Interaction of ampholyte dendrimers with linear polyelectrolytes

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.     

Fluorescence observations on complex formation between linear and hyperbranched polyelectrolytes in dilute aqueous solutions

The complexation between poly(ethylene imine) (PEI) and poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS) or AMPS copolymers was investigated with the relative excimer emission intensity I_E/I_M of a cationic probe 1-pyrenemethylamine hydrochloride (PyMeA · HCl), fluorescence nonradiative energy transfer (NRET) I_Py/I_Np of naphthalene to pyrene labels, the fluorescence anisotropy r and I_E/I_M of pyrene labels. PEI was a hyperbranched weak polycation in acid solution, which formed complex with anionic polyelectrolytes due to the electrostatic attraction. The I_E/I_M of PyMeA · HCl probe decreased to zero, the intra-, intermolecular NRET I_Py/I_Np and I_E/I_M of pyrene labels on the AMPS copolymers reached their maxima when χ was increased from 0 to 2.4, which was defined as the mole ratio of the amino group in PEI to the AMPS group in the polyanion. These facts indicated the formation of nonstoichiometric complex of the oppositely charged polyelectrolytes when χ = 2.4 at the concentration much lower than their overlap concentrations. The intermolecular aggregate appeared as indicated by an increase in the intermolecular I_Py/I_Np and r with χ up to 2.4 due to neutralizing and hydrophobizing the polyelectrolytes and the bridging effect of the PEI chain bound on different polyanion chains. At high pH, PEI became a neutral polymer and did not bind with the AMPS anion to form the complex as illustrated by the constant value of r for the pyrene labels attached to the AMPS polyanion as that without addition of PEI. The amino group in PEI quenched pyrene and naphthalene emission, resulting a decrease in both I_Np and I_Py.     

Charge transfer processes in conjugated triarylamine-oligothiophene-perylenemonoimide dendrimers

The synthesis and charge transfer properties of triarylamine-oligothiophene-perylenemonoimide dendrimers, TPA(T2-PMI)3 and TPA(T4-PMI)3, are described. The fluorescence quantum yields indicate strong emission quenching by electron transfer [phi(THF) = 0.004 for TPA(T2-PMI)3, phi(THF) = 0.003 for TPA(T4-PMI)3, and phi(THF) = 0.8 for PMI]. Moreover, with the increase of the solvent polarity, the quantum yields decrease indicating that the A+* D-* (acceptor/donor) couple is more stabilized. The femtosecond transient absorption spectra show a very fast charge separation process (approximately 2 ps; k(cs) approximately 5 x 10(11) s(-1)) and a charge recombination of more than 1 order of magnitude slower (approximately 50 ps; k(cr) approximately 2 x 10(10) s(-1)), as observed from the rise time and decay of the radical anion and radical cation absorption bands. The analysis of the transient absorption spectroscopy and of the energetics of the process using Marcus theory indicates that in the electron transfer process the thiophene unit is the first electron donor. The triarylamine is not functioning as a second electron donor, as also substantiated by the absence of an effect of the addition of acid on the emission intensity of the dendrimers. The presence of the triarylamine and/or the proximity of the oligothiophenes does improve the donor capabilities of the oligothiophene unit slightly and enhances its conjugation as seen in the absorption spectra and the transients of the radial cations. These results can be used for a better design of molecular materials for, e.g., photovoltaic applications.     

Effects of topology and size on statics and dynamics of complexes of hyperbranched polymers with linear polyelectrolytes

Brownian dynamics simulations with explicit hydrodynamic interactions have been employed to study generic effects of size and topology in noncovalent (Coulombic-driven) complexes formed by irregular-shaped hyperbranched polymers and linear polyelectrolytes. The behavior of the complexes was explored in detail in terms of static and dynamic properties, both in local and in the entire complex scale. The results were compared to previous studies on perfect dendrimers and other hyperbranched molecules where available. It was found that both molecular weight and structure may impart significant changes to key factors known to be associated with the ability of these systems to take part in relevant nanoscale applications.     

Interaction of interpolyelectrolyte complexes formed by a linear polyelectrolyte and dendrimers or spheres

The interaction between polyelectrolyte complexes formed by a linear polyelectrolyte and a dendrimer or a spherical particle with the opposite charge has been investigated via computer simulation. The influence of the compositions of the complexes on the effective force of the interaction between them has been studied. It has been shown that the effective attraction between the complexes appears at short distances in the vicinity of the isoelectric point. This attraction is correlative in nature and stronger for the complexes of the linear polyelectrolyte with spherical particles than for the complexes with dendrimers.     

