Effect of pH on complexation in mixed dilute aqueous solutions of poly(acrylic acid), poly(ethylene glycol), and Cu2+ ions

The phase states of mixed dilute solutions of PAA, PEG, and Cu²⁺ ions largely determines the mechanism governing the growth of metal nanoparticles during the subsequent reduction of copper ions. Mixtures with PAA: PEG > 1 base-mol/base-mol and PAA: Cu²⁺ ≥ 5 base-mol/mol are studied. It is shown that the simultaneous complexation of PAA with PEG and Cu²⁺ ions in these mixtures at pH values below the intrinsic pH of a solution is accompanied by phase separation related to insolubility of PAA-PEG interpolymer complexes. A decrease in the pH of the ternary mixture is caused by the release of a strong low-molecular-mass acid due to complexation with Cu²⁺ ions. The minimum pH value, above which the PAA-PEG-Cu²⁺ system becomes single-phase (a transparent solution), depends on the concentration ratio between PAA and PEG chains (the mean degree of polymerization). This value is either 6.8–7.0 (if all macromolecules are incorporated in the insoluble interpolymer complex with PEG) or 4.0 (if chains occur in excess). Methods of preparing single-phase systems in the pH range 4.0–7.0 via exchange reactions of the PAA-Cu²⁺ complex with PEG or the nonstoichiometric soluble interpolymer complex PAA-PEG are developed. Viscometry, electron microscopy, and dynamic light scattering are used to investigate the compositions and structures of soluble complexes, in which either each chain (if the chain is long) may be linked with both PEG and Cu²⁺ ions or PAA chains are redistributed between two complexes (at comparable lengths of PAA and PEG chains).     

Stabilization of copper nanoparticles prepared by reduction from solutions of poly(acrylic acid) complexes with Cu2+ ions and poly(ethylene glycols)

Copper sols are prepared via the reduction of copper ions with hydrazine borane in dilute aqueous solutions of mixtures of the PAA-Cu²⁺ complex and poly(ethylene glycols) of various molecular masses at PEG: PAA = 0.25 base-mol/base-mol and PAA: Cu²⁺ = 10 base-mol/mol in the pH range 4.0–7.0. The stability of sols against oxidation (dissolution) or aggregation (enlargement) of metal nanoparticles is much higher than that of sols prepared in the absence of PEG. With an increase in the initial pH or a decrease in the molecular mass of PEG, the formed copper nanoparticles are much larger (no less than 20 nm in diameter) than copper nanoparticles occurring in the sol prepared in a solution of the PAA double complex with Cu²⁺ ions and high-molecular-mass PEG at a low initial pH (3–10 nm in diameter). Copper nanoparticles in sols prepared in solutions of complexes based on the high-molecular-mass PEG do not aggregate during exposure, thereby indicating the high stability of polymer screens on their surfaces.     

Nonstoichiometric polyelectrolyte complexes of chitosan soluble in neutral solutions

The technique of preparing nonstoichiometric polyelectrolyte complexes of chitosan soluble in neutral solutions is developed. Chitosan complexes soluble in neutral solutions and meeting the behavioral criteria of water-soluble nonstoichiometric polyelectrolyte complexes are prepared via mixing of strongly acidic solutions of chitosan and polystyrenesulfonate anions taken in a nonequimolar charge-charge ratio and subsequent neutralization of the products by a solution of alkali. Thus, the region of existence of soluble complexes narrows with a decrease in the length of the host polyanion up to its full degeneration in the case of oligomeric anions. The critical concentration of a salt that brings about phase separation decreases with an increase in the relative content of the guest chitosan in a mixture and depends on the ratio of chain lengths of polymer components.     

Nonstoichiometric polyelectrolyte complex of carboxymethylcellulose and N‐methylated poly(2‐vinylpyridine): Formation of a gel‐like structure

The formation of polyelectrolyte complexes between carboxymethylcellulose and N‐methylated poly(2‐vinylpyridine), at a nonstoichiometric mixing ratio, was studied. Various methods, such as viscometry, turbidimetry, electrophoresis, and optical spectroscopy, were used to investigate the complexes with respect to their composition, structure, and stability in aqueous systems of different ionic strengths. A gel‐like structure was proposed for the nonstoichiometric polyelectrolyte complexes. Two steps of complex formation—ionic bond formation followed by its rearrangement—were identified. The conformational change of the polyelectrolyte chains in the complexes, responsible for the slower and latter step, was followed by viscometry, and the results were interpreted on the basis of a model proposed for the kinetics of swelling of hydrogels. A similarity was found between the kinetics of diffusion of polymer segments responsible for the swelling of a macrogel of a nonionic polymer and the rearrangement of ionic bonds leading to the formation of a nonstoichiometric polyelectrolyte complex el. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2288–2295, 2003     

