表面接枝季铵盐型高分子材料抗菌过程的特性研究

考察了一种表面接枝季铵盐型高分子材料对水溶液中大肠杆菌的抗菌过程特性,发现此材料可以在短时间内迅速降低溶液中的大肠杆菌的活菌量.用菌体耗氧测定法与扫描电镜观察法研究了其抗菌过程.结果表明,其抗菌过程由吸附和杀灭两个步骤构成,其中吸附过程由纤维与大肠杆菌表面静电作用所控制,是一个快速过程,而杀灭过程则伴随着细胞壁在纤维表面的溶解,是一个慢过程.菌体耗氧测定法与扫描电镜观察法所获得的结果具有一致性,并可广泛应用于研究抗菌纤维的抗菌作用机理及过程特性.     

季铵化聚乙烯亚胺的抗菌性能研究

采用叔胺化反应与季铵化反应两步高分子反应过程,制备了季铵化的聚乙烯亚胺(QPEI);以大肠杆菌(E.coli)为致病菌体,重点研究了高分子季铵盐QPEI的抗菌活性;采用平板活菌记数法考察了季铵化度及pH值等因素对其抗菌性能的影响规律;并采用β-半乳糖苷酶活性测定法,研究了QPEI的抗菌机理.研究结果表明,QPEI具有很强的抗菌能力,对浓度为109CFU/mL的菌悬液,在药剂量为15mg/L、接触时间为4min的条件下,杀菌率可达100%;QPEI的季铵化度对其抗菌性能影响很大,季铵化度越高,抗菌性能越好;在一定的pH值范围内,pH值越高,抗菌性能越好.β-半乳糖苷酶活性测定结果表明,QPEI的抗菌机理是基于杀菌过程,而不只是抑菌作用.     

接枝有抗菌与温度敏感共聚物的聚乙烯薄膜制备及抗菌性能初探

通过紫外光引发表面共接枝的方法,在聚乙烯薄膜表面引入了具有杀菌功能和温度敏感共聚物,聚(甲基丙烯酰氧乙基苄基二甲基氯化铵-co-N-异丙基丙烯酰胺)(P(DMAE-BC-co-NIPAAm)).利用红外光谱(IR)和表面接触角(CA)对共接枝膜的化学结构与表面性能进行了表征.研究了因温度改变引起共接枝膜表面疏水性改变,而导致接枝膜对大肠杆菌(E.coli)吸附作用和菌体内膜破裂作用的改变.大肠杆菌被抗菌膜吸附后,在1 mol/L的NaCl浓盐溶液中只有部分被洗脱,在膜表面疏水情况下,可洗脱菌体比例降低.β-半乳糖苷酶活性测定结果表明,因温度升高而引起接枝膜表面疏水性增强时,会使抗菌膜对大肠杆菌菌体的破裂作用增强.     

壳聚糖及其衍生物抗菌机理研究进展

壳聚糖及其衍生物的抗菌活性和优良加工性能,使其成为具有巨大潜力的抗菌材料,可用于食品保鲜、伤口敷料和组织工程等方面。本文综述了近年来在壳聚糖基材料抗菌模型、影响抗菌活性因素及抗菌活性优化方案方面的研究进展,希望对壳聚糖衍生物抗菌材料的制备及优化提供参考。     

具有双重抗菌作用的两性离子水凝胶

合成了一种甲基丙烯酰胺类两性离子单体,采用自由基聚合法制备了具有双重抗菌作用的水凝胶。利用1 H-NMR和FT-IR表征单体和水凝胶,考察了水凝胶释放水杨酸的动力学曲线。以导入绿色荧光蛋白的大肠杆菌为试验菌,荧光显微镜观察水凝胶表面细菌黏附情况;以金黄色葡萄球菌和大肠杆菌为试验菌,研究水凝胶抗菌性能。结果表明,该水凝胶可有效防止细菌黏附并且通过释放水杨酸实现抗菌功能。     

壳聚糖基抗菌材料的制备研究新进展

壳聚糖及其衍生物的抗菌活性和优良加工性能,使其成为巨大潜力的抗菌材料,可用于食品保鲜、伤口敷料、纺织品功能化和组织工程等方面。本文综述了近年来壳聚糖基抗菌材料的制备研究新进展,并讨论了壳聚糖基材料的抗菌模型及影响抗菌活性的因素,希望对壳聚糖基抗菌材料的制备及抗菌活性的优化提供指导。     

