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.     

Polymer-metal complexes in polyelectrolyte multilayer films as catalysts for oxidation of toluene

We report on the binding of metal ions (Me(2+); Co(2+) and Cu(2+)) with weak polyelectrolyte multilayers (PEMs), as well as on catalytic activity of PEM-Me(2+) films for oxidation of toluene. Using several types of PEM films constructed using branched polyethyleneimine (BPEI) or quaterinized poly-4-vinylpyridines (QPVPs) as polycations and poly(acrylic acid) (PAA) or poly(styrene sulfonate) (PSS) as polyanions, we found that binding of Co(2+) and Cu(2+) ions with a PEM matrix can occur both through coordination to polycationic amino groups and/or ionic binding to polyacid groups. The amount of metal ions loaded within the film increased linearly with film thickness and was strongly dependent on polyelectrolyte type, film assembly pH, and fraction of permanent charge in polymer chains. Among various PEM-Me(2+) systems, BPEI/PAA-Co(2+) films assembled at pH 8.5 show the best catalytic performance, probably because of the preservation of high mobility of Co(2+) ions coordinated to amino groups of BPEI in these films. With BPEI/PAA-Co(2+) films, we demonstrated that films were highly permeable to reagents and reaction products within hundreds of nanometers of the film bulk; i.e., film catalytic activity increased linearly with layer number up to 30 bilayers and slowed for thicker films.     

Direct determination of the thermodynamics of polyelectrolyte complexation and implications thereof for electrostatic layer-by-layer assembly of multilayer films

Interpolyelectrolyte complex (IPEC) formation between poly(styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) has been studied over a range of ionic strengths by isothermal titration calorimetry (ITC), turbidity titration, and electrostatic layer-by-layer assembly (ELBL). The results indicate that IPEC formation of PSS/PAH in aqueous solution is predominantly entropy-driven. The thermodynamic parameters suggest the formation of different types of complexes and aggregates due to salt-induced conformational changes in the polyelectrolyte conformation. Differences in polyelectrolyte behavior in the different salt-concentration regimes are described in terms of changes in the Debye screening length of the polyelectrolytes. The relationship of the results to the effect of salt concentration on the assembly of polyelectrolyte multilayer films (PEMs) is discussed.     

Polyelectrolyte blend multilayer films: surface morphology, wettability, and protein adsorption characteristics

We report the influence of polyelectrolyte (PE) multilayer films prepared from poly(styrene sulfonate)-poly(acrylic acid) (PSS-PAA) blends, deposited in alternation with poly(allylamine hydrochloride) (PAH), on film wettability and the adsorption behavior of the protein immunoglobulin G (IgG). Variations in the chemical composition of the PAH/(PSS-PAA) multilayer films, controlled by the PSS/PAA blend ratio in the dipping solutions, were used to systematically control film thickness, surface morphology, surface wettability, and IgG adsorption. Spectroscopic ellipsometry measurements indicate that increasing the PSS content in the blend solutions results in a systematic decrease in film thickness. Increasing the PSS content in the blend solutions also leads to a reduction in film surface roughness (as measured by atomic force microscopy), with a corresponding increase in surface hydrophobicity. Advancing contact angles (theta) range from 7 degrees for PAH/PAA films through to 53 degrees for PAH/PSS films. X-ray photoelectron spectroscopy measurements indicate that the increase in film hydrophobicity is due to an increase in PSS concentration at the film surface. In addition, the influence of added electrolyte in the PE solutions was investigated. Adsorption from PE solutions containing added salt favors PSS adsorption and results in more hydrophobic films. The amount of IgG adsorbed on the multilayer films systematically increased on films assembled from blends with increasing PSS content, suggesting strong interactions between PSS in the multilayer films and IgG. Hence, multilayer films prepared from blended PE solutions can be used to tune film thickness and composition, as well as wetting and protein adsorption characteristics.     

