一种复合聚硅氧烷膜的结构与形貌及性能研究

在乙酸乙酯稀溶液中,将氨值为0.6 mmol/g、Mn=14100的聚(N-β-氨乙基-γ-氨丙基甲基硅氧烷-co-二甲基硅氧烷)(ASO)与羧值为0.3 mmol/g、Mn=4048的聚[γ-(β-羧基丙烯酰胺基)丙基甲基硅氧烷-co-十二烷基甲基硅氧烷-co-二甲基硅氧烷](RCAS)共混自组装,可获得一种静电复合的聚硅氧烷ASO/RCAS.以单晶硅和棉纤维织物作载膜基质,用原子力显微镜(AFM)和光电子能谱(XPS)等仪器对ASO/RCAS的膜形貌及应用性能进行了研究.结果表明,由ASO和RCAS复合成的ASO/RCAS,微观形貌呈连续丘陵状凸起,膜厚度为1.501 nm,在2μm×2μm扫描范围内其均方根粗糙度为0.5 nm.将其附着固定在棉纤维表面,ASO/RCAS不仅能引起纤维表面条纹状沟壑消失,而且能使纤维表面的均方根粗糙度从处理前的24.6 nm降低为处理后的11.7 nm.另外,用ASO/RCAS处理的棉织物,其弯曲刚度明显降低、亲水性增加,且表面有舒适的油润感.当ASO与RCAS的质量比为1∶1时,复合聚硅氧烷ASO/RCAS的应用性能最佳.     

聚醚-紫外侧基聚硅氧烷的结构表征与膜形态

利用聚甲基氢硅氧烷(PHMS)与4-(β-羟基-γ-烯丙氧)丙氧基-2-羟基二苯甲酮(MUV-O)、α-烯基聚醚(F6)的硅氢化加成反应,合成了一种新型聚醚-二苯甲酮衍生物侧基聚硅氧烷PE-PUVSi,用红外光谱(IR)、紫外光谱(UV)、核磁共振氢谱(1H-NMR)以及原子力显微镜(AFM)等仪器对产物的结构和成膜形态进行了研究。结果表明,新合成的PE-PUVSi对波长为243.6、289.2、325.0nm的紫外光有强吸收作用。在纤维及单晶硅表面,PE-PUVSi均可成膜。但宏观上平滑的PE-PUVSi膜,微观上实则呈非均一、相分离结构,其中UV侧基以纤细尖峰分布在聚硅氧烷膜表面,而亲水性聚醚基团则卷曲堆积成峰包。     

聚乳酸蜂窝状多孔膜的形成与控制

以单一组分聚L-乳酸(PLLA)为成膜材料,利用水辅助法制备了聚乳酸(PLLA)蜂窝状多孔膜.利用扫描电镜(SEM)和原子力显微镜(AFM)观察多孔膜形貌.研究溶剂、溶液浓度、环境温度和湿度等因素对所成多孔膜结构的影响.实验结果表明,高湿度环境和具有一定浓度的聚合物溶液是制备蜂窝状多孔膜的必要条件.溶剂的挥发性是形成规整蜂窝状孔结构的关键因素.环境相对湿度由43%增加到91%,PLLA多孔膜的孔径由(1.75±0.24)μm增加到(11.50±1.43)μm,且孔呈现六边形的蜂窝状结构.扫描电镜断面和AFM表明:膜表面形成了深度约为1.8μm的单层孔结构.通过控制溶液浓度、环境温度和湿度等因素来控制膜的表面形貌及其所成蜂窝状孔的大小.最佳的成膜条件为溶剂CH2Cl2,湿度75%RH,温度34℃,浓度3 wt%.讨论了蜂窝状多孔膜的形成机理.     

