重氮树脂型聚电解质复合物与SDS相互作用研究

由于聚电解质与表面活性剂的相互作用具有很多特别的性质而倍受关注［１～１０］,但具有感光性的重氮树脂作为正离子聚电解质与表面活性剂相互作用尚未见报道．本文研究了重氮树脂（ＤＲ）与聚苯乙烯磺酸钠（ＰＳＳ）形成的聚电解复合物（ＤＲ－ＰＳＳ）与十二烷基硫酸钠...     

PSS/PDDA自组装膜形成过程中的临界浓度效应

Decher等提出的阴阳聚电解质层层组装膜技术(LbL),方便快捷,结构有序,其纳米级可控,可用于生物传感器、杂多酸多层膜修饰电极及天然多糖类功能膜等领域．LbL膜的厚度直接影响其性能,而膜厚度与紫外吸光度(A)成正比．故A是通常用于评价膜厚度的一种简便方法．紫外吸光度与聚电解质溶液浓度(cp)往往呈递增关系,随着溶液中cp的增大,单位面积上吸附聚电解质的量也增加。     

Layer-by-layer assembled protein/polymer hybrid films: nanoconstruction via specific recognition

In the present study it is shown that streptavidin-containing multilayer films with varying numbers of polyelectrolyte spacer layers can be fabricated reproducibly using optimized deposition conditions. Direct alternation of streptavidin and PLB leads to multilayer systems with an average streptavidin thickness of 5.3 nm which is in good agreement with the dimensions of the protein. When the streptavidin layers are spacered by more polyelectrolyte layers the distance between the protein sheets is increased up to e.g. 6.5 nm in the case of (PLB/PSS/PAH/PSS/PLB) as spacer layer. X-ray reflectivity reveals that streptavidin increases the surface roughness of the films probably due to the rigid three-dimensional structure of the protein. The control of surface roughness seems to be essential for a successful multilayer build-up. The property of PLB to provide for multilayer construction by two different interactions (electrostatic and specific) allowed to probe the interpenetration depth of adjacent layers. For the [PLB/(PSS/PL)₂/streptavidin] system an interpenetration depth of about 4 polymer layers corresponding to approximately 3.4 nm has been derived. These data are in agreement with a model for pure polyelectrolyte films obtained from neutron and X-ray reflectivity data.     

Layer-by-layer assembly of salt-containing polyelectrolyte complexes for the fabrication of dewetting-induced porous coatings

The layer-by-layer (LbL) assembly of salt-containing nonstoichiometric polyelectrolyte complexes (PECs) with oppositely charged uncomplexed polyelectrolyte for the fabrication of dewetting-induced porous polymeric films has been systematically investigated. Salt-containing poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) complexes (noted as PAH-PAA) with a molar excess of PAH were LbL assembled with polyanion poly(sodium 4-styrenesulfonate) (PSS) to produce PSS/PAH-PAA films. The structure of the PAH-PAA complexes is dependent on the concentration of NaCl added to their aqueous dispersions, which can be used to tailor the structure of the LbL-assembled PSS/PAH-PAA films. Porous PSS/PAH-PAA films are fabricated when salt-containing PAH-PAA complexes with a large amount of added NaCl are used for LbL assembly with PSS. In-situ and ex-situ atomic force microscopy measurements disclose that the dewetting process composed of pore nucleation and pore growth steps leads to the formation of pores in the LbL-assembled PSS/PAH-PAA films. The present study provides a facile way to fabricate porous polymeric films by dewetting LbL-assembled polymeric films comprising salt-containing PECs.     

