Layer by layer self-assembled polyelectrolyte multilayers with embedded phospholipid vesicles

We describe a method to embed phospholipid vesicles into polyelectrolyte multilayers built up by the alternate deposition of polyanions and polycations. Before deposition, the vesicles are rigidified by polycation adsorption onto their surface avoiding their fusion once deposited on the multilayer surface. The vesicles adsorb to form a compact and "hard" monolayer as imaged by atomic force microscopy. The thickness of the adsorbed vesicle layer, of the order of 250 nm, is very close to the diameter of the vesicles in solution. This work should open the route to the buildup of multilayer films containing phospholipid vesicles that could act as "reservoirs" for drugs or enzymatic nanoreactors.     

Free-standing membranes via covalent cross-linking of polyelectrolyte multilayers with complementary reactivity

Polyelectrolyte multilayers were prepared by the layer-by-layer (LbL) technique from polyanions bearing aldehyde and polycations with 4-methylpyridinium moieties. The aldol reaction of these complementary reactive groups can be followed by the formation of fluorescent merocyanine dyes, resulting in cross-linked, ultrathin polymer films. The efficient stabilization of the polymer films allows for their intact removal from high surface energy supports, such as glass or surface oxidized silicon wafers, by simple treatment with salt solutions, yielding free-standing membranes. Increasing separation of the reactive polycation and polyanion layers with layers of inert polycation and polyanion analogues only gradually prevents the coupling reaction. From this dependence, polyions assembled in consecutive adsorption layers seem to be able to penetrate into as far as three neighboring layers.     

Dipping versus spraying: exploring the deposition conditions for speeding up layer-by-layer assembly

Polyelectrolyte film fabrication by successive spraying of polycation and polyanion solutions is described and compared to classic dipping. The poly(styrenesulfonate)/poly(allylamine) system is examined in detail. The influence of various parameters such as spraying time, polyelectrolyte concentration, and effect of film drying during multilayer construction is investigated. It is found that film deposition by spraying is easily controlled and very reliable. The thickness of the multilayers grows linearly with the number of deposition cycles similarly to what is observed when dipping substrates or when polyelectrolyte solutions flow over a surface. The assembly of films is very fast and leads to films with small surface roughness as estimated by atomic force microscopy and X-ray reflectometry. Spray deposition allows achieving regular multilayer growth even under conditions for which dipping fails to produce homogeneous films (e.g., extremely short contact times). Moreover, because drainage constantly removes a certain quantity of the excess material arriving at the surface, one can even skip the rinsing step and, thus, speed up even further the whole buildup process.     

Assembly of poly(N-isopropylacrylamide)-co-acrylic acid microgel thin films on polyelectrolyte multilayers: Effects of polyelectrolyte layer thickness, surface charge, and microgel solution pH

Temperature- and pH-sensitive poly(N-isopropylacrylamide)?Cco-acrylic acid (pNIPAm-co-AAc) microgels were deposited on glass substrates coated with polyelectrolyte multilayers composed of the polycation poly(allylamine hydrochloride) (PAH) and the polyanion poly(sodium 4-styrenesulfonate) (PSS). The microgel density and structure of the resultant films were investigated as a function of: (1) the number of PAH/PSS layers (layer thickness); (2) the charge on the outer layer of the polyelectrolyte multilayer film; and (3) the pH of microgel deposition solution. The resultant films were studied by differential interference contrast optical microscopy, atomic force microscopy, and scanning electron microscopy. It was found that the coverage of the microgels on the surface was a complex function of the pH of the deposition solution, the charge on the outer layer of the polyelectrolyte thin film and the PAH/PSS layer thickness; although it appears that microgel charge plays the biggest role in determining the resultant surface coverage.     

Polyelectrolyte multilayers prepared from water-soluble poly(alkoxythiophene) derivatives.

