磷酰胆碱基共聚物的合成及其稳定聚合物涂层表面的构筑

设计并合成了侧基分别含有磷酰胆碱(PC)亲水基团和胆固醇(Chol)疏水基团的两亲性二元无规共聚物PMC,用其对疏水基材聚丙烯中空纤维膜(PPHF)表面进行亲水改性,并以疏水基团为十二烷基柔性烷烃的磷酰胆碱基两亲性二元无规共聚物PML为参照聚合物,研究了聚合物涂层加热处理及空气中久置后涂层表面的稳定性.用1H-NMR和DSC对二元随机共聚物PMC和PML的结构和熔点(Tm)进行测定,用ARTR和XPS表征磷酰胆碱基共聚物构筑的两性离子表面的化学成分,用接触角研究其表面亲水性,并用水的动态接触角(DCA)评价涂层表面功能基团重新迁移取向的能力.结果发现,所得二元无规共聚物PMC和PML中组成与投料比相近且PMC的熔点Tm(190.5℃)远高于PML的(90.3℃);与PML改性PPHF表面相比,PMC-PPHF表面亲水性提高,而且经100℃高温处理2 h和空气中放置8个月后,接触角和表面磷元素相对含量基本不发生变化,说明表面功能基团基本不发生重新迁移取向,表面结构稳定性好.     

表面引发接枝聚合法制备凹凸棒土/聚甲基丙烯酸甲酯杂化粒子的研究

将γ-氨丙基三乙氧基硅烷(APTES)接枝到凹凸棒土(AT)表面,制得表面键合伯氨基的改性粒子AT-APTES;通过AT-APTES表面的伯氨基和过硫酸铵(APS)构成氧化-还原引发体系,采用无皂乳液法实现甲基丙烯酸甲酯(MMA)在AT表面接枝聚合,制得最高接枝率为29.4%的杂化粒子AT-g-PMMA;采用红外光谱(FTIR)、拉曼光谱(Raman)、透射电镜(TEM)以及热失重分析(TGA)等方法对杂化粒子AT-g-PMMA进行了表征;研究了主要配方及工艺条件对表面引发接枝聚合接枝率的影响.结果表明,伯氨基-过硫酸铵引发体系可以有效引发MMA在AT表面接枝聚合,由于引发点位于AT表面,故接枝率较高.本研究体系适宜的温度为65℃,单体MMA用量为水质量的6%,APS用量为单体质量的1%,此工艺条件下可有效减小均聚反应对接枝聚合反应的影响.先接枝到AT表面的聚合物对后续的接枝聚合反应产生抑制作用,接枝率越高,抑制作用越大.     

PEGDA/HEMA水凝胶等离子体表面改性的研究

采用紫外光聚合法合成了聚乙二醇双丙烯酸酯(PEGDA)/甲基丙烯酸-2-羟基乙酯(HEMA)复合凝胶,在不同的条件下进行等离子处理后,紫外光下进行表面接枝改性。在凝胶表面引入亲水性基团,改善材料的亲水性。研究了不同等离子体处理条件及辐射条件对丙烯酰胺(AAm)接枝率的影响。研究表明,丙烯酰胺接枝率随着等离子体处理时间的增加先增大后减小,随着紫外光照射时间、丙烯酰胺浓度的增大而增大。     

Langmuir-Blodgett方法构建聚合物仿细胞外层膜结构涂层

以盖玻片为基质,采用Langmuir-Blodgett(LB)方法制备含磷酰胆碱基团的两亲性无规共聚物聚(2-甲基丙烯酰氧基乙基磷酰胆碱(MPC)-甲基丙烯酸十八烷基酯(SMA)-γ-甲基丙烯酰氧丙基三甲氧基硅(TSMA)(简称PMST)的单层、双层和三层薄膜.薄膜的表面亲疏水性和表面形貌分别用动态接触角(DCA)和原子力显微镜(AFM)进行测试.结果表明,PMST在盖玻片表面形成了致密的膜层,薄膜的致密程度随层数而增加.在水中前进/后退测试DCA过程中,聚合物薄膜在气相/水相界面存在基团的迁移取向,且膜层内会发生交联.双层膜具有仿细胞外层膜结构,单层和三层膜具有反细胞外层膜结构;双层膜的亲水性比单层和三层膜的要好.     

