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.     

两亲性树状接枝己内酯共聚物的合成与表征

通过树状接枝聚己内酯的侧羟基及端羟基与氯甲酰化的聚乙二醇进行接枝反应,得到带有亲水性聚乙二醇链段的新型两亲性树状接枝共聚物.1H-NMR分析显示,接枝率为50%左右.GPC分析结果表明,共聚物分子量呈较窄的单峰分布,分子量与接枝前相比明显增高.两亲性共聚物能直接分散在水中形成胶束溶液.以芘为荧光探针的测试结果表明其临界胶束浓度有降低.动态光散射测得胶束平均粒径在16至31 nm之间,粒径分散指数适中,PDI在0.25至0.39之间.TEM显示胶束粒子为不规整球形,由更小的粒径为几个纳米的微粒聚集而成,这些微粒的大小刚好与单个大分子的尺寸相匹配.因此,两亲性树状接枝聚己内酯在水相中存在单分子胶束与多分子组装胶束的平衡.得益于支化聚合物结构中的纳米空腔,两亲性树状接枝聚合物胶束对紫杉醇具有优良的包载能力.     

多重敏感性双亲共聚物P(DM-co-AA-co-CA)的自组装及性能

以甲基丙烯酸二甲胺乙酯（DM）、丙烯酸（AA）和香豆素丙烯酸酯化物（CA）为共聚单体,通过普通自由基溶液聚合合成了多重敏感性双亲共聚物P(DM-co-AA-co-CA),用傅里叶变换红外（FTIR）、核磁共振（1H-NMR）、凝胶渗透色谱（GPC）和差示扫描量热仪（DSC）对聚合物结构进行表征．在选择性溶剂四氢呋喃/水中对所得多重敏感性双亲共聚物P(DM-co-AA-co-CA)进行自组装,结果表明,调节组装环境的pH值可以得到荷正电或负电的两性胶束粒子．用紫外可见光分光光度计、荧光分光光度计、Zeta电位测定仪、DLS和TEM研究了多重敏感性双亲共聚物的溶液自组装及其组装体的性能,结果显示,调节pH值可以有效的控制胶束的粒径大小及其LCST,并在pH为8.54时胶束溶液的紫外吸收和荧光发射强度达到最大值,且该胶束溶液在酸碱性较强时具有良好的乳化性能．     

荧光标记法研究水含量对两亲性超支化共聚物组装体形貌的影响

合成了丹磺酰基(DNS)标记的两亲性超支化共聚物,DNS-PEHO-star-PEO.用荧光标记法研究了DNS-PEHO-star-PEO在四氢呋喃(THF)/H2O混合溶剂中不同水含量下的自组装行为.结果表明,水含量对DNS-PEHO-star-PEO形成的组装体形貌影响显著.含水含量小于20 vol%时,DNS-PEHO-star-PEO组装成纳米尺寸的球形胶束;随着水含量增加到?75 vol%时,DNS-PEHO-star-PEO组装成"多胶束聚集体";纯水中(水量100 vol%),DNS-PEHO-star-PEO形成微米尺寸的聚合物大囊泡.利用不同形貌聚集体中DNS的荧光发射谱不同的特性,我们绘制了不同聚集体中DNS的荧光最大发射峰波长与水含量的关系图,直观地反映了水含量对DNS-PEHO-star-PEO组装体形貌的影响.     

烷基链封端的两亲性超支化聚缩水甘油的合成及自组装

通过阳离子开环聚合和端基改性的方法合成了以亲水性超支化聚缩水甘油为核和疏水性十六烷基链为臂的两亲性超支化多臂共聚物(HPG-g-C16),研究了十六烷基疏水臂的接枝率对该两亲性聚合物在溶剂中自组装行为的影响.结果表明:接枝率45%以上的HPG-g-C16在四氢呋喃(THF)中以单分子胶束的形式存在,在THF与水的混合溶剂中会自组装形成尺寸为1～10 μm的巨型囊泡,而接枝率为15% 的HPG-g-C16能直接在水中自组装形成球形胶束.     

