Complexation between polyelectrolyte and polyampholyte chains in poor solvent conditions for the polyelectrolyte backbone has been studied by molecular dynamics simulations. In a poor solvent a polyelectrolyte forms a necklace-like structure consisting of polymeric globules (beads) connected by strings of monomers. The simulation results can be explained by assuming the existence of two different mechanisms leading to the necklace formation. In the case of weak electrostatic interactions, the necklace formation is driven by optimization of short-range monomer-monomer attraction and electrostatic repulsion between charged monomers on the polymer backbone. In the case of strong electrostatic interactions, the necklace structure appears as a result of counterion condensation. While the short-range attractions between monomers are still important, the correlation-induced attraction between condensed counterions and charged monomers and electrostatic repulsion between uncompensated charges provide significant contribution to optimization of the necklace structure. Upon forming a complex with both random and diblock polyampholytes, a polyelectrolyte chain changes its necklace conformation by forming one huge bead. The collapse of the polyelectrolyte chain occurs due to the neutralization of the polyelectrolyte charge by polyampholytes. In the case of the random polyampholyte, the more positively charged sections of the chain mix with negatively charged polyelectrolyte forming the globular bead while more negatively charged chain sections form loops surrounding the collapsed core of the aggregate. In the case of diblock polyampholyte, the positively charged block, a part of the negatively charged block, and a polyelectrolyte chain form a core of the aggregate with a substantial section of the negatively charged block sticking out from the collapsed core of the aggregate. In both cases the core of the aggregate has a layered structure that is characterized by the variations in the excess of concentration of monomers belonging to polyampholyte and polyelectrolyte chains throughout the core radius. These structures appear as a result of optimization of the net electrostatic energy of the complex and short-range attractive interactions between monomers of the polyelectrolyte chain. 相似文献
The adsorption of two polyampholytes (a random copolymer of
-glutamic acid and
-lysine, and a well-defined tetramer of
-lysyl-
-glutamyl-glycine) onto positively and negatively charged latex was studied as a function of the pH and the ionic strength. The adsorbed amount proved to be almost independent of the salt concentration. The pH dependence was found to follow the same trends on negatively charged and positively charged latex. At low pH, where the polyampholytes are positively charged, a high adsorbed amount was found irrespective of the sign of the surface charge. At high pH, where the macromolecules are negatively charged, no adsorption was measured, not even with the positive latex. This is probably due to the very good solubility of the polyampholytes at this pH. Electrophoretic mobility measurements revealed that already at very low concentrations of polyampholyte charge reversal of the particles occurred. 相似文献
A novel cellulose-based polyampholyte derivative, carboxylethyl quaternized cellulose (CEQC), was homogeneously synthesized by introducing positively charged quaternary ammonium groups and negatively charged carboxyl groups to the backbone of cellulose. The structure and dilute solution properties of CEQCs were characterized with elemental analysis, FTIR, NMR, viscometer, light scattering and zeta-potential measurement. The nitrogen content and total degree of substituent of acylamino and carboxyl groups increased with an increase of the molar ratio of acrylamide to the anhydroglucose unit of quaternized cellulose (QC). The salt-resistance of CEQC was improved remarkably by introducing opposite charged carboxyl to the QC chains. The intrinsic viscosity of the prepared polyampholytes was found to be very sensitive to the pH of the solutions. CEQC-1, the sample with relative low content of carboxyl groups, behaved as a classical cationic polyelectrolyte. However, CEQC-2 and CEQC-3, the samples with higher content of carboxyl groups, displayed typical polyampholyte behavior, and the isoelectric points (IEP) were determined to be 5.0 and 3.8 respectively. This work provided a facile method for the synthesis of novel cellulose-based polyampholytes with different IEP. 相似文献
The structure of spherical brushes formed by symmetric diblock polyampholytes end-grafted onto small spherical particles in aqueous solution is examined within the framework of the so-called primitive model using Monte Carlo simulations. The properties of the two blocks are identical except for the sign of their charges. Three different chain flexibilities corresponding to flexible, semiflexible, and stiff blocks are considered at various polyampholyte linear charge densities and grafting densities. The link between the two blocks is flexible at all conditions, and the grafted segments are laterally mobile. Radial and lateral spatial distribution functions of different types and single-chain properties are analyzed. The brush structure strongly depends on the chain flexibility. With flexible chains, a disordered polyelectrolyte complex is formed at the surface of the particle, the complex becoming more compact at increasing linear charge density. With stiff blocks, the inner blocks are radially oriented. At low linear charged density, the outer blocks are orientationally disordered, whereas at increasing electrostatic interaction the two blocks of a polyampholyte are parallel and close to each other, leading to an ordered structure referred to as a polyampholyte star. As the grafting density is increased, the brush thickness responds differently for flexible and nonflexible chains, depending on a different balance between electrostatic interactions and excluded volume effects. 相似文献