Interactions between macromolecules and metal nanoparticles in aqueous-saline media

The influence of the concentration of low-molecular-mass salt additives in the reaction medium on the size characteristics of copper nanoparticles in sols formed through the reduction of Cu²⁺ ions in the presence of a cationic polyelectrolyte and nonionogenic polymers with hydrophilic (poly(ethylene oxide) and hydrophobic (poly(N-vinylpyrrolidone)) main chains has been studied. Formation of sols with a narrow size (diameter) distribution of metal nanoparticle indicates the pseudomatrix character of formation of the metal phase under the studied conditions. Effects of the neutral salt and its concentration in the reaction medium on the synthesis of copper sols and on the mean size of metal nanoparticles are related to a change in the nature or character (when oppositely charged polyelectrolyte macromolecules and copper nanoparticles are involved in interaction) of noncovalent interactions stabilizing the macromolecule-nanoparticle complex on passage from the salt-free aqueous medium to the aqueous-saline medium with a sufficiently high concentration of the neutral salt.     

Interaction of cationic surfactant and anionic polyelectrolytes in mixed aqueous solutions

Surfactant–polymer interactions in aqueous solutions have been studied using dynamic surface tension, polyelectrolyte titration, nephelometric turbidity, and dynamic light scattering. For the preparation of complexes, a technical cationic surfactant was used in combination with two poly(maleic acid-co-polymers) of similar structure but different hydrophobicity. The dynamic surface tensions of mixed solutions as functions of surfactant concentration at constant polyelectrolyte content, as well as changes in the surface activity due to the influence of polyanion at constant surfactant concentration are discussed in terms of a complex or aggregate formation in the bulk phase. The interaction of the surfactant with poly(maleic acid-alt-propene) (P-MS-P) and poly(maleic acid-alt--methylstyrene) (P-MS-MeSty), respectively, is strong in both cases and results in the formation of nanoparticles with properties depending on the composition of the corresponding mixture.     

Formation of copper sols via reduction of Cu2+ ions in solutions of cationic and anionic polyelectrolytes

Zero-valence copper sols are prepared at 20°C via the chemical reduction of Cu(II) ions in aqueous solutions of high-molecular-mass cationic and anionic polyelectrolytes [(poly(1,2-dimethyl-5-vinylpyridium methyl sulfate) and poly(sodium styrenesulfonate), respectively]. In both sols, metal nanoparticles are characterized by narrow size distribution, indicating the pseudomatrix mechanism of their formation; however, the diameter of spherical copper particles formed in the polycation solution (3–14 nm) is much smaller than that of particles formed in the solution of polyanion (10–30 nm). Causes of different sizes of metal nano-particles formed in solutions of polyelectrolytes with different chain charges are discussed in terms of the pseudomatrix mechanism of new phase synthesis in polymer solutions and classical electrocapillary theory.     

Water-soluble nonstoichiometric polyelectrolyte complexes of chitosan with a polystyrenesulfonate anion

Chitosan complexes that meet the performance criteria of water-soluble nonstoichiometric polyelectrolyte complexes have been first prepared via the interaction of chitosan with excess polystyrenesulfonate anions in acidic media. Thus, the region of the existence of soluble complexes can be narrowed down through a decrease in the degree of polymerization of a lyophilizing polyanion until fully degenerates as in the case of oligomeric anions. The critical concentration of a salt that brings about phase separation decreases with an increase in the relative content of a blocking chitosan in a mixture and depends on the ratio of chain lengths of polymer components. This is also typical of nonstoichiometric polyelectrolyte complexes. The results of this study may be useful for designing soluble chitosan complexes with polyanions, including those of biological origin.     