共溶剂性质对双亲性无规共聚物P(St-co-DM)胶束化行为及其性能的影响

以苯乙烯(St)和甲基丙烯酸二甲氨乙酯(DMAEMA)为共聚单体, 通过普通自由基溶液聚合合成了双亲性无规共聚物P(St-co-DM). 用傅里叶变换红外(FTIR)光谱、核磁共振氢谱(¹H NMR)、凝胶渗透色谱(GPC)和差示扫描量热(DSC)仪对聚合物结构进行表征. 研究了共溶剂的性质对P(St-co-DM)自组装胶束结构及其乳化性能的影响. 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. 通过测量胶束在甲苯/水界面的接触角表征胶束表面性能. 结果表明: P(St-co-DM)以四氢呋喃(THF)为共溶剂自组装时, 胶束的临界聚集水含量较大, 胶束表面亲水性较强, 流体力学半径较大; 用二氧六环或THF为共溶剂, 水为选择性溶剂, P(St-co-DM)自组装可以得到外层松散、内层比较密实的球状胶束, 用N,N-二甲基甲酰胺(DMF)为共溶剂时, 胶束整体呈现比较密实的球状胶束; 分别用DMF、二氧六环和THF为共溶剂制备的胶束, 其接触角均值都小于90°, 可形成O/W型(水包油型)乳液. 乳化实验结果表明, 以二氧六环和THF为共溶剂制备的胶束作为颗粒乳化剂制备的乳液性能较好.     

两亲性聚氨基酸三嵌段共聚物构筑pH/溶剂可控多级纳米结构

通过开环聚合(ROP)和原子转移自由基聚合(ATRP)合成了一种pH响应性三嵌段共聚物聚乙二醇-b-聚赖氨酸-b-聚苯乙烯(PEG-b-PLL-b-PS),在水-有机溶剂混合溶液中进行组装,并采用透射电子显微镜(TEM)、原子力显微镜(AFM)和衰减全反射红外光谱法(ATR-IR)表征.该三嵌段共聚物在四氢呋喃(THF)与水的混合溶剂(V∶V=1∶1)中可组装成疏水性聚苯乙烯为核、亲水性聚赖氨酸和聚乙二醇分别为内壳和外壳的球状胶束.采用TEM和AFM发现该球状胶束在四氢呋喃(THF)水溶液中退火7 d后可进一步转变为纤维状结构.进一步除去THF后,可恢复至粒径略小的冻结球状胶束.另外,球状胶束的粒径随着pH的增加而增加,当pH为13时,聚赖氨酸的二级结构由无规卷曲构象过渡到α-螺旋构象,聚集体由球形结构过渡到空心囊泡.溶液经透析后可使囊泡恢复至球状胶束.     

聚苯乙烯-丙烯酸嵌段共聚物在Ca~(2 )或乙二胺存在下的自组装行为

近 1 0年来 ,人们对于具有纳米尺度聚合物自组装结构的研究日益增多 .其中 ,嵌段共聚物在选择性溶剂中的胶束行为的研究非常引人瞩目 [1～ 3] .其表现出诸多常规尺寸所不具备的特殊性能 ,使得纳米胶束不仅在理论上有研究价值 ,而且在材料化学、生物医学和环境科学等领域都具有广阔的应用前景 .Ma等[4 ] 对聚丙烯酸和聚苯乙烯接枝共聚物的研究发现聚合物接枝率和聚合物浓度以及溶液离子强度对胶束结构有影响 ;Zhang等 [1,5] 对不同嵌段比例的苯乙烯 -丙烯酸嵌段共聚物的自组装行为的研究 ,发现不同嵌段比例所对应的纳米结构不同 ;而胶束表面…     

