Heparin-containing block copolymers

Newly synthesized heparin-containing block copolymers, consisting of a hydrophobic block of polystyrene (PS), a hydrophilic spacer-block of poly(ethylene oxide) (PEO) and covalently bound heparin (Hep) as bioactive block, were coated on aluminium, glass, polydimethylsiloxane (PDMS), PS or Biomer substrates. Surfaces of coated materials were characterized by transmission electron microscopy (TEM), contact angle measurements and X-ray photoelectron spectroscopy for chemical analysis (XPS). It was demonstrated by TEM that thin films of PS-PEO and PS-PEO-Hep block copolymers consisted of heterogeneous microphase separated structures. Using sessile-drop and Wilhelmy plate dynamic contact angle measurements, insight was provided into the hydrophilicity of the surfaces of the coatings. Measurements with hydrated coatings of PS-PEO and PS-PEO-Hep block copolymers revealed that the surfaces became more hydrophilic during immersion in water, due to relaxation/reorientation, or swelling of PEO or PEO-Hep domains, respectively. XPS results for PS, PEO, heparin and PS-PEO as powder agreed well with qualitative and quantitative predictions. XPS results for films of PS-PEO and PS-PEO-Hep block copolymers showed enrichments of PEO in the top layers of the coatings. This effect was more pronounced for hydrated surfaces. Only small amounts of heparin were detected at the surface of coatings of PS-PEO-Hep block copolymers.     

Linear and Hyperbranched Polyglycerol Derivatives as Excellent Bioinert Glass Coating Materials

The non‐specific adsorption of proteins to surfaces in contact with biofluids constitutes a major problem in the biomedical and biotechnological field, due to the initiation of biofilm formation and the resulting improper function of devices. Therefore, non‐fouling surfaces modified with poly(ethylene glycol) (PEG) are usually applied. In this study, we report the synthesis of triethoxysilane modified glycerol based polymers of linear and branched architecture for the preparation of covalently attached monolayers on glass. Evaluation of the biocompatibility of these surfaces was performed in comparison to bare non‐coated glass, hydrophobic hexadecane modified glass, and mPEG modified glass as the controls. Protein adsorption of BSA and fibrinogen (1 mg · mL^?1 in PBS) after 4 and 24 h immersion was reduced by more than 96 and 90%, respectively, compared to the adsorption on bare glass substrates. In addition, mouse NIH‐3T3 fibroblast cells showed only marginal adhesion on the polyglycerol and mPEG coated slides after 3 and 7 d incubation in cell suspension, which demonstrates the long‐term stability of the applied glass coatings. The non‐adhesive properties of these coatings were further reflected in bacterial adhesion tests of Escherichia coli K12 and three clinically relevant Gram‐positive and negative strains (Staphylococcus aureus, Pseudomonas aeruginosa, and Aeromonas hydrophila), since linear polyglycerol (LPG(OH)), linear poly(methyl glycerol) (LPG(OMe)), and hyperbranched polyglycerol (HPG) reduced the adhesion for all tested strains by more than 99% compared to bare glass. Therefore, polyglycerol derivatives present an excellent non‐fouling surface coating as an alternative to PEG with feasibility for surface modification of various substrates.     

Plasma-treated polyethersulfone coated with crosslinked poly(vinyl alcohol): composite membranes for pervaporation dehydration of ethanol

Composite membranes with crosslinked poly(vinyl alcohol) matrix as selective layer coated on a polyethersulfone supporting porous layer were prepared aiming at separating ethanol/water mixtures by pervaporation. A polyethersulfone asymmetric microporous membrane was synthesized by the wet phase inversion process. The support membrane was then exposed to air plasma to activate the surface. The selective dense layer was obtained by coating of PVA and a crosslinking agent over the polyethersulfone substrate, followed by thermal treatment. The morphology was examined by scanning electron microscopy (SEM) for both, support membrane and the coated polymeric layers. Surface physicochemical properties were evaluated through measuring the contact angle (θ) and the estimation of surface free energy (γ_S) and adhesion work. The surface chemical composition of support membrane and coated hydrophilic layers were characterized by infrared spectra with horizontal attenuated total reflectance (FT-IR/HATR). The swelling degree of PVA dense membranes, and the pervaporation performance of the crosslinked PVA/PES composite membranes, manufactured with several coating steps, were evaluated with water/ethanol (20/80 wt%) mixtures at temperatures in the range of 30–60 C. Results of the effective pervaporation dehydration of ethanol are discussed in terms of membrane morphology and the solution-diffusion transport mechanism.     

