Magnesium and Calcium-Dependent Membrane Potential of Poly(Pyrrole) Films Doped with Adenosine Triphosphate

Polypyrrole-adenosinotriphosphate (PPy-ATP) films (membranes) were electropolymerized on platinum or glassy carbon and made sensitive to magnesium and calcium ions by conditioning. Close-to-Nernstian potentiometric sensitivity was observed for the films under equilibrium. During equilibration provoked by the change in concentration of magnesium and/or calcium ions, a characteristic transitory potential response of PPy-ATP film was observed. This behaviour is ascribed to the surface concentration changes of magnesium and calcium ions during equilibration via ion-exchange at ATP membrane sites.It is suggested that PPy-ATP film may be used as a model membrane to study the potential formation of the biological membranes, where the calcium and magnesium interaction with ATP is of primary importance.     

Optimization of the thickness of a conducting polymer, polyaniline, deposited on the surface of poly(vinyl chloride) membranes: a new way to improve their potentiometric response

Repeated depositions of polyaniline (PANI) have been used to control the thickness of the polymeric film deposited on poly(vinyl chloride) (PVC) membrane surface. The oxidation of aniline was carried out in a dispersion mode, i.e. in the presence of poly(N-vinylpyrrolidone) (PVP). Two kinds of PVC were used for this purpose: a non-plasticized PVC for the study of PANI deposition and PVC, plasticized with nitrophenyl octyl ether (NPOE), as a prototype of a liquid membrane electrode. The results of UV-visible and FTIR spectroscopies and electron microscopy showed that (1) the film thickness increased by about equal increments of ∼40 nm after each polymerization, and (2) the interface with PVC was constituted by PANI film and adhering PANI-PVP colloidal particles.The various thicknesses of the deposited PANI films affected the potentiometric response of the NPOE/PVC membrane with and without an anion-exchanger. The potentiometric anionic response was observed with a minimal thickness of PANI film on the blank NPOE/PVC membrane. Sensitivity of the PANI film to pH occurred only with a blank NPOE/PVC membrane coated with a thick polymeric film, while it was strongly suppressed by the presence of a lipophilic anion-exchanger, tridodecylmethylammonium chloride (TDDMACl), in the membrane, regardless of the thickness of the polymer film. The thickness of the PANI film did not affect the anionic selectivity pattern of TDDMACl-based membranes to any great extent, but its presence improved and stabilized their potentiometric characteristics (sensitivity, linear-response range).     

The potentiometric response of polypyrrole electrosynthesised in alkaline media

The study has been focused on the potentiometric response of polypyrrole films electrosynthesised in alkaline solutions onto vitreous carbon electrodes. The influence of different conditions for electropolymerisation and soaking on the potentiometric sensitivity of the film is analysed. A simple model allows to interpreting the ion sensitivity observed. The participation of OH⁻ in the ion-exchange process is demonstrated, in agreement with previous results.     

Control of surface topography in biomimetic calcium phosphate coatings

The behavior of cells responsible for bone formation, osseointegration, and bone bonding in vivo are governed by both the surface chemistry and topography of scaffold matrices. Bone-like apatite coatings represent a promising method to improve the osteoconductivity and bonding of synthetic scaffold materials to mineralized tissues for regenerative procedures in orthopedics and dentistry. Polycaprolactone (PCL) films were coated with calcium phosphates (CaP) by incubation in simulated body fluid (SBF). We investigated the effect of SBF ion concentration and soaking time on the surface properties of the resulting apatite coatings. CaP coatings were examined by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectrometry (FTIR), and energy dispersive X-ray spectrometry (EDX). Young's modulus (E(s)) was determined by nanoindentation, and surface roughness was assessed by atomic force microscopy (AFM) and mechanical stylus profilometry. CaP such as carbonate-substituted apatite were deposited onto PCL films. SEM and AFM images of the apatite coatings revealed an increase in topographical complexity and surface roughness with increasing ion concentration of SBF solutions. Young's moduli (E(s)) of various CaP coatings were not significantly different, regardless of the CaP phase or surface roughness. Thus, SBF with high ion concentrations may be used to coat synthetic polymers with CaP layers of different surface topography and roughness to improve the osteoconductivity and bone-bonding ability of the scaffold.     