Electronically conducting polyanion and polycation based on poly(alkoxythiophene) derivatives, poly-3-(3'-thienyloxy)propanesulfonate (P3TOPS) and poly-3-(3'-thienyloxy)propyltriethylammonium (P3TOPA) have been synthesized. Both polymers are water-soluble and exhibit high conjugation length in solution and in the solid state. These polyelectrolytes were used to prepare conducting and electroactive polyelectrolyte multilayers by the sequential layer-by-layer adsorption technique. In aqueous solutions multilayers of P3TOPS with inactive polyelectrolytes (e.g., poly(diallyldimethylammonium chloride), PDADMA) displayed electrochemical and optical behavior similar to polythiophene films prepared in organic media. Their in-plane conductivity was low (ca. 1.6 x 10(-)(5) S cm(-)(1)). The conductivity could, however, be increased by a factor of ca. 40 in "all-thiophene" films, in which P3TOPA was substituted for the inactive polycation (PDADMA). The interpenetration of layers is of prime importance in films containing conducting components. The interpenetration of P3TOPS was studied by measuring the charge-transfer rate across an insulating polyelectrolyte multilayer between the substrate and the P3TOPS layer with modulated electroreflectance. The extent of interpenetration was 8-9 polyelectrolyte layers, the length scale (7-15 nm) depending on the nature of the insulating layer and, especially, on the ionic strength of the solution used for the adsorption of P3TOPS.     

New 2-in-1 polyelectrolyte step-by-step film buildup without solution alternation: from PEDOT-PSS to polyelectrolyte complexes

Although never emphasized and increasingly used in organic electronics, PEDOT-PSS (poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate)) layer-by-layer (lbl) film construction violates the alternation of polyanion and polycation rule stated as a prerequisit for a step-by-step film buildup. To demonstrate that this alternation is not always necessary, we studied the step-by-step construction of films using a single solution containing polycation/polyanion complexes. We investigated four different systems: PEDOT-PSS, bPEI-PSS (branched poly(ethylene imine)-poly(sodium 4-styrene sulfonate)), PDADMA-PSS (poly(diallyl dimethyl ammonium)-PSS), and PAH-PSS (poly(allylamine hydrochloride)-PSS). The film buildup obtained by spin-coating or dipping-and-drying process was monitored by ellipsometry, UV-vis-NIR spectrophotometry, and quartz-crystal microbalance. The surface morphology of the films was characterized by atomic force microscopy in tapping mode. After an initial transient regime, the different films have a linear buildup with the number of deposition steps. It appears that, when the particles composed of polyanion-polycation complex and complex aggregates in solution are more or less liquid (case of PEDOT-PSS and bPEI-PSS), our method leads to smooth films (roughness on the order of 1-2 nm). On the other hand, when these complexes are more or less solid particles (case of PDADMA-PSS and PAH-PSS), the resulting films are much rougher (typically 10 nm). Polycation/polyanion molar ratios in monomer unit of the liquid, rinsing, and drying steps are key parameters governing the film buildup process with an optimal polycation/polyanion molar ratio leading to the fastest film growth. This new and general lbl method, designated as 2-in-1 method, allows obtaining regular and controlled film buildup with a single liquid containing polyelectrolyte complexes and opens a new route for surface functionalization with polyelectrolytes.     

Controlled Stripping of Polyelectrolyte Multilayers by Quaternary Ammonium Surfactants

The quartz crystal microbalance with dissipation technique (QCM‐D) and atomic force microscopy (AFM) have been employed to study the interaction of N‐tetradecyl trimethyl ammonium bromide (TdTmAB) with polyelectrolyte multilayers containing poly(sodium 4‐styrene sulfonate) (PSS) as the polyanion and either poly(allylamine hydrochloride) (PAH) or poly(diallyl dimethyl ammonium chloride) (PDADMAC) as the polycations. The multilayers were exposed to aqueous solutions of TdTmAB. This resulted in a selective removal of PDADMAC PSS layers while layers with PAH as polycation remained stable. It is suggested that PDADMAC/PSS multilayers can be employed as strippable protecting layers.

     

Assembly of multilayer films from polyelectrolytes containing weak and strong acid moieties

Multilayer films were assembled from a copolymer containing both weakly and strongly charged pendant groups, poly(4-styrenesulfonic acid-co-maleic acid) (PSSMA), deposited in alternation with poly(allylamine hydrochloride) (PAH). The strongly charged groups (styrene sulfonate, SS) are expected to form electrostatic linkages (to enhance film stability), while the weakly charged groups (maleic acid, MA) can alter multilayer film properties because they are responsive to external pH changes. In this study, we varied several assembly conditions such as pH, SS/MA ratio in PSSMA, and the ionic strength of the polyelectrolyte solutions. The multilayer films were also treated by immersion into pH 2 and 11 solutions after assembly. Quartz crystal microgravimetry and UV-visible spectrophotometry showed that the thickness of PSSMA/PAH multilayers decreases with increasing assembly pH regardless of whether salt was present in the polyelectrolyte solutions. When no salt was added, the multilayers are thinner, smoother, and grow less regularly. Atomic force microscopy images indicate that the presence of salt in polyelectrolyte solutions results in rougher surface morphologies, and this effect is especially significant in multilayers assembled at pH 2 and pH 11. When both polyelectrolytes are adsorbed at conditions where they are highly charged, salt was necessary to promote regular multilayer growth. Fourier transform infrared spectroscopy studies show that the carboxylic acids in the multilayers are essentially ionized when assembled from different pHs in 0.5 M sodium chloride solutions, whereas some carboxylic acids remain protonated in the multilayers assembled from solutions with no added salt. This resulted in different pH stability regimes when the multilayers were exposed to different pH solutions, post assembly.     