Layer-by-Layer assembly of TiO2 nanoparticles for stable hydrophilic biocompatible coatings

Stable, super-hydrophilic (water contact angle approximately equal to 0 degrees) titanium dioxide nanoparticle thin films have been obtained on substrates with different initial wettability such as glass, poly(methyl methacrylate) and poly(dimethyl siloxane) using layer-by-layer nano-assembly method. Titanium dioxide nanoparticles were alternated with poly(styrene sulfonate) to form films of thickness ranging from 11 nm to 220 nm. The hydrophilicity of these thin films increases with increasing number of deposited PSS/TiO2 bilayers. It was found that 2, 5 and 20 layers were needed to form super-hydrophilic TiO2 coating on glass, PMMA and PDMS respectively. Oxygen plasma treatment of substrate surfaces enhanced the formation of homogeneous TiO2 films and accelerated the formation of hydrophilic layers. Super-hydrophilicity has been shown to be unique to PSS/TiO2 films as compared with other polyelectrolyte/nanoparticle layers, and UV irradiation may restore hydrophilicity even after months of storing of the samples. Biocompatibility of TiO2 nanoparticle films has been demonstrated by the successful cell culture of human dermal fibroblast.     

Nanogel surface coatings for improved single-molecule imaging substrates

Surfaces that resist protein adsorption are important for many bioanalytical applications. Bovine serum albumin (BSA) coatings and multi-arm poly(ethylene glycol) (PEG) coatings display low levels of non-specific protein adsorption and have enabled highly quantitative single-molecule (SM) protein studies. Recently, a method was developed for coating a glass with PEG–BSA nanogels, a promising hybrid of these two low-background coatings. We characterized the nanogel coating to determine its suitability for SM protein experiments. SM adsorption counting revealed that nanogel-coated surfaces exhibit lower protein adsorption than covalently coupled BSA surfaces and monolayers of multi-arm PEG, so this surface displays one of the lowest degrees of protein adsorption yet observed. Additionally, the nanogel coating was resistant to DNA adsorption, underscoring the utility of the coating across a variety of SM experiments. The nanogel coating was found to be compatible with surfactants, whereas the BSA coating was not. Finally, applying the coating to a real-world study, we found that single ligand molecules could be tethered to this surface and detected with high sensitivity and specificity by a digital immunoassay. These results suggest that PEG–BSA nanogel coatings will be highly useful for the SM analysis of proteins.     

Achieving One‐Step Surface Coating of Highly Hydrophilic Poly(Carboxybetaine Methacrylate) Polymers on Hydrophobic and Hydrophilic Surfaces

It is highly desirable to develop a universal nonfouling coating via a simple one‐step dip‐coating method. Developing such a universal coating method for a hydrophilic polymer onto a variety of surfaces with hydrophobic and hydrophilic properties is very challenging. This work demonstrates a versatile and simple method to attach zwitterionic poly(carboxybetaine methacrylate) (PCB), one of the most hydrophilic polymers, onto both hydrophobic and hydrophilic surfaces to render them nonfouling. This is achieved by the coating of a catechol chain end carboxybetaine methacrylate polymer (DOPA‐PCB) assisted by dopamine. The coating process was carried out in water. Water miscible solvents such as methanol and tetrahydrofuran (THF) are added to the coatings if surface wettability is an issue, as for certain hydrophobic surfaces. This versatile coating method was applied to several types of surfaces such as polypropylene (PP), polydimethyl siloxane (PDMS), Teflon, polystyrene (PS), polymethylmethacrylate (PMMA), polyvinyl chloride (PVC) and also on metal oxides such as silicon dioxide.     

聚乙烯醇接枝聚异丁烯马来酸酐的合成及自组装

主要研究了以聚乙烯醇(PVA)为主链,聚异丁烯马来酸酐(PIBSA)为支链的两亲性接枝共聚物的制备及在溶液中的自组装行为.接枝共聚物由PIBSA和PVA1799通过酯化反应得到,改变投料比能得到不同接枝率的共聚物.以二甲基亚砜(DMSO)做共溶剂,水做选择性溶剂,室温下自组装得到了稳定的聚集体溶液.扫描电镜和透射电镜观...     