Complex Formation of Polyphosphate Sodium with Cationic Polymers

Abstract

The products of the interaction of opposite charged complementary macromolecules, the so called polyelectrolyte complexes (PEC) in polyphosphate sodium-hydrochlorided poly-2-vinylpyridine (PPhNa-P2VPy.HCl) and polyphosphate sodium-polynexamethylenguanidine (PPhNa-PMG) systems, are studied. The composition of PEC was determined by electrochemical methods. At [polyanionl]:[polycationl=l (base-mol) ratio the forming stoichiometric complex precipitates. The investigation in solutions were carried out at [polyanionl: :[polycationl=1.25 ratio. In Figure the dependencies of the reduced viscosity of PPhNa-P2VPy.HCl solutions on pH at different degrees of polymerization of PPhNa (n) are given. The curves resemble those for polyampholytes. Probably PEC can be considered as poly-ampholyte in some cases. For PPhNa-PMG systems the η_SP/C-pH dependencies point to the weakly expressed character of complex formation.     

Nonstoichiometric polymer-surfactant complexes obtained in a lamellar lyotropic medium

The addition of a polyelectrolyte to lamellar media formed by an oppositely charged surfactant often leads to the coexistence of several phases without macroscopic phase separation, which makes their characterization difficult. Here, the effect of the polydiallyldimethylammonium chloride (PD) on the lamellar liquid crystal formed by the anionic surfactant Aerosol OT (AOT) and water is investigated. Small-angle X-ray scattering results are discussed regarding the changes in the lamellar spacing as a function on the PD or AOT concentrations. In most of the samples, two lamellar phases, without macroscopic phase separation, are detected. One of them is a typical swollen phase, while the other is a collapsed phase, which corresponds to the polymer-surfactant complex. At concentrations of polymer up to 3?wt%, the two lamellar phases coexist; however, at a critical concentration higher than 3?wt%, the swollen phase becomes isotropic, and a macroscopic phase separation takes place. A simple model is proposed to calculate the composition of the phases when macroscopic phase separation does not occur. The results thus calculated show that generally the polymer-surfactant complexes are nonstoichiometric containing a lesser amount of polymer than ideally expected.     

Preparation and adsorption of refined polyelectrolyte complex nanoparticles

We report on bulk and surface properties of centrifuged nonstoichiometric polyelectrolyte complex (PEC) dispersions. PECs were prepared by mixing poly(diallyldimethylammonium chloride) (PDADMAC) and sodium poly(maleic acid-co-alpha-methylstyrene) (PMA-MS) at the monomolar mixing ratio of 0.6 and polymer concentration >/=1 mmol/l. Centrifugation of initial PEC dispersions revealed three phases: supernatant (SUP), coacervate (COAC), and an insoluble precipitate. Mass, turbidity, particle hydrodynamic radii (R(h)), and the titratable charge amount were determined for those phases. The turbid COAC phase consisted of 200-nm nanoparticles and carried 60% of the polymer mass and 20% of the titratable charge amount of the initial PEC dispersion. The SUP phase showed no turbidity and no such nanoparticles, but carried 80% of the initial titratable charge amount, presumably caused by excess polycations. Furthermore, linear dependences of turbidity and R(h) on COAC concentration was observed. COAC adsorption was studied at polyelectrolyte multilayer (PEM) modified silicon surfaces in dependence on both adsorption time and concentration using attenuated total-reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. The adsorption data were fitted by the simple Langmuir model. Comparison of COAC particles and polystyrene latices revealed similar adsorption features. SEM and AFM measurements resulted in hemispherically shaped adsorbed COAC particles with coverages >/=25%, whose calculated volumes correlated well with those in dispersion obtained by PCS.     

Colloidal complexes from poly(vinyl amine) and carboxymethyl cellulose mixtures

The phase behaviors of polyelectrolyte complexes formed from dilute solutions of poly(vinyl amine) (PVAm) and carboxymethyl cellulose (CMC) were determined as a function of overall composition and pH. The phase diagram included regions with soluble complexes, colloidal complexes, and macroscopic precipitates. Colloidal complexes were stable when either polymer was in sufficient excess to give electrosteric stabilization. The polymer mixing ratios giving complexes with an isoelectric point of 7 could be predicted from a simple model using the degree of ionization vs pH data for PVAm and CMC. The model failed at extreme pH values because not all added polymer was incorporated into the complexes. At pH 7, essentially all the added polymer was incorporated into the colloidal complex or precipitate, as long as the mixing ratio was within +/-10% of charge stoichiometry. The interaction of PVAm and CMC at pH 7 was endothermic, supporting the generally accepted viewpoint that the interaction of oppositely charged polyelectrolytes is entropy-driven. Although the colloidal complexes had a broad particle size distribution, the average particle size was rather insensitive to mixing ratio. By contrast, complex size was sensitive to electrolyte concentration with no complex formation when the NaCl concentration was > or =2 M.     