Formation and dielectric properties of polyelectrolyte multilayers studied by a silicon-on-insulator based thin film resistor

The formation of polyelectrolyte multilayers (PEMs) is investigated using a silicon-on-insulator based thin film resistor which is sensitive to variations of the surface potential. The buildup of the PEMs at the silicon oxide surface of the device can be observed in real time as defined potential shifts. The influence of polymer charge density is studied using the strong polyanion poly(styrene sulfonate), PSS, combined with the statistical copolymer poly(diallyl-dimethyl-ammoniumchloride-stat-N-methyl-N-vinylacetamide), P(DADMAC-stat-NMVA), at various degrees of charge (DC). The multilayer formation stops after a few deposition steps for a DC below 75%. We show that the threshold of surface charge compensation corresponds to the threshold of multilayer formation. However, no reversion of the preceding surface charge was observed. Screening of polyelectrolyte charges by mobile ions within the polymer film leads to a decrease of the potential shifts with the number of layers deposited. This decrease is much slower for PEMs consisting of P(DADMAC-stat-NMVA) and PSS as compared to PEMs consisting of poly(allylamine-hydrochloride), PAH, and PSS. From this, significant differences in the dielectric constants of the polyelectrolyte films and in the concentration of mobile ions within the films can be derived.     

Strong response of multilayer polyelectrolyte films to cationic surfactants

The influence of common cationic surfactants on the physical properties of differently composed polyelectrolyte films prepared by the layer-by-layer (LbL) technology was investigated. Free-standing polyelectrolyte films as microcapsules showed a fast, strong response to the addition of less than 1 mM cationic surfactant cetyltrimethylammonium bromide (CeTAB). As a function of the polyelectrolyte composition, the behavior of the capsules varied from negligible changes to complete disintegration via strong swelling. The response of microcapsules consisting of (poly(allylamine hydrochloride)(PAH)/poly(styrene sulfonate)(PSS))(4) was associated with a 5-fold volume increase, a fast switch of permeability, and in the case of fluorescently labeled films a 4-fold increase in fluorescence intensity. The kinetics and strengths of the interaction process were investigated by confocal laser scanning microscopy (CLSM) and fluorescence spectroscopy. Also, the relative stabilities of the polycation/polyanion and surfactant/polyanion complexes were determined. A mechanism was suggested to explain the interactions between the cationic surfactants and polyelectrolyte capsules. The strong response can be exploited in potential applications such as the triggered release of drugs or other encapsulated materials, the fluorescence-based detection of cationic detergents, and a switchable stopper in microchannels. However, the high sensitivity of LbL films to traces of cationic surfactants can also limit their applicability to the encapsulation of drugs or other materials because pharmaceutical or technical formulations often contain cationic surfactants as preservatives such as benzalkonium salts (BAC). It was demonstrated that undesired capsule opening can be effectively prevented by cross-linking the polyelectrolyte multilayers.     

Reinvestigation on the buildup mechanism of alternate multilayers consisting of poly(L-glutamic acid) and poly(L-, D-, and DL-lysines)

The buildup mechanism of polypeptide multilayers prepared by the layer-by-layer deposition of a polyanion (poly(L-glutamic acid) (PGA)) and polycations (poly(L-lysine) (PLL), poly(D-lysine) (PDL), and copoly(DL-lysine)(PDLL)) was reinvestigated by using in situ ATR-IR spectroscopy. A difference spectral technique applied to analyze the spectra indicated that the deposition of both the PGA and PLL (PDL) layers accompanies the formation of secondary structures consisting mainly of the antiparallel pleated sheet (the beta-sheet) structure, and that the formation of the beta-sheet structure cannot always be explained in terms of polyanion/polycation complex formation or charge compensation between the polyanion and polycations, although it has been considered as a major process in the multilayer buildup process. Instead, the present paper proposes the following mechanism. During the deposition of the polyelectrolyte, a small amount of the beta-sheet structures are produced at the interface as a result of charge compensation between a polyelectrolyte and an oppositely charged polyelectrolyte in the multilayer. The beta-sheets act as nuclei from which further propagation of the structure takes place at the solution/multilayer interfaces. The driving force of the buildup process in the new mechanism is a kinetically favorable insolubilization of each polyelectrolyte in solution at the interfaces.     