Morphology and oxygen sensor response of luminescent Ir-labeled poly(dimethylsiloxane)/polystyrene polymer blend films

Polymer films consisting of a linear poly(dimethylsiloxane) end-functionalized with a luminescent Ir(III) complex (Ir-PDMS), blended with polystyrene (PS), function as optical oxygen sensors. The sensor response arises by quenching of the luminescence from the Ir(III) chromophore by oxygen that permeates into the polymer film. The morphology and luminescence oxygen sensor properties of blend films consisting of Ir-PDMS and PS have been characterized by fluorescence microscopy, atomic force microscopy, and scanning electron microscopy. The investigations demonstrate that microscale phase segregation occurs in the films. In blends that contain a relatively small amount of Ir-PDMS in PS (ca. 10 wt %), the Ir-PDMS exists as circular domains, with diameters ranging from 2 to 5 mum, surrounded by the majority PS phase. For larger weight fractions of Ir-PDMS in the blends, the film morphology becomes bicontinuous. A novel epifluorescence microscopy method is applied that allows the construction of Stern-Volmer quenching images that quantify the oxygen sensor response of the blend films with micrometer spatial resolution. These images provide a map of the oxygen permeability of the polymer blend films with a spatial resolution of ca. 1 mum. The results of this investigation show that the micrometer-sized Ir-PMDS domains display a 2-3-fold higher oxygen sensor response compared to the surrounding PS matrix. This result is consistent with the fact that PDMS is considerably more gas permeable compared to PS. The relationship of the microscale morphology of the blends to their performance as macroscale optical oxygen sensors is discussed.     

ZnO/Cu2O异质结中深能级表面光伏特性

采用恒电压沉积法在导电玻璃(FTO)上制备了具有三棱柱金字塔状的ZnO/Cu2O异质结薄膜. 利用场发射扫描电镜(FESEM)与X射线衍射仪(XRD)对薄膜的微观形貌和晶体结构进行了表征. 利用表面光电压谱(SPS)、场诱导表面光电压谱(FISPS)和相位谱(PS)研究了单一Cu2O与ZnO/Cu2O异质结薄膜的表面光伏性质. 结果表明, 与单一Cu2O薄膜相比, ZnO/Cu2O异质结薄膜的光伏响应范围拓展到了600~800 nm. 根据SPS, FISPS和PS的作用原理, 拓展部分的光伏响应归因于ZnO/Cu2O异质结中Cu2O层的深能级跃迁, 该跃迁在ZnO-Cu2O界面电场(方向由ZnO指向Cu2O)的作用下得到加强, 同时深能级跃迁产生的电子-空穴对在ZnO-Cu2O界面电场的作用下得到了有效分离和传输.     

Influence of substrate nature and growth conditions on the morphology of thin DMOAP films

We report some preliminary results on the morphology of thin N,N -dimethyl- n -octadecyl-3-aminopropyltrimethoxysilyl chloride (DMOAP) films. When deposited on a glass substrate, DMOAP forms a mono- or multi-layer structure parallel to the substrate. The surface topography of the film is probed by atomic force microscopy. In general, the free surface of such a film is not flat and smooth. Islands and holes are formed on the free surface of the films when a sufficiently flat substrate is used. The thin film surface topography depends strongly on the nature of the bare substrate, the curing conditions, and the immersion time of the substrate in the DMOAP solution. The film is always rougher than the bare substrate used. Annealing roughens the surface of the alkoxysilane thin films deposited on a glass substrate. For films on glass plates covered with an indium tin oxide layer, annealing has minor effects. The surface topography affects the microstructure of homeotropic smectic samples.     