Dynamics of counterions in polyelectrolyte multilayers studied by electro-optics

The electro-optical behavior of a multilayer constructed via layer-by-layer deposition of poly(sodium 4-styrenesulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) onto ellipsoidal β-FeOOH particles is examined using electric light scattering method. For fully charged polymers (at pH 4.5), the electro-optical effect is found to increase with polyelectrolyte layer number, showing a tendency to saturation in the linear growth regime. The effect is greater and of lower frequency of relaxation for the films ending with PAH in comparison to those with top PSS layer. Evidence is given that polarization of “condensed” counterions along the chains of the last-adsorbed polymer is mainly responsible for the observed electro-optical behavior of the polyelectrolyte multilayer. Although incorporation of “condensed” small ions into the film bulk seems probable for the PSS/PAH multilayer, their participation in the electro-optical effect is found negligible. The structural changes in the PSS/PAH multilayer due to the PAH deprotonation at pH 7.5 and the corresponding changes in the electro-optical effect confirm the key role of the last-adsorbed polymer for the behavior of the entire PSS/PAH film.     

Functionalization of organic membranes by polyelectrolyte multilayer assemblies: application to the removal of copper ions from aqueous solutions

The functionalization of an organic polyethersulfone membrane (PES) was performed by alternating deposition of poly(allylamine hydrochloride) (PAH) and poly(sodium 4-styrene sulfonate) (PSS), leading to the formation of a polyelectrolyte multilayer film (PEM). The resulting assembly was characterized by tangential streaming potential measurements to determine the charge of the modified membranes as a function of the polyelectrolyte solution concentration and as a function of the immersion time of the membrane in the polyelectrolyte solutions. Then, the modified membranes were used to perform the ultrafiltration of aqueous solutions containing copper(II) ions. Different operating conditions were tested including: polyelectrolyte concentration, polyelectrolyte nature, thickness of the PEM film or pH of the Cu(2+) solutions. These filtration experiments demonstrated that it was possible to obtain a satisfactory retention of the copper ions (88%), thus proving that this type of assembly can be useful for the removal of copper ions from contaminated aqueous solutions.     

Electrical monitoring of polyelectrolyte multilayer formation by means of capacitive field-effect devices

The semiconductor field-effect platform represents a powerful tool for detecting the adsorption and binding of charged macromolecules with direct electrical readout. In this work, a capacitive electrolyte–insulator–semiconductor (EIS) field-effect sensor consisting of an Al-p-Si-SiO₂ structure has been applied for real-time in situ electrical monitoring of the layer-by-layer formation of polyelectrolyte (PE) multilayers (PEM). The PEMs were deposited directly onto the SiO₂ surface without any precursor layer or drying procedures. Anionic poly(sodium 4-styrene sulfonate) and cationic weak polyelectrolyte poly(allylamine hydrochloride) have been chosen as a model system. The effect of the ionic strength of the solution, polyelectrolyte concentration, number and polarity of the PE layers on the characteristics of the PEM-modified EIS sensors have been studied by means of capacitance–voltage and constant-capacitance methods. In addition, the thickness, surface morphology, roughness and wettabilityof the PE mono- and multilayers have been characterised by ellipsometry, atomic force microscopy and water contact-angle methods, respectively. To explain potential oscillations on the gate surface and signal behaviour of the capacitive field-effect EIS sensor modified with a PEM, a simplified electrostatic model that takes into account the reduced electrostatic screening of PE charges by mobile ions within the PEM has been proposed and discussed.

胶体颗粒在聚电解质多层膜表面的可控组装

利用原子力显微镜和扫描电子显微镜研究了磺化聚苯乙烯胶体颗粒在由聚二甲基二烯丙基氯化铵和聚苯乙烯磺酸钠层状自组装而成的多层膜表面的组装.该组装受表面性质影响,通过对多层膜的最外层的组装条件或利用盐溶液对多层膜进行后处理可以控制胶体颗粒在膜表面的组装密度.     

