Synthesis and characterization of surface-grafted polyacrylamide brushes and their inhibition of microbial adhesion

A method is presented to prevent microbial adhesion to solid surfaces exploiting the unique properties of polymer brushes. Polyacrylamide (PAAm) brushes were grown from silicon wafers by atom transfer radical polymerization (ATRP) using a three-step reaction procedure consisting of immobilization of a coupling agent gamma-aminopropyltriethoxysilane, anchoring of an ATRP initiator 4-(chloromethyl)benzoyl chloride, and controlled radical polymerization of acrylamide. The surfaces were characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, ellipsometry, and contact-angle measurements. The calculated grafting density pointed to the presence of a dense and homogeneous polymer brush. Initial deposition rates, adhesion after 4 h, and detachment of two bacterial strains (Staphylococcus aureus ATCC 12600 and Streptococcus salivarius GB 24/9) and one yeast strain (Candida albicans GB 1/2) to both PAAm-coated and untreated silicon surfaces were investigated in a parallel plate flow chamber. A high reduction (70-92%) in microbial adhesion to the surface-grafted PAAm brush was observed, as compared with untreated silicon surfaces. Application of the proposed grafting method to silicone rubbers may offer great potential to prevent biomaterials-centered infection of implants.     

In vitro drug release from silicone rubber–polyacrylamide composite

Composite materials containing drugs were prepared from silicone rubber and hydrogel. Cross linked polyacrylamide (PAAm) hydrogel particles were incorporated into a silicone rubber to enhance the hydrophilicity and drug release capacity of silicone rubber as a matrix. Progesterone and Thymol Blue were used as a hydrophobic and hydrophilic drug model, respectively. Different amounts of polyacrylamide (PAAm) were mixed with the drugs and uncured silicone rubber at room temperature. The composite matrices were formed using a compression molding press and cured by thermal and γ-irradiation curing methods. In vitro drug release behavior of composites and their physical and mechanical properties were investigated. The results indicated that the hydrophilic character of silicone rubber was more pronounced with increasing the amount of PAAm. Also, a significant effect on the drug release profiles was observed. The γ-irradiation curing method improved mechanical properties of composites and affected the drug release profiles. It was found that the amounts of released progesterone from γ-irradiated samples increased in comparison with the thermally cross linked composite since released Thymol Blue was reduced.     

Platelet adhesion and protein adsorption on silicone rubber surface by ozone-induced grafted polymerization with carboxybetaine monomer

Platelet adhesion and protein adsorption on the silicone rubber film grafted with N,N'-dimethyl-N-methacryloyloxyethyl-N-(2-carboxyethyl) ammonium (DMMCA) was studied. The grafting was carried out by means of ozone-induced method and was confirmed by ATR-FTIR and XPS investigations. The grafted films possessed relatively hydrophilic surface revealed by contact angle measurement. The blood compatibility of the grafted film was evaluated in vitro by platelet adhesion in platelet-rich plasma (PRP) and protein absorption in bovine fibrinogen (BFG) using silicone film as the reference. No substantial platelet adhesion was observed for the grafted films incubated in PRP for 60 and 180 min. The protein absorption was also significantly reduced after incubated in bovine fibrinogen for 60 min. Both the results indicated that the blood compatibility of silicone rubber was greatly improved by ozone-induced grafting of carboxybetaine zwitterionic polymer onto its surface.     

In vitro cytotoxicity evaluation of natural rubber latex film surface coated with PMMA nanoparticles

In order to increase surface roughness of the sulphur-prevulcanized natural rubber (SPNR) film and, hence, decrease the direct contact between the rubber and skin, the poly(methyl methacrylate) (PMMA) latex particles were deposited onto the SPNR film grafted with polyacrylamide (SPNR-g–PAAm). The surface coverage of PMMA particles on the SPNR-g–PAAm increased with increasing latex immersion time, particle size and concentration. Prior to the in vitro cytotoxicity evaluation on L-929 fibroblasts, the SPNR and SPNR-g–PAAm coated with PMMA particles were extracted by using the culture medium. Results showed that the cytotoxicity effect could be significantly reduced by coating PMMA particles onto the rubber film. At the extract concentrations of ≤12.5% for 24 h at 37 °C, no toxicity potential was detected. The study will be helpful for development of gloves designed for the hypersensitive person.     