Dilational viscoelasticity of anionic polyelectrolyte/surfactant adsorption films at the water–octane interface

In this article, the interfacial tension and interfacial dilational viscoelasticity of polystyrene sulfonate/surfactant adsorption films at the water–octane interface have been studied by spinning drop method and oscillating barriers method respectively. The experimental results show that different interfacial behaviors can be observed in different type of polyelectrolyte/surfactant systems. Polystyrene sulfonate sodium (PSS)/cationic surfactant hexadecanetrimethyl–ammonium bromide systems show the classical behavior of oppositely charged polyelectrolyte/surfactant systems and can be explained well by electrostatic interaction. In the case of PSS/anionic surfactant sodium dodecyl sulfate (SDS) systems, the coadsorption of PSS at interface through hydrophobic interaction with alkyl chain of SDS leads to the increase of interfacial tension and the decrease of dilational elasticity. For PSS/nonionic surfactant TX100 systems, PSS may form a sub-layer contiguous to the aqueous phase with partly hydrophobic polyoxyethylene chain of TX100, which has little effect on the TX100 adsorption film and interfacial tension.     

静电层层自组装制备聚苯乙烯微球(核)/MCM-41纳米粒子(壳)阶层结构复合微粒

采用聚苯乙烯磺酸钠(PSS)和聚二烯丙基二甲基氯化铵(PDDA)两种聚电解质, 通过静电层层自组装成功地将MCM-41介孔二氧化硅纳米粒子包覆到聚苯乙烯(PS)微球表面. 实验结果表明, 当以尺寸为1.4 μm的PS微球为核时, 包覆了两个聚电解质双层(PDDA/PSS)2的PS(PDDA/PSS)2(PDDA/MCM-41)复合结构微粒与包覆了一个聚电解质双层(PDDA/PSS)的PS(PDDA/PSS)(PDDA/MCM-41)复合结构微粒相比, 复合结构微粒之间的交联程度降低, 但是MCM-41纳米粒子在聚苯乙烯微球表面的包覆都比较松散, 且产物中存在大量杂质. 而当以尺寸为5 μm的聚苯乙烯微球为核时, MCM-41纳米粒子紧密地包覆在聚苯乙烯微球表面, 复合结构微粒之间只有少量桥连物, 且产物中杂质很少.     

Effect of Molecular Weight on the Interfacial Dilational Viscoelasticity of Anionic Polyelectrolyte/Surfactant Systems

In this article, the effect of molecular weight on the interfacial tension and interfacial dilational viscoelasticity of polystyrene sulfonate/surfactant adsorption films at the water-octane interface have been studied by spinning drop method and oscillating barriers method respectively. The experimental results show that different interfacial behaviors can be observed in different type of polyelectrolyte/surfactant systems. PSS/cationic surfactant CTAB systems show the classical behavior of oppositely charged polyelectrolyte/surfactant systems and can be well explained by electrostatic interaction. Molecular weight of PSS plays a crucial role in the nature of adsorption film. The complex formed by CTAB and higher molecular weight PSS, which has larger dimension and stronger interaction, results in higher dilational modulus at lower surfactant bulk concentration. In the case of PSS/anionic surfactant SDS systems, the co-adsorption of PSS at interface through hydrophobic interaction with alkyl chain of SDS leads to the increase of interfacial tension and the decrease of dilational modulus at lower surfactant bulk concentration. For PSS/nonionic surfactant T × 100 systems, PSS may form a sublayer contiguous to the aqueous phase, which has little effect on interfacial tension but slightly decreases dilational modulus.     

Redox processes of cytochrome c immobilized on solid supported polyelectrolyte multilayers

