双亲性无规共聚物自组装胶束结构及其乳化性能

以不同交联度、溶胀程度的双亲无规共聚物聚[(苯乙烯-alt-马来酸酐)-co-(7-对乙烯基苄氧基-4-甲基香豆素-alt-马来酸酐)](PSMVM)胶束作为聚合物胶束乳化剂稳定甲苯/水体系, 重点研究光交联度对胶束结构及其乳化性能的影响. 结果表明, 胶束交联度、溶胀度和荷电性对胶束结构及乳化性能有较大影响.     

双亲性无规共聚物P（VM-co-AMPS）的自组装及其性能

以2-丙烯酰胺基-2-甲基丙磺酸（AMPS）和苯乙烯类光敏单体7-（4-乙烯基苄氧基）-4-甲基香豆素（VM）为共聚单体,采用自由基聚合法制备了光敏性双亲共聚物P（VM-co-AMPS）。P（VM-co-AMPS）在溶剂水中自组装胶束化,用原子力显微镜（AFM）表征了自组装胶体粒子的形态、粒径及其分布。紫外光照使胶体粒子中香豆素基元发生光二聚反应,用紫外-可见光分光光度计（UV-Vis）跟踪其光二聚交联过程,用光学显微镜考察了胶体粒子的乳化性能。结果表明：胶体粒子具有较好的紫外吸收性能和较好的乳化性能。该胶束制备工艺简单,条件温和,避免了溶剂的使用。     

聚合物-纳米金在油水界面的自组装及有序结构的构筑

聚合物-纳米金复合物既具有金纳米粒子的光、电及催化性能,又具有聚合物的可加工性及对外界的刺激响应性,因此已成为高分子科学及材料科学研究的热点。本文主要介绍了我们实验室在聚合物-纳米金在油水界面的自组装及有序结构的构筑研究方面的相关工作:(1)利用界面聚合的方法制备侧链接枝亲水性金纳米粒子的聚苯乙烯及杂化聚合物在水溶液中的自组装;(2)亲水性金纳米粒子及疏水性聚合物(或疏水性磁性纳米粒子)在油水界面的自组装研究;(3)利用金纳米粒子为交联点制备具有温度响应性聚合物微凝胶的研究。     

光敏感双亲性梳状SMA聚合物的合成及其胶束化

以含香豆素型苯乙烯类光敏单体(coumarin-containing styrene monomer, CS)与苯乙烯(St)、马来酸酐(MA)为反应单体, 以偶氮二异丁腈(AIBN)为引发剂制备了光敏感三元苯乙烯-马来酸酐共聚物(SMA)双亲交替聚合物P(St/CS-alt-MA), 再利用羧酸酐基元与正辛胺的室温胺解反应获得光敏感双亲性梳状聚合物P(St/CS-alt-MAA8). 用傅立叶变换红外光谱(FTIR)、凝胶渗透色谱(GPC)、1H核磁共振(1H-NMR)等对该双亲梳状聚合物进行结构表征. 通过香豆素基元的光二聚作用, 使梳状聚合物溶解在DMSO中进行光照预交联; 非交联与预交联聚合物分别在选择性溶剂中自组装形成胶束; 利用羧酸基元与NaOH的离子化作用改变聚合物胶束的亲疏水性质. 动态激光光散射(DLS)与芘荧光探针实验表明预交联聚合物胶束较非交联胶束粒径大, 负载芘的能力强; 离子化作用使聚合物胶束解离重组成粒径更小的胶束, 但预交联胶束较非交联胶束小, 离子化后胶束疏水微区更加紧密, 负载芘的能力也增大.     

基于有机硅组分交联稳定纳米胶束的研究进展

综述了基于有机硅组分交联稳定纳米胶束的研究进展,对制备方法和交联区域的选择以及应用领域的研究进行了较为详细的阐述.指出将有机硅引入双亲性高分子链中,利用有机硅部分的溶胶-凝胶转变对双亲高分子胶束的具体区域进行交联,能够使其胶束结构固定下来并形成杂化材料,在提高高分子胶束稳定性的同时又赋予其无机材料的刚性、低生理毒性、便于纯化等优点,为双亲性高分子的制备以及药物的运载、控制释放等带来极大的帮助.     

双亲性共聚物P(St/VBT-co-MA)自组装胶束的制备及其乳化性能

以1-(4-乙烯基苄基)胸腺嘧啶(VBT)、苯乙烯(St)、马来酸酐(MA)为共聚单体,采用自由基聚合法制备了双亲性共聚物P(St/VBT-co-MA)(PSVM)。PSVM在选择性溶剂N,N-二甲基甲酰胺(DMF)的水溶液中进行自组装可形成胶束。利用透射电镜(TEM)和动态激光光散射(DLS)表征了自组装胶束的形态和粒径分布。以该胶束作为颗粒乳化剂稳定白油-水体系形成乳液,研究了PSVM胶束浓度、pH、盐浓度等对其乳化性能的影响,并用光学显微镜(OM)表征了其乳液形态。结果表明:通过自由基聚合的方法成功合成了双亲共聚物PSVM,其自组装形成粒径分布均匀的球形胶束;该胶束具有优异的乳化效率,其乳液长期稳定且具有pH响应性及强耐盐性,静置四个月后,乳液仍具有良好的乳化效果且乳液层高度基本不变。     