(肝素/壳寡糖/Pluronic(R))静电组装多层膜的构建

以壳寡糖/Pluronic(R)聚合物纳米聚集体(COPNs)、肝素为组装基元构建仿(肝素/壳聚糖)多层膜,验证多层膜负载疏水药物的可行性.Pluronic(R)P123与1,3-丙烷磺内酯反应合成末端磺酸化的Pluronic(R)聚合物,其与Pluronic(R)F127在水溶液中自组装形成表面带负电荷的混合胶束.利用壳寡糖与混合胶束的静电作用,获得COPNs,粒径与表面电位分析、透射电镜表征COPNs为直径(27.61±2.46) nm、表面zeta电位(6.12±1.82)mV、稳定的球形结构.石英晶体微天平(QCM)跟踪检测证明COPNs与肝素可在基材表面实现交替沉积;原子力显微镜(AFM)表征多层膜表面拓扑形貌,证明COPNs在表面沉积过程中稳定.将疏水的荧光探针芘载入COPNs参与多层膜的构建,荧光光谱实验结果表明多层膜可成功包载芘,且多层膜内芘的载入量与组装层数相关.以葛根素为模型药物,载药量测定与体外释药实验结果表明多层膜具有包载和缓释疏水药物的能力.     

SEBS/PMMA共混物膜的表面和本体形态结构

用扫描电镜(SEM)和原子力显微镜(AFM)研究了两种不同共混比的聚(苯乙烯-嵌-乙烯/丁烯-嵌-苯乙烯)(SEBS)和聚甲基丙烯酸甲酯(PMMA)共混膜的表面形态和相分离行为。结果表明,当膜厚为25μm时,两种共混膜表面均未见明显的相分离形貌,而在膜体相中可见宏观相分离结构。当膜厚为120 nm时,质量比为30/70的共混膜表面可见明显的“海-岛”状宏观相分离;而质量比为60/40的共混膜表面未见明显宏观相分离,仅有少量PMMA小颗粒嵌于SEBS基体中,形成SEBS趋于包裹PMMA微区的稳定“笼型”结构,其尺度属于介观相分离。退火后,两样品膜的体相形态与表面形貌趋于一致,均呈现宏观的相分离结构。     

铝合金表面原位自组装超疏水膜层的制备及耐蚀性能

采用阳极氧化法在铝合金表面原位构造粗糙结构, 经表面自组装硅氧烷后得到超疏水自清洁表面, 与水滴的接触角最大可达157.5°±2.0°, 接触角滞后小于3°. 通过傅立叶变换红外(FT-IR)光谱分析仪、场发射扫描电子显微镜(FE-SEM)、能谱仪(EDS)、原子力显微镜(AFM)和接触角测试对阳极氧化电流密度、硅氧烷溶液中水的含量和自组装时间等参数进行了分析, 并得到制备超疏水自清洁表面的最优工艺参数. FE-SEM及AFM的测试结果表明, 由自组装硅氧烷膜层的无序性形成的纳米结构和阳极氧化构造的微米级粗糙结构与硅氧烷膜层的低表面能的协同作用构成了稳定的超疏水表面. 电化学测试(动电位极化)的结果表明, 原位自组装超疏水膜层极大地提高了铝合金的耐蚀性.     

硫醇在Au(111)上SA单分子层膜研究

采用自组装(SA)技术制备了正丁硫醇、正十二硫醇及两种硫醇等摩尔混合物的SA单分子层膜。用椭圆偏振仪、接触角测量仪、扫描电子显微镜(SEM)、X-射线光电子能谱仪(XPS)和原子力显微镜(AFM)对3种SA膜进行了分析表征。结果表明SA膜是取向有序的纳米级超薄膜,分子链长、基片表面的晶格取向和表面的洁净度等对膜有一定的影响,长链分子膜表面是疏水性的。用椭圆偏光、XPS和AFM3种方法测定3种单分子层膜的厚度分别为0.59～0.67nm,1.60～1.69nm,1.23～1.32nm。AFM图象进一步证实了混合单分子层膜是由两种不同厚度的微畴组成。     

辛基三乙氧基硅烷/十八烷基三氯硅烷均相混合自组装单分子膜的表征及其形成机制

使用接触角、原子力显微镜(AFM)、静电力显微镜(EFM)和傅里叶变换红外(FTIR)光谱对辛基三乙氧基硅烷(C8TES)/十八烷基三氯硅烷(OTS)均相混合自组装单分子膜(SAM)及其形成过程中样品表面的润湿性、表面形貌、表面电势和膜内分子的有序度进行了表征,对采用分步法利用C8TES分子空间位阻制备C8TES/OTS均相混合SAM的反应机制进行了研究.结果表明,C8TES/OTS均相混合SAM表面接触角为105°,样品表面平整、光滑;对样品表面电势进行分析后发现,混合SAM表面电势分布均匀,电势频率分布为典型的正态分布;在均相混合SAM的形成过程中,样品表面电势的分布始终十分均匀,电势频率分布均为典型的正态分布;C8TES/OTS均相混合SAM是一种具有上下两层分子排列密度不同的膜结构的单分子膜,其内部结构至少在500 nm×500 nm到20μm×20μm尺度上是高度均匀一致的,膜内没有明显的特征结构,具有典型的均相混合SAM特征.     