PS胶体粒子表面逐层自组装固定化SOD及其生物活性

通过逐层自组装技术成功地把超氧化物歧化酶(SOD)吸附在聚苯乙烯(PS)胶体粒子表面.zeta电位和TEM证明了聚阳离子或聚阴离子型SOD与相反电荷的聚电解质在PS胶体粒子表面的交替吸附.通过测定SOD被胶体粒子吸附后上清液的生物活性,得到聚阴离子型SOD(pH=8.0)和聚阳离子型SOD(pH=4.3)在PS胶体粒子表面的吸附量分别为12和51IU,相对活性分别为23.4%和2.9%.聚阴离子型SOD在PS胶体粒子表面能形成平滑规整的膜,导致较高的相对活性.研究结果表明,通过调节pH值,可以优化自组装固定化酶的聚集状态和生物活性     

具有双重抗菌作用的两性离子水凝胶

合成了一种甲基丙烯酰胺类两性离子单体,采用自由基聚合法制备具有双重抗菌作用的水凝胶。利用1 H-NMR和FT-IR表征单体和水凝胶,考察了水凝胶释放水杨酸的水解曲线。以导入绿色荧光蛋白的大肠杆菌为试验菌,荧光显微镜下观察水凝胶表面的细菌黏附情况;以金黄色葡萄球菌和大肠杆菌为试验菌,研究水凝胶的抗菌性能。结果表明,该水凝胶可有效防止细菌黏附并且通过释放水杨酸实现抗菌性能。     

季铵盐高分子抗菌剂的工艺优化与抗菌性能研究

采用正交实验设计,进行公斤级批量制备DMAEMA-DB季铵盐单体和抗菌聚合物的研究,对影响单体合成的关键因素以及聚合的条件进行优化,并采用FT-IR和NMR等方法对所合成的单体和聚合物分别进行了结构表征,通过平板活菌计数法测定了单体以及聚合物的抗菌性能.结果表明,DMAEMA-DB单体的优化合成条件为:反应温度55℃,反应时间30h,反应物浓度为V<,s>:V<,l>=1:1,反应物配比为DMAEMA:DB=1:1.1.Poly(AAm/DMAEMA-DB)的最佳合成工艺条件为:聚合温度70℃,聚合时间8h,单体浓度为0.4mol/L,引发剂用量为单体用量的0.4mol%,在该条件下合成的聚合物平均得率达89%.将它们用于杀灭大肠杆菌时,接触时间5min对大肠杆菌的抑菌率可达99%,接触时间30min抑菌率达到100%.     

新型抗菌型丙烯酸单体的合成及在牙科修复树脂中的应用

制备了2种具有抗菌活性的丙烯酸酯类单体6-溴己酸-2-(2-甲基丙烯酰氧)乙基酯吡啶盐(MEBH-Py)和11-溴十一酸-2-(2-甲基丙烯酰氧)乙基酯吡啶盐(MEBU-Py),分别将其添加到牙科修复树脂Single BondⅡ纳米黏结剂中共聚,得到具有抗菌活性的改性黏结剂.MEBH-Py和MEBU-Py具有较好的热稳定性;以大肠杆菌JM05(E.coli JM05)为受试菌,MEBH-Py和MEBU-Py的最小抑菌浓度分别为6和1 mg/mL,改性黏结剂固化后表面抗菌效率可达98%;抗菌单体溶出少,并向表面富集.     

Preparation and Antibacterial Function of Quaternary Ammonium Salts Grafted Cellulose Fiber Initiated by Fe2 +-H2O2 Redox

The surface contact disinfecting technique is a newly developed method for water sterilization. In this paper, the grafted quaternary ammonium salts (QAS) antibacterial fibers were prepared and designed to apply for the surface contact disinfecting process in water treatment. The antibacterial fibers were directly prepared by grafting methacryloxylethyl benzyl dimethyl ammonium chloride (DMAE-BC) onto cellulose fiber using thiocarbonate-H₂O₂ redox system. All kinds of factors in the grafting reactions, such as reaction time, reaction temperature, monomer concentration, initiator concentration, which influence the percentage of grafting, were studied and optimized. The modified cellulose fibers were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope(SEM). The effects of the percentage of grafting of the grafted cellulose fibers on bactericidal activity were also studied. The spread plate method was used to characterize the bactericidal activity. The disinfection process was further investigated by directly observing the morphology of the bacterial cells adsorbed on the antibacterial fibers with SEM and measuring extracelluar total protein concentration in suspension. The poly(DMAE-BC)-grafted cellulose ?ber was found to exhibit particularly high activity against E.coli.     