光敏共聚物P(St/VM-co-MA)自组装胶体粒子及其性能

以苯乙烯类光敏单体7-(4-乙烯基苄氧基)-4-甲基香豆素(VM)、苯乙烯(St)、马来酸酐(MA)为共聚单体,采用自由基聚合法制备了光敏性双亲共聚物P(St/VM-co-MA).在选择性溶剂(N,N-二甲基甲酰胺(DMF)/H2O)中对P(St/VM-co-MA)进行自组装,用透射电镜(TEM)和动态激光光散射(DLS)表征了自组装胶体粒子的形态、粒径大小及其分布.利用紫外光照使胶体粒子中香豆素基元发生光二聚反应,形成交联胶体粒子,并用紫外-可见光分光光度计(UV-Vis)跟踪其交联过程.用DLS研究了交联和未经交联胶体粒子的粒径和结构稳定性,用激光扫描共聚焦显微镜(LSCM)和光学显微镜考察了胶体粒子的乳化、包覆性能.结果表明:交联和未经交联胶体粒子均具有乳化性,且在乳化过程中可实现对油溶性染料的包覆.胶体粒子交联后,粒径有所减小,结构稳定性、乳化性能、包覆性能均有所提高.     

无规共聚物自组装球形胶束表面亲水性的耗散粒子动力学模拟

建立了含不同亲疏水粒子比的双亲性无规共聚物粗粒化模型. 采用耗散粒子动力学方法模拟了两亲性无规共聚物选择性溶剂自组装球形胶束表面的亲水性能. 模拟结果表明, 无规共聚物在选择性溶剂中自组装得到实心球形胶束, 球形胶束表面的亲水性与聚合物链亲水粒子含量、溶剂的选择性有关. 随着聚合物链所含亲水粒子增加, 球形胶束表面的亲水性增强. 球形胶束表面的亲水性随着疏水粒子与溶剂粒子间的排斥参数增大而增强, 模拟结果与实验结论一致. 该模拟方法给出的胶束微结构信息可以为双亲无规共聚物分子设计及自组装双亲胶束制备提供一定的理论指导.     

基于含苯硼酸聚合物的双响应性胶束

分别合成了苯硼酸修饰的嵌段聚合物聚乙二醇-b-聚(天冬氨酸-co-天冬酰氨基苯硼酸)[PEG-b-P(Asp-co-AspPBA)]和含有二硫键及多元二醇的小分子3,3'-二硫代二[1,2(S)-丙二醇](DTBPD). 以DTBPD为小分子交联剂, 通过二醇单元与苯硼酸之间的共价酯化作用, 诱导PEG-b-P(Asp-co-AspPBA)自组装形成以苯硼酸环酯为核、 PEG为壳的交联胶束. 利用核磁共振氢谱和激光光散射对胶束的结构进行了表征, 并分别测定了该胶束在葡萄糖和氧化-还原试剂二硫苏糖醇(DTT)刺激下的响应行为. 结果表明, DTBPD可与聚合物链上的苯硼酸形成苯硼酸环酯, 通过交联作用诱导聚合物形成胶束. 交联度不同时, 胶束对于外界刺激(葡萄糖和DTT的响应行为也不同: 随着DTT和葡萄糖浓度的增加, 交联度高的胶束只发生响应性溶胀, 交联度低的胶束则先溶胀, 之后溶胀程度较大的部分胶束则发生解体, 导致胶束的平均粒径减小.     

Papain/HA-Phe自组装复合纳米粒子及乳化性能

用L-苯丙氨酸乙酯(L-Phe)改性透明质酸(HA)双亲性生物大分子(HA-Phe)负载生物活性分子木瓜蛋白酶(papain),HA-Phe和Papain通过静电、氢键和疏水相互作用自组装形成生物基Papain/HA-Phe复合纳米粒子.用动态光散射(DLS)和透射电镜(TEM)对复合纳米粒子的尺寸和形貌进行表征.结果显示,形成的复合纳米粒子为球形结构,粒径约308 nm.以此复合纳米粒子为颗粒乳化剂稳定白油,形成水包油型Pickering乳液.乳液的扫描电镜(SEM)显示,复合纳米粒子吸附在油水界面,形成复合纳米粒子的吸附层以稳定乳液.详细研究了pH和盐浓度对复合纳米粒子性质和复合纳米粒子乳化性能的影响.结果表明,随着pH增加,复合纳米粒子在油滴表面的吸附数目减少,乳化性能降低;随着盐浓度增加,复合纳米粒子的形变能力增强,乳化性能提高.进一步研究了乳液中木瓜蛋白酶的活性及美白效果.研究表明,制备的乳液保留了一定的活性,且具有一定的美白效果.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

解决能源问题的新途径——光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。     

黄酮化合物的合成研究进展

黄酮化合物是一类具有多种生物活性的天然产物,其经典的合成方法主要为查耳酮路线和β-丙二酮路线.近年来出现了许多新技术、新方法.本文介绍了2'-羟基查尔酮的氧化关环法、黄烷酮氧化法、改进的Baker-Venkataraman法及其他合成黄酮化合物的方法.