Investigation of the effect of various shellac coating compositions containing different water-soluble polymers on in vitro drug release

In this study drug pellets were coated with aqueous shellac coating formulations containing different amounts of polyvinyl alcohol (PVA), hydroxypropyl methylcellulose (HPMC), and carbomer 940. The coating level needed for enteric coating was determined. The influence of different amounts of PVA, HPMC, and carbomer on drug release and mechanism; the porosity, and the stability of shellac coatings was investigated. The results show that the incorporation of different concentrations of HPMC into shellac coatings, due to the increasing of pores, could considerably increase the drug release from the pellets in purified water. Moreover, the swelling effect of carbomer 940 leads to much more diffusivity through shellac coatings in water. In addition, PVA results in small cracking in the films and much more diffusion of drug in water. Furthermore, all coating systems containing different hydrophilic polymers that were used in the present work could prevent the dissolution of drug in simulated gastric juice for 2 hours. On the other hand, a rapid and complete release of drug within 45 minutes was observed in simulated intestinal fluid. Drug release from shellac coated pellets and ones containing different amounts of carbomer was affected between 3-6 months, whereas shellac coatings containing different amounts of PVA or HPMC show the same dissolution profiles with small deviation after 12 months.     

硬脂酸改性聚乙烯醇/纳米纤维素复合阻隔涂料的制备

目的 为了以安全环保的方式提高聚乙烯醇(PVA)阻水阻气性,制备高阻隔PVA涂料,提高PVA的性能与应用范围。方法 在聚乙烯醇中填充纳米纤维素(Cellulose Nanofiber,CNF),并在此基础上添加硬脂酸进行耐水改性,探究对阻隔性能的影响,利用傅里叶红外光谱,X射线衍射,氧气、水蒸气透过率测试仪对其进行结构性能表征。结果 硬脂酸与PVA的酯化反应可以提高涂层的耐水性,PVA与CNF间能产生氢键,提高涂层结晶性能与阻隔性能,适量的硬脂酸的加入未降低CNF的结晶度,只降低了PVA的结晶性能,硬脂酸添加量为16%时涂层水蒸气透过率达到最低2.2 g/(m².d),氧气透过率达到1.3 cm³/(m².d)。结论 利用CNF填充与硬脂酸酯化协同改性制备的PVA阻隔涂料具有较高的阻隔性能,使其在阻隔涂层方面具有广阔的应用前景。     

Polydopamine/liposome coatings and their interaction with myoblast cells

Surface-mediated drug delivery is a recent concept, where active surface coatings are employed to deliver therapeutic cargo to cells. Herein, we explore the potential of liposomes embedded in polydopamine (PDA) coatings to serve as drug deposits stored on planar substrates. We quantify the PDA growth rate on glass by XPS and show that PDA coatings support myoblast adherence and proliferation. Further, PDA capping layers were deposited on glass substrates precoated with poly(L-lysine) and zwitterionic liposomes. Already thin PDA capping layers render liposome coated surfaces cell adhesive. We experimentally show for the first time, the internalization of a model hydrophobic cargo, that is, fluorescent lipids embedded within the lipid bilayer of liposomes by the cells from the surface. This is evident from the fluorescence exhibited by the cells grown on PDA coatings containing fluorescently labeled liposomes, with the highest fluorescent intensity found in the close proximity of the cell nuclei. The cargo uptake efficiency depends on the thickness of the PDA capping layer and the cell residence time on the coated substrates. Taken together, we demonstrate the first step toward the establishment of a versatile approach using liposomal drug deposits in polymer thin films for surface-mediated drug delivery.     

ITO多层减反膜系设计及制备研究进展

玻璃基片表面沉积ITO薄膜赋予玻璃诸多优异的电学、光学性能,但ITO薄膜的沉积也使得玻璃在可见光区透过率下降10%左右,在近红外区呈现高吸收、强反射现象,一定程度上弱化了ITO玻璃的部分应用。通过ITO多层减反膜的设计可以有效地解决上述问题,拓宽ITO薄膜玻璃的应用范围。本文首先阐述ITO薄膜沉积后光学曲线及该曲线各波段光学性能变化的理论解释,进而概述常规的减反膜系设计方法及膜层材料选择,并重点介绍ITO多层减反膜系的相关研究动态,本文结尾对ITO多层减反膜的设计和制备进行了展望。     

Anomalous light transmission by nematic liquid crystal cells

Light transmission through nematic liquid crystal (NLC) cells with a planar alignment and various boundary conditions has been studied as a function of the bias voltage in the regimes of maximum transmittance and complete extinction. The phenomenon of anomalous light leakage in the regime of complete extinction has been observed in the NLC sells with alignment layers of amorphous hydrogenated carbon (a-C:H) and poly(vinyl alcohol) (PVA), in which an anisotropy was induced by rubbing the electrode surface (for a-C:H) and the alignment layer (for PVA). The anomalous transmission is caused by the deformation of nematic molecules, which are situated near the surface, in the direction perpendicular to the direction of rubbing. The magnitude of anomalous transmission increases with the bias voltage. This behavior is explained by the anisotropy of the surface anchoring energy of nematic molecules at the interface.     

