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.     

Layer by layer buildup of polysaccharide films: physical chemistry and cellular adhesion aspects

The formation ofpolysaccharide films based on the alternate deposition of chitosan (CHI) and hyaluronan (HA) was investigated by several techniques. The multilayer buildup takes place in two stages: during the first stage, the surface is covered by isolated islets that grow and coalesce as the construction goes on. After several deposition steps, a continuous film is formed and the second stage of the buildup process takes place. The whole process is characterized by an exponential increase of the mass and thickness of the film with the number of deposition steps. This exponential growth mechanism is related to the ability of the polycation to diffuse "in" and "out" of the whole film at each deposition step. Using confocal laser microscopy and fluorescently labeled CHI, we show that such a diffusion behavior, already observed with poly(L-lysine) as a polycation, is also found with CHI, a polycation presenting a large persistence length. We also analyze the effect of the molecular weight (MW) of the diffusing polyelectrolyte (CHI) on the buildup process and observe a faster growth for low MW chitosan. The influence of the salt concentration during buildup is also investigated. Whereas the CHI/HA films grow rapidly at high salt concentration (0.15 M NaCl) with the formation of a uniform film after only a few deposition steps, it is very difficult to build the film at 10(-4) M NaCl. In this latter case, the deposited mass increases linearly with the number of deposition steps and the first deposition stage, where the surface is covered by islets, lasts at least up to 50 bilayer deposition steps. However, even at these low salt concentrations and in the islet configuration, CHI chains seem to diffuse in and out of the CHI/HA complexes. The linear mass increase of the film with the number of deposition steps despite the CHI diffusion is explained by a partial redissolution of the CHI/HA complexes forming the film during different steps of the buildup process. Finally, the uniform films built at high salt concentrations were also found to be chondrocyte resistant and, more interestingly, bacterial resistant. Therefore, the (CHI/HA) films may be used as an antimicrobial coating.     

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.     

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.     

Biogenic Polyelectrolyte Multilayers on Poly(L-lactide) Films for Control of Osteoblast Adhesion

Cell adhesion and spreading are important events during cell-biomaterial interaction, which control survival, growth and differentiation of cells. Layer-by-layer technique was used to generate multilayer coatings for regulating adhesion of primary osteoblasts on biomaterials. Polyelectrolyte multilayers (PEM) were based on poly (ethylene imine) as primary polycation layer. PEM were then prepared from chitosan (CHI) as polycation and heparin (HEP), or sulfated HA (sHA) as polyanions. It was observed that attachment and spreading of primary osteoblasts (pOB) was highly dependent on the composition of multilayers, as well as pH values of polyelectrolyte solutions. Results presented in this paper may pave the way for application of PEM surface coatings for bone-contacting implant materials.     

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.     

Layer-by-layer films from hyaluronan and amine-modified hyaluronan

Hyaluronan is a polysaccharide that is increasingly investigated for its role in cellular adhesion and for the preparation of biomimetic matrices for tissue engineering. Hyaluronan gels are prepared for application as space fillers, whereas hyaluronan films are usually obtained by adsorbing or grafting a single hyaluronan layer onto a biomaterial surface. Here, we examine the possibility to employ the layer-by-layer technique to deposit thin films of cationic-modified hyaluronan (HA+) and hyaluronan (HA) of controlled thicknesses. The buildup conditions are investigated, and growth is compared to that of other polyelectrolyte multilayer films containing either HA as the polyanion or HA+ as the polycation. The films could be formed in a low ionic strength medium but are required to be cross-linked prior to contact with a physiological medium. NIH3T3 fibroblasts were perfectly viable on self-assembled hyaluronan films with, however, a preference for hyaluronan ending films. These findings point out the possibility to tune the thickness of thin hyaluronan films at the nanometer scale. Such architectures could be employed for investigating cell/substrate interactions or for functionalizing biomaterial surfaces.     

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.     

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.     

聚丙烯酸钠与聚(苯乙烯-co-4-乙烯基吡啶)阳离子复合作用的研究

聚电解质复合物 (Ｐｏｌｙｅｌｅｃｔｒｏｌｙｔｅｃｏｍｐｌｅｘ)是指带有相反电荷的两种聚电解质之间通过库仑力而结合形成的一类特殊的高分子材料[1 ] .由于生物体内的很多反应以及生物化学合成过程都是通过高分子复合物进行的 ,因此对高分子间相互作用及其聚集体形成的研究受到了人们的极大重视 .目前研究得较多的体系是聚苯乙烯衍生物 ,如Ｉｏｐｌｅｘ 1 0 1即由聚苯乙烯磺酸钠和聚氯化乙烯基苄基三甲基铵反应而得[2 ,3] .本文报道了不同电荷密度及相对分子质量的聚苯乙烯 ｃｏ 4 乙烯基吡啶的硫酸甲酯盐 ,与不同分子质量的聚丙烯酸钠…     

