Electrochemical Study of a Polypyrrole Film/Decanethiol Self-Assembled Monolayer on a Gold Electrode

Cyclic voltammetry and chronoamperometry were used to study the deposition of polypyrrole on a decanethiol self-assembled monolayer modified gold electrode (PPY/SAM/Au). The voltammetric behavior of the PPY/SAM film was investigated in the presence of several different electrolytes. It is found that the SAM shows great influence on the nucleation and growth of the PPY film. The reaction of the SAM and the anions causes the different voltammetric behavior of the polymerization of pyrrole on the modified electrode. Chronoamperometry shows the nucleation and growth of the PPY is initially inhibited but followed by a rapid increase. The SAM also influences electrochemical behavior of PPY film. Experiments show that the SAM can greatly depress the diffusion of anions in the PPY film, and minimize the background capacitance current.     

Controlled electrochemical synthesis of polypyrrole nanoparticle thin film and its redox transition to a highly conductive and stable polypyrrole variant

We demonstrated here a unique method to produce a highly stable and conductive polypyrrole (PPY) nanoparticle film. The procedure entails controlling the redox switching and the electrochemical synthesis of PPY. PPY was synthesized at a very low forming potential or reaction rate in nonaqueous CH2Cl2 solvent to promote the PPY nanoparticle formation. Then its property was further optimized by first electrochemically reducing it at a hydrogen evolution potential in a neutral 0.1 M NaClO4, then in a slightly acidic 0.05 M asparagine electrolyte. The PPY nanoparticle thin film was characterized by AFM, UV-vis and EQCM. The procedures described here have proven to be reproducible. The data provided by the EQCM shows a reversible doping and undoping mechanism of asparagine indicating the presence of a highly conductive PPY variant. Both UV-vis and electrochemical characterization suggest that the PPY film made using our approach has excellent redox activity as well as high stability when characterized in asparagine solution. The reversible doping and undoping of asparagine during redox switching shows great potential of these PPY nanoparticle films as biological membranes for a broad range of biological applications.     

Fabrication of Conductive Polypyrrole Doped Chitosan Thin Film for Sensitive Detection of Sulfite in Real Food and Biological Samples

In this study, we reported electrochemical synthesis of conductive polypyrrole‐chitosan (PPY‐CHI) thin film for sensitive detection of sulfite in real samples. The synthesized PPY‐CHI film was characterized in terms of surface morphology, optical property, binding energy, conductivity and electrochemical properties. The synthesized copolymeric PPY‐CHI film displayed good electrocatalytic behaviour towards oxidation of sulfite. The synthesized PPY‐CHI film was used for sulfite detection using differential pulse voltammetric technique with detection limit, sensitivity and linearity of 0.21 μM (S/N=3), 15.28 μA μM cm^?2 and 50–1100 μM respectively. In addition, the current responses of PPY‐CHI film towards sulfite were repeatable, reproducible response and unaffected by selected electroactive interferents. Finally, the synthesized PPY‐CHI was successfully and satisfactorily applied for determination of sulfite in real food and biological samples. The results obtained from this study highly placed PPY‐CHI film as a promising sensor for sensitive and accurate detection of sulfite in food and biological samples for human health protection.     

Plasma protein adsorption and thrombus formation on surface functionalized polypyrrole with and without electrical stimulation

A surface modification technique was developed in which heparin was covalently immobilized onto electrically conductive polypyrrole (PPY) film through poly(ethylene glycol) methacrylate (PEGMA) graft copolymerization and subsequent cyanuric chloride activation. In vitro plasma protein adsorption and thrombus formation experiments were carried out on the various films. The PEGMA-graft-copolymerized PPY surfaces with immobilized heparin have good bioactivity indicated by low level of protein adsorption, high ratio of albumin to fibrinogen adsorption, and low thrombus formation, making them potentially good candidates for biomedical applications. Since the PPY film retained significant electrical conductivity after surface modification, the effect of electrical stimulation on protein adsorption and thrombus formation was also evaluated. The covalently immobilized heparin on the PPY film was able to retain its bioactivity after 4 days of immersion in PBS. The film after long-term immersion in PBS also retained sufficient electrical conductivity for electrical stimulation still to be effective for reducing protein adsorption.     