The heme protein cytochrome c (Cyt-c), immobilized on polyelectrolyte multilayers on a silver electrode, was studied by stationary and time-resolved surface-enhanced resonance Raman (SERR) spectroscopy to probe the redox site structure and the mechanism and dynamics of the potential-dependent interfacial processes. The layers were built up by sequential adsorption of polycations (poly[ethylene imine] (PEI); polyallylamine hydrochloride (PAH)) and polyanions (poly[styrene sulfonate] (PSS)). All multilayers terminated by PSS electrostatically bind Cyt-c. On PEI/PSS coatings, Cyt-c is peripherally bound and fully redox-active. Due to the interfacial potential drop, the apparent redox potential is lowered by 40 mV compared to that in solution. The rate constant for the heterogeneous electron transfer (ET) of ca. 0.1 s(-1) is consistent with electron tunneling through largely ordered PEI/PSS layers. ET is coupled to a reversible conformational transition of Cyt-c that involves a change of the coordination pattern of the heme. Additional (PAH/PSS) double layers cause a broadening of the redox transition and a drastic negative shift of the redox potential, which is attributed to the formation of PSS/Cyt-c complexes. It is concluded that Cyt-c can effectively compete with PAH for binding of PSS, resulting in a rearrangement of the layered structure and a penetration of the PSS-bound Cyt-c into the PAH/PSS double layers. This conclusion is consistent with SERR intensity and quartz microbalance measurements. ET was found to be overpotential-independent and faster than that for PEI/PSS coatings, which is interpreted in terms of specific PSS/Cyt-c complexes serving as gates for the heterogeneous ET.     

High-flux nanofiltration membranes prepared by adsorption of multilayer polyelectrolyte membranes on polymeric supports

Layer-by-layer deposition of anionic and cationic polyelectrolytes readily converts polymeric ultrafiltration membranes into materials capable of nanofiltration. ATR-FTIR spectra confirm that layer-by-layer deposition occurs on the ultrafiltration substrates, and adsorption of as few as 2.5 bilayers of poly(styrenesulfonate) (PSS)/protonated poly(allylamine) (PAH) or 3.5 bilayers of PSS/poly(diallyldimethylammonium chloride) (PDADMAC) reduces the molecular weight cutoff of polyethersulfone ultrafiltration supports from 50 kDa to <500 Da. Deposition of multilayer polyelectrolyte films on 300 and 500 kDa membranes also decreases molecular weight cutoffs, but solute rejections are significantly lower when using these supports, suggesting that the polyelectrolyte films do not completely cover large (0.2-0.4 microm in diameter) pores. On the 50 kDa substrates, PSS/PDADMAC films containing 3.5 bilayers exhibit a 95% rejection of SO(4)(2-) and a chloride/sulfate selectivity of 27, whereas 4.5-bilayer PSS/PAH coatings show a glucose/raffinose selectivity of 100. Pure water flux for [PSS/PAH](3)PSS-coated membranes at 4.8 bar is 1.6 m(3)/(m(2)day), which is more than 2-fold higher than that through a commercial 500 Da membrane.     

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.     

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.     

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.     

Assembly and mechanical properties of phosphorus dendrimer/polyelectrolyte multilayer microcapsules

We report the preparation, characterization, and mechanical properties of polyelectrolyte/phosphorus dendrimer multilayer microcapsules. The shells of these microcapsules are composed either by alternating poly(styrenesulfonate) (PSS) and positively charged dendrimer G4(NH+Et2Cl-)96 or by alternating poly(allylamine hydrochloride) (PAH) and negatively charged dendrimer G4(CH-COO-Na+)96. The same multilayers were constructed on planar support to examine their layer-by-layer growth and to measure the multilayer thickness. Surface plasmon resonance spectroscopy (SPR) showed regular linear growth of the assembly upon each bilayer deposited. We probe the mechanical properties of these polyelectrolyte/dendrimer microcapsules by measuring force-deformation curves with the atomic force microscope (AFM). The experiment suggests that they are much softer than PSS/PAH microcapsules studied before. This softening is attributed to an enhanced permeability of the polyelectrolyte/dendrimer multilayer shells as compared with multilayers formed by linear polyelectrolytes. In contrast, Young's modulus of both dendrimer-based multilayers was found to be on the same order as that of PSS/PAH multilayers.     