PET/PC共混体系的酯交换反应对其高压结晶行为的影响

利用转矩流变仪、DSC、SEM及WAXD等表征手段研究了PET/PC共混体系的酯交换反应对其高压结晶行为的影响.SEM观察表明,PET和PC熔混时的酯交换反应有利于PET/PC体系在高压结晶时生成厚度较大的伸直链晶体,且可以促进其高压下酯交换反应的发生.楔形伸直链晶体和弯曲伸直链晶体的存在证明链滑移扩散和酯交换反应两种机制对体系中聚酯伸直链晶体的增厚有贡献.拟合分峰法和War-ren-Averbach傅里叶分析法的计算结果表明,随PET/PC体系熔混时酯交换反应程度的增加,高压结晶共混物的结晶度降低,PET的平均微晶尺寸增大,点阵畸变平均值则减小,而微晶尺寸分布变宽.提出了在共聚物组分都具备结晶能力时,结晶诱导化学反应和化学反应诱导结晶两种过程在一定条件下可同时发生的观点.     

Effect of chain length and charge density on the construction of polyelectrolyte multilayers on colloidal particles

Two combinations of sodium poly(4-styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) of different chain length and charge density are employed to construct multilayer films. The polyelectrolytes are assembled layer-by-layer on colloidal particles in the absence of salt. We have investigated the formation and electrical characteristics of the films by using electric light scattering technique. The results show that the film thickness is independent of the chain length when fully charged PAH (at pH 4.6) is combined with fully charged PSS. When the films are prepared with less charged PAH (at pH 6.7) and fully charged PSS, lower thickness is found for the film with shorter polymer chains. In all cases, the thickness increment realized on addition of the polymer with lower molar concentration is partially lost on exposure to the solution with higher concentration of the oppositely charged partner. When the film growth is regular (at equal molar concentrations of the fully charged polyelectrolytes), the ratio of PSS to PAH charge, estimated from the electro-optical effect values, exceeds 1. The electro-optical effect is also higher for the films ending with PSS when fully charged PSS is combined with less charged PAH (at pH 6.7). This reveals the key role of the charge in the last-adsorbed layer for the electro-optical behavior of the whole film.     

Dynamics of ion exchange between self-assembled redox polyelectrolyte multilayer modified electrode and liquid electrolyte

A probe beam deflection (PBD) study of ion exchange between an electroactive polymer poly(allylamine)-bipyridyl-pyridine osmium complex film and liquid electrolyte is reported. The PBD measurements were made simultaneously to chronoamperometric oxidation-reduction cycles, to be able to detect kinetic effects in the ion exchange. Layer-by-layer (LbL) self-assembled redox polyelectrolyte films with osmium bipyridyl complex covalently attached to poly(allylamine) (PAH-Os) and poly(styrene sulfonate) (PSS) have been built by alternate electrostatic adsorption from soluble polyelectrolytes. The ionic exchange during initial conditioning of the film ("break-in") undergoing oxidation-reduction cycles and recovery after equilibration in the reduced state have shown an exchange of anions and cations with time lag between them. The effect of the nature of cation on the ionic exchange has been investigated with dilute HCl, LiCl, NaCl, and CsCl electrolytes. The ratio of anion to cation exchanged at the film-electrolyte interface has a strong dependence on the nature of charge in the topmost layer, that is, when negatively charged PSS is the capping layer, a larger proportion of cation exchange is observed. This demonstrates that the electrical potential distribution at the redox polyelectrolyte multilayer (PEM)/electrolyte interface determines the ionic flux in response to charge injection in the film.     

Influence of solvent quality on the growth of polyelectrolyte multilayers

The effect of solvent conditions on the growth of polyelectrolyte (PE) multilayer films comprising poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate sodium salt) (PSS) on planar substrates was investigated by means of surface plasmon resonance spectroscopy (SPRS), quartz crystal microbalance (QCM), and atomic force microscopy techniques. The solvent quality was varied by the addition of ethanol to the PE solutions used for deposition of the layers, thus tuning the relative strength of electrostatic and secondary intermolecular and intramolecular interactions. Experiments were performed with PE solutions both without added electrolyte and containing 0.5 M NaCl. Decreasing the solvent quality (i.e., increasing the amount of ethanol in the adsorption solution) resulted in a marked increase of both the multilayer film thickness and mass loading, as determined from the SPRS spectra and QCM frequency shifts, respectively. With the solution composition approaching the precipitation point, thick PAH/PSS films were formed due to the screening of the electrostatic intra- and interchain repulsions and enhanced hydrophobic interactions between the polyelectrolyte chains. However, the films formed from water/ethanol mixtures remained stable upon subsequent exposure to water or salt-containing solutions: no significant film desorption occurred after up to 24 h of exposure to water or 0.5 M NaCl solutions. In addition, the effect of postdeposition exposure to water/ethanol mixtures was investigated for PE multilayers assembled from aqueous solutions. In this case, the optical thickness of the films was determined during exposure to water/ethanol mixtures, and instead of swelling, the polyelectrolyte films collapse to the surface as a result of the unfavorable segment-solvent interactions.     