多官能单体TMPTA在LDPE表面光接枝聚合研究

以二苯甲酮(BP)为光引发剂、丙酮和水的混合物为溶剂,研究了室温下多官能单体三羟甲基丙烷三丙烯酸酯(TMPTA)在低密度聚乙烯(LDPE)表面的光接枝聚合(λ>300nm).研究表明,多官能单体的接枝速率较快,接枝聚合易产生交联结构,聚合后仍残留双键;延长聚合反应时间、增加单体用量有利于单体接枝转化率的提高;随引发剂用量增加,单体接枝转化率出现一峰值;在研究范围内,混合溶剂中水含量增加可使单体接枝转化率明显提高.扫描电镜观察到接枝膜表面形成了许多小球,表面粗糙度增加,疏水性提高.     

紫外光引发LDPE膜接枝含氟丙烯酸酯的研究

通过紫外光引发表面接枝聚合反应的方法 ,把含氟丙烯酸酯单体R 5 6 1 0引到LDPE薄膜上 .对经丁酮抽提后的接枝膜进行FTIR、ESCA、SEM和DSC等表征 ,证实含氟聚合物以化学键的方式接枝在LDPE基体膜上 .在一定范围内 ,增加紫外光强、引发剂和单体浓度以及反应温度等均有利于提高接枝率 .经计算R 5 6 1 0的紫外光引发接枝聚合反应总活化能为 5 4 2kJ mol.接枝膜的接触角随着接枝率的提高逐步增大 ,直至趋于恒定 .作者提出接枝膜存在一个在接触角测定时影响基体膜与探测水滴相互作用过程的边界层 .当接枝率较低、接枝层厚度小于边界层临界厚度时 ,基体LDPE影响接触角的大小 ,但随着接枝率提高 ,接枝层逐渐变厚 ,氟聚合物层对接触角的贡献逐渐占优势 ,导致接触角随之增大 .当接枝率超过一定值以后 ,接枝层厚度超过边界层临界厚度 ,接枝层对接枝膜的接触角起全部贡献 ,接触角测定值随之稳定     

Surface modification of polyethylene fiber by graft polymerization

To improve the wettability and adhesion, graft polymerization of acrylamide (AAm) and glycidyl methacrylate (GMA) was performed onto the surface of ultra-high modulus polyethylene (UHMPE) fiber pretreated with Ar plasma. Following the plasma treatment and the subsequent exposure to air to introduce peroxides onto the fiber surface, graft polymerization onto the UHMPE fiber was allowed to proceed from the polymer peroxides either in deaerated monomer solution at an elevated temperature (degassing method), or in aerated monomer solution containing riboflavin at 30°C under UV irradiation (photoinduction method). The monomer solution was prepared from water and dioxane for AAm and GMA, respectively. After rigorous removal of homopolymers, surface analysis of the grafted fibers was performed with ATR-FTIR and XPS, which revealed that PAAm and PGMA chains were grafted in the surface region of fibers. The grafting rate of PAAm by the photoinduction method was much higher than that by the degassing method when compared at the same concentration of the AAm solution. The amount of PGMA grafted was greatly affected by UV irradiation time, but depended on plasma treatment time to an insignificant extent if the treatment was carried out for longer than 30 s. Reaction of propylamine with the PGMA-grafted surface resulted in the appearance of a nitrogen peak in the XPS spectrum, suggesting the presence of epoxy groups on the surface of PGMA grafted fiber. © 1994 John Wiley & Sons, Inc.     

Oxidation of polyethylene surface by glow discharge and subsequent graft copolymerization of acrylic acid

Plasma-induced graft copolymerization of acrylic acid, which was incorporated into PE films, was investigated here. The influence of plasma conditions such as plasma treatment gases, power, pressure, time, monomer concentration, and graft copolymerization time on polymerization yield was determined. The samples were characterized by ESCA, IR, and water contact angle. A respective chemical shift of the C1s signal of Ar or O₂ plasmatreated and untreated PE films was revealed by ESCA, in which the presence of the grafted PAAc was also verified. An increase in polymerization yield with plasma treatment duration and power was found. That the grafted copolymerization was limited to a very thin surface region was revealed by optical microscopy on the cross section of the grafted film. © 1993 John Wiley & Sons, Inc.     