液相法制备具有双尺寸粗糙度的超疏水铜表面

基于简单的液相法,以硫代硫酸钠和氯化铜为原料在铜片表面上构筑了具有微/纳米双尺寸粗糙度的硫化铜膜.用X射线衍射(XRD)仪、扫描电镜(SEM)、能量色散X射线(EDX)光谱仪及光学视频接触角仪对处理前后的铜表面进行了表征和分析.处理后的超亲水铜表面经硬脂酸修饰后具有超疏水效应,静态接触角高达161°,5μL水滴滚动角低至2.5°左右.超疏水性能归因于表面具有双尺寸粗糙度和低表面能的硬脂酸.该方法简单,无需复杂制备过程和苛刻设备,所得超疏水铜表面具有优异的不粘附性、长时间储存的稳定性和一定的耐摩擦性能.     

光学活性偶氮苯自组装膜的制备及其蛋白吸附行为

研究了在紫外光作用下, 牛血清白蛋白(BSA)在偶氮苯自组装膜上光控可逆的吸附行为. 首先合成羧基偶氮苯衍生物, 并在金膜表面制备偶氮苯自组装膜, 采用紫外吸收光谱(UV)、原子力显微镜(AFM)观察偶氮苯衍生物的光学顺反异构现象以及偶氮苯自组装膜表面形貌的变化. 同时利用等离子体表面谐振仪(SPR)考察偶氮苯光学异构对牛血清白蛋白(BSA)在自组装膜表面上的吸附行为的影响. 结果表明, BSA在偶氮苯自组装膜表面的吸附作用主要来自于BSA分子与自组装膜之间的静电作用及亲疏水作用. 在紫外光作用下, 偶氮苯自组装膜可以实现光控可逆的牛血清白蛋白分子吸附行为.     

多环芳二酐型聚酯亚胺膜的透气性能

多环芳二酐型聚酯亚胺膜的透气性能李悦生，丁孟贤，徐纪平（浙江大学高分子科学与工程研究所，杭州，３１００２７）（中国科学院长春应用化学研究所）关键词聚醚酰亚胺，聚酯酰亚胺，膜，透气性通常的聚酰亚胺加工性能较差，在芳环二酐的苯环间引入醚键等柔性基团后，其...     

Determination and study on residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil

A QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for the determination of benazolin-ethyl and quizalofop-p-ethyl in rape and soil by high-performance liquid chromatography-tandem mass spectrometry has been developed in this study. The residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil were determined with the developed method. The half-lives of benazolin-ethyl in rape straw and soil were 3.7–5.1 days and 14.3–26.3 days, respectively. The half-lives of quizalofop-p-ethyl in rape straw and soil were 5.0-6.1 days and 0.3–9.7 days, respectively. The residue of benazolin-ethyl and quizalofop-p-ethyl in rapeseed and soil were below the detection limit (i.e., 0.5?mg?kg^?1, the maximum residue level of European Union for quizalofop-p-ethyl).     

微量元素与疾病诊断治疗的研究现状及展望

对国内外微量元素与疾病的关系及其诊断治疗的研究现状及研究动向进行了综述，包括：微量元素与地方病、癌肿、心血管病、糖尿病、眼病、神经系统病等。参考文献72篇。     

Ti-V基储氢合金及其氢化物的物相结构与组分优化设计

Ti-V基储氢合金在室温、常压下即可表现出良好的储氢特性,且质量储氢容量明显高于传统AB₅型储氢合金,从而在氢气的精制和回收、运输和储存及热泵等方面有较早的应用。 此外,在混合气体分离、核反应堆中处理氢的同位素、镍氢电池及燃料电池负极材料等方面也得到了广泛的研究与关注。 基于目前Ti-V基储氢合金的研究现状,概述了该类合金的优势、限制性因素(包括成因)及改性手段。 此外,为了进一步理解Ti-V基合金储氢机理、构建合金组分与储氢特性之间的对应关系,本工作重点围绕Ti-V基储氢合金及其氢化物的结构、组分优化设计展开综述,并对其未来研究方向做出展望。     