重氮树脂与牛血清白蛋白共价结合自组装膜及其表面细胞培养

细胞支架作为组织工程的组成部分为细胞生长提供了最佳微环境 ,并对细胞生长与功能进行控制 .由于细胞对支架表面的生物识别是细胞附着、生长和增殖的基本前提 ,所以对材料表面的功能化是一个重要的课题 [1,2 ] . Shoichet等 [3 ] 通过化学反应或等离子体处理的方法 ,将蛋白质引入到材料表面而使其功能化 .基片在两种带有相反电荷的聚电解质溶液中交替吸附 ,其表面形成致密有序的超薄自组装膜 ,这种层 -层自组装技术不仅制备方法简单 ,无需特殊的设备 ,而且对膜组成和厚度能随意调控 ,以水为介质 ,对环境友好 [4～ 6] ,无疑是一项重要的表…     

Layer by layer self-assembled polyelectrolyte multilayers with embedded phospholipid vesicles obtained by spraying: integrity of the vesicles

In a previous paper (Michel, M.; Vautier, D.; Voegel, J.-C.; Schaaf, P.; Ball, V. Langmuir 2004, 20, 4835), we showed that phospholipid vesicles can be incorporated into poly(glutamic-acid)/poly(allylamine) (PGA/PAH) multilayered polyelectrolyte films built by the alternated dipping of a surface in polyanion and polycation solutions. AFM imaging, quartz crystal microbalance, and ellipsometry suggested that the vesicles remain intact when adhering on the surface. In the present paper, we show that such films can also be realized by spraying both the polyelectrolyte solutions and the vesicles onto the surface. Using such vesicles filled with ferrocyanide ions, we prove by cyclic voltammetry that the sprayed vesicles remain intact when embedded in the multilayers. We show that multilayers containing two distinct layers of intact vesicles separated by several polyanion/polycation bilayers can also be constructed. Polyelectrolyte multilayers containing layers of phospholipid vesicles could act as reservoirs for drug or other biologically active molecules in controlled release bioactive coatings.     

Effect of molecular weight on the exponential growth and morphology of hyaluronan/chitosan multilayers: a surface plasmon resonance spectroscopy and atomic force microscopy investigation

The layer-by-layer growth of multilayer assemblies of two polysaccharides, the polyanion hyaluronan (HA) and the polycation chitosan (CH), was investigated using atomic force microscopy (AFM) and surface plasmon resonance (SPR) spectroscopy, with primary emphasis on the effect of the polysaccharide molecular weights on the film thickness and surface morphology. The HA/CH multilayers exhibit an exponential increase of the optical film thickness with the number of deposited bilayers. We show that the multilayer thickness at a given stage depends on the size of both CH, the diffusing polyelectrolyte, and HA, the non-diffusing species. Assemblies (12 bilayers) of high molecular weight polysaccharides (HA, 360,000; CH, 160,000) were twice as thick (approximately 900 nm vs approximately 450 nm) as those obtained with low molecular weight polymers (HA, 30,000; CH, 31,000), as assessed by AFM scratch tests. The exponential growth rate is the same for the high and low molecular weight pairs; the larger film thicknesses observed by SPR and by AFM arising from an earlier onset of the steep exponential growth phase in the case of the high molecular weight pair. In all cases, isolated islets form during the deposition of the first CH layer onto the underlying HA. Upon further film growth, individual islets coalesce into larger vermiculate features. The transition from distinct islands to vermiculate structures depends on the molecular weights of the polysaccharides and the lower molecular weight construct presents larger worm-like surface domains than the high molecular weight pair.     

PbS纳米粒子与全共轭高分子的自组装膜原位复合及其光电转换性质

无机纳米粒子因其在催化、磁学、光子学等方面的特殊性质而越来越受到关注,纳米粒子粒径及分布可以人为控制,由此能够改变与有机聚合物所形成的纳米复合材料性能,在各种无机纳米粒子／有机聚合物复合材料制备方法中,纳米反应器(Nanoreactor)技术正日益受到关注,与常规的作为化学反应特定场所的化学反应器不同,纳米反应器不是一般的具体的机械设备,     

Influence of humic acid on the flocculation of clay

The aim of this study was to improve the flocculation of wastewater from gravel pits, especially the separation of the finely dispersed inorganic particles and the removing of humic acid. Clay was used as a model to investigate the influence of humic acid on the flocculation with two different types of polycation. The dependence of the sedimentation behaviour on time was investigated as well as the turbidity of the supernatant and the light absorption as a measure for humic acid removal. Bridging of particles remained the dominant mechanism of particle destabilisation by treating the clay in water with cationic polyacrylamides of very high molecular mass (CPAM). Poly(diallyldimethylammonium chloride) (PDADMAC) of lower molar mass (35 000 g/mol) was found to act by charge neutralisation. In this case the so-called flocculation window was very small. This behaviour is the same for systems containing humic acid. However, the need for cationic flocculant increases because humic acid as a weak polyanion can interact with the polycation. By using CPAMs with low charge this interaction does not play a significant role. The optimum flocculation concentration is relatively high. The flocs are larger and the velocity of sedimentation is higher than for the short-chain and highly charged polycation PDADMAC. However, because the latter is more effective in removal of humic acid at the point of optimum flocculation it is more advantageous to combine the highly charged polycation with a high molecular weight polyanion (dual system).     