In situ layer-by-layer film formation kinetics under an applied voltage measured by optical waveguide lightmode spectroscopy

Layer-by-layer (LbL) thin film assembly occurs via the alternate adsorption of positively and negatively charged macromolecular species. We investigate here the control of LbL film growth through the electric potential of the underlying substrate. We employ optical waveguide lightmode spectroscopy (OWLS) to obtain in situ kinetic measurements of poly(allylamine hydrochloride)/poly(sodium 4-styrenesulfonate) (PAH/PSS) and poly(L-lysine)/dextran sulfate (PLL/DXS) multilayer film formation in the presence of an applied voltage difference (deltaV) between the adsorbing substrate, an indium tin oxide- (ITO-) coated waveguiding sensor chip, and a parallel platinum counterelectrode. We find initial layer adsorption to be significantly enhanced by an applied potential for both polyelectrolyte systems: the mass and thickness of (positively charged) PAH and PLL layers on ITO are about 60% and 500% larger, respectively, at deltaV = 2 V than at open circuit potential (OCP), in apparent violation of electrostatics. A kinetic analysis reveals the initial attachment rate constant to decrease with voltage, in agreement with electrostatics. To reconcile these results, we propose a more coiled and loosely bound adsorbed polymer conformation at higher applied potential. Following 10 adsorption steps, the mass and thickness of a PAH/PSS film grown under deltaV = 2 V are about 15% less than those of a comparable film grown under OCP, reflecting a lower degree of complexation between adsorbing polyanions and more highly coiled adsorbed polycations. Following 14 adsorption steps, the mass and thickness of a PLL/DXS film grown under deltaV = 2 V are about 70% greater than those of a comparable film grown under OCP, reflecting the increased charge overcompensation in the initial layer. We find the scaling of film mass () with the number of adsorption steps (n) to be linear in the PAH/PSS system and exponential (i.e., approximately eyn) in the PLL/DXS system, irrespective of applied voltage. We observe to decrease with applied voltage and to exhibit a crossover to a smaller value around n = 5. Extrapolation reveals PLL/DXS multilayer films to be suppressed by increased voltage in the limit of large n: the mass of films grown at OCP and deltaV = 1 V would surpass that of a film grown under deltaV = 2 V at about the 23rd and 18th adsorption steps, respectively. The formation kinetics of PLL/DXS, but not PAH/PSS, change qualitatively under voltage: PLL adsorption is slow to reach a plateau, possibly due to the formation of secondary structure, and a decrease in film mass occurs toward the end of each DXS adsorption step, suggesting spontaneous removal of some PLL/DXS complexes from the film.     

Thermal behavior of polyelectrolyte multilayer microcapsules: 2. Insight into molecular mechanisms for the PDADMAC/PSS system

Polyelectrolyte multilayer capsules consisting of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(styrene sulfonate) (PSS) were used as a model system to study the temperature-dependent behavior of polyelectrolyte multilayer films in aqueous media. Shells terminated with PSS shrink upon heating, whereas PDADMAC-terminated ones swell, independent of the nature of the first layer, as measured by means of confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). Elemental analysis shows that the initial exponential layer growth of the film leads to a nearly neutral overall charge in the first case or a high positive excess charge in the latter. Depending on this overall charge either surface tension, due to an unfavorable polymer-solvent interaction, or electrostatics dominates, resulting in a shrinkage or expansion of capsules, respectively. Thus, it is possible to swell temperature-shrunk capsules by coating them with an additional PDADMAC layer. Micro-DSC measurements prove that polyelectrolyte multilayers undergo a glass transition in water at which the wall material softens, allowing the rearrangements to occur. It is found that the thermal history has an influence on the temperature behavior of capsules, especially on those ones terminated with PDADMAC. Also, the molecular weight of the polyelectrolytes affects the rearrangement of capsules. The lower the molecular weight and thus the smaller the entanglement of chains, the easier polyelectrolytes can rearrange.     