Synthesis and characterization of acrylamide-N-isopropyl acrylamide copolymer grafts on silicone rubber substrates

Radiation grafting has been used to modify the surface composition of a polymeric biomaterial without changing its mechanical properties. The graft copolymer surface modifications may result in significant changes in protein and cell adhesion to the surface, and thus in the overall biological response to the foreign material. In this paper we present a study of the radiation grafting of an unusual monomer, N-isopropyl acrylamide, and its copolymers with acrylamide, onto silicone rubber. This graft system may be able to influence protein adsorption and cell interactions in a unique fashion due to the special hydrophilic/hydrophobic balance and the unusual hydration character of the grafted copolymer.     

Protein adhesion on silicon-supported hyperbranched poly(ethylene glycol) and poly(allylamine) thin films

Hyperbranching poly(allylamine) (PAAm) and poly(ethylene glycol) (PEG) on silicon and its effect on protein adhesion was investigated. Hyperbranching involves sequential grafting of polymers on a surface with one of the components having multiple reactive sites. In this research, PAAm provided multiple amines for grafting PEG diacrylate. Current methodologies for generating PEG surfaces include PEG-silane monolayers or polymerized PEG networks. Hyperbranching combines the nanoscale thickness of monolayers with the surface coverage afforded by polymerization. A multistep approach was used to generate the silicon-supported hyperbranched polymers. The silicon wafer surface was initially modified with a vinyl silane followed by oxidation of the terminal vinyl group to present an acid function. Carbodiimide activation of the surface carboxyl group allowed for coupling to PAAm amines to form the first polymer layer. The polymers were hyperbranched by grafting alternating PEG and PAAm layers to the surface using Michael addition chemistry. The alternating polymers were grafted up to six total layers. The substrates remained hydrophilic after each modification. Static contact angles for PAAm (32-44 degrees) and PEG (33-37 degrees) were characteristic of the corresponding individual polymer (30-50 degrees for allylamine, 34-42 degrees for PEG). Roughness values varied from approximately 1 to 8 nm, but had no apparent affect on protein adhesion. Modifications terminating with a PEG layer reduced bovine serum albumin adhesion to the surface by approximately 80% as determined by ELISA and radiolabel binding studies. The hyperbranched PAAm and PEG surfaces described in this paper are nanometer-scale, multilayer films capable of reducing protein adhesion.     

Oil coating of hydrophobic surfaces from aqueous media: formation and kinetic study

We perform oil coating of hydrophobic solid surfaces via aqueous media, from emulsions, and under the presence of a shear flow. The principle of such coating is based on the use of a system at the limit of aggregation to give rise to adhesion, with asymmetrical interfaces (oil droplet/water and solid surface/water) in order to favor the oil/surface adhesion in comparison to the oil/oil adhesion. This way, droplets stick to the solid substrate, whereas they are stable and homogeneously dispersed in the bulk. We have realized coatings from two systems of emulsions made of a mixture of hydroxy-terminated silicone oil and classical silicone oil and a mixture of sunflower oil and mineral oil. The kinetics of the coating is described by a Langmuir model where the adhesion between the oil particle and the surface is modeled as a first-order reaction. The resulting coatings are formed of oil droplets uniformly covering the solid surface. The coating density can vary with the nature of the experimental systems.     

Research and synthesis of organosilicon nonthrombogenic materials containing sulfobetaine group

A novel organosilicon sulfobetaine was synthesized through the reaction of organosilicon containing tertiary amino with 1,3-propanesulfone. Then this organosilicon sulfobetaine was coated onto polyurethane and organosilicon surface to improve their blood compatibility. The existence of sulfobetaine structure on the surface of materials was revealed by ATR-FTIR and XPS. The thermo-capability of synthesized silicone rubber, containing sulfobetaine was revealed by TGA. The blood compatibilities of organosilicon sulfobetaine and other materials such as silicone and PU as reference coated with them were evaluated by platelet-rich plasma adhesion experiment. The novel segmented silicone rubber containing sulfobetaine structure showed perfect blood compatibility.     