Influence of the nature of the polycation on the adsorption kinetics and on exchange processes in polyelectrolyte multilayer films

The deposition of polyelectrolyte multilayer films (PEMs) appears more and more as a versatile tool to functionalize a broad range of materials with coatings having controlled thicknesses and properties. To increase the control over the properties of such coatings, a good knowledge of their deposition mechanism is required. Since Cohen Stuart et al. (Langmuir 18 (2002) 5607-5612) showed that the adsorption of one polyelectrolyte could induce desorption of polyelectrolyte complexes instead of regular deposition, more and more findings highlight peculiarities in the deposition of such films. Herein we demonstrate that the association of sodium polyphosphate (PSP) as the polyanion and either poly(-L-lysine hydrobromide) (PLL) or poly(allylamine chloride) (PAH) as the polycations may lead to non-monotonous film deposition as a function of time. Complementary, films containing PSP and PLL can be obtained from a (PLL-HA)(n) template films after the exchange of HA (hyaluronic acid) from the sacrificial template by PSP from the solution. This exchange is accompanied by pronounced film erosion. However, when starting from a (PAH-HA)(n) template, the film erosion and exchange due to the contact with PSP is by far less pronounced, nevertheless the film morphology changes. These findings show that the nature of the polycation used to deposit the PEM film may have a profound influence of the film's response to a competing polyanion.     

Influence of the polyelectrolyte molecular weight on exponentially growing multilayer films in the linear regime

Alternated deposition of polyanions and polycations on a charged solid substrate leads to the buildup of polyelectrolyte multilayer (PEM) films. Two types of PEM films were reported in the literature: films whose thickness increases linearly and films whose thickness increases exponentially with the number of deposition steps. However, it was recently found that, for exponentially growing films, the exponential increase of the film thickness takes place only during the initially deposited pairs of layers and is then followed by a linear increase. In this study, we investigate the growth process of hyaluronic acid/poly(L-lysine) (HA/PLL) and poly(L-glutamic acid)/poly(allylamine) (PGA/PAH) films, two films whose growth is initially exponential, when the growth process enters the linear regime. We focus, in particular, on the influence of the molecular weight (Mw) of the polyelectrolytes. For both systems, we find that the film thickness increment per polyanion/polycation deposition step in the linear growth regime is fairly independent of the molecular weights of the polyelectrolytes. We also find that when the (HA/PLL)n films are constructed with low molecular weight PLL, these chains can diffuse into the entire film during each buildup cycle, even for very thick films, whereas the PLL diffusion of high molecular weight chains is restricted to the upper part of the film. Our results lead to refinement of the buildup mechanism model, introduced previously for the exponentially growing films, which is based on the existence of three zones over the entire film thickness. The mechanism no longer needs all the "in" and "out" diffusing polyanions or polycations to be involved in the buildup process to explain the linear growth regime but merely relies on the interaction between the polyelectrolytes with an upper zone of the film. This zone is constituted of polyanion/polycation complexes which are "loosely bound" and rich in the polyelectrolyte deposited during the former deposition step.     

Antibacterial polyelectrolyte micelles for coating stainless steel

In this study, we report on the original synthesis and characterization of novel antimicrobial coatings for stainless steel by alternating the deposition of aqueous solutions of positively charged polyelectrolyte micelles doped with silver-based nanoparticles with a polyanion. The micelles are formed by electrostatic interaction between two oppositely charged polymers: a polycation bearing 3,4-dihydroxyphenylalanine units (DOPA, a major component of natural adhesives) and a polyanion (poly(styrene sulfonate), PSS) without using any block copolymer. DOPA units are exploited for their well-known ability to anchor to stainless steel and to form and stabilize biocidal silver nanoparticles (Ag(0)). The chlorine counteranion of the polycation forms and stabilizes biocidal silver chloride nanoparticles (AgCl). We demonstrate that two layers of micelles (alternated by PSS) doped with silver particles are enough to impart to the surface strong antibacterial activity against gram-negative E. coli. Moreover, micelles that are reservoirs of biocidal Ag(+) can be easily reactivated after depletion. This novel water-based approach is convenient, simple, and attractive for industrial applications.     