Acceleration of laser-induced formation of gold nanoparticles in a poly(vinyl alcohol) film

Gold nanoparticles (AuNps) were fabricated in a poly(vinyl alcohol) (PVA) film using the photochemically generated benzophenone ketyl radical and PVA radical by laser irradiation as a reducing agent. The measurements of the surface plasmon band of AuNps indicated that AuNps continued growing in the PVA film for several hours or days after the laser irradiation. The formation process of AuNps in the PVA film was investigated by using laser flash photolysis and UV-vis absorption spectroscopy. Additive doping (formic acid or sodium 2-mercaptoethanesulfonate) in the PVA film dramatically accelerated or inhibited the formation rate of the AuNps, respectively. The doping of formic acid accelerated the formation rate of the AuNps by a factor of 10-20. On the contrary, doping of 2-mercaptoethanesulfonate inhibited the formation of AuNps. The mechanisms of the acceleration and inhibition were investigated by using laser flash photolysis. The effects of additives on the formation process of AuNps are discussed.     

氯霉素分子印迹复合膜的制备及电化学

采用电化学聚合法合成了对氯霉素（CAP）有快速响应和高灵敏度的聚苯胺/聚吡咯分子印迹复合膜修饰电极。 通过微分脉冲伏安法、扫描电子显微镜对制备的分子印迹复合膜的电化学性质及表面形貌进行了表征。 结果表明,以铁氰化钾为电化学探针,该膜对CAP的测定电化学信号响应快速、灵敏度高、选择性和膜再生性能良好。 对CAP检测的线性范围为5.00×10-8～1.05×10-6 mol/L,检测限为2.09×10-9 mol/L。     

Analysis of mono-nitrotoluenes in water samples by using nano-structured polypyrrol as a sorbent of solid-phase microextraction

Nano-structured polypyrrole (PPY) was used as a coating of solid-phase microextraction (SPME) fibre to increase the extraction efficiency of headspace solid phase microextraction (HS-SPME) of mono-nitrotoluene (MNT) isomers in water samples. The nano-structured PPY was prepared electrochemically by template-free method in the presence of dodecylbenzene sulphonate (DBS) as dopant. Nano-fibrous structures of PPY with a diameter in the range of 38–129 nm were obtained. The porous surface structure of the film, revealed by scanning electron microscopy (SEM), provided high surface areas and allowed for high extraction efficiency of MNT isomers. The extraction procedure was optimised by selecting the appropriate extraction parameters including the time and temperature of adsorption, salt concentration and stirring rate. The calibration graphs obtained by HS-SPME using the proposed fibre followed by GC-FID analysis were linear in a concentration range of 0.1–500 µg L^?1 (r > 0.999) with detection limits below 0.012 µg L^?1 for three isomers. Repeatability of the method was less than 6% (RSD%, n = 4). Good recoveries (88–108%) were obtained for the extraction of mono-nitrotoluenes in real water samples.     

Synthesis of poly(vinyl alcohol) containing asymmetric nucleic acid base derivatives as grafted pendants

The preparations of new model polymers of polynucleotides with linear poly(vinyl alcohol) (PVA) backbones and an optically active nucleic acid base derivative as a pending side chain are described. (±)-, (+)-, and (?)-2-(thymin-1-yl)propionic acid were grafted onto PVA through ester bonds by direct coupling with dicyclohexylcarbodiimide (DCC) in the presence of highly active catalyst 4-pyrrolidinopyridine (PPY) to give optically active graft polymers. The corresponding monomer and dimer models have been prepared.     

Monolayer alignment on azobenzene surfaces during UV light irradiation: analysis of optical polarized absorption measurement results and theoretical treatment

The influence of the charge separation during the trans-cis conformational change on the surface of azobenzene 6Az10PVA monolayer on the polar liquid-crystal monolayer film, such as 4-n-pentyl-4'-cyanobiphenyl(5CB), is investigated. The effective anchoring energy (in the Rapini-Papolar form) is phenomenologically described in the framework of the molecular model, which takes into account the interaction between the surface polarization and surface electric field, for number of conformational states of the boundary surface. It is shown, using the experimental data for the voltage across the 6Az10PVA+5CB film, provided by the surface-potential technique, that the charge separation during the conformational changing, caused by the UV irradiation, may lead to changing of the surface alignment of liquid-crystalline molecules. The influence of the photoisomerization process on the orientational order parameter S2(t) using the optical polarized absorption measurement is also investigated.     