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.     

PS胶体粒子表面逐层自组装固定化SOD及其生物活性

通过逐层自组装技术成功地把超氧化物歧化酶(SOD)吸附在聚苯乙烯(PS)胶体粒子表面.zeta电位和TEM证明了聚阳离子或聚阴离子型SOD与相反电荷的聚电解质在PS胶体粒子表面的交替吸附.通过测定SOD被胶体粒子吸附后上清液的生物活性,得到聚阴离子型SOD(pH=8.0)和聚阳离子型SOD(pH=4.3)在PS胶体粒子表面的吸附量分别为12和51IU,相对活性分别为23.4%和2.9%.聚阴离子型SOD在PS胶体粒子表面能形成平滑规整的膜,导致较高的相对活性.研究结果表明,通过调节pH值,可以优化自组装固定化酶的聚集状态和生物活性     

Polyelectrolyte complexes from polysaccharides: formation and stoichiometry monitoring

Colloids were obtained from non-stoichiometric polyelectrolyte complexes with two polysaccharides of opposite charge: chitosan and dextran sulfate (DS) as the polycation and polyanion, respectively. The complexes were elaborated by a one-shot addition of the polymer in default to the one in excess. The colloids were positively or negatively charged according to the nature of the polymer in excess. Dynamic light scattering (DLS) demonstrated that particles were formed at a very early stage in the complexation process. The consumption of the excess polyelectrolyte was monitored with a dye assay specific for dextran sulfate (toluidine blue) or chitosan (orange II). From these experiments, two different mechanisms of colloidal PEC formation were evidenced, according to the nature of the polymer in excess. On adding chitosan to DS in excess, regular consumption of the polyanion was observed at a constant stoichiometry, in the 1.5 to 1.85 range (sulfate residues for one glucosamine group), according to the molar mass of the polycation. When DS was added to chitosan in excess, the overall stoichiometry varied from ca. 6 (glucosamine residues for one sulfate group) down to 1 as the charge molar mixing ratio R=n+/n- decreased from 20 to 1. The existence of various mechanisms, according to the nature of the polymer in excess, could be attributed to the differences in chemical reactivity (strong vs low) of the ion in excess and the conformation and flexibility of the macromolecular chains related to their electrostatic potential.     

交联结构对肝素/壳聚糖层层组装多层膜内皮细胞相容性的影响

采用1-乙基-(3-二甲基氨基丙基)碳酰二亚胺交联技术对具有抗凝血抗菌作用的肝素/壳聚糖多层膜进行交联, 研究了交联结构对多层膜稳定性和血管内皮细胞亲和性的影响. QCM-D结果显示, 交联可有效地提高多层膜的稳定性, 在模拟人体血液流速(3.0 cm/s)下保持良好的稳定. 体外内皮细胞的研究结果显示, 多层膜的交联可有效地调节肝素/壳聚糖多层膜表面粘弹性, 并显著增加内皮细胞的粘附与生长. 交联的肝素/壳聚糖多层膜有望成为理想的心血管功能界面涂层材料.     

Polyelectrolyte complexes. II. Specific aspects of the formation of polycation/dye/polyanion complexes

We report on the formation of the polycation/dye/polyanion (PC/D/PA) complexes by the interaction between nonstoichiometric polycation/dye (PC/D) complexes with polyanions. Polycations differed in their content of the (N,N‐dimethyl‐2‐hydroxypropylene ammonium chloride) units in the main chain. Poly(sodium acrylate) (NaPA), poly(sodium 2‐acrylamido‐2‐methylpropane sulfonate) (NaPAMPS) and poly(sodium styrenesulfonate) (NaPSS) were used as polyanions. Crystal Ponceau 6R (CP6R) and Ponceau 4R (P4R) with two or three sulfonic groups were used as anionic dyes. The interaction between nonstoichiometric PC/D complexes and polyanions was followed by UV‐VIS spectroscopy, viscometry, and conductometry measurements. Formation of PC/D/PA complexes takes place mainly by the electrostatic interaction between the polyanion and the free positive charges of the nonstoichiometric PC/D complex. The stoichiometry and the stability of the tricomponent complexes depended on the polycation structure, the structure and molecular weight of polyanion, the dye structure, and the P/D molar ratio. A high amount of the dye was excluded from the complex before the end point when a branched polycation was used. The higher the solubility of the dye the lower the stability of the PC/D/PA complexes. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 409–418, 1999