Preparation of electrically conducting cellulose fibres utilizing polyelectrolyte multilayers of poly(3,4-ethylenedioxythiophene):poly(styrene sulphonate) and poly(allyl amine)

The primary goal with this work is to create electrically conductive cellulose fibres, this has been done to explore possible new applications for fibre based material. This research uses various methods to create polyelectrolyte multilayers (PEMs) on bleached softwood fibres and on SiO₂ model surfaces, by sequentially treating these materials with poly(3,4-ethylenedioxythiophene):poly(styrene sulphonate) (PEDOT:PSS) and poly(allyl amine) (PAH). Paper sheets were then produced from the PEM-modified pulp and evaluated in terms of tensile strength, adsorbed amount of polymer, and electrical conductivity. To evaluate the influence of fibre charge on the measured paper properties, pulps of two different initial fibre charge densities were prepared via carboxymethylation. Because of the bluish colour of PEDOT:PSS, the build-up of PEM could be easily followed, since the fibres grew increasingly darker blue throughout the modification sequence. The conductivity of the fibre network increased by 2−3 orders of magnitude when the pulp of a higher fibre charge density was used. This suggests that it is more important to create a fibrous network with a high fibre-fibre joint strength and a large total joined area in the sheet rather than to maximize the adsorbed amount of PEDOT:PSS. A difference in conductivity could also be noted depending on the polyelectrolyte adsorbed in the outer layer, PAH lowered the conductivity compared to PEDOT:PSS. Evaluating the mechanical properties revealed that the use of PEDOT:PSS reduces the tensile strength of the paper. When five double layers had been adsorbed onto the carboxymethylated sample in which PEDOT:PSS formed the outer layer, calculations indicated a 25% decrease in tensile strength compared to that of reference material without PEMs. ESEM studies indicate that PEM treatment produces a significantly changed and somewhat smoother fibre surface.     

Layer-by-layer electrostatic self-assembly of single-wall carbon nanotube polyelectrolytes

We have used anionic and cationic single-wall carbon nanotube polyelectrolytes (SWNT-PEs), prepared by the noncovalent adsorption of ionic naphthalene or pyrene derivatives on nanotube sidewalls, for the layer-by-layer self-assembly to prepare multilayers from carbon nanotubes with polycations, such as poly(diallyldimethylammonium) or poly(allylamine hydrochloride) (PDADMA or PAH, respectively), and polyanions (poly(styrenesulfonate), PSS). This is a general and powerful technique for the fabrication of thin carbon nanotube films of arbitrary composition and architecture and allows also an easy preparation of all-SWNT (SWNT/SWNT) multilayers. The multilayers were characterized with vis-near-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), surface plasmon resonance (SPR) measurements, atomic force microscopy (AFM), and imaging ellipsometry. The charge compensation in multilayers is mainly intrinsic, which shows the electrostatic nature of the self-assembly process. The multilayer growth is linear after the initial layers, and in SWNT/polyelectrolyte films it can be greatly accelerated by increasing the ionic strength in the SWNT solution. However, SWNT/SWNT multilayers are much more inert to the effect of added electrolyte. In SWNT/SWNT multilayers, the adsorption results in the deposition of 1-3 theoretical nanotube monolayers per adsorbed layer, whereas the nominal SWNT layer thickness is 2-3 times higher in SWNT/polyelectrolyte films prepared with added electrolyte. AFM images show that the multilayers contain a random network of nanotube bundles lying on the surface. Flexible polyelectrolytes (e.g., PDADMA, PSS) probably surround the nanotubes and bind them together. On macroscopic scale, the surface roughness of the multilayers depends on the components and increases with the film thickness.     