钒与糖代谢及糖尿病

微量元素钒作为生物体内必需元素，经证实有很重要的生理学功能，与机体糖代谢有十分密切的关系，且能降低糖尿病动物模型的高血糖，极有可能被开发为治疗糖尿病的药物。     

Ferrocene and ferrocenium modified clays and their styrene and EVA composites

In this work, ferrocene- and ferrocenium-containing salts were employed to modify montmorillonite. X-ray measurements show an increase in the interlayer spacing upon clay modification, which means that the larger and more organophilic cations were inserted into the gallery space of montmorillonite. Attempts to prepare nanocomposites of polystyrene and ethylene vinyl acetate copolymers lead to immiscible systems; the morphology of these systems was elucidated with TEM, XRD and cone calorimetry. The thermal stability of the composites is greater than that of the virgin polymer.     

Synthesis and Optical and Redox Properties of Symmetric and Asymmetric BODIPYs

Herein, we present the synthetic route and the photophysical, electrochemical as well as laser properties of novel red‐emitting boron‐dipyrromethenes (BODIPYs) bearing arylethyne moieties. Such functionality is added along the main axis of the chromophore leading to single‐ and double‐substituted derivatives. The relationship between the dye structure and the lasing properties is studied in detail with the help of the photophysical and electrochemical properties as well as quantum mechanical simulations. The asymmetric substitution of the parent dye induces inhomogeneities in the charge distribution, which leads to an overall loss of the fluorescence capacity, mainly in polar media. Such non‐radiative deactivation processes can be softened by decreasing the electron‐donor ability of the substituent or even avoided by symmetrical substitution. Thus, grafting of the arylethyne moieties at the longitudinal axis of the indacene core results in an effective strategy to develop red‐edge BODIPYs with highly efficient and photostable laser emission.     

Synthesis of Tyrosol and Hydroxytyrosol Glycofuranosides and Their Biochemical and Biological Activities in Cell-Free and Cellular Assays

Tyrosol (T) and hydroxytyrosol (HOT) and their glycosides are promising candidates for applications in functional food products or in complementary therapy. A series of phenylethanoid glycofuranosides (PEGFs) were synthesized to compare some of their biochemical and biological activities with T and HOT. The optimization of glycosylation promoted by environmentally benign basic zinc carbonate was performed to prepare HOT α-L-arabino-, β-D-apio-, and β-D-ribofuranosides. T and HOT β-D-fructofuranosides, prepared by enzymatic transfructosylation of T and HOT, were also included in the comparative study. The antioxidant capacity and DNA-protective potential of T, HOT, and PEGFs on plasmid DNA were determined using cell-free assays. The DNA-damaging potential of the studied compounds for human hepatoma HepG2 cells and their DNA-protective potential on HepG2 cells against hydrogen peroxide were evaluated using the comet assay. Experiments revealed a spectrum of different activities of the studied compounds. HOT and HOT β-D-fructofuranoside appear to be the best-performing scavengers and protectants of plasmid DNA and HepG2 cells. T and T β-D-fructofuranoside display almost zero or low scavenging/antioxidant activity and protective effects on plasmid DNA or HepG2 cells. The results imply that especially HOT β-D-fructofuranoside and β-D-apiofuranoside could be considered as prospective molecules for the subsequent design of supplements with potential in food and health protection.     

Conformations and steric and stacking interactions of trisubstituted ureas and thioureas with alkyl and phenyl groups

The monomeric ν(N—H) vibrations of various trisubstituted ureas of the R₂UPh type and -thioureas of the R₂TUPh type have been studied. The trans—out isomerism in the former and the trans—out—cis isomerism in the latter are discussed from the point of view of steric effect. The monomeric ν(N—H) vibrations of RPhUPh and RPhTUPh are also examined. The single band appearing in the spectrum of both ureas is characteristic of the cis form; this suggests the existence of phenyl—phenyl interaction (the stacking interaction proposed by Galabov et al. [10]). Behavior of ν(N—H) vibrations at several concentrations is shown to be clearly different in the three forms (trans, out and cis). The presence of the cis form is confirmed by solvent effect experiments.