Covalent attachment of a bioactive hyperbranched polymeric layer to titanium surface for the biomimetic growth of calcium phosphates

This work is investigating the chemical grafting on Ti surface of a polymer/calcium phosphate coating of improved adhesion for enhanced bioactivity. For this purpose, a whole new methodology was developed based on covalently attaching a hyperbranched poly(ethylene imine) layer on Ti surface able to promote calcium phosphate formation in a next deposition stage. This was achieved through an intermediate surface silanization step. The research included optimization both of the reaction conditions for covalently grafting the intermediate organosilicon and the subsequent hyperbranched poly(ethylene imine) layers, as well as of the conditions for the mechanical and chemical pretreatment of Ti surface before coating. The reaction steps were monitored employing FTIR and XPS analyses, whereas the surface morphology and structure of the successive coating layers were studied by SEM combined with EDS. The analysis confirmed the successful grafting of the hybrid layer which demonstrated very good ability for hydroxyapatite growth in simulated body fluid.     

Annealing of sputter-deposited nanocrystalline Cr-Ta coatings in a low-oxygen-containing atmosphere

As a protective hard coating on glass molding dies, Cr-Ta coatings were fabricated on binderless tungsten carbide substrates with a Ti interlayer by RF magnetron sputtering. The nanocrystalline Cr-Ta coatings were deposited at 550 °C, which revealed one nanocrystalline phase for the Ta-rich coating and two nanocrystalline phases for the Cr-rich coating. Annealing treatment was conducted at 600 °C in a 12 ppm O₂-N₂ atmosphere to evaluate the coating performance in a realistic glass molding environment. Both Auger electron spectroscopy and X-ray photoelectron spectroscopy depth profiles verified the outward diffusion of Cr, which formed a protective coating for the Cr-rich coatings. A scale of Cr₂O₃ and a Cr-depleted transition zone near the surface were identified by conducting a transmission electron microscopy investigation on the annealed Cr_0.71Ta_0.29 coating. The Cr-rich coating absorbed a smaller amount of oxygen, exhibited greater hardness, and maintained nanoscale surface roughness after annealing in the glass molding atmosphere, thus making it an appropriate protective coating for the die material.     

Design of multi-layer anti-reflection coating for terrestrial solar panel glass

To date, there is no ideal anti-reflection (AR) coating available on solar glass which can effectively transmit the incident light within the visible wavelength range. However, there is a need to develop multifunctional coating with superior anti-reflection properties and self-cleaning ability meant to be used for solar glass panels. In spite of self-cleaning ability of materials like TiO₂ and ZnO, these coatings on glass substrate have tendency to reduce light transmission due to their high refractive indices than glass. Thus, to infuse the anti-reflective property, a low refractive index, SiO₂ layer needs to be used in conjunction with TiO₂ and ZnO layers. In such case, the optimization of individual layer thickness is crucial to achieve maximum transmittance of the visible light. In the present study, we propose an omni-directional anti-reflection coating design for the visible spectral wavelength range of 400–700 nm, where the maximum intensity of light is converted into electrical energy. Herein, we employ the quarter wavelength criteria using SiO₂, TiO₂ and ZnO to design the coating composed of single, double and triple layers. The thickness of individual layers was optimized for maximum light transmittance using essential Mcleod simulation software to produce destructive interference between reflected waves and constructive interference between transmitted waves.     

Hochreflektierende Beschichtungen auf Kunststoffoptiken

Metallized polymer substrates offering highest reflectance are not yet state of the art. Coating organic substrate materials is still a task that is connected with multiple problems. Insufficient adhesion of coatings on polymer substrates represents one of the main difficulties. We could show by experiment that aluminium and silver layers indicate good coating adhesion on many different polymers if they are deposited by vacuum evaporation considering certain process parameters. High reflectance values and a good climatic stability of the metal coated polymer parts are other important challenges to plastic mirrors. By performing roughness measurements on the different polymer samples and by comparing reflection values obtained after coating these samples the impact of the polymers surface quality on the reflectance after metal coating has been investigated. Particularly high reflectance above 97% was realized with a protected silver mirror as well as with dielectric enhanced aluminium. Applying these layer systems excellent reflection properties has been obtained on several plastic substrates comparable to those on glass mirrors. Furthermore the dielectric layers used for reflection enhancement showed the ability to protect the aluminium coating against climatic influences.     