提高聚氨酯表面硅橡胶涂层粘接性研究

利用表面处理并借助硅烷偶联剂大幅提高了聚氨酯/硅橡胶(PU/SR)的界面粘接性.利用红外光谱、水接触角以及表面元素分析对PU表面处理效果及偶联剂的反应效果进行检测,利用扫描电镜对材料的表面形貌及界面情况进行观察.并对不同方法得到的PU/SR界面进行剪切和振动疲劳测试以考察其粘接效果并进行比较.结果表明,经过硫酸短时处理过的PU表面生成大量羟基,使得亲水性提高,并大大增强了端异氰酸酯基硅烷偶联剂与PU的接枝反应效果.当室温缩合固化的硅橡胶预聚体涂覆到其表面后,以化学键联接在PU表面的硅烷偶联剂又可以与硅橡胶一起缩合,从而有效的提高了PU/SR的界面粘接性.     

Hydrophobic modification of poly(phthalazinone ether sulfone ketone) hollow fiber membrane for vacuum membrane distillation

New hydrophobic poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber composite membranes coated with silicone rubber and with sol–gel polytrifluoropropylsiloxane were obtained by surface-coated modification method. The effects of coating time, coating temperature and the concentration of silicone rubber solution on the vacuum membrane distillation (VMD) properties of silicone rubber coated membranes were investigated. It was found that high water permeate flux could be gotten in low temperature and low concentration of silicone rubber solution. When the coating temperature is 60 °C, the coating time is 9 h and the concentration of silicone rubber solution is 5 g L⁻¹ the water permeate flux of the silicone rubber coated membrane is 3.5 L m⁻² h⁻¹. The prepolymerization time influence the performance of polytrifluoropropylsiloxane coated membranes, and higher prepolymerization time decrease the water permeate flux of the membrane. The water permeate flux and the salt rejection was 3.7 L m⁻² h⁻¹ and 94.6%, respectively in 30 min prepolymerization period. The VMD performances of two composite membranes during long-term operation were studied, and the results indicated that the VMD performances of two composite membranes are quite stable. The salt rejection of silicone rubber coated membrane decreased from 99 to 95% and the water permeate flux fluctuated between 2.0 and 2.5 L m⁻² h⁻¹. The salt rejection of polytrifluoropropylsiloxane coated membrane decreased from 98 to 94% and the water permeate flux fluctuated in 1 L m⁻² h⁻¹ range.     

加成型液体硅橡胶的研究进展

结合加成型液体硅橡胶的硫化原理,综述了加成型液体硅橡胶导热性能、耐高温性能及粘结性能的最新研究进展,发现加入金属氮化物导热填料是提高加成型液体硅橡胶导热性能的有效途径;改善分子结构是提高加成型液体硅橡胶耐高温性能的主要途径;共混粘结促进剂是提高加成型液体硅橡胶粘结性能的重要途径。介绍了加成型液体硅橡胶的最新应用领域,提出功能化加成型液体硅橡胶,如3D个性化打印硅橡胶、人体器官硅橡胶、高折光封装硅橡胶等功能材料是未来加成型液体硅橡胶的发展方向。     

Novel poly(vinyl chloride) based thermoplastic elastomers incorporating vinyl-functionalized silicone rubber

ABSTRACT

Novel poly(vinyl chloride) (PVC) based thermoplastic elastomers were developed by blending with different proportions of vinyl-functionalized silicone rubber. Scanning electron microscopy (SEM) confirmed good compatibility between PVC and silicone rubber which allowed enhancement of the stress-strain behavior. On the contrary to neat PVC, exposure to heat or UV radiation was found not to cause any considerable deterioration to the stress-strain behavior. Fourier Transform Infrared (FTIR) revealed a possible chemical interaction between the blend components involving the vinyl groups from the silicone rubber, which is thought to be the reason for maintaining the mechanical properties unaltered. Further investigation with ultraviolet-visible (UV-Vis.) spectroscopy signified absence of intensive dehydrochlorination usually encountered for PVC after exposure to heat or UV radiation, which indicates a potential stabilizing effect for the silicone rubber and build up of a network structure comprising both hard and soft segments.     