In this work we display recent findings on the conformations and dynamics of polyampholytes (PAs; polymers with positively and negatively charged monomers) in external electrical fields. We consider the case in which the interactions between the charges are less important (weak coupling limit) and also the case in which they are fundamental (strong coupling case). In the weak coupling limit we present analytical results for Gaussian and also for freely-jointed chains. Through scaling arguments we discuss the influence of the excluded volume on the PA's configurations. Furthermore we evaluate the dynamics of PAs in the framework of the Rouse and of the Zimm models. In the strong-coupling regime PAs with vanishing total charge form spherical globules. Using a droplet analogy we examine the response of PAs to external fields and show the onset of an instability reminiscent of a first-order phase transition. 相似文献
The thermodynamic properties of 6-mer polyampholyte chains were simulated with the multicanonical Monte Carlo method in a three-dimensional off-lattice model. The results demonstrate that the number of the charged monomers on the chain and the sequence significantly affect the transition behaviors of polyampholyte chains. In the case of the random distribution of the charged monomers, two oppositely charged monomers act as two stickers during a collapse process, due to which the movement of monomers is suppressed and the chains can more directly reach their solid state. Interestingly, in a proper arrangement of the charged monomers, the chains may have a proteinlike nondegenerate state, i.e., the chain is designable. The transition of such polyampholyte chains appears to be of a two-state, all-or-none type. 相似文献
Solution properties of copolymers [C(MA-Py)x] of methacrylic acid and 4-vinylpyridine and intermacromolecular complexes of poly(methacrylic acid) (PMAA) and poly(4-vinylpyridine) (PVP) in the presence or absence of a proton-accepting water-soluble polymer such as poly(ethylene glycol) (PEG) in water/methanol mixed solvent are studied by potentiometric titration, turbidity and viscosity methods. These copolymers behave like polyampholytes and their solubilities are strongly dependent with pH changes. The pH regions where they are precipitated around their isoelectric points are narrower than those of the intermacromolecular complex of PMAA with PVP. The polyampholyte can form an intermacromolecular complex with PEG in acidic solution but this complex is soluble in the medium. 相似文献
This paper summarizes investigations on the radical polymerization of cationic vinyl monomers with respect to the peculiarities of the reaction in aqueous solution, the synthesis of model polymers and polyelectrolytes with regular structure as well as to a new process of stabilized precipitation polymerization. The rate of polymerization depends on the ionic strength of the solution. Random copolymers of diallyldimethylammonium chloride and acrylamide with variable charge density but equal molecular weight were synthesized by a feeding technique. Block copolymers consisting of charged and uncharged monomelic units with different hydrophilicity are available using macroazoinitiators. The novel polymers are powerful stabilizers in the precipitation polymerization of water soluble cationic vinyl monomers in aqueous salt solution leading to a dispersion of fine polymer particles. Polyampholytes with alternating positively and negatively charged monomelic units in the backbone were obtained by cyclocopolymerization of diallylanmine compounds and derivatives of maleic acid. 相似文献
Weak polyampholytes are charged polymers, where the charge asymmetry can be tuned by varying the solution pH. We determine the size of a randomly charged weak polyampholyte in dilute solution as a function of charge asymmetry, Bjerrum length, salt concentration, pH, and degree of polymerization, using a self‐consistent method. It is known that in the limiting cases of low and high charge asymmetries, polyampholytes behave as neutral polyampholytes and polyelectrolytes, respectively. We explore in detail the regime of intermediate charge asymmetry where a polyampholyte show non‐monotonic change in the chain size as a function of Bjerrum length. A hierarchy of structures exists at different length scales, ranging from ideal coils at low Bjerrum length, extended rod‐like state at intermediate Bjerrum length to globular states at high Bjerrum length. The transition between ideal coil and rod‐like states is continuous, while that between rod‐like and globular states is discontinuous. The addition of salt changes the nature of the rod‐to‐globule transition from discontinuous to continuous. The effective free energy shows a double minimum at intermediate charge asymmetry, indicating the coexistence of globules and extended states. The size as a function of the solution pH shows a minimum at the isoelectric point. The size of neutral polyampholytes at the isoelectric pH increases with the increase in the salt concentration. The size of charge excess polyampholytes far away from the isoelectric pH decreases with the increase in the salt concentration.