Resistance to nonspecific protein adsorption by poly(vinyl alcohol) thin films adsorbed to a poly(styrene) support matrix studied using surface plasmon resonance.

Thin films of poly(vinyl alcohol) (PVA) polymer were prepared on a flat, nonporous, poly(styrene) support matrix by adsorption from aqueous solution and were characterized in order to investigate the nonspecific adsorption of proteins to a chromatographically relevant surface. The integrity and surface coverage of the PVA thin films were established by surface analysis and atomic force microscopy imaging. The adsorption of the PVA polymers to the poly(styrene) substrate and the nonspecific adsorption of proteins to the PVA-coated surface were monitored using surface plasmon resonance. PVA was strongly bound to the poly(styrene) surface, but the surface density of the adsorbed PVA polymers was affected substantially by the concentration, molecular weight, and degree of hydrolysis of PVA polymers used. There was evidence of increasing degrees of unfolding of the PVA polymer onto the poly(styrene) surface as the concentration of the the PVA coating solution increased. Complete PVA coverage of the poly(styrene) surface was observed at PVA concentrations of 0.1 mg/mL or greater but with significant influence of both molecular weight and degree of hydrolysis of the PVA polymers. Resistance of the PVA-coated poly(styrene) surface to the nonspecific adsorption of human serum albumin (HSA) correlated with the degree of surface coverage of the PVA. The use of anti-HSA as a probe for adsorbed HSA suggested that HSA was displacing PVA from the poly(styrene) surface at the lower PVA surface coverage. A complete barrier to nonspecific protein adsorption was observed with a PVA coating solution concentration of greater than 0.1 mg/ mL with a degree of hydrolysis of <88%.     

Kunststoffoptiken mit Antireflex‐ und Antibeschlageigenschaften durch Plasmaätzen und Beschichtung

Plastic optics exhibiting anti‐reflection and anti‐fogging properties produced by plasma etching and coating Plasma treatments are capable to generate antireflective surface structures on various polymers. On PMMA a self organized surface with nep‐like bumps exhibits excellent optical properties. Many other materials like polycarbonate, zeonex and lacquers can be etched after depositing a very thin initial layer to form a more holey structure. These surfaces attain high transmission values too and can be better stabilized by coatings than the nep‐ structure on PMMA. Interesting for practical applications are hydrophilic top‐layers to provide anti‐fogging properties in combination with improved transmission.     

Combined Langmuir-Blodgett and sol-gel coatings

Optical properties and in-depth structure of double-layer coatings on glass substrates were investigated. One of the layers was prepared by dip coating either from silica or titania sol, the other layer was made from ca. 130 nm Stöber silica particles by the Langmuir-Blodgett (LB) technique. Two different types of combined coatings were prepared: (1) nanoparticulate LB films coated with sol-gel (SG) films and (2) nanoparticulate LB films drawn onto SG films.Scanning electron microscopy and optical methods, i.e. UV-vis spectroscopy and scanning angle reflectometry were applied for analyzing the structure and thickness of coatings. These measurements revealed that the precursor sols could not penetrate into the particulate LB film completely in case of coating type (1). For coating type (2) very little overlap between the SG and LB layers was found resulting in significant improvement of light transmittance of combined coatings compared to single SG films.To show some possible advantages of the combination of these techniques additional studies were carried out. Surface morphology of combined coatings (1) was studied by atomic force microscopy. Surfaces with different roughness were developed depending on the thickness of the sol-gel film (titania: ca. 70 nm; silica: ca. 210 nm). The adhesive peel off test revealed improved mechanical stability of combined coatings (2), in comparison to LB films which makes them good candidates for further applications.     

Effect of substrate temperature during combustion chemical vapour deposition on the formation of silica films

Combustion chemical vapour deposition was applied to deposit thin silica films on soda-lime-silica glass substrates. For this purpose, a flame loaded with tetramethylsilane was passed one to 15 times over the substrate. The deposition was carried out using different substrate temperatures in the range from 50 to 500 °C. The coatings were characterized by scanning electron microscopy, atomic force microscopy, profilometry and UV/vis spectroscopy. All layers show a particle-like structure. Higher substrate temperatures resulted in a smaller deposition rate. The thicknesses of the coatings were in the range from 20 to 180 nm. All coated glasses showed a higher light transmission than the uncoated substrate. Increasing the thickness of the coatings, resulted in a higher transmission.