The influence of contact electrification on the adhesion of dielectric elastic spheres subjected to external loads before detachment

The influence of a static load on the adhesion of an elastic sphere to a rigid smooth surface has been investigated. The change in ratio of the electrostatic component of the adhesion force resulting from the formation of an electric double layer to the molecular one as a result of the contact pressure has been evaluated theoretically. The tearing-off force and the surface density of the charge forming in the contact between the silicone rubber sphere and a steel plate were determined simultaneously. It is shown that the observed increase in sticking force of the sphere after its compression may be explained by an increase in the electrostatic component of the adhesion force, which is proportional to the contact area.     

Introduction of O-butyrylchitosan with a photosensitive hetero-bifunctional crosslinking reagent to silicone rubber film by radiation grafting and its blood compatibility

Based on an in vitro test for an improvement of the blood compatibility of silicone rubber (SR) films by grafting O-butyrylchitosan (OBCS), OBCS was covalently immobilized onto SR film surface using the photosensitive hetero-bifunctional crosslinking reagent, 4-azidobenzoic acid, which was previously bonded to OBCS by reaction between an acid group of the crosslinking reagent and a free amino group of OBCS. Surface properties of SR film were investigated by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), electron spectroscopy for chemical analysis (ESCA) and the water contact angle measurements. The blood compatibility of SR film was evaluated by platelet rich plasma (PRP) contacting experiments and the results were observed by scanning electron microscopy (SEM). The state of platelet adhesion was described. The suitable modifications could be carried out to tailor SR films biomaterial to meet the specific needs of different biomedical applications. These results suggest that the blood compatible of SR films/OBCS films show their suitability as potential biomaterials.     

白炭黑增强型硅橡胶的组成及抗原子氧性能分析

为明确空间级硅橡胶的化学组成及填料添加对材料物理性能的影响, 采用填料复合方式制备硅橡胶高聚物材料, 并通过化学成分测试、 原子氧暴露试验及力学性能测试等研究其结构组成与物理性能. 经微观粒径测试得出硅橡胶中白炭黑填料粒径主要分布在8~16 μm; 经傅里叶变换红外光谱(FTIR)、 核磁共振波谱( ¹H NMR和 ²⁹Si NMR)和溶胶凝胶渗透色谱(GPC)测试得出硅橡胶中含有Si—Me, Si—Ph, Si—O—Si等基团和甲基、 苯基等官能团, 其分子量分散系数为1.56, 并进一步推断出硅橡胶的分子结构及基胶与交联剂的反应类型为脱羟胺型; 经原子氧暴露试验及力学试验证实, 与未改性白炭黑填充的硅橡胶高聚物材料相比, 经硅烷改性白炭黑填充的硅橡胶高聚物材料表现出更好的抗原子氧性能, 动态力学测试后储能模量高54%, 并具有更好的应力应变响应性能. 研究结果表明, 采用表面改性处理方式可增强填料与硅橡胶基质的相互作用, 从而提高填料复合型硅橡胶高聚物材料的抗原子氧性能及综合力学性能.     

有机硅弹性体表面生物相容性的研究进展

生物材料表面的生物相容性一直是生物材料研究领域倍受关注的问题.本文综述了对有机硅弹性体进行改性以提高其表面生物相容性的研究进展,介绍了各种常用的化学改性方法如本体接枝、等离子体处理、光化学诱导接枝、臭氧活化接枝以及硅氢加成反应、原子转移自由基聚合反应在有机硅弹性体表面改性中的应用.对改性后的有机硅弹性体表面抗非特异性蛋白质和血小板的能力等方面进行了评述,并进一步分析了有机硅弹性体表面化学改性的发展趋势和研究重点.     

The measurement temperature: an important factor relating physicochemical and adhesive properties of yeast cells to biomaterials