聚丙烯微孔膜表面肝素化及其对低密度脂蛋白的吸附特性

为了赋予聚丙烯微孔膜(PPMM)选择性吸附低密度脂蛋白(LDL)的能力,发展了一种有效的PPMM表面共价固定肝素的方法.基于紫外引发丙烯酸的接枝聚合,通过碳二亚胺活化,以乙二胺为间隔臂,将肝素共价固定于PPMM表面,获得表面肝素化的PPMM.ATR-FTIR和XPS分析确证了修饰过程中膜表面基团及化学成分的变化.采用静...     

聚丙烯片基不同气氛下等离子体改性及DNA原位合成研究

分别采用氮气／氢气、氨气和氧气三种不同气氛的等离子体处理了聚丙烯片基,先使其表面接枝功能性基团,然后分别进行寡核苷酸原位合成．光电子能谱(XPS)证实了在其表面分别接枝了大量氨基和其它含氮基团．荧光扫描分析并比较了在三种方法处理的聚丙烯片基上合成的寡核苷酸与靶序列杂交后的荧光强度．结果表明：三种方法处理的聚丙烯片基都可用于DNA原位合成,但从处理工艺和荧光分析结果来看,以氮气／氢气等离子体处理的聚丙烯片基最佳。     

多巴胺基多重相互作用协同构筑抗污-杀菌双重功能涂层

在弱碱性和空气条件下, 以多巴胺(DA)为多重相互作用模型分子, 调控羧甲基壳聚糖(CMC)和侧基含 伯氨基(—NH₂)的磷酰胆碱基聚合物(PMA)与DA之间的相互作用, 采用一步共沉积法构筑表面富含磷酰胆碱两性离子基团和CMC杀菌性聚合物的双重抗菌涂层. 研究发现, DA分子的万能黏附特性有利于诱导CMC 和PMA在基材表面发生共沉积, 增强涂层中各组分及其与基材之间的界面结合力, 所得涂层在体积分数为75%的乙醇水溶液中超声2 h后, 表面水接触角数值几乎保持不变, 稳定性良好; 而CMC和PMA聚合物链中的—NH₂侧基与DA及其衍生物之间发生氢键、 席夫碱和/或迈克尔加成反应等多重相互作用, 协同改善DA分子氧化-自聚行为和沉积过程, 获得形貌较为均一的涂层表面. 所得表面同时含有两性离子基团和CMC聚合物链, 兼具良好抗生物污染和杀菌活性, 能够有效抑制细菌生物膜的形成.     

仿细胞膜结构共聚物的合成及涂层性能

采用饥饿法将2-甲基丙烯酰氧乙基磷酰胆碱(MPC)分别与甲基丙烯酸十八烷基酯(SMA)、 甲基丙烯酸十二烷基酯(LMA)及甲基丙烯酸正丁酯(BMA)聚合, 通过改变投料比例和沉淀剂种类, 合成了一系列含磷酰胆碱基团的仿细胞膜结构的两亲性二元随机共聚物. ¹H NMR和元素分析结果表明, 合成的两亲性二元随机共聚物的组成与投料比相近. DSC结果表明, 聚合物具有较低的玻璃化转变温度. 表面张力及水的动态接触角(DCA)研究发现, 聚合物涂层表面具有明显的两亲性及表面结构易变性, 在空气中憎水基团在表面取向, 在水环境中亲水的磷酰胆碱基团则迁移取向到涂层表面形成仿细胞外层膜结构界面, 最终形成不溶于水的仿细胞膜结构涂层.     