Nonstoichiometric interpolyelectrolyte complexes as colloidal dispersions based on NaPAMPS and their interaction with colloidal silica particles

Preparation and characterization of some nonstoichiometric interpolyelectrolyte complexes (NIPECs) as stable colloidal dispersions by the interaction between poly(sodium 2-acrylamido-2-methylpropanesulfonate) (NaPAMPS) and three strong polycations bearing quaternary ammonium salt centres in the backbone, poly(diallyldimethylammonium chloride) (PDADMAC) and two polycations containing N,N-dimethyl-2-hydroxypropyleneammonium chloride units (PCA₅ and PCA₅D₁), have been followed in this study as a function of the polycation structure and polyelectrolyte concentration. Complex characteristics were followed by polyelectrolyte titration, turbidity and quasi-ellastic light scattering. Almost monodisperse NIPECs nanoparticles with a good storage stability were prepared when total concentration of polyelectrolyte was varied in the range 0.85-6.35 mmol/L, at a ratio between charges (n⁻/n⁺) of 0.7. NIPECs as a new kind of flocculants were used to flocculate a stable monodisperse silica suspension. The main advantage of NIPECs as flocculants is the broad flocculation window, which is a very important aspect for industrial applications.     

Water-soluble nonstoichiometric polyelectrolyte complexes of modified chitosan

A modified polysaccharide that, in each deacetylated unit, carries a functional secondary amino group and a quaternized amino group that provides a positive charge and solubility to the polymer throughout the pH range is prepared by the alkylation of primary amino groups of chitosan with glycidyltrimethylammonium chloride. The mixing of modified chitosan solutions with solutions of polystyrenesulfonate or polymethacrylate anions in neutral solutions gives rise to negatively charged nonstoichiometric polyelectrolyte complexes soluble and stable under physiological conditions. The effects of pH, ionic strength, the degree of polymerization, the nature of the lyophilizing polyanion, and the charge-to-charge ratio of components on the boundaries of existence of soluble complexes are ascertained. The collected experimental data may serve as a basis for designing biocompatible and biodegradable means useful for the delivery of genetic material and drugs to living cells.     

Needlelike and spherical polyelectrolyte complex nanoparticles of poly(l-lysine) and copolymers of maleic acid

We report on the bulk and surface properties of dispersions consisting of nonstoichiometric polyelectrolyte complex (PEC) nanoparticles. PEC nanoparticles were prepared by mixing poly(l-lysine) (PLL) or poly(diallyldimethylammonium chloride) (PDADMAC) with poly(maleic acid-co-alpha-methylstyrene) (PMA-MS) or poly(maleic acid-co-propylene) (PMA-P). The monomolar mixing ratio was n-/n+ = 0.6, and the concentration ranged from 1 to 6 mmol/L. Subsequent centrifugation enabled the separation of the excess polycation, resulting in a stable coacervate phase further used in the experiments. The bulk phase parameters turbidity and hydrodynamic radius (R(h)) of the PEC nanoparticles showed a linear dependence on the total polymer content independently of the mixed polyelectrolytes. This can be interpreted by the increased collision probability of the polyelectrolyte chains when the overlap concentration is approached or exceeded. Different morphologies of the cationic PEC nanoparticles, which were solution-cast onto Si supports, were obtained by atomic force microscopy (AFM). The combinations of PLL/PMA-MS and PDADMAC/PMA-MS revealed more or less hemispherical particle shapes, whereas that of PLL/PMA-P revealed an elongated needlelike particle shape. Circular dichroism and attenuated total reflection Fourier transform infrared (ATR-FTIR) measurements proved the alpha-helical conformation for the PEC PLL/PMA-P and the random coil conformation for the PEC PLL/PMA-MS. We conclude that stiff alpha-helical PLL induces anisotropic elongated PEC nanoparticles, whereas randomly coiled PLL forms isotropic spherical PEC nanoparticles.     