Adsorption of poly(styrene sulfonate) of different molecular weights on alpha-alumina: effect of added sodium dodecyl sulfate

The adsorption of poly(styrene sulfonate), PSS, of different molecular weights (70,000, 500,000, and 1,000,000 mol/kg), from aqueous solutions on alpha-alumina has been investigated. PSS of the lower molecular weight adsorbs less than the others whose adsorption isotherms overlap. The adsorption is found to increase with increasing ionic strength of the solutions indicating that both electrostatic and non-electrostatic contributions are involved in the adsorption process. Upon addition of the anionic surfactant, sodium dodecyl sulfate, SDS, PSS is found to adsorb less the more SDS added. SDS is found to be preferentially adsorbed as shown both from the simultaneous adsorption of the components and also from the sequential adsorption process where SDS in all cases displaces preadsorbed PSS from the solid surface. The displacement of preadsorbed polyelectrolyte by surfactant is a very slow process and the displacement is less pronounced as the molecular mass of the polyelectrolyte increases indicating the fewer number of contact points to the surface. This is further underlined by the effect on the displacement of PSS by SDS upon increasing the ionic strength of the solutions.     

聚电解质PSS/PDDA分子沉积膜表面性能研究

PSS PDDAMD膜紫外 可见吸光度与层数呈线性关系 ,其延长线基本为零证实了是一单分子层层状沉积过程 ;利用接触角测量仪跟踪MD膜沉积过程 ,其结果表明 ,层数较少时PSS PDDAMD膜表面润湿性呈“奇 偶”性规律变化 ,层数较多时规律性不明显 ,这说明聚电解质MD膜结构缺陷随着层数的增加有增大趋势 ;通过对原子力显微镜 (AFM)测定结果的分析 ,进一步证实了多层PSS PDDAMD膜存在结构缺陷 .     

Destructive effect of polystyrene sulfonate on the structure of hemoproteins

The mechanism of the destruction of horse heart hemoglobin (Hb) and spermwhale muscle myoglobin (Mb), two hem-containing proteins, by polystyrene sulfonate, an anionic polyelectrolyte, was studied. Measurements of the optical absorption of the prostetic group of the hem in the visible spectrum and of the circular dichroism in the absorption bands of the peptide groups and aromatic amino acid residues demonstrated that the compact structure of both proteins experiences destruction in the presence of polystyrene sulfonate (PSS) at PSS concentrations ten times as low as that of the protein (in wt %) and that the content of α-helix structure in Hb and Mb decreases from 81% in the native state to 43% in their complexes with PSS. The distinctions in the mechanisms of the destruction of Hb and Mb by PSS were found to be as follows: (1) in contrast to Mb, Hb forms insoluble complexes with PSS at low PSS concentrations and (2) Mb-PSS solutions at Mb-to-PSS ratios >1 were found to contain free hems (that absorb at 397 nm), a feature not observed for Hb; the kinetics of the destruction of both the proteins by the polyelectrolyte was demonstrated to be a two-stage process. The first stage of the destruction of Hb (τ ≈ 24.5 s) was found to be four times as slow as that of Mb (τ ≈ 6 s); the second (slow) stage had a halftime of ～6 h for both the proteins under study. To determine the localization of regions at the protein molecule surface that are capable of binding polyelectrolyte molecules, the distribution of the electrostatic potential over the surface of the Hb and Mb molecules was numerically calculated with the help of the Poisson-Boltzmann equation at pH 6.2 and an ionic strength of 100 mmol/l. Based on experimental and theoretical studies of the mechanism of the interaction of the polyelectrolyte with the proteins, the structural-functional properties of proteins responsible for their destruction by the polyelectrolyte are determined.     

Polyelectrolyte-protein complexes: structure and conformation of each specie revealed by SANS

We report here the structure of complexes made of proteins (lysozyme, positively charged) and polyelectrolytes (PSSNa, negatively charged). We stay in conditions where the volume fractions of the components are of the same order and where PSS concentrations correspond to a semidilute regime. The final complexes structure is determined by SANS. We obtain three main types of structures: (i) For a protein excess and for long polyelectrolyte chains, the network preformed by PSS chains still exists but chains are partially shrunk due to cross-linking by lysozyme. Macroscopically, samples are gelled. (ii) For a protein excess and for short polyelectrolyte chains, PSS chains are locally shrunk and do not form a network anymore. Lysozyme and PSS chains are embedded in dense 3-D aggregates that arrange in a fractal network at a larger scale. Macroscopically, samples are liquid. (iii) For a polyelectrolyte excess and whatever the chain length, the internal structure of the lysozyme changes. After an initial strong electrostatic binding, lysozyme is progressively unfolded thanks to a hydrophobic contact with PSS. The two chainlike objects are finally organized in a homogeneous costructure. Macroscopically, samples are liquids.     