对氨基苯磺酸两步法修饰多壁碳纳米管

用混酸处理多壁碳纳米管, 利用侧壁生成的羧酸基团, 在N,N-二环己基碳酰亚胺的作用下, 使对氨基苯磺酸接枝到碳纳米管表面. 以浓硫酸为磺化剂, 室温下制备了磺化聚醚醚酮(SPEEK). 然后采用溶液共混法制备了磺化聚醚醚酮/接枝多壁碳纳米管复合膜. 采用傅立叶变换红外光谱(FT-IR)、热重分析(TGA)、透射电镜(TEM)、拉曼光谱(Raman)等技术对碳纳米管的结构和性能进行了表征. 红外谱图表明对氨基苯磺酸上的氨基与碳纳米管表面的羧基发生了反应, 生成酰胺基团. 热重曲线表明碳管表面接枝的有机基团的比重达到40%. 拉曼光谱显示处理前后碳管的I_D/I_G值变化不大, 表明碳管的石墨结构的含量基本不变. 复合膜的力学性能测试结果表明, 对氨基苯磺酸接枝的碳管可以提高膜的拉伸强度.     

细胞膜仿生修饰树枝状聚酰胺-胺的研究

利用2-丙烯酰氧基乙基磷酸胆碱的双键与树枝状聚酰胺-胺表面的氨基进行Michael加成反应,实现树枝状聚酰胺-胺表面的磷酸胆碱仿生修饰,修饰过程用FTIR、1H-NMR进行了表征.体外细胞活性测定和细胞形貌观察证实磷酸胆碱仿生修饰有效地改善了聚酰胺-胺树枝状聚合物的生物相容性;修饰后的聚酰胺-胺树枝状聚合物表面剩余的氨基仍然可以有效的与DNA复合,有可能作为一种潜在的基因载体得到广泛应用.     

Surface immobilization of poly(ethylene oxide): Structure and properties

We covalently immobilized poly(ethylene oxide) (PEO) chains onto a fluorinated ethylene propylene copolymer (FEP) surface. On the FEP surface, aldehyde groups were first deposited by plasma polymerization of acetaldehyde or acrolein. Then, amino‐PEO chains were immobilized through Schiff base formation, which was followed by reduction stabilization with sodium cyanoborohydride. The PEO‐grafted polymer surfaces thus prepared were characterized by X‐ray photoelectron spectroscopy (XPS), atomic force microscopy, contact‐angle measurements, and protein adsorption. The dramatic increase in the C O intensity of the high‐resolution XPS C 1s spectrum, together with an overall increase in oxygen content, indicated the successful attachment of PEO chains onto the acetaldehyde plasma surfaces. The amount of grafted PEO chains depended on the superfacial density of the plasma‐generated aldehyde groups. The grafted monoamino‐PEO chains formed a brushlike structure on the polymer surface, whereas the bisamino‐PEO chains predominately adopted a looplike conformation. The PEO surface had a regular morphology with greater roughness than the aldehyde surface underneath. Surface hydrophilicity increased with the grafting of PEO. Also, the bisamino‐PEO‐grafted surface had slightly higher surface hydrophilicity than its monoamino‐PEO counterpart. These PEO coatings reduced fibrinogen adsorption by 43% compared with the substrate FEP surface. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2323–2332, 2000     

表面化学接枝改性阻燃棉织物的制备与性能

采用高碘酸钠对棉织物表面进行选择性氧化生成醛基,选取乙二胺与醛基反应,通过膦氢化加成反应将阻燃剂亚磷酸二甲酯接枝到棉织物表面,最后通过三羟甲基三聚氰胺对棉织物表面进行接枝改性,制备了含三羟甲基三聚氰胺/乙二胺/亚磷酸二甲酯阻燃棉织物.通过傅里叶红外光谱（FTIR）对改性后棉织物的结构进行了表征,通过极限氧指数（LOI）测试研究了其阻燃性能,通过锥形量热测试研究了其燃烧行为,通过在40℃皂水中洗涤10次考察了其耐水性能,通过扫描电子显微镜测试了其表面及燃烧后炭层的形貌.研究结果表明,经表面改性后,棉织物的LOI值由（19.5±1.0）%提高到了（43.1±1.0）%,经耐水洗测试后,LOI值仅下降至（42.6±1.0）%,保持了非常好的阻燃性能,表明通过表面接枝方法制备的三羟甲基三聚氰胺/乙二胺/亚磷酸二甲酯阻燃棉织物具有非常好的耐水洗性能.表面阻燃改性提高了棉织物在燃烧过程中的成炭性能,形成的连续膨胀的炭层较好地保护了内部织物,抑制了织物的降解和燃烧,从而提高了棉织物的阻燃性能.     

