated with polyelectrolyte chains simultaneously.A large number of literatures illustrate that strong polyelectrolytes(SPs)are insensitive to pH,which severely limmits the applications of SPs as smart materials.However,our studies have demonstrated that the CMHB makes SPs pH-responsive.This perspective discusses the mechanism of pH responsiveness of SPs and the pH-tunable properties of SPs,based on the pH-controlled CMHB effect.The future research directions on the pH responsiveness of SPs are also discussed here.It is anticipated that the study of the pH responsiveness of SPs not only will provide a new understanding of the fundamental properties of SPs,but also will greatly expand the applications of SPs in the field of smart materials.展开更多
The title complex bis（2-acetylpyridine thiosemicarbazonato）-indium（iii） perchlo-rate hydrate has been synthesized by the reaction of 2-acetylpyridine thiosemicarbazide（L） with indium（iii） perchlorate,and its s...The title complex bis（2-acetylpyridine thiosemicarbazonato）-indium（iii） perchlo-rate hydrate has been synthesized by the reaction of 2-acetylpyridine thiosemicarbazide（L） with indium（iii） perchlorate,and its structure was characterized by elemental analysis,IR and single-crystal X-ray diffraction.The crystal of the title compound（[In（C8H9N4S）2]ClO4·H2O） belongs to monoclinic,space group P21/c with a = 12.6438（18）,b = 12.6259（18）,c = 15.116（2） nm,β = 105.800（2）°,Z = 4,V = 2321.9（6） nm3,Mr = 618.79,Dc = 1.770 g/cm3,μ = 1.359 mm-1,F（000） = 1240,R = 0.0265 and wR = 0.0675.X-ray analysis indicates that various intriguing hydrogen patterns involving both the solvent intermedia and polyatomic counterions play crucial roles in the self-assembly of functional supramolecules.展开更多
Scaling theory of charged cylindrical polyelectrolyte brushes is developed. The dependence of brush thickness on the grafting density, charge fraction, and chain length is analyzed. A full phase diagram is established...Scaling theory of charged cylindrical polyelectrolyte brushes is developed. The dependence of brush thickness on the grafting density, charge fraction, and chain length is analyzed. A full phase diagram is established. Characteristics and boundaries between different regimes of cylindrical polyelectrolyte brushes are summarized. Special attentions are paid to electrostatic interaction induced stiffening and counterion condensation effects. If the Bjerrum length of the solution is larger than the Kuhn length of the polyelectrolyte chains, counterion condensation occurs in the strongly charged polyeleetrolyte brushes. On the contrary, the electrostatic interaction stretches the strongly charged grafted polyelectrolyte chains to their contour length.展开更多
The extent to which counterions bind to polyelectrolytes influences a variety of polymer-based applications, including polyelectrolyte enhanced ultrafiltration and forward osmosis using polyelectrolytes as draw agents...The extent to which counterions bind to polyelectrolytes influences a variety of polymer-based applications, including polyelectrolyte enhanced ultrafiltration and forward osmosis using polyelectrolytes as draw agents. Potentiometric titrations of poly (2-vinylpyridine) (P2VP), poly (3-vinylpyridine) (P3VP), and poly (4-vinylpydine) (P4VP) were performed using HBr, HCl, HNO<sub>3</sub>, and HClO<sub>4</sub> in both the presence and absence of added NaCl. Because of the systematic differences among the three polyelectrolytes, titration results provide insight into the role of polymer structure in the relative extents to which various counterions bind. Titration data reveal that ionization properties vary as functions of polymer investigated, titrant used, degree of protonation, and added salt concentration. Acid dissociation constants of the pyridinium moieties were found to generally increase with increasing degree of protonation, though appreciable differences were exhibited among the three polymers investigated. For all three polymers, Cl<sup>-</sup> demonstrated the lowest affinity for the charged pyridinium residues, while the affinities associated with Br<sup>-</sup> and NO<sup>-</sup>3</sub> were nearly identical to each other. The relative extent of binding for CIO<sup>-</sup>4</sub> varied across the polymers investigated, and was greatest for P4VP.展开更多
Long-range electrostatic interactions in proteins/peptides associating to nucleic acids are reflected in the salt-dependence of the binding process.According to the oligocationic binding model,which is based on counte...Long-range electrostatic interactions in proteins/peptides associating to nucleic acids are reflected in the salt-dependence of the binding process.According to the oligocationic binding model,which is based on counterion condensation theory,only the cationic residues of peptides/proteins near the binding interface are assumed to affect the salt dependence in the association of peptides and proteins to nucleic acids.This model has been used to interpret and predict the binding of oligocationic chains-such as oligoarginines/lysines-to nucleic acids,and does an excellent job in these kinds of systems.This simple relationship,which is used to compare or count the number of ionic interactions in protein-nucleic acid complexes,does not hold when acidic residues,i.e.glutamate and aspartate,are incorporated in the protein matrix.Here,we report a combined molecular mechanics(by means of energy-minimization of