Film Formation and Redispersion of Waterborne Latex Coatings

Poly(vinyl acetate-co-ethylene) latex dispersions are prepared and their films investigated with a focus on the effect of composition upon redispersion. Films of dispersions containing sufficient amounts of poly(vinyl alcohol) (PVA) can be redispersed in water. This property is lost in the presence of surfactant, a fact which suggests a procedure to control film formation. It is demonstrated that redispersion is due to a PVA-membrane which separates the particles. Loss of redispersibility in the presence of surfactant proceeds with the breakup of the membranes and a corresponding change of film properties. Experimental data is provided by light microscopy, mechanical testing, and TEM in conjunction with a staining method new to the field. The hypothesis is developed that interaction with surfactant leads to imperfect PVA-membranes that are no longer able to prevent latex polymer interdiffusion. Fluorescence correlation spectroscopy demonstrates the formation of surfactant micelles, as well as the simultaneous adsorption and aggregation of PVA onto the micelles. It is concluded that the competing surface of the surfactant micelles traps enough PVA to cause thinning and fragmentation of the membranes surrounding the particles, which enables interdiffusion of latex polymer. This effect can be used to convert the system from one forming a redispersible coating to one forming a nonredispersible (permanent) film. Copyright 2000 Academic Press.     

Adipogenic differentiation of individual mesenchymal stem cell on different geometric micropatterns

Micropatterned surfaces are very useful to control cell microenvironment and investigate the physical effects on cell function. In this study, poly(vinyl alcohol) (PVA) micropatterns on polystyrene cell-culture plates were prepared using UV photolithography. Cell adhesive polystyrene geometries of triangle, square, pentagon, hexagon, and circle were surrounded by cell nonadhesive PVA to manipulate cell shapes. These different geometries had the same small surface areas for cell spreading. Human mesenchymal stem cells (MSCs) were cultured on the micropatterned surface, and the effect of cell geometry on adipogenic differentiation was investigated. MSCs adhered to the geometric micropatterns and formed arrays of single cell with different shapes. The distribution patterns of actin filaments were similar among these cell shapes and remolded during adipogenesis. The adipogenic differentiation potential of MSCs was similar on the small size triangular, square, pentagonal, hexagonal, and circular geometries according to lipid vacuoles staining. This simple micropatterning technique using photoreactive molecules will be useful for creating micropatterns of arbitrary design on an organic surface, and cell functions can be directly and systematically compared on a single surface without external factors resulting from separate cell culture and coating method.     

PEG-grafted PVA Membrane and Its Blood Compatibility

Preparation and blood compatibility of different shape polyvinyl alcohol(PVA) membrane were investigated. Firstly, the tabular and tubular[polytetrafluoroethylene(PTFE) capillary as supporter] PVA membranes were prepared; then, methoxy polyethylene glycol(mPEG) was grafted onto the surface of the PVA membranes. The effects of the shape, structure and properties of the membrane surface on blood compatibility were studied in detail. The experiment results show that mPEG modified PVA membranes, especially mPEG modified tubular membrane, could availably repel the adhesion of the platelets. In addition, the anticoagulant mechanism of mPEG with a steric repulsion effectiveness was confirmed further via different grafting methods.     

Fully-biodegradable poly(3-hydroxybutyrate)/poly(vinyl alcohol) blend films with compositional gradient

Fully-biodegradable bacterial poly(3-hydroxybutyrate) (PHB)/chemosynthetic poly(vinyl alcohol) (PVA) blend films with compositional gradient from one surface to the other surface of the films were prepared by a dissolution-diffusion technique. Three kinds of PVA samples, high- and low-molecular weight atactic PVA and highly syndiotactic PVA (s-PVA), were used in order to investigate the effects of molecular weight and tactic structure on the generation of compositional gradient. The solution of PHB in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), which is also a good solvent for PVA, was cast on the PVA film and then the solvent HFIP was evaporated. By selecting the optimum volume of solvent and the evaporation rate, the PHB/PVA blend film with compositional gradient was obtained. The formation of compositional gradient was confirmed by FT-IR microscopy and ATR-FT-IR analysis. The 50%/50% PHB/s-PVA blend film with a nearly ideal compositional gradient, that is, the composition of PHB (or PVA) in the film changing gradually from 100% at one surface to 0% at the other surface of the film was obtained by casting PHB/HFIP solution on to the s-PVA film. Positional dependence of the absorbance of C==O and OH stretching bands along the film thickness direction for the PHB/S-PVA cast films.     