Surface modification of microporous polypropylene membranes by the grafting of poly(γ-stearyl-l-glutamate)

A polypeptide, poly(γ-stearyl-l-glutamate) (PSLG), was grafted on the surface of hydrophobic polypropylene hollow fiber membranes through the ring opening polymerization of N-carboxyanhydride (NCA) of γ-stearyl-l-glutamate initiated by amino groups which was generated by ammonia plasma. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), together with water contact angle and bovium serum albumin adsorption measurements were used to characterize the modified membrane surface. The XPS and FT-IR spectra demonstrated that polypeptide was actually grafted on the membrane surface despite of the low degree of graft polymerization due to the hydroxyl groups on the membrane surface. To subject the ammonia plasma-treated membrane with γ-(aminopropyl)triethanoxysilane (γ-APS) which can react with hydroxyl groups and leave amino groups, the degree of graft polymerization could be improved. The bovium serum albumin adsorption measurement was conducted to further examine the surface properties of modified and original membranes. Potential applications of the PSLG grafted membranes are expected for enantiomer separation and/or enzyme immobilization.     

Photoelectron spectroscopy studies of the functionalization of a silicon surface with a phosphorylcholine-terminated polymer grafted onto (3-aminopropyl)trimethoxysilane

The structure of a biomimetic phosphorylcholine (PC)-functionalized poly(trimethylene carbonate) (PC-PTMC-PC), linked to a silicon substrate through an aminolysis reaction at 120 degrees C with (3-aminopropyl)trimethoxysilane (APTMS), was studied using photoelectron spectroscopy. Two chemical states were found for the unreacted APTMS amine, a neutral state and a protonated state, where the protonated amine on average was situated closer to the silicon substrate than the neutral amine. The experiments also indicated the presence of a third chemical state, where amines interact with unreacted silanol groups. The PTMC chains of the grafted films were found to consist of only 2-3 repeat units, with the grafted chains enriched in the zwitterionic end group, suggesting that these groups are attracted to the surface. This was further supported by the experiments showing that the PC groups were situated deeper within the film.     

丙烯醛在聚苯乙烯小球表面预辐射接枝及其对蛋白质固定化

作为免疫化学标记物的载体,聚苯乙烯小球被广泛应用于放免药盒［１］,在这一应用中,聚苯乙烯与抗体等蛋白质之间靠非特异性物理吸附结合在一起．但这种固定化较微弱,吸附量难以控制,时间稍长后,蛋白质易于脱落而使放免药盒失效,为解决这一问题,有人曾在聚苯乙烯小...     

Functionalization of hydrogen-terminated silicon via surface-initiated atom-transfer radical polymerization and derivatization of the polymer brushes

Surface-initiated atom-transfer radical polymerization (ATRP) of poly(ethylene glycol) monomethacrylate (PEGMA) was carried out on the hydrogen-terminated Si(100) substrates with surface-tethered alpha-bromoester initiator. Kinetic studies confirmed an approximately linear increase in polymer film thickness with reaction time, indicating that chain growth from the surface was a controlled "living" process. The "living" character of the surface-grafted PEGMA chains was further ascertained by the subsequent extension of these graft chains, and thus the graft layer. Well-defined polymer brushes of near 100 nm in thickness were grafted on the Si(100) surface in 8 h under ambient temperature in an aqueous medium. The hydroxyl end groups of the poly(ethylene glycol) (PEG) side chains of the grafted PEGMA polymer were derivatized into various functional groups, including chloride, amine, aldehyde, and carboxylic acid groups. The surface-functionalized silicon substrates were characterized by reflectance FT-IR spectroscopy and X-ray photoelectron spectroscopy (XPS). Covalent attachment and derivatization of the well-defined PEGMA polymer brushes can broaden considerably the functionality of single-crystal silicon surfaces.     