Charge transfer complexes of 9-vinyl-carbazole with pi acceptors in homogeneous and in micellar solutions

The molecular association of 9-vinyl-carbazole (CBZ) with three electron acceptors, p-chloranil (CHL), 2,7-dinitro-9-fluorenone (FL), and tetracyano-p-quinodimethane (TCNQ), is studied in acetonitrile and in micellar aqueous solution of sodium dodecyl sulfate (SDS). In both media, stable charge transfer (CT) complexes are formed with association constants in the range of 8-500 M(-1). CBZ and FL form a 1:2 complex in acetonitrile, but in SDS micelles the association is 1:1 due to size restriction and occupancy statistics in the host aggregates. The combination of absorption and fluorescence emission spectroscopy data indicates that the bimolecular CT complex of CBZ with TCNQ is stabilized in two distinct environments of the SDS micelles providing then two separated CT absorption bands.     

Linear polyelectrolytes in tetravalent salt solutions

The effect of adding tetravalent salt of different sizes to a solution of linear and flexible polyelectrolytes is investigated by molecular dynamics simulations. Upon the addition of salt, a chain reexpansion takes place, following a well-known collapsed conformation. The degrees of collapse and reexpansion increase with ion size. In the solution, tetravalent counterions replace monovalent ones and condense onto the chains. The condensation for small ions displays a profile different from that for large ones. In a high-salt region, ions can form layering orders around a polyelectrolyte and locally overcompensate the charge inside. Consequently, the integrated charge distribution reveals an oscillatory behavior away from a chain. By studying the radial distribution function between monomers on different polyelectrolytes, like-charge attraction between chains is demonstrated. This attraction is a prerequisite to chain aggregation or precipitation. The results show a strong dependence of salt concentration and ion size on the properties of polyelectrolyte solutions.     

Absence of charge inversion on rodlike polyelectrolytes with excess divalent counterions

Filamentous viruses such as fd and M13 are highly charged rodlike polyelectrolytes. In this study, we employ fd virus to test the recent prediction of charge inversion [Nguyen, Rouzina, and Shklovskii, J. Chem. Phys. 112, 2562 (2000)]. Light scattering measurements show bundle formation and resolubilization of fd viruses when MgCl(2) was added from 0 to 600 mM. The effective charge of fd was studied by measuring their electrophoretic mobility using a filament tracking method uniquely suited for the system. Monte Carlo simulations were performed under canonical ensemble to predict the charge distribution around the rodlike virus. Charge inversion, which has been suggested theoretically to accompany with bundle resolubilization, was not observed in either experiments or simulations. A modified analysis of force balance is called upon to account for these new findings.     

Viscometric and conductometric study of polyelectrolytes of low charge density in salt free aqueous solutions

Viscometric and conductometric measurements have been performed on dilute, salt free solutions of poly(vinyl alcohol) (PVA) and poly(vinyl alcohol, vinyl sulphate ester) copolymer salts in order to get information on transition from a neutral to charged macromolecules. With increasing linear charge density from a very low value to a moderate one a non linear dependence of polyelectrolyte effect on copolymer composition was observed. A comparison has shown that there is a close analogy between the expansion of polyanions and swelling of polyelectrolyte networks at comparable linear charge density range. Due to the intra- and inter-molecular mobile ionic bridges a considerable contraction was pointed out by viscometry for barium, magnesium and copper salts. However, the differences in properties of counterions of higher charge number indicates that in addition to the valency, there is a definite chemical effect, too. It has been revealed by the electric conductance measurements that the transition from a neutral to charged macromolecules could be a very complex one calling for a new and more detailed theoretical consideration of polyelectrolyte solutions.     

Intrinsic viscosity of polyelectrolytes in salt solutions

The dependence of the intrinsic viscosity of polyelectrolytes on the concentration of added salt is given satisfactorily by a formula obtained recently. A new viscosity—molecular weight relation gives satisfactory agreement with experiments.     

Interpolyelectrolyte complexes formation in dependence on the nature of polyelectrolytes

Interpolyelectrolyte complexes (PECs) were obtained starting from polycations with (N,N-dimethyl-2-hydroxypropylenammonium chloride) units in the main chain and sodium salts of the poly(acrylic acid), on one hand, and poly (2-acrylamido-2-methylpropane sulfonic acid), on the other hand, as polyanions. The polycations were different as concerns both the content of the quaternary ammonium salt groups and the degree of branching. The polyanions were different both by their structure and molecular weight. The complex formation was followed through the variation of the reduced viscosity and of the conductivity of the reaction medium vs. the unit molar ratio polyanion/polycation in two ranges of concentration.     

Electrostatic-interaction-induced phase separation in solutions of flexible-chain polyelectrolytes

A model of a polyelectrolyte solution has been formulated on the basis of the formalism of the thermodynamic perturbation theory. Macromolecules have been described in terms of the model of a flexible chain with an excluded volume and a variable electrical charge. During construction of the thermodynamic perturbation theory, a set of three independent subsystems—polyelectrolyte macromolecules placed in a structureless charge background of counterions, counterions placed in a structureless charge background of macromolecules, and Coulomb gas ions of a low-molecular-mass salt—has been taken as the reference system. In the framework of this model, liquid-liquid phase separation due to strong correlation-induced attraction has been predicted. The behavior of the degree of ionization over a wide monomer concentration range, including the region of phase separation either in a salt-free solution or in the presence of univalent ions of a low-molecular-mass salt in the solution, has been studied. It has been shown that macromolecules in the coexisting phases should have different degrees of ionization. The occurrence of phase separation under normal conditions in the case when dimethylformamide is taken as a solvent and the nonoccurrence of this phase separation in the case of aqueous solutions of flexible-chain polyelectrolytes are predicted.     