SPEEK/PVA-AgNPs复合膜的制备与表征

首先,以磺化聚醚醚酮(SPEEK)为光敏自由基载体,以聚乙烯醇(PVA)为分散稳定剂,制备了具有光生自由基功能的SPEEK/PVA高分子膜;然后,通过在SPEEK/PVA膜上紫外光诱导Ag+还原生成纳米银颗粒(AgNPs),从而得到SPEEK/PVA-AgNPs复合膜。采用紫外可见分光光度计(UV-Vis)、扫描电镜(SEM)、能谱仪(EDS)、X射线光电子能谱分析(XPS)及傅里叶变换红外光谱(FT-IR)等手段对SPEEK/PVA-AgNPs材料进行了表征。结果显示:生成的银颗粒为纳米级,较均匀地分布在SPEEK/PVA高分子膜表面,SPEEK/PVA-AgNPs复合膜整体呈现棕色;形成的银纳米颗粒具有较完整的晶型,且价态分析显示其为单质。     

In situ mineralization of hydroxyapatite on electrospun chitosan-based nanofibrous scaffolds

A biocomposite of hydroxyapatite (HAp) with electrospun nanofibrous scaffolds was prepared by using chitosan/polyvinyl alcohol (CS/PVA) and N-carboxyethyl chitosan/PVA (CECS/PVA) electrospun membranes as organic matrix, and HAp was formed in supersaturated CaCl2 and KH2PO4 solution. The influences of carboxylic acid groups in CECS/PVA fibrous scaffold and polyanionic additive poly(acrylic acid) (PAA) in the incubation solution on the crystal distribution of the HAp were investigated. Field-emission scanning electron microscopy (FE-SEM), energy-dispersive spectroscopy (EDS), wide-angle X-ray diffraction (WAXD), and Fourier transform infrared (FTIR) were used to characterize the morphology and structure of the deposited mineral phase on the scaffolds. It was found that addition of PAA to the mineral solution and use of matrix with carboxylic acid groups promoted mineral growth and distribution of HAp. MTT testing and SEM imaging from mouse fibroblast (L929) cell culture revealed the attachment and growth of mouse fibroblast on the surface of biocomposite scaffold, and that the cell morphology and viability were satisfactory for the composite to be used in bioapplications.     

Preparation of uniform silica/polypyrrole core/shell microspheres and polypyrrole hollow microspheres by the template of modified silica particles using different modified agents

Silica/polypyrrole (PPY) core/shell microspheres and PPY hollow microspheres were prepared by the template of silica particles whose surface character was modified with different modified agents. The morphology and structure of the particles were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Elemental analysis and X-ray photoelectron spectroscopy (XPS) were carried out to characterize the structure of PPY hollow microspheres. We investigated the effect of different modified agents on the surface character of silica particles and the effect of surface character of silica particles on the morphology of PPY hollow microspheres. The effect of reaction conditions on the size of core/shell particles and hollow particles was also studied.     

Surface Modification of Carbon Nanotube by Poly(ethylene glycol) for the Preparation of Poly(vinyl alcohol) Nanocomposite

Herein, PEGylated multi-walled carbon nanotube (MWNT) was prepared for the successive fabrication of poly(vinyl alcohol) PVA/MWNT nanocomposite film by solution casting. The surface modified MWNT showed a good colloidal stability in a polar solvent, i.e., water. Also, the PEGylated MWNT had an improved dispersion stability in aqueous PVA solution. The mixture of PEGylated MWNT and PVA dissolved in water was film casted and the dispersion uniformity and corresponding improvement of electrical conductivity were investigated. The electrical conductivity of PVA/modified MWNT composite film was three-fold higher than that of PVA/pristine MWNT composite film due to the much improved distribution uniformity of modified MWNT in PVA matrix.     

魔芋葡甘聚糖/聚乙烯醇纳米纤维膜及其释药行为研究

为了研制药物缓释效果优良的薄膜材料,利用静电纺丝设备研制不同比重的魔芋葡甘露聚糖/聚乙烯醇纳米纤维膜,并通过扫描电镜、傅里叶变换红外光谱和示差扫描量热法表征纳米纤维膜的结构和性能,结合体外实验和数学模型研究其缓释行为.结果显示当魔芋葡甘露聚糖含量占纳米纤维膜总质量约76%时,纳米纤维膜中微纤丝粗细最均匀且结点较少,纳米纤维膜中魔芋葡甘聚糖和聚乙烯醇之间存在明显的相互作用,含有5-氨基水杨酸的纳米纤维膜在pH=7.4 PBS磷酸盐缓冲液中25 h的累积释放量大约为45%,显示出良好的药物缓释效果,其缓释行为与Higuchi模型具有较高的拟合度.研究表明利用静电纺丝设备研制的魔芋葡甘聚糖/聚乙烯醇纳米纤维膜可以为药物缓释载体的开发提供理论依据.     