the structure under the influence of an empirical energy function)and Poisson-Boltzmann(PB)study on the salt-dependence in binding to tRNA of two important enzymes that are involved in the seminal step of peptide formation in the ribosome:Glutamine synthetase(GluRS)and Glutaminyl synthetase(GlnRS)bound to their cognate tRNA.These two proteins are anionic and contain a significant number of acidic residues distributed over the entire protein.Some of these residues are located in the binding interface to tRNA.We computed the salt-dependence in association,SKpred,of these enzyme-tRNA complexes using both the linear and nonlinear solution to the PoissonBoltzmann Equation(PBE).Our findings demonstrate that the SKpred obtained with the nonlinear PBE is in good agreement with the experimental SKobs,while use of the linear PBE resulted in the SKpred being anomalous.We conclude that electrostatic interactions between the binding partners in these systems are less favorable by means of charge-charge repulsion between negatively charged protein residues and phosphateoxygens in the tRNA backbone but also play a significant role in the association process of proteins to tRNA.Some unfavorable electrostatic interactions are probably compensated by hydrogen-bonds between the carboxylate group of the side chain in the interfacial acidic protein residues and the tRNA backbone.We propose that the low experimentally observed SKobs values for both GlnRS-and GluRS-tRNA depend on the distribution and number of anionic residues that exist in these tRNA synthetases.Our computed electrostatic binding free energies were large and unfavorable due to the Coulombic and de-solvation contribution for the GlnRS-tRNA and GluRS-tRNA complexes,respectively.Thus,low SKobs values may not reflect small contributions from the electrostatic contribution in complex-formation,as is often suggested in the literature.When charges are”turned off”in a computer-experiment,our results indicated that”turning off”acidic residues far from a phosphate group significantly influences SKpred.If cationic residues are“turned off”,less impact on SKpred is observed with respect to the distance to the nearest phosphate-group。展开更多
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.
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.
基金supported by the National Natural Science Foundation of China(Nos.21476166 and 21878221)the Foundation for Innovative Research Groups of the National Natural Science Foundation of China(No.21621004)。
文摘Polymer-grafted ion exchange adsorbents were of great interest for the development of high-performance protein chromatography in biopharmaceutical and related fields.In this work,protein retention was systematically investigated in ion exchange chromatography packed respectively with dextran-grafted cation exchange adsorbents containing sulphopropyl(SP)ligand,SP Sepharose XL and Capto S,and non-grafted cation exchange adsorbent,SP Sepharose FF,using five proteins.With an increase of buffer p Hs,retention factors of proteins decreased among all the adsorbents,demonstrating the dominant role of electrostatic interaction for protein binding on cation exchange adsorbents.The evidences further revealed that the scattered positive charges on the surface of protein molecules,rather than net charge of protein molecule,determined protein retention on cation exchange adsorbent.Likely,counterions including NH4^+,K^+,Na^+and Mg^2+exhibited distinct influence on protein retention.It was well ascribed to solvent-mediated indirect ion-macromolecule interactions and direct ion-macromolecule interactions.Compared with SP Sepharose FF,polymer structure in dextran-grafted cation exchange adsorbents ultimately brought about different ligand distributions and smaller pore sizes,thereby regulating protein retention in cation exchange chromatography.By comparing the retention of myoglobin andβ-lactoglobulin B in SP Sepharose XL and Capto S,we reasonably speculated that the enhancement of nonelectrostatic interaction caused by reducing the space arm length was a major reason for an increasing retention factor of myoglobin in Capto S.The results in this research help us understand adsorption mechanism of protein in polymer-grafted adsorbents and give scientific guidance for the development of chromatographic materials.
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Project supported by the National Natural Science Foundation of China （No. 20577010）.
文摘The effects of variant counterions with ionic strength of 0.05, 0.10, 0.20 and 0.25 mol·kg^-1 on the stability and particle size of silica sols have been studied using the traditional methods of Ubbelohde viscosity measurement, TEM and titration respectively, finding that the stability and particle size of the silica sols are all concerned with the acidic, positively electric properties and the sizes of the counterions, as well as the attraction between the counterions and surface silicon hydroxyl groups of the silica sols. The small positively charged counterions lead to the decrease in particle sizes, making the silica sol the most stable. But the larger weakly acidic counterions can restrict the particle sizes of the silica sols and easily make the sols coagulate. It was also found that there existed a linear relationship between log r and log η, which has not ever been reported. The effect of temperature on the stability and particle sizes was also discussed.