Electrical properties of multilayers from low- and high-molecular-weight polyelectrolytes

The formation of stable multilayer films by using as constituents sodium poly(4-styrene sulfonate) (PSS) and poly(4-vinyl pyridine) (PVP) was studied by electrooptics. A strong increase in basicity of the pyridine rings in the electrical field of the oppositely charged PSS chains was suggested to be the driving force for multilayer film formation. A linear increase in the film thickness was registered after deposition of the first three layers, with no dependence on the polyelectrolyte molecular weight. The electrooptical effect was found to increase with increasing area of each next layer, but depended on the molecular weights of both polymers. Polarization of "condensed" counterions along the chains of the last-adsorbed layer was suggested to explain this dependence. Following the counterion dynamics, we come to the conclusion that the electrical properties of the top layer govern the electrooptical behavior of the PSS/PVP film.     

Unusual collapse of highly hydrated polyelectrolyte multilayers with the ionic strength

Highly hydrated polyelectrolyte multilayers (PEMs) were fabricated by “layer by layer” (LBL) assembly of poly (diallyl dimethyl ammonium chloride) (PDADMAC) and poly (sodium 4‐styrene sulfonate) (PSS) in 0.5 M NaCl. Both thickness and hydration of the film were determined in situ as the multilayer was assembled by means of the quartz crystal microbalance with dissipation (QCM‐D) and the Spectroscopic Ellipsometry techniques combined in a single device. For PEMs of 17 total layers in water, a final thickness of up to 300 nm and a hydration of 69% were measured. The response towards the ionic strength was then studied by means of QCM‐D. PEMs of 17 layers, with PDADMAC as last layer, shrunk dramatically and lost water when exposed to aqueous NaCl solutions of increasing concentration. Indeed, a thickness variation up to 100 nm and reduction in the 50% of the water content were observed when the PEM was exposed to 1 M NaCl. On the contrary, PEMs where PSS appears on top showed no measurable change upon the variation in the ionic strength. This brings the possibility to control the responsive character of the PEMs simply by selecting the last polyelectrolyte layer (PDADMAC or PSS) deposited. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Responsive Polyelectrolyte Multilayers Assembled at High Ionic Strength with an Unusual Collapse at Low Ionic Strength

Responsive polyelectrolyte multilayers (PEMs) of poly(diallyl dimethyl ammonium chloride) (PDADMAC) and poly(styrene sodium sulfonate) (PSS) with thicknesses between 350 and 400 nm for 11 deposited polyelectrolyte layers were fabricated assembling the polyelectrolytes at 3 M NaCl. When the 3 M NaCl bulk solution is replaced by water, the PEMs release water, approximately a 46% of the total mass, and experience a thickness reduction of more than 200 nm. Changes in thickness and water content are fully reversible. The film recovers its original thickness and water content when it is exposed again to a 3 M NaCl solution. A responsive polymer film is achieved with the capability of swelling at high ionic strength and collapsing in water with variations in thickness of hundred of nanometers.     

Permeability and conductivity of red blood cell templated polyelectrolyte capsules coated with supplementary layers

The permeability of ions and small polar molecules through polyelectrolyte multilayer capsules templated on red blood cells was studied by means of confocal microscopy and electrorotation. Capsules were obtained by removing the cell after polyelectrolyte multilayer formation by means of NaOCl treatment. This procedure results in cross-linking of poly(allylamine hydrochloride) (PAH) molecules and destroying poly(styrene sulfonate) (PSS) within the multilayer. Capsules are obtained being remarkably different from layer-by-layer (LbL) capsules. These capsules are rather permeable for low as well as for high molecular weight species. However, upon adsorption of extra polyelectrolyte layers the permeability decreased remarkably. The assembly of six supplementary layers of PAH and PSS rendered the capsule almost impermeable for fluorescein. Resealing by supplementary layers is a potential means for filling and release control. By means of electrorotation measurements, it was shown that the capsule walls obtained isolating properties in electrolyte solutions. Conclusions are drawn concerning the mechanism of permeability through cell templated polyelectrolyte multilayer capsules.