We have investigated the adsorption of randomly annealed polyampholytes containing [2-(dimethylamino)ethyl methacrylate)] (DMAEMA), methacrylic acid (MAA), and [3-(2-methylpropionamido)propyl] trimethylammonium chloride (MAPTAC) with various molar compositions. The adsorption was performed from dilute aqueous solutions onto silicon substrates. The adsorbed layers were characterized by reflectivity techniques such as reflectometry, ellipsometry, and neutron specular reflection. As expected for annealed polyampholytes, the adsorption was found to depend strongly on the pH, with a maximum within the isoelectric domain of the polyampholyte. The monomer volume fraction profiles of the adsorbed layers were determined from neutron specular reflection measurements. In the isoelectric domain, the polyampholyte chains adopt a compact conformation, with a layer thickness of about 60 A. The polyampholyte layer is as dense as the adsorbed layer of fully charged polyelectrolyte but much thicker. Finally, we found that changing the ratio of neutral units along the polyampholyte chain in the isoelectric domain had no significant effect on the concentration profile of the adsorbed layer. 相似文献
The synthesis of 2'-amino-LNA (the 2'-amino derivative of locked nucleic acid) has opened up a number of exciting possibilities with respect to modified nucleic acids. While maintaining the excellent duplex stability inferred by LNA-type oligonucleotides, the nitrogen in the 2'-position of 2'-amino-LNA monomers provides an excellent handle for functionalisation. Herein, the synthesis of amino acid functionalised 2'-amino-LNA derivatives is described. Following ON synthesis, a glycyl unit attached to the N2'-position of 2'-amino-LNA monomers was further acylated with a variety of amino acids. On binding to DNA/RNA complements, the modified ONs induce a marked increase in thermal stability, which is particularly apparent in a buffer system with a low salt concentration. The increase in thermal stability is thought to be caused, at least in part, by decreased electrostatic repulsion between the negatively charged phosphate backbones when positively charged amino acid residues are appended. Upon incorporation of more than one 2'-amino-LNA modification, the effects are found to be nearly additive. For comparison, 2'-amino-LNA derivatives modified with uncharged groups have been synthesised and their effect on duplex thermal stability likewise investigated. 相似文献
We report molecular dynamics simulations of DNA adsorption on a single-walled carbon nanotube (SWNT) in an aqueous environment. We have modeled a DNA segment with 12 base pairs (Dickerson dodecamer) and a (8,8) SWNT in water, with counterions to maintain total charge neutrality. Simulations show that DNA binds to the external surface of an uncharged or positively charged SWNT on a time scale of a few hundred picoseconds. The hydrophobic end groups of DNA are attracted to the hydrophobic SWNT surface of uncharged SWNTs, while the hydrophilic backbone of DNA does not bind to the uncharged SWNT. The binding mode of DNA to charged SWNTs is qualitatively different from uncharged SWNTs. The phosphodiester groups of the DNA backbone are attracted to a positively charged SWNT surface while DNA does not adsorb on negatively charged SWNTs. There is no evidence for canonical double-stranded DNA wrapping around either charged or uncharged SWNTs on the very short time scales of the simulations. The adsorption process appears to have negligible effect on the internal stacking structure of the DNA molecule but significantly affects the A to B form conversion of A-DNA. The adsorption of A-DNA onto an uncharged SWNT inhibits the complete relaxation of A-DNA to B-DNA within the time scale of the simulations. In contrast, binding of the A-DNA onto a positively charged SWNT may promote slightly the A to B conversion. 相似文献
A poly(phenylene ethynylene) conjugated polymer (PPE-NMe(3)(+)-COO(-)) containing tetraalkylammonium groups and carboxylate groups has been synthesized by Sonogashira coupling. Due to the presence of the strong cationic and weak anionic pendant units, the polymer undergoes a pH-induced transition from cationic polyelectrolyte to polyampholyte due to deprotonation of the carboxylic acid units in basic solution. Studies of the pH dependence of the polymers' optical properties reveal changes in absorption oscillator strength and fluorescence quantum efficiency that are triggered by the transition from cationic polyelectrolyte to polyampholyte nature. Stern-Volmer fluorescence quenching of PPE-NMe(3)(+)-COO(-) with a negatively charged quencher 1,4,5,8-naphthalenediimide-N,N-bis(methylsulfonate) (NDS) shows that the polymer fluorescence quenching is amplified at low pH where the polymer is a polycation, whereas the quenching efficiency is considerably less at high pH. 相似文献
The electrosurface properties and aggregation stability of aqueous titanium-dioxide suspensions are studied in wide ranges of medium pH values and poly(methacrylic acid) concentrations. Using the 2pK model, the ionization constants of surface hydroxyl groups of titanium dioxide are found and it is established that the adsorption of poly(methacrylic acid) macromolecules substantially decreases the fraction of neutral (uncharged) hydroxyl groups and affects the ratio between the positively and negatively charged surface hydroxyl groups. 相似文献