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.
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.
基金Project(50778065)supported by the National Natural Science Foundation of China
文摘The removal of phosphate from aqueous solution by Donnan dialysis with anion-exchange membrane was investigated.The results show that phosphate could be removed from aqueous solution without supplying external high pressure or electrical potential.Under the conditions of influent phosphate of 2.0 mg/L,counterion(Cl-)concentration of 0.1 mol/L,stirring speed of 500 r/min and phase temperature of 298 K,the removal of phosphate achieves 70.0%.Decreasing counterion concentration has little influence on the removal of phosphate,but phosphate amount in anion-exchange membrane increases significantly.With the increase of stirring speed and phase temperature,the removal efficiency of phosphate greatly is improved.Existing forms of phosphate in aqueous solution affected transport of phosphate and only strong acidic pH of feed solution(pH=3.0)decreases the removal of phosphate.Transport of phosphate is also accompanied by change of pH value of feed solution.In consequence,it might be a promise potential process for phosphate advanced wastewater treatment,especially in the area where high salted nature water can be utilized.
基金the National High-Tech R&D Program of China ‘‘863’’ (No.2012AA020403)the National Basic Research Program of China ‘‘973’’ (Nos.2012CB721005,2013CB966802)+1 种基金National Natural Science Foundation of China(Nos.21377085,21303101,31121064,J1210047)MOE New Century Excellent Talents in University(No.NCET-12-0354)
文摘Laccase is a promising oxidase with environmental applications, such as lignin degradation and chlorophenol detoxification. Laccase immobilization can significantly improve physiochemical stability and reusability compared to the free enzymes. In this work, anion effect was investigated in entrapment of Cu-alginate matrix with five types of anions, including perchlorate （ClO4）, nitrate （NO3）, sulfate （SO42 ）, chloride （Cl）, and acetate （CH3CO2-）. Accordingly, chloride inhibition and acetate activation were detected in the o-tolidine kinetic experiments, while effects of the other three anions were much smaller. Such counteranion effects were also observed in the laccase-catalyzed biodegradation of 2,4- dichlorophenol. The results indicated that counteranions in the enzyme immobilization process are crucial for catalytic capacity, probably due to the competition with the carboxylate groups in alginate. Our results also imply that these anions might coordinate the copper cations in laccase.
基金financially supported by the National Natural Science Foundation of China(21476005,21878003)the National Natural Science Fund for Innovative Research Groups(51621003)。
文摘The wettability of the membrane surface has shown obvious influent on the separation performance of the membrane.In this work,a hydrophilic PDA-[PDDA/TiO2]+Cl-membrane was prepared by a one-step codeposition of poly(diallyldimethylammonium chloride)(PDDA)polyelectrolyte solution containing positively charged TiO2@PDDA nanoparticles with the assistance of dopamine(DA).Such positively charged membrane can be transformed into a hydrophobic membrane PDA-[PDDA/TiO2]+PFO-via the counterion exchange between Cl-and PFO-(perfluorooctanoate).The transformation between hydrophilicity and hydrophobicity is reversible.For both hydrophilic and hydrophobic membranes,the nanofiltration performances were respectively investigated by the aqueous solution and ethanol solution of dyes including methyl blue(MB),Congo red(CR)and Evans blue(EB),and as well metal salt aqueous solution.The consecutive running stability and anti-fouling performance of both hydrophilic and hydrophobic membranes were explored.The results revealed that both membranes showed high nanofiltration performances for retention of dyes in(non)aqueous solution.For the hydrophilic membrane,the rejection of salts in a sequence is MgSO4>Na2SO4>MgCl2>NaCl.Moreover,both of the hydrophilic and hydrophobic membranes showed high stability and antifouling property.
基金financial support from the National Natural Science Foundation of China(Nos.22175033 and 51902124).