Anomalous thickness evolution of multilayer films made from poly-L-lysine and mixtures of hyaluronic acid and polystyrene sulfonate

Using a mixture of polyanions or polycations offers a new way to control the properties of polyelectrolyte multilayer (PEM) films. The central issue of PEM films made from blended polyelectrolyte solutions is the relation between the properties of the blended architecture and the properties of the films made from each pure component. Two situations are possible: either (i) the properties of the blended films are intermediate between those corresponding to the single components or (ii) new effects may emerge leading, for instance, to improved mechanical properties. Situation (i) is expected when the chemical natures of both polyelectrolytes from the blended mixture are close, whereas situation (ii) is more probable when the polyelectrolytes from the blend are very different. In this study, we focus on the buildup of PEM films made by the alternate spray deposition of a polyanion blend [a mixture of polystyrene-4-sulfonate (PSS) and hyaluronic acid (HA) in different mass fractions] and a polycation solution of poly-L-lysine (PLL). Whereas (HA-PLL) films exhibit a strong exponential growth with the number of deposition steps, the (PSS-PLL) system is only weakly exponential. We find that when the composition of the polyanion blend ranges from pure (HA-PLL) to pure (PSS-PLL), the films can always be constructed. However, the polyanion composition of the films is far from that of the polyanion solutions used for the buildup. One observes a strong preference for the incorporation of PSS over HA into the films. Moreover, the most striking feature is that the film thickness does not evolve monotonously with the polyanion solution composition but passes through a sharp minimum for a polyanion solution containing 90-95% HA. A possible mechanism for this peculiar finding is proposed.     

Diffusive dynamics of vesicles tethered to a fluid supported bilayer by single-particle tracking

We recently introduced a method to tether intact phospholipid vesicles onto a fluid supported lipid bilayer using DNA hybridization (Yoshina-Ishii, C.; Miller, G. P.; Kraft, M. L; Kool, E. T.; Boxer, S. G. J. Am. Chem. Soc. 2005, 127, 1356-1357). Once tethered, the vesicles can diffuse in two dimensions parallel to the supported membrane surface. The average diffusion coefficient, D, is typically 0.2 microm(2)/s; this is 3-5 times smaller than for individual lipid or DNA-lipid conjugate diffusion in supported bilayers. In this article, we investigate the origin of this difference in the diffusive dynamics of tethered vesicles by single-particle tracking under collision-free conditions. D is insensitive to tethered vesicle size from 30 to 200 nm, as well as a 3-fold change in the viscosity of the bulk medium. The addition of macromolecules such as poly(ethylene glycol) reversibly stops the motion of tethered vesicles without causing the exchange of lipids between the tethered vesicle and supported bilayer. This is explained as a depletion effect at the interface between tethered vesicles and the supported bilayer. Ca ions lead to transient vesicle-vesicle interactions when tethered vesicles contain negatively charged lipids, and vesicle diffusion is greatly reduced upon Ca ion addition when negatively charged lipids are present both in the supported bilayer and tethered vesicles. Both effects are interesting in their own right, and they also suggest that tethered vesicle-supported bilayer interactions are possible; this may be the origin of the reduction in D for tethered vesicles. In addition, the effects of surface defects that reversibly trap diffusing vesicles are modeled by Monte Carlo simulations. This shows that a significant reduction in D can be observed while maintaining normal diffusion behavior on the time scale of our experiments.     

Layer‐by‐layer assembly of weak‐strong copolymer polyelectrolytes: A route to morphological control of thin films