Formation Mechanism of a Silane‐PVA/PVAc Complex Film on a Glass Fiber Surface

Mechanical properties of glass fiber reinforced composite materials are affected by fiber sizing. A complex film formation, based on a silane film and PVA/PVAc (polyvinyl alcohol/polyvinyl acetate) microspheres on a glass fiber surface is determined at 1) the nanoscale by using atomic force microscopy (AFM), and 2) the macroscale by using the zeta potential. Silane groups strongly bind through the Si? O? Si bond to the glass surface, which provides the attachment mechanism as a coupling agent. The silane groups form islands, a homogeneous film, as well as empty sites. The average roughness of the silanized surface is 6.5 nm, whereas it is only 0.6 nm for the non‐silanized surface. The silane film vertically penetrates in a honeycomb fashion from the glass surface through the deposited PVA/PVAc microspheres to form a hexagonal close pack structure. The silane film not only penetrates, but also deforms the PVA/PVAc microspheres from the spherical shape in a dispersion to a ellipsoidal shape on the surface with average dimensions of 300/600 nm. The surface area value S_a represents an area of PVA/PVAc microspheres that are not affected by the silane penetration. The areas are found to be 0.2, 0.08, and 0.03 μm² if the ellipsoid sizes are 320/570, 300/610, and 270/620 nm for silane concentrations of 0, 3.8, and 7.2 μg mL^?1, respectively. The silane film also moves PVA/PVAc microspheres in the process of complex film formation, from the low silane concentration areas to the complex film area providing enough silane groups to stabilize the structure. The values for the residual silane honeycomb structure heights (H_a) are 6.5, 7, and 12 nm for silane concentrations of 3.8, 7.2, and 14.3 μg mL^?1, respectively. The pH‐dependent zeta‐potential results suggest a specific role of the silane groups with effects on the glass fiber surface and also on the PVA/PVAc microspheres. The non‐silanized glass fiber surface and the silane film have similar zeta potentials ranging from ?64 to ?12 mV at pH’s of 10.5 and 3, respectively. The zeta potentials for the PVA/PVAc microspheres on the glass fiber surface and within the silane film significantly decrease and range from ?25 to ?5 mV. The shapes of the pH‐dependent zeta potentials are different in the cases of silane groups over a pH range from 7 to 4. A triple‐layer model is used to fit the non‐silanized glass surface and the silane film. The value of the surface‐site density for Γ_Xglass and Γ_Xsilane, in which X denotes the Al? O? Si group, differs by a factor of 10^?4, which suggests an effective coupling of the silane film. A soft‐layer model is used to fit the silane‐PVA/PVAc complex film, which is approximated as four layers. Such a simplification and compensation of the microsphere shape gives an approximation of the relevant widths of the layers as the follows: 1) the layer of the silane groups makes up 10 % of the total length (27 nm), 2) the layer of the first PVA shell contributes 30 % to the total length (81 nm), 3) the layer of the PVAc core contributes 30 % to the total length (81 nm), and finally 4) the layer of the second PVA shell provides 30 % of the total length (81 nm). The coverage simulation resulted in a value of 0.4, which corresponds with the assumption of low‐order coverage, and is supported by the AFM scans. Correlating the results of the AFM scans, and the zeta potentials sheds some light on the formation mechanism of the silane‐PVA/PVAc complex film.     

Structure and Mechanical Properties of Chitosan/Poly(Vinyl Alcohol) Blend Films

Summary: The origins of the thermal and mechanical properties of chitosan and poly(vinyl alcohol) (PVA) with inter- and intra-hydrogen bonds were investigated systematically by using X-ray, DSC, positron annihilation and viscoelastic measurements. Based on their individual properties, the characteristics of the blend films were estimated in relation to their morphology and mechanical properties as a function of chitosan content. The characteristics of the blend films were also analyzed in terms of the deviation from a simple additive rule of chitosan and PVA content. These results suggested that the miscibility of chitosan and PVA could be ensured by entanglement of the amorphous chain segments of chitosan and PVA. Further detailed analysis revealed that the chitosan content on the film surface is higher than that of the admixture content of chitosan after elongation, although the chitosan and PVA chains were crystallized independently. The elongation could be achieved for the blend films whose PVA content was higher than 50% and the drawn blend films were transparent. Thus, it may be expected that sufficiently entangled meshes formed between chitosan and PVA amorphous chains within the film, the PVA content being higher than 50%, were maintained under the elongation process.