文摘Understanding the relationship between structure and properties is critical to the development of solidstate luminescence materials with desired characteristics and performance optimization. In this work, we elaborately designed and synthesized a pair of mononuclear iridium(Ⅲ) complexes with similar structures but different degrees of cationization. [Ir2-f][2PF_(6)] with two counterions is obtained by simple Nmethylation of the ancillary ligand of [Ir1-f][PF_(6)] which is a classic cationic iridium(Ⅲ) complex. Such a tiny modification results in tremendously different optical properties in dilute solutions and powders.[Ir1-f][PF_(6)] exhibits weak light in solution but enhanced emission in solid-state as well as poly(methyl methacrylate) matrix, indicative of its aggregation-induced emission(AIE) activity. On the sharp contrary, [Ir2-f][2PF_(6)] is an aggregation-caused quenching(ACQ) emitter showing strong emission in the isolated state but nearly nonemissive in aggregation states. Benefiting from the appealing characteristics of mechanochromic luminescence and AIE behavior, [Ir1-f][PF_(6)] has been successfully applied in reversible re-writable data recording and cell imaging. These results might provide deep insights into AIE and ACQ phenomenon of iridium(Ⅲ) complexes and facilitate the development of phosphorescent materials with promising properties.
基金Project supported by the Natural Science Foundation of Fujian Province of China(Grant No.2012J05008)
文摘We present the results of molecular dynamics simulations of net positively charged fullerene nanoparticles in salt- free and salt-added solution. The aggregation of fullerene （C60）-like nanoparticle and counterion are studied in detail as a function of temperatures and a finite salt concentration. Our simulations show that the strong conformation changes as temperature changes. The net positively-charged nanoparticles do not repel each other but are condensed under proper temperatures. If salts are added, the aggregated nanoparticles will be disaggregated due to the Debye screening effect.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.21204065 and 20934004)the Natural Science Foundation of Zhejiang Province,China(Grant No.Y4110357)
文摘DNA condensation is an important process in many fields including life sciences, polymer physics, and applied technology. In the nucleus, DNA is condensed into chromosomes. In polymer physics, DNA is treated as a semi-flexible molecule and a polyelectrolyte. Many agents, including multi-valent cations, surfactants, and neutral poor solvents, can cause DNA condensation, also referred to as coil–globule transition. Moreover, DNA condensation has been used for extraction and gene delivery in applied technology. Many physical theories have been presented to elucidate the mechanism underlying DNA condensation, including the counterion correlation theory, the electrostatic zipper theory, and the hydration force theory. Recently several single-molecule studies have focused on DNA condensation, shedding new light on old concepts. In this document, the multi-field concepts and theories related to DNA condensation are introduced and clarified as well as the advances and considerations of single-molecule DNA condensation experiments are introduced.
基金supported by the National Natural Science Foundation of China(Nos.22273098,52033001,22373003 and 22103002)the Fundamental Research Funds for the Central Universities(No.WK2480000007).
文摘The counterion-mediated hydrogen bonding(CMHB)is related to the hydrogen bonding between bound counterions and polyelectrolyte chains in polyelectrolyte systems,where the counterions can both electrostatically bind to the charged groups of polyelectrolyte chains and act as hydrogen bond donors or acceptors to form hydrogen bonds with the hydrogen bond sites associated with polyelectrolyte chains simultaneously.A large number of literatures illustrate that strong polyelectrolytes(SPs)are insensitive to pH,which severely limmits the applications of SPs as smart materials.However,our studies have demonstrated that the CMHB makes SPs pH-responsive.This perspective discusses the mechanism of pH responsiveness of SPs and the pH-tunable properties of SPs,based on the pH-controlled CMHB effect.The future research directions on the pH responsiveness of SPs are also discussed here.It is anticipated that the study of the pH responsiveness of SPs not only will provide a new understanding of the fundamental properties of SPs,but also will greatly expand the applications of SPs in the field of smart materials.
基金Financially supported from the Science Research Foundation of Shandong Entry-Exit InspectionQuarantine Bureau (No. SK201042)Weifang Medical University (No. KQ2007030)
文摘The title complex bis（2-acetylpyridine thiosemicarbazonato）-indium（iii） perchlo-rate hydrate has been synthesized by the reaction of 2-acetylpyridine thiosemicarbazide（L） with indium（iii） perchlorate,and its structure was characterized by elemental analysis,IR and single-crystal X-ray diffraction.The crystal of the title compound（[In（C8H9N4S）2]ClO4·H2O） belongs to monoclinic,space group P21/c with a = 12.6438（18）,b = 12.6259（18）,c = 15.116（2） nm,β = 105.800（2）°,Z = 4,V = 2321.9（6） nm3,Mr = 618.79,Dc = 1.770 g/cm3,μ = 1.359 mm-1,F（000） = 1240,R = 0.0265 and wR = 0.0675.X-ray analysis indicates that various intriguing hydrogen patterns involving both the solvent intermedia and polyatomic counterions play crucial roles in the self-assembly of functional supramolecules.