Surface morphology of poly(cyano-p-xylylene) thin films

The surface morphology of poly(cyano-p-xylylene) thin films of different thicknesses (25–1500 nm or more than 5 μm) that were synthesized by vapor-deposition polymerization on the substrate surface in the temperature range from −22 to +35°C has been studied by atomic force microscopy. The surface topography is quantified through analysis of the height-height correlation function. The surface of all films is characterized by a similar granular morphology with a transverse size of granules of 50–500 nm. The surface morphology changes with the polymerization temperature (the substrate temperature) and the film thickness. The effect of film annealing on its surface morphology is considered. It has been established that annealing at 200°C leads to a change in the surface morphology of the films. Original Russian Text ? A.I. Buzin, D.S. Bartolome, K.A. Mailyan, A.V. Pebalk, S.N. Chvalun, 2006, published in Vysokomolekulyamye Soedineniya, Ser. A, 2006, Vol. 48, No. 9, pp. 1640–1646. This work was supported by the Russian Foundation for Basic Research (project nos. 03-03-32665 and 03-03-32634) and the Russian Science Support Foundation.     

Effect of honeycomb-patterned surface topography on the adhesion and signal transduction of porcine aortic endothelial cells

Surface topography has vital roles in cellular response. Here, to investigate the mechanism behind cellular response to surface topography, we prepared honeycomb (HC)-patterned films from poly(epsilon-caprolactone) (PCL) with micropatterned surface topography by casting a polymer solution of water-immiscible solvent under high humidity. We characterized the adsorption of fibronectin (Fn) on the film using atomic force microscopy (AFM) and confocal laser scanning microscopy (CLSM). The response of porcine aortic endothelial cells (PAECs) to adsorbed Fn molecules onto HC-patterned films was observed by immunofluorescence labeling of vinculin and the actin fiber of PAECs cultured for 1 and 72 h in serum-free medium. The expression of focal adhesion kinase autophosphorylated at the tyrosine residue (pFAK) at 1 h culture was determined using an immunoprecipitation method. Fn adsorbed selectively around the pore edges to form ring-shaped aggregates. The immunostaining results revealed that PAECs adhered to the HC-patterned films at focal contact points localized around pore peripheries. These points correspond to adsorption sites of Fn. The expression of pFAK after 1 h on the HC-patterned film was 3 times higher than that on a corresponding flat film, indicating that the signaling mediated by the binding between Fn and the integrin receptor was more highly activated on the HC-patterned film. These results suggest that the cellular response to HC-patterned films (e.g., adhesion pattern and phosphorylation of FAK) originates from the regularly aligned adsorption pattern of Fn determined by the pore structure of the film.     

多酸含量对无机/高分子复合薄膜结构及光致变色性能的影响

制备了一系列不同浓度的钨磷酸/聚乙烯醇(PWA/PVA)复合薄膜, 通过红外光谱、原子力显微镜、紫外-可见吸收光谱对复合薄膜的结构和光致变色性能进行了研究. 红外光谱分析结果表明, Keggin结构钨磷酸和聚乙烯醇分子的基本结构在复合薄膜中仍然存在, 钨磷酸分子与高分子底物间存在氢键作用, 形成电荷转移桥. 原子力显微镜(AFM)结果表明复合前后PVA薄膜表面形貌发生了显著变化, 复合膜表面形貌随钨磷酸含量的不同而不同. 在紫外光照射下, 复合薄膜由无色变为蓝色. 复合膜的升色速度和褪色速度均随着钨磷酸含量的增加而加快. 这些结果表明钨磷酸含量对复合膜的微结构存在影响, 从而导致了复合膜具有不同的光致变色性能.     

Influence of substrate nature and growth conditions on the morphology of thin DMOAP films

We report some preliminary results on the morphology of thin N,N -dimethyl-n-octadecyl-3-aminopropyltrimethoxysilyl chloride (DMOAP) films. When deposited on a glass substrate, DMOAP forms a mono- or multi-layer structure parallel to the substrate. The surface topography of the film is probed by atomic force microscopy. In general, the free surface of such a film is not flat and smooth. Islands and holes are formed on the free surface of the films when a sufficiently flat substrate is used. The thin film surface topography depends strongly on the nature of the bare substrate, the curing conditions, and the immersion time of the substrate in the DMOAP solution. The film is always rougher than the bare substrate used. Annealing roughens the surface of the alkoxysilane thin films deposited on a glass substrate. For films on glass plates covered with an indium tin oxide layer, annealing has minor effects. The surface topography affects the microstructure of homeotropic smectic samples.     