Influence of polyelectrolyte multilayer adsorption on the temperature sensitivity of poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide) (PNiPAM) microgels

The electrophoretic mobility and temperature-dependent particle size of poly(N-isopropylacrylamide) (PNiPAM) microgels after alternating adsorption of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(sodium 4-styrenesulfonate) (PSS) have been determined. First a PNiPAM-co-acrylic acid (AAc) shell was added to the PNiPAM microgel, then PDADMAC and PSS were adsorbed alternately. The studies of the electrophoretic mobility revealed charge reversal when a polyelectrolyte (PE) layer was adsorbed. Particle size measurements revealed a strong influence of polyelectrolyte adsorption on the temperature-dependent particle swelling. The strong influence of the adsorbed polyelectrolyte on the particle size is in contrast to polyelectrolyte multilayer adsorption on rigid particles.     

Fabrication of free-standing multilayer films by using pH-responsive microgels as sacrificial layers

A facile way to prepare free-standing polyelectrolyte multilayer films of poly(sodium 4-styrenesulfonate)(PSS)/poly(diallyldimethylammonium)(PDDA) was developed by applying a new pH-dependent sacrificial system based on cross-linked poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) microgels. The tertiary amine groups of PDMAEMA microgels can be protonated in acidic environment, and the protonated microgels were deposited by layer-by-layer (LbL) technique with PSS. PSS/PDDA multilayer films were constructed on the top of the PSS/microgels sacrificial layers. The LbL assembly process was investigated by UV–vis spectroscopy. Further study shows that the free-standing PSS/PDDA multilayer films can be obtained within 3 min by treating the as-prepared films in alkali aqueous solution with a pH of 12.0. The pH-triggered exfoliation of PSS/PDDA multilayer films provides a simple and facile way to prepare LbL assembled free-standing multilayer films.     

Surface stress, thickness, and mass of the first few layers of polyelectrolyte

The effects of surface stress and mass loading upon the adsorption of polyelectrolytes onto flexible silicon micromechanical cantilever sensors (MCSs) were studied in situ. A self-assembled monolayer of 2-mercaptoethylamine chloride (2-MEA) on gold was used to achieve single-side adsorption on the MCS. Such a preparation gave a positive surface potential, whereas a bare SiOx surface gave a negative surface potential. Wide scan X-ray photoelectron spectroscopy confirmed that the adsorption of polystyrenesulfonate (PSS) and polyallylamine hydrochloride (PAH) followed the general rule expected from the electrostatic interaction between the substrate and the polyelectrolyte, whereas the adsorption polyethyleneimine (PEI) did not. The adsorption of PAH on SiO(x) from a 3 mM water solution containing 1 M NaCl was associated with a deflection of the MCS toward the polyelectrolyte monolayer (tensile surface stress) owing to the hydrogen bonding between neighboring amino groups. Here, a surface stress change of 1.4 +/- 0.1 N/m was estimated. The adsorption of PSS from a 3 mM water solution containing 1 M NaCl on a 2-MEA surface induced a deflection of the MCS away from the polyelectrolyte layer (compressive stress), toward the SiO(x) side. Here, a surface stress change of 3.1 +/- 0.3 N/m was determined. The formation of a PAH layer on top of the PSS layer resulted in a deflection of the MCS toward the PAH layer. This indicated that the adjacent PSS layer was deswelling, corresponding to a surface stress change of 0.5 +/- 0.1 N/m.