Osmotic deswelling of microgels by linear polyelectrolytes

Polyacrylate microgels used as absorbers or viscosifiers in water are known to have these useful qualities reduced in the presence of linear poly-electrolytes. An osmotic deswelling mechanism is postulated whereby the counterions from linear chains sterically excluded from the gel act to draw solvent from the gel phase. This postulate is tested using intrinsic viscosity measurements of Carbopol microgels, made with the linear polyelectrolyte considered as parr of the solvent. The intrinsic viscosity is used to calculate the swollen-to-dry volume ratio for the microgel in the presence or absence of 0.1% linear sodium polyacrylate over a range in ionic strength. Simultaneously, a standard treatment for the free energy of a network of non-Gaussian chains containing fixed charges is modified to include the osmotic effect of the excluded counterions. In the absence of linear polymer, the theory is fit to the data, the fitting parameter being the 3100 monomer units between crosslink sites in the network. In the presence of high (350 000) molecular weight linear polymer, good agreement is found between the observed deswelling and that predicted if the linear chains are totally excluded. Lower molecular weight linear chains are found to give a reduced deswelling which is shown to be self-consistent with their partitioning into the network.Presented in part at the 64th Colloid and Surface Science Symposium, Lehigh University, June 1990     

Precipitation of oppositely charged polyelectrolytes in salt solutions

We study phase separation in symmetric solutions of weakly charged flexible chains of opposite sign. Precipitation is caused by effective attractions due to charge fluctuations and by short-range attractions between monomers. The contribution from charge fluctuations is computed within the random phase approximation (RPA), which takes into account the connectivity of charges in the polyions. The impenetrability of the ions is accounted for by using a modified Coulomb potential in the RPA. In good solvent conditions the precipitate monotonically swells and eventually dissolves upon addition of salt. However, near the theta-solvent condition, but still in the good solvent, the precipitate can be stable at any salt concentration. Moreover, the density of the precipitate after initial decrease can increase with addition of salt. This effect is a result of redistribution of salt between the precipitate and the supernatant, which is due to an interplay of electrostatic and hardcore interactions. For not too weakly charged polyions the precipitate properties become strongly dependent on temperature even in good solvent conditions.     

Nematic ordering in dilute solutions of rodlike polyelectrolytes

Quantitative theory of orientational behavior of rodlike polyelectrolytes in dilute solution is developed. We find that in salt-free solutions many-body Coulomb interactions between macro- and counterions favor nematic ordering. It is shown that the orientationally isotropic phase of the solution becomes unstable toward nematic ordering at polymer concentration smaller than the overlap concentration. Our predictions are consistent with experimental observations for synthetic polyelectrolytes poly(p-phenylene)sulfonates in aqueous solutions.     

A unified analytical treatment of the acid-dissociation equilibria of weakly acidic linear polyelectrolytes and the conjugate acids of weakly basic linear polyelectrolytes

 The influence of added sodium chloride concentration levels on the acid-dissociation equilibria of a weakly acidic linear polyelectrolyte and a conjugate acid of weakly basic linear polyelectrolyte has been investigated potentiometrically by use of polyacrylic acid (PAA) and poly(N-vinylimidazole) (PVIm) as examples of polyelectrolytes. Both equilibria are strongly influenced by the degree of dissociation of the polyacids as well as the concentration levels of sodium chloride due to an electrostatic effect originating from the negatively or positively charged polymer surfaces. These have been analyzed in a unified manner by taking accounts of two-phase properties of the charged linear polyions. Distribution of counterions and coions between a polyelectrolyte phase formed around the polymer skeleton and a bulk solution phase has been rationalized by a Donnan’s relation. Introduction of a volume term for the polyelectrolyte phase permits definition of averaged concentrations of mobile ions in the vicinity of the polyion molecules, which enables us to define hypothetical intrinsic acid-dissociation constants in the polyion domain. The intrinsic constants estimated by extrapolation of apparent acid-dissociation constants at zero-charge state are in good agreement with the acid-dissociation constants of the monomer analogs of the polymers, i.e., acetic acid for PAA and imidazole for PVIm, respectively. The difference between the apparent and intrinsic acid-dissociation constants for PVIm was much higher than that for PAA at defined degree of dissociation of the polyacids, even though the separations of the functionalities fixed on the linear polymers are approximately equal to each other. Received: 4 February 1997 Accepted: 26 May 1997