恒电位脉冲法制备聚苯胺薄膜及其表征

采用恒电位脉冲法制备聚苯胺薄膜, 利用扫描电子显微镜(SEM)、红外光谱(IR)、X射线衍射(XRD)及荧光光谱对所制备的薄膜进行比较与表征. 分别考察了循环周期、占空比及脉冲时间对薄膜形貌的影响. SEM形貌分析结果表明, 随着占空比的减小, 聚苯胺薄膜表面颗粒细化; 随循环周期的增加, 聚苯胺薄膜由片层结构转变为纵向生长的颗粒状结构. 荧光光谱分析结果表明, 聚苯胺薄膜具有光致发光性能, 发射峰位置约520 nm, 且发光强度随占空比的增大而增强. 电化学性能测试结果表明, 恒电位脉冲电位法制备的聚苯胺薄膜具有良好的电容特性.     

3D topography design of membranes for enhanced mass transport

This work describes the process of fabrication of 3D topography membranes and the fully quantitative characterisation of their topography using atomic force microscopy (AFM), small-angle light scattering (SALS), scanning electron microscopy (SEM) and polarizing optical microscopy (POM). The use of these membranes and the impact of the 3D membrane topography on the enhancement of mass transport during solute recovery (hexyl acetate) from a viscous room temperature ionic liquid 1-n-butyl-3-methyl-imidazolium tetrafluoroborate ([C₄mim] [BF₄]) by organophilic pervaporation is presented and discussed.     

辣根过氧化物酶活性膜结构及生物电催化性能

通过分子沉积法研究了在聚对苯二甲酸乙二醇酯（PET）表面及金电极表面组装辣根过氧化物酶（HRP）/聚对苯乙烯磺酸钠（PSS）多层生物活性膜，用原子力显微镜(AFM)研究了组装膜的表面形貌，并研究了组装膜的形貌、粗糙度和活性关系.应用循环伏安法（CV）研究了组装HRP膜后电极对H2O2的电化学催化还原作用.实验发现，采用亚甲基蓝（MB）溶液为介质，在H2O2浓度为0.2～5.0 mmol•L－1时，其响应电流对H2O2浓度变化基本呈线性.     

Chemical modification and characterization of poly(ethylene terephthalate) surfaces for collagen immobilization

The functionalization of poly(ethylene terephthalate) (PET) surface films by reactions with multifunctional amines such as triethylenetetramine (TETA), and tetraethylenepentamine (TEPA) was investigated. For the functionalization of PET films surface we used a new way of treatment, a “sandwich model”. Physical-chemical properties of functionalized PET films were analysed. Qualitative and quantitative determination of the introduced amine groups were examined by means of Fourier Transform Infrared Attenuated Total Reflexion (FTIR — ATR), X-ray photoelectron spectroscopy (XPS), and potentiometric titration. Gained wetting properties were determined by using contact angle measurements and thoroughly analysed by acid-base approach. In addition, surface topography was investigated by atomic force microscopy (AFM). The amount of the introduced amino groups after TETA incorporation has been found to be two times higher as compared to TEPA. Wetting properties were significantly improved after aminolysis. Surface free energy was higher for PET — TETA treated film than that observed for PET — TEPA treated which is in accordance with titration results. The collagen immobilization onto PET treated films was evidenced by using AFM and subsequently by using XPS.      

Integrated mechanism for the morphological structure development in HDPE melt‐blown and machine‐direction‐oriented films

The morphologies of a series of blown films and machine‐direction‐oriented (MDO) films, all produced from high density polyethylene, were characterized. In the blown film process, the crystalline morphology develops while the melt is under extensional stress. In the MDO process, drawing takes place in the solid state and deforms the crystalline morphology of the starting film. The films were characterized by wide‐angle X‐ray scattering (WAXS), small‐angle X‐ray scattering (SAXS) and atomic force microscopy to determine the lamellar morphology. The effect of the type of deformation on the lamellar morphology was studied and relationships were developed between the lamellar and polymer chain morphology using SAXS and WAXS. Blown and MDO films were found to have very different morphologies. However, an integrated mechanism was developed linking the sequential events in the deformation and morphology development in blown and MDO films. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1834–1844, 2007     