氨基化多壁碳纳米管的制备与表征

以多壁碳纳米管(MWNTs)为原料, 经自由基反应, 制备了氰基改性的多壁碳纳米管, 然后采用Al-NiCl₂·6H₂O-THF体系还原氰基得到了氨基化的碳纳米管。通过拉曼光谱仪、热重分析仪、X射线光电子能谱仪和透射电子显微镜对产物的结构与形貌进行了表征。结果表明:氨基通过共价键枝接在MWNTs的表面, 氨基化多壁碳纳米管每1000个表面碳原子中有17.1个转化为氨基;该反应条件温和, 反应时间短, 且不破坏MWNTs的结构。     

Glass surfaces grafted with high-density poly(ethylene glycol) as substrates for DNA oligonucleotide microarrays

Surfaces carrying a dense layer of poly(ethylene glycol) (PEG) were prepared, characterized, and tested as substrates for DNA oligonucleotide microarrays. PEG bis(amine) with a molecular weight of 2000 was grafted onto silanized glass slides bearing aldehyde groups. After grafting, the terminal amino groups of the PEG layer were derivatized with the heterobifunctional cross-linker succinimidyl 4-[p-maleimidophenyl]butyrate to permit the immobilization of thiol-modified DNA oligonucleotides. The stepwise chemical modification was validated with X-ray photoelectron spectroscopy. Goniometry indicated that the PEG grafting procedure reduced surface inhomogeneities present after the silanization step, while atomic force microscopy and ellipsometry confirmed that the PEG layer was dense and monomolecular. Hybridization assays using DNA oligonucleotides and fluorescence imaging showed that PEG grafting improved the yield in hybridization 4-fold compared to non-PEGylated maleimide-derivatized surfaces. In addition, the PEG layer reduced the nonspecific adsorption of DNA by a factor of up to 13, demonstrating that surfaces with a dense PEG layer represent suitable substrates for DNA oligonucleotide microarrays.     

氨基化多壁碳纳米管的制备与表征

以多壁碳纳米管(MWNTs)为原料,经自由基反应,制备了氰基改性的多壁碳纳米管,然后采用Al-NiCl2.6H2O-THF体系还原氰基得到了氨基化的碳纳米管。通过拉曼光谱仪、热重分析仪、X射线光电子能谱仪和透射电子显微镜对产物的结构与形貌进行了表征。结果表明:氨基通过共价键枝接在MWNTs的表面,氨基化多壁碳纳米管每1000个表面碳原子中有17.1个转化为氨基;该反应条件温和,反应时间短,且不破坏MWNTs的结构。     

Grafting of amino functional monomer onto initiator-modified polystyrene particles

Polystyrene nanoparticles with grafted chains of an amino functionalized polymer were prepared by a two-step polymerization process. In the first step, the polystyrene seed particles were synthesized by the conventional batch emulsion polymerization using terpolymer HAS (hydroperoxide monomer, acrylic acid, and styrene) as a surface-active initiator. The surface of the obtained particles contains carboxyl groups, which are responsible for the latex stability, and residual undecomposed hydroperoxide groups. Therefore, in the second step, an amino functional monomer was grafted onto the hydroperoxide modified polystyrene particles by a "grafting from" approach. X-ray photoelectron spectroscopy, NMR, and scanning electron microscopy were used to examine the surface of the amino functionalized particles. The amount of incorporated amino groups onto the particles was determined by fluorescenometric titration. In general, the number of amino groups on the particle surface increased with the increase of the functional monomer content in the reaction mixture. The incorporation of the functional monomer was also confirmed by electrophoretic measurements. Final particles possess amphoteric character due to the presence of amino and carboxyl groups on the surface. Adsorption of human immunoglobulins G onto the amino functionalized particles was studied as a function of pH and ionic strength. The covalent binding of human IgG was performed using the glutaraldehyde preactivation method. The immunoreactivity of the latex-IgG complex was examined by the latex agglutination test.