基金Supported by National Natural Science Foundation of China under Grant Nos. 20973176,20990234,20874111973 Program of the Ministry of Science and Technology (MOST) 2011CB808502
文摘Scaling theory of charged cylindrical polyelectrolyte brushes is developed. The dependence of brush thickness on the grafting density, charge fraction, and chain length is analyzed. A full phase diagram is established. Characteristics and boundaries between different regimes of cylindrical polyelectrolyte brushes are summarized. Special attentions are paid to electrostatic interaction induced stiffening and counterion condensation effects. If the Bjerrum length of the solution is larger than the Kuhn length of the polyelectrolyte chains, counterion condensation occurs in the strongly charged polyeleetrolyte brushes. On the contrary, the electrostatic interaction stretches the strongly charged grafted polyelectrolyte chains to their contour length.
文摘The extent to which counterions bind to polyelectrolytes influences a variety of polymer-based applications, including polyelectrolyte enhanced ultrafiltration and forward osmosis using polyelectrolytes as draw agents. Potentiometric titrations of poly (2-vinylpyridine) (P2VP), poly (3-vinylpyridine) (P3VP), and poly (4-vinylpydine) (P4VP) were performed using HBr, HCl, HNO<sub>3</sub>, and HClO<sub>4</sub> in both the presence and absence of added NaCl. Because of the systematic differences among the three polyelectrolytes, titration results provide insight into the role of polymer structure in the relative extents to which various counterions bind. Titration data reveal that ionization properties vary as functions of polymer investigated, titrant used, degree of protonation, and added salt concentration. Acid dissociation constants of the pyridinium moieties were found to generally increase with increasing degree of protonation, though appreciable differences were exhibited among the three polymers investigated. For all three polymers, Cl<sup>-</sup> demonstrated the lowest affinity for the charged pyridinium residues, while the affinities associated with Br<sup>-</sup> and NO<sup>-</sup>3</sub> were nearly identical to each other. The relative extent of binding for CIO<sup>-</sup>4</sub> varied across the polymers investigated, and was greatest for P4VP.
基金NSF-CHEM-0137961(to MOF)and in part by the Institute for Mathematics and its Applications with funds provided by the National Science Foundation.
文摘Long-range electrostatic interactions in proteins/peptides associating to nucleic acids are reflected in the salt-dependence of the binding process.According to the oligocationic binding model,which is based on counterion condensation theory,only the cationic residues of peptides/proteins near the binding interface are assumed to affect the salt dependence in the association of peptides and proteins to nucleic acids.This model has been used to interpret and predict the binding of oligocationic chains-such as oligoarginines/lysines-to nucleic acids,and does an excellent job in these kinds of systems.This simple relationship,which is used to compare or count the number of ionic interactions in protein-nucleic acid complexes,does not hold when acidic residues,i.e.glutamate and aspartate,are incorporated in the protein matrix.Here,we report a combined molecular mechanics(by means of energy-minimization of the structure under the influence of an empirical energy function)and Poisson-Boltzmann(PB)study on the salt-dependence in binding to tRNA of two important enzymes that are involved in the seminal step of peptide formation in the ribosome:Glutamine synthetase(GluRS)and Glutaminyl synthetase(GlnRS)bound to their cognate tRNA.These two proteins are anionic and contain a significant number of acidic residues distributed over the entire protein.Some of these residues are located in the binding interface to tRNA.We computed the salt-dependence in association,SKpred,of these enzyme-tRNA complexes using both the linear and nonlinear solution to the PoissonBoltzmann Equation(PBE).Our findings demonstrate that the SKpred obtained with the nonlinear PBE is in good agreement with the experimental SKobs,while use of the linear PBE resulted in the SKpred being anomalous.We conclude that electrostatic interactions between the binding partners in these systems are less favorable by means of charge-charge repulsion between negatively charged protein residues and phosphateoxygens in the tRNA backbone but also play a significant role in the association process of proteins to tRNA.Some unfavorable electrostatic interactions are probably compensated by hydrogen-bonds between the carboxylate group of the side chain in the interfacial acidic protein residues and the tRNA backbone.We propose that the low experimentally observed SKobs values for both GlnRS-and GluRS-tRNA depend on the distribution and number of anionic residues that exist in these tRNA synthetases.Our computed electrostatic binding free energies were large and unfavorable due to the Coulombic and de-solvation contribution for the GlnRS-tRNA and GluRS-tRNA complexes,respectively.Thus,low SKobs values may not reflect small contributions from the electrostatic contribution in complex-formation,as is often suggested in the literature.When charges are”turned off”in a computer-experiment,our results indicated that”turning off”acidic residues far from a phosphate group significantly influences SKpred.If cationic residues are“turned off”,less impact on SKpred is observed with respect to the distance to the nearest phosphate-group。