Electrostatic free energy of weakly charged macromolecules in solution and intermacromolecular complexes consisting of oppositely charged polymers

When oppositely charged polyelectrolytes are mixed in water, attraction between oppositely charged groups may lead to the formation of polyelectrolyte complexes (associative phase separation, complex coacervation, interpolymer complexes). Theory is presented to describe the electrostatic free energy change when ionizable (annealed) (macro-)molecules form a macroscopic polyelectrolyte complex. The electrostatic free energy includes an electric term as well as a chemical term that is related to the dissociation of the ionic groups in the polymer. An example calculation for complexation of polyacid with polybase uses a cylindrical diffuse double layer model for free polymer in solution and electroneutrality within the complex and calculates the free energy of the system when the polymer is in solution or in a polyelectrolyte complex. Combined with a term for the nonelectrostatic free energy change upon complexation, a theoretical stability diagram is constructed that relates pH, salt concentration, and mixing ratio, which is in qualitative agreement with an experimental diagram obtained by Bungenberg de Jong (1949) for complex coacervation of arabic gum and gelatin. The theory furthermore explains the increased tendency toward phase separation when the polymer becomes more strongly charged and suggests that complexation of polyacid or polybase with zwitterionic polymer (e.g., protein) of the same charge sign (at the "wrong side" of the iso-electric point) may be due (in part) to an induced charge reversal of the protein.     

Reversible temperature-induced transformations of poly(N-ethyl-4-vinylpyridinium) complexes with dodecyl sulfate in aqueous salt solutions

Supramolecular organization of complexes formed by poly(N-ethyl-4-vinylpyridinium bromide) and sodium dodecylsulfate in aqueous salt solutions was studied as a function of temperature and concentration of the complexes. It was shown that a decrease in temperature and/or concentration of complexes led to their reversible disaggregation into a molecularly dispersed (“unipolymer”) state. The ratio between the components in complex particles remained unchanged in this case. It was first found that phase separation in aqueous solutions of the complexes upon temperature elevation is accompanied by the precipitation of a nonstoichiometric complex.     

Viscosity behavior of poly(glyceryl methacrylate) in the presence of borate and phenylboronate ions

The viscosity behavior of polyelectrolyte solutions induced by borate or phenylboronate complexation with poly(glyceryl methacrylate) (PGM) has been investigated. In dilute solutions borate ions can form monodiol (1/1) complexes and didiol (2/1) intramolecular complexes. Both types of complex are anionic. Thus, the polymer is characterized by the existence of charged sites on the chain and loops formed by intramolecular complexation. On the contrary, phenylboronate can only give monodiol 1/1 complexes. In the presence of passive salt, the charges are screened. By addition of borate ion to a PGM solution, a decrease of the initial polymer viscosity due to loop formation is first observed, then the anionic charges fixed on the chain by complex formation induce an expansion of the polyelectrolyte and the viscosity of the solution increases. The situation is different for the PGM-phenyl boronate system, where no intramolecular crosslink is present. In this case the viscosity of the solution increases with phenyl boronate concentration. But for a fixed complexing ion concentration it will tend to that of the neutral polymer when NaCl is added. ©1995 John Wiley & Sons, Inc.     

Mutual enhancement of the complexing properties of components in tertiary systems containing copper nanoparticles, poly(acrylic acid), and poly(ethylene glycol)

It is shown that nonstoichiometric interpolymer complexes composed of high-molecular-mass poly( acrylic acid) and PEG of various molecular masses are more efficient stabilizers of copper sols than each component of the complex taken separately. This conclusion is based on comparison of dimensions of copper nanoparticles in sols formed via reduction of copper(II) ions in solutions of poly (acrylic acid), PEG, and their blends and on the enhanced stability of sols protected by the interpolymer complex against aggregation and oxidation of metal particles. Much shorter PEG chains than those necessary for formation of corresponding interpolymer complexes in the absence of nanoparticles can be involved in formation of tertiary complexes including copper nanoparticles, poly(acrylic acid), and PEG. On the basis of the experimental data, it is inferred that the mutual enhancement of the complexing behavior of components occurs in tertiary complexes containing copper nanoparticles and both polymers.     

The complex formation between polyacrylamide containing glycine end groups and bovine serium albumin in the presence of copper (II) in neutral aqueous media

Complex formation between end group containing polyacrylamide and BSA has been studied in neutral water. Water soluble and insoluble complexes are formed when divalent copper ions are added to the solution.The contacts between protein and polyelectrolyte are achieved via chelate unit formation in which the copper ion is attached at the center. The solubility of the polycomplexes depends on protein/polymer ratio. Starting with very low concentration of protein in the system, phase separation takes place. Above the critical ratio of the protein/polymer, the mixture again exhibits water soluble character. The velocity of the formation of insoluble ternary complexes has been investigated by spectrophotometric method at different reaction conditions (preparation of mixture, ratio of components, low molecular salts, temperature and stirring, molecular weight of polyelectrolyte and Cu²⁺ concentration). A hypothetical structural scheme for the formation of soluble and insoluble ternary polycomplexes is proposed.