The surface of silicon carbide (SiC) particles previously subjected to passive oxidation has been characterized using various techniques such as adsorption of positively and negatively charged surfactants in aqueous solution, immersion microcalorimetry in three probe liquids, and flow microcalorimetry in organic media. Adsorption data show that around one quarter of the surface appears negatively charged and thus hydrophilic, while three quarters appear uncharged and hydrophobic. This is attributed to dissociation of silanols groups. Immersion calorimetry in liquids having well-defined polar and nonpolar components of surface energy shows that the Lifshitz-van der Waals component of SiC is very high and that the acid and basic components are weak. The experimental results appear to be consistent with both computations of surface energy using Lifshitz theory and experimental data previously obtained with other minerals. The three indexes are discussed and it is argued that they represent different terms of the solid surface energy. Copyright 2000 Academic Press. 相似文献
The interactions of two partially charged ampholytic terpolymers [consisting of acrylamide, sodium 2-acrylamido-2-methylpropanesulphonate,
and 2-(methacryloyloxyethyl)trimethylammonium chloride segments with molar compositions 80/12/08 and 80/08/12] and two fully
charged ampholytic copolymers (containing only the two latter comonomers with molar compositions of 80/20 and 50/50), with
cationic surfactants [tetradecyl- trimethylammonium bromide (TTAB) and cetyltrimethylammonium bromide (CTAB)] and the anionic
surfactant sodium dodecylsulphate (SDS), are investigated. The studies include phase behaviour (swelling, solubilisation,
precipitation), viscometry, electrical conductivity, and potentiometry (bromide ion and surfactant ion-specific electrodes).
The 80/08/12 and 80/12/08 polyampholytes swell in water and are solubilised in the presence of cationic or anionic surfactants
above a particular surfactant concentration that is proportional to the polymer concentration. The polyampolyte 80/20 is soluble
in water but precipitates in the presence of TTAB, whereas 50/50 is insoluble in water and in the presence of TTAB, but is
solubilised upon addition of SDS. The results indicate that TTAB binds to 80/12/08 with little or no cooperativity. Solubilisation
appears to be the result of the increasing polyelectrolyte character of the polyampholyte upon neutralisation of its charged
sites by bound surfactant ions of opposite charge. The binding of TTAB by the 50/50 polyampholyte is very weak and non-cooperative.
In contrast, 80/20 binds TTAB cooperatively, much like a true polyelectrolyte-surfactant system of opposing charges. In particular,
the binding is characterised by the existence of a critical aggregation concentration. A partial phase diagram for this system
has been determined from the TTA+-electrode potential data. The behaviour of true polyelectrolytes and polyampholytes, with respect to their interaction with
surfactants, is discussed.
Received: 22 July 1998 Accepted: 14 September 1998 相似文献
The conformation and titration curves of weak (or annealed) hydrophobic polyelectrolytes have been examined using Monte Carlo simulations with screened Coulomb potentials in the grand canonical ensemble. The influence of the ionic concentration pH and presence of hydrophobic interactions has been systematically investigated. A large number of conformations such as extended, pearl-necklace, cigar-shape, and collapsed structures resulting from the subtle balance of short-range hydrophobic attractive interactions and long-range electrostatic repulsive interactions between the monomers have been observed. Titration curves were calculated by adjusting the pH-pK(0) values (pK(0) represents the intrinsic dissociation constant of an isolated monomer) and then calculating the ionization degree alpha of the polyelectrolyte. Important transitions related to cascades of conformational changes were observed in the titration curves, mainly at low ionic concentration and with the presence of strong hydrophobic interactions. We demonstrated that the presence of hydrophobic interactions plays an important role in the acid-base properties of a polyelectrolyte in promoting the formation of compact conformations and hence decreasing the polyelectrolyte degree of ionization for a given pH-pK(0) value. 相似文献
The interaction of ampholyte propylenimine dendrimers containing peripheral carboxyl groups and inner tertiary amino groups with linear polyelectrolytes has been studied. Both in acidic and alkaline media up to pH ~ pI, dendritic polyampholytes can form interpolyelectrolyte complexes with flexible linear polyanions and polycations. A variation in the composition of complexes with a change in pH is associated with the formation of intramolecular zwitterion pairs in a dendrimer molecule. The ability of interpolyelectrolyte complexes to dissolve in water is shown to be determined by the degree of dissociation of ionogenic groups of the dendrimer not directly involved in the formation of interpolyelectrolyte salt bonds stabilizing the complex. It has been demonstrated that the territorial separation of carboxyl and tertiary amino groups in the polyampholyte dendrimers is reflected in different structures of interpolyelectrolyte complexes formed by dendrimers with oppositely charged linear polyions. 相似文献