Tailoring the properties of electrospun PHBV mats: Co-solution blending and selective removal of PEO

Microstructure, surface topography, thermal and mechanical features of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) electrospun non-woven mats were modified, modulated and tailored through blending with different polyethylene oxide (PEO) amounts (20, 30 and 50% wt/wt). The optimal parameters of the soaking protocol for the selective removal of the sacrificial polymer were accurately identified by means of scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy, simultaneous thermogravimetric and differential analyses (TG-DTA) and differential scanning calorimetry (DSC). The complete PEO removal after soaking in H₂O for 7 days with daily refreshment was confirmed. The resulting samples were only comprised of PHBV fibers characterized by a remarkable decrease of the average size with respect to the respective blends. Their surface topography was corrugated and rough and presented nodules, pits, nanopores, shallow and elongated nanostructured indents/grooves along the fiber axis. A remarkable reduction (>75%) of the tensile modulus (E) of electrospun PHBV mats (15–20 MPa) was obtained, maintaining comparable elongation at break (ε_max) values (20–30%).     

Optical properties and orientation in polyethylene blown films

We report structural factors affecting the optical properties of blown polyethylene films. Two types of blown polyethylene films of similar degrees of crystallinity were made from (1) single‐site‐catalyst high‐density polyethylene (HDPE; STAR α) and (2) Ziegler–Natta‐catalyst HDPE (ZN) resins. The STAR α film exhibited high clarity and gloss, whereas the ZN film was turbid. Small‐angle X‐ray scattering (SAXS), small‐angle light scattering (SALS), and optical microscopy gave quantitative and qualitative information regarding structure and orientation in the films. A new approach is described for determining the three‐dimensional lamellar normal orientation from SAXS. Both the clear STAR α and turbid ZN films had similar lamellar crystalline structures and long periods but displayed different degrees of orientation. It is demonstrated that optical haze is related to surface features that seem to be linked to the bulk morphology. The relationship between haze and structural orientation is described. The lamellar orientation is linked to rodlike structures seen in optical microscopy and SALS through a stacked lamellar or cylindrite morphology on a nanometer scale and through a fiberlike morphology on a micrometer scale. The micrometer‐scale, rodlike structures seem directly related to surface roughness in a comparison of index‐matched immersion and surface micrographs. The higher haze and lower gloss of the ZN film was caused by extensive surface roughness not observed in the STAR α film. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2923–2936, 2001     

离子液体中聚(3-溴噻吩)的电化学合成和电色效应研究

以1-丁基-3-甲基咪唑六氟磷酸盐离子液体[BMIM]PF₆既作为溶剂又作为支持电介质, 通过恒电流、循环伏安等方法制备聚(3-溴噻吩)(PBrT)膜. 采用红外光谱(FT-IR)和扫描电子显微镜(SEM)对PBrT膜的结构和形貌进行表征, 用热重和差热分析法(TG-DTA)研究聚合膜的热稳定性, 并利用紫外-可见光谱(UV-Vis)、计时电流和计时吸收曲线研究该聚合膜电化学和电致变色的特性. 研究结果表明, 与传统方法比较, 在离子液体[BMIM]PF₆中制备的PBrT膜更致密、光滑, 具有良好的氧化还原可逆性和充放电能力, 电活性高, 热稳定性好. 以该方法制备的PBrT膜颜色变化明显, 响应时间快(0.5 s), 同时由于离子液体具有电位窗宽、导电率高、可循环利用等优点, 因此在电化学聚合等方面具有良好的应用前景.     

自组装制备二氧化铪图案化薄膜

采用短波紫外光(UV)在十八烷基三氯硅烷(OTS)自组装单分子层刻蚀不同的微型图案,利用液相自组装技术在OTS模板表面沉积HfO₂图案化薄膜。通过XRD、AFM、SEM、EDS等测试手段对OTS膜和HfO₂薄膜进行表征,结果表明：以OTS为模板利用液相自组装技术成功制备出边缘轮廓清晰、粗糙度较小、条纹宽度为10μm的立方晶型的HfO₂图案化薄膜。