Multilayer films were assembled from a strong polyelectrolyte (poly(diallyldimethylammonium chloride), PDADMAC) and a copolymer containing both strongly charged styrene sulfonate moieties and weakly charged maleic acid moieties (poly(4‐styrenesulfonic acid‐co‐maleic acid), PSSMA). Growth of PSSMA/PDADMAC multilayers was linear, as characterized by UV‐vis spectroscopy and quartz crystal microgravimetry. The influence of both the pH of the PSSMA adsorption solutions and the ratio of SS:MA in the PSSMA on multilayer properties was investigated. Fourier transform infrared spectroscopy results showed that the ionization of carboxylic acid groups in PSSMA/PDADMAC multilayers did not vary significantly with changes in the PSSMA assembly pH. However, the multilayers showed different thicknesses, surface morphologies, and stability to post‐assembly pH treatment. We also demonstrate that PSSMA/PDADMAC multilayers are significantly more stable than PSSMA/PAH multilayers after post‐assembly pH treatment (i.e. the films remain intact when exposed to pH extremes). In addition, the surface morphology of two films (PSSMA 1:1 assembled at pH 5.8, post‐treated at pH 2 and PSSMA 3:1 assembled at pH 5.8, post‐treated at pH 11) changed significantly when the films were exposed to solutions of different pH and, in the former case, this change in film morphology was reversible. The porous morphology after treatment at pH 2 could be reversed to give a significantly smoother film after subsequent exposure to water for 24 h. Our results demonstrate that by the rational choice of the assembly pH of PSSMA, stable and pH‐responsive films can be obtained via the sequential assembly of PSSMA and PDADMAC. These films have potential in controlled release applications where film stability and pH‐responsive behavior are essential. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4341‐4351, 2007     

Comparison of polyelectrolyte multilayers built up with polydiallyldimethylammonium chloride and poly(ethyleneimine) from salt-free solutions by in-situ surface plasmon resonance measurements

Polyelectrolytes offer a widespread potential for the defined modification of planar inorganic or polymer surfaces. Essential parameters for the regular adsorption of subsequent polymer layers by electrostatic interactions are the charge of polyelectrolyte and of the outermost surface region, the surface of the substrate, and the molar mass of the polyelectrolyte. To study such effects in mono- and multilayers we used poly(diallyldimethylammonium chloride (PD) with a molar mass from 5000 to 400000 g/mol as a strong polycation and poly(ethyleneimine) (PEI) with 75000 g/mol as a weak polycation and poly(sodium styrenesulfonate) (PSS) from 70000 to 1Mio g/mol in the diluted and semi-diluted region. The characterization of the layers was performed by streaming potential, in-situ SPR and UV-Vis spectroscopy. Thereby the layer built up at the solid/liquid-interface could be followed and quantified at the molecular level. SPR revealed that the thicknesses of the multilayer depends strongly on pK values of the polyelectrolyte (strong or weak) and the molar masses. We observed a linear growth if both polyelectrolytes are strong and an exponential growth if one polyelectrolyte is weak. The thickness increased with higher molar masses of the polyelectrolytes. The process was followed in-situ in short time steps.     

Counter-ion activity and microstructure in polyelectrolyte complexes as determined by osmotic pressure measurements

We have investigated the activity of counter-ions at 60 degrees C through the osmotic coefficient K in solutions of anionic and cationic polyelectrolyte complexes of variable compositions. For excess of polyanion in the complexes (molar fraction of polycation f < 0.5), K increases as the polyanion is neutralized by the polycation (f getting closer to 0.5). By contrast, for an excess of polycation (f > 0.5), K stays constant or even slightly decreases as the polycation is getting neutralized by the polyanion. This asymmetric behavior depending on the charge of the complexes indicates that the globally negatively charged complexes are homogeneous and can be treated as a single polyelectrolyte of reduced linear charge density. On the other hand, the positively charged complexes show a micro-phase separation between neutral fully compensated microdomains and domains where the excess polycation is locally segregated. These two different microstructures are reminiscent of the coacervation and segregation regimes observed at higher concentrations and salinities, and also of polyelectrolyte complexes with oppositely charged surfactants. This interpretation is supported by two simple predictive models.     

Studies on the interaction of poly(4-vinylpyridiniumchloride) with poly(sodiumphosphate) in an aqueous solution by conductometry

A reaction between poly(4-vinylpyridiniumchloride) and poly(sodiumphosphate) in the presence and absence of NaCl and NaBr salts was studied in aqueous solution by conductometry. The interaction of polycation and polyanion gave insoluble polyelectrolyte complex which contained polycation and polyanion in unit mole ratio in a salt-free solution. A deviation from stoichiometry was observed at high polyion concentration and in the presence of NaCl and NaBr salts. The resultant complex showed swelling property in different solvent mixtures. A maximum degree of swelling was obtained in the solvent mixture of NaBr + water and NaBr + water + acetone. Furthermore, polyelectrolyte complex sorbed salts from aqueous electrolyte solutions. The sorption of salts increased with increasing salt concentration. © 1996 John Wiley & Sons, Inc.