Flow chambers applied to the study of the initial adhesion process of Candida parapsilosis are rarely found in the literature. The ability of these microorganisms to proliferate and form biofilms in environments at temperatures around 22 or 37 degrees C is reflected in the contamination of laboratory instruments and material or in human implant infections, respectively. The initial interaction between yeasts and substrata is mediated by physicochemical forces, which in turn originate from the physicochemical surface properties of both interacting phases. In this context, this work aims to relate the initial rates of adhesion rates to glass and silicone of Candida parapsilosis, strains 294 and 289, grown at 22 and 37 degrees C with the theoretical predictions of the adhesion process, expressed by the interaction free energies and calculated through the physicochemical parameters, which are also measured at 22 and 37 degrees C. The results indicate that physicochemical parameters of yeasts are changed not only by the culture temperature but also by the measurement temperature; only when the measurement temperature is equal to the growth temperature a coherent relation between in vitro adhesion data and interaction free energies can be established. In this sense, the adhesion to glass is mediated by long-range forces or, what amounts to the same thing, by Lifshitz-van der Waals interaction free energy. On the other hand, the adhesion to silicone rubber seems to be moderated by acid-base interaction free energy, which involves the presence of short-range forces. Based on these results, it can be assumed that the substratum surface properties are directly related to the kind of force acting on the initial microbial adhesion process, while cell surface properties dictate the changes in the strength of the force between different samples.     

硅氢加成型室温固化硅橡胶胶粘剂的研究

<正> 我们研制了一种硅氢加成型室温固化硅橡胶,这种橡胶不但有较好的力学性能,而且与各类材料如金属、塑料、陶瓷、玻璃等都有很好的粘结力,是一种具有弹性的胶粘剂。该胶粘剂是利用一种含乙烯基聚硅氧烷、含氢聚硅氧烷以及二氧化硅补强剂在铂催化剂     

聚氯乙烯表皮成分对加成型硅橡胶固化的影响

采用流变学方法研究了双组分加成型硅橡胶在不同聚氯乙烯(PVC)表皮上的固化动力学,并利用红外光谱、核磁共振波谱、电感耦合等离子体质谱仪等手段分析了PVC表皮成分,以确定导致双组分加成型硅橡胶不固化的具体原因。 结果表明,PVC表皮中导致硅橡胶不固化的主要元素为P元素。 在固定硅橡胶厚度为1 mm的情况下,当PVC表皮中的P元素质量分数低于3×10^-3%时,浇注在其上的双组分加成型硅橡胶依然能固化;而当PVC表皮中的P元素质量分数超过约2.4×10^-2%时,虽然浇注在其上的双组分加成型硅橡胶的中间层依然能固化,但与PVC表皮接触部分的硅橡胶不固化,且不固化层厚度随P元素质量分数增加而增加。 本文还研究了在P元素质量分数低于3×10^-3%的PVC表皮上,降低硅橡胶厚度至微米级时的固化行为,在P元素质量分数低于3×10^-3%的PVC表皮上,当硅橡胶厚度低于2 μm时,硅橡胶出现不完全固化现象。 双组分加成型硅橡胶在含有P元素的PVC表皮表面的固化行为主要是由硅橡胶样品中铂催化剂总含量及PVC表皮中的P元素含量确定的,同时也会受到双组分加成型硅橡胶反应速率以及铂催化剂、P元素在硅橡胶中的扩散速率的影响。     

Thermal Oxidative Degradation and Ageing Performance of Silicone Rubber Filled with Attapulgite

The natural attapulgite (NAPT) was disaggregated by high-pressure homogenization technology combined with extrusion process to prepare the attapulgite with disaggregated rod crystal bundles (DAPT) and large specific surface area of 133.7 m²/g. NAPT and DAPT were incorporated into the silicone rubber to obtain the composite NAPT-SR and DAPT-SR by mechanical blending method, respectively. After thermal oxidative ageing at 300 ℃ for 0.5 h, temperature for the 5% weight loss increased greatly from 385 ℃ of the neat silicone rubber to 396℃ - 399 ℃ with addition of NAPT and DAPT. NAPT and DAPT enhanced the interaction between the filler nanoparticles and rubber matrix thus inhibited the nanoparticle agglomeration. The conservation rate of the side methyl group in NAPT-SR and DAPT-SR was greatly improved after ageing. Therefore, the thermal oxidative degradation and ageing performance of the silicone rubber composites was significantly reinforced. Moreover, DAPT could greatly restrain the growth of nanoparticles after ageing. Therefore, DAPT-SR showed the better retention of tensile strength (40.6%), elongation at break (34.9%) and tear strength (30.1%) compared with the corresponding mechanical properties of the neat silicone rubber (10.6%, 7.4%, and 5.0%) after ageing.