PVDF Hollow fiber Membrane with High Flux and High Rejection Ratio Prepared by Irradiation Induced Grafting of PAA

Summary: A modified poly (vinylidene fluoride) (PVDF) hollow fiber membrane with higher flux and flux recovery rate was prepared by γ-radiation induced grafting of acrylic acid (AA). The influence of radiation dose and monomer concentration on the grafting degree was investigated. The results indicated that the grafting degree increased in the lower monomer volume fraction until the monomer volume fraction exceeded 20%. The grafting degree increased with the increase of radiation dose. Structural and morphological of the original and grafted membrane surface were characterized by FT-IR, scanning electron microscopy (SEM). The results indicated that acrylic acid was grafted onto PVDF hollow fiber membrane and the grafted membrane was more hydrophilic than original PVDF. There was a slight increase of breaking strength and yield stress with the increase of the grafting degree of AA. The pure water flux increased initially but decreased subsequently with the raise of grafting degree. When the grafting degree was 4.4%, the maximum pure water flux reached 1496.3 L/m² × h, 1.79 times of original membrane. The pure water flux, flux recovery rate and rejection ratio for bovine serum albumin could improve simultaneously in a low grafting degree (<4.4%).     

氯丁胶乳乳液接枝甲基丙烯酸甲酯的反应动力学

采用乳液聚合法将甲基丙烯酸甲酯(MMA)接枝到氯丁胶乳上,红外光谱和核磁共振氢谱证实了接枝产物的生成。 研究了反应温度、乳化剂浓度、引发剂浓度和单体浓度对表观聚合速率的影响。 结果表明,当反应温度为50 ℃,引发剂叔丁基过氧化氢 四乙烯五胺（t-BHP/TEPA）用量为氯丁胶乳干重的0.5%,单体/聚合物质量比m(M)∶m(P)=3∶5,乳化剂十二烷基连苯醚二磺酸钠（DSB）用量为单体总质量1%时,单体转化率和接枝效率分别为99.1%和54.9%。 聚合反应动力学关系式为：Rp=Kc(E)0.15c(I)0.30c(MMA)1.41,式中,K为常数,在40~55 ℃范围内,聚合反应的表观活化能Ea＝60.2 kJ/mol。 接枝聚合基本符合自由基反应机理。     

SURFACE MODIFICATION OF MICROPOROUS POLYPROPYLENE MEMBRANES BY GRAFT POLYMERIZATION OF N,N-DIMETHYLAMINOETHYL METHACRYLATE

Surface modification of microporous polypropylene hollow fiber membranes was performed by radical-induced graft polymerization of N,N-dimethylaminoethyl methacrylate (DMAEMA). The influences of temperature, monomer concentration and pre-adsorbed amount of benzoyl peroxide on grafting degree were studied respectively. It was found that the appropriate graft temperature was 75℃, at which the grafting degree was the highest and the hydrolytic decomposition of DMAEMA the lowest. Scanning electron photomicrography and the average pore diameters of the modified membranes demonstrated that part of the micropores on the membrane surface was plugged by the grafted polyDMAEMA chains, especially at high grafting degree. Contact angle and water swelling experiments showed that a moderate grafting degree could improve the hydrophilicity of the membranes. In the range of I 1.3%o-12.0% grafting degree, the water swelling percentage reached its maximum (51.1%) and the contact angle reached its minimum (74 degrees). The bovine serum albumin (BSA) adsorption experiment indicated that the grafted polyDMAEMA had a dual effect on protein adsorption. At the first stage, the BSA adsorption decreased with increasing of DMAEMA grafting degree. As the interaction between BSA and polyDMAEMA on membrane surface increased, the BSA adsorption increased with increasing of DMAEMA grafting degree.     

Preparation and Properties of Polyether Pentaerythritol Mono‐maleate grafted Linear Low Density Polyethylene by Reactive Extrusion

A reactive type nonionic surfactant, polyether pentaerythritol mono‐maleate (PPMM) was synthesized in our laboratory. PPMM was adopted as a functionalizing monomer and grafted onto linear low density polyethylene (LLDPE) with a melt reactive extrusion procedure. FT‐IR was used to characterize the formation of grafting copolymer and evaluate their degree of grafting. The effects of monomer concentration, reaction temperature and screw run speed on the degree of grafting were studied systematically. Isothermal crystallization kinetics of LLDPE and LLDPE‐g‐PPMM samples was carried out using DSC. Crystallization rates of grafted LLDPE were faster than that of plain LLDPE at the same crystallization temperature. The tensile properties and light transmission of blown films were determined. Comparing with neat LLDPE film, no obvious changes could be found for the tensile strength, elongation at break and right angle tearing strength of LLDPE‐g‐PPMM film. The wettability is expressed by the water contact angle. With an increasing percentage of PPMM, the contact angles of water on film surface of LLDPE‐g‐PPMM decrease monotonically. The acceleration dripping property of film samples was investigated. The dripping duration of LLDPE‐g‐PPMM film and commercial anti‐fog dripping film at 60°C were 76 days and 17 days, respectively.