两亲性嵌段共聚物在选择性溶液中吸附行为的理论研究

通过自洽场理论方法研究了在圆形孔道以及水平基板受限情况下两亲性嵌段共聚物在选择性稀溶液中的自组装形态,考察受限管壁、管壁极性以及基板间距对聚合物吸附行为的影响.中性圆形孔道中,随着溶剂对疏水链的排斥作用增强和对亲水段的亲水作用增大,聚合物以蘑菇形状吸附于管壁上.疏水链、亲水链与溶剂的相互作用差异性越大,越容易产生吸附现象.在亲水性孔道中,吸附现象有所缓解,随着管壁对亲水段吸引作用的增强,聚合物在管壁附近形成规则排列的球状胶束.当疏水链、亲水链与溶剂的相互作用相差非常大时,即使管壁对亲水嵌段的吸附作用增强,也不能消除聚合物吸附现象.在中性水平基板中,随着基板间距的增加,两亲性嵌段共聚物在基板附近依次出现球状胶束-蘑菇状胶束-单层球状胶束-高分子刷-双层球状胶束-对称高分子刷的自组装形态.     

乙基纤维素接枝聚N-异丙基丙烯酰胺共聚物合成及其胶束化研究

通过单电子转移“活性”/可控自由基聚合的方法制备了具有双亲性及温度响应性的乙基纤维素接枝聚N-异丙基丙烯酰胺共聚物(EC-g-PNIPAm). 通过凝胶渗透色谱、核磁氢谱和红外光谱等对合成的接枝共聚物进行了表征. 我们发现此反应在混合溶剂四氢呋喃/甲醇的混合溶剂中是活性可控的. EC-g-PNIPAm接枝共聚物能够在选择性溶剂水中发生自组装现象, 形成稳定的以乙基纤维素为核、聚N-异丙基丙烯酰胺为壳的球形胶束. 并且随着温度的升高, 支链聚N-异丙基丙烯酰胺发生塌缩使得球形胶束发生收缩.     

Furyl- and thienyl-silatranes and germatranes

We review our research on the synthesis and study of the physical and biological properties of furyl- and thienylgermatranes and -silatranes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 725–732, June, 1992.     

Review and patents and literature

The use of the insect cell/baculovirus expression system for producing recombinant proteins of bacterial, plant, insect, and mammalian origin has become widespread. The popularity of this eukaryotic expression system is due to many factors, including (1) potentially high protein expression levels, (2) ease and speed of genetic engineering, (3) ability to accommodate large DNA inserts, (4) protein processing similar to higher eukaryotic cells (e.g., mammalian cells), and (5) ease of insect cell growth (e.g., suspension growth). The following review of the literature discusses two engineering aspects of recombinant protein synthesis by insect cell cultures: bioreactor scale-up and insect cell line selection. Following this review patent abstracts and additional literature pertaining to expression of recombinant proteins in insect cell culture are listed.     

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...     

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。     

Preparation and photolysis of poly-p-ethylacrylophenone and poly-p-chloroacrylophenone and their copolymers with styrene and methyl methacrylate

Poly-p-ethylacrylophenone (PPEtAP) and poly-p-chloroacrylophenone (PPClAP) and their copolymers with styrene (PEtAP/S) and (PClAP/S) and with methyl methacrylate (PEtAP/MMA) and (PClAP/MMA) were prepared. Quantum yields of main-chain scissions at 366 nm at room temperature in benzene solution are of the same order as those of the unsubstituted polyacrylophenone and its copolymers. Substitution with chlorine and ethyl group in the para position compared to the unsubstituted polyacrylophenone and its copolymers leads to an increase of the lifetime for the n–π^* excited triplet state, as is evident from the measured quenching constants of photolysis. The low-temperature emission spectra of the copolymers are similar to the spectra of the model compounds in a polymer film. For the homopolymer, however, the character of the emission spectrum changes considerably.     

Concentrations and distributions of trace and minor elements in Chinese and Canadian coals and ashes

A total of 35 trace and minor elements including some of environmental significance were determined in each of a selection of 15 Chinese and 6 Canadian thermal coals and their ashes by using the SLOWPOKE-2 nuclear reactor facility of the University of Toronto. The concentrations and distributions of these constituents among the coals and their combustion products (viz. ash and volatile matter) are presented together with an interpretation of their significance in relation to the large scale combustion of these coals as thermal fuels in industrialized countries such as China and Canada. The detailed results showed wide variations in trace impurity concentrations (up to a factor of 100 and more) among the coals studied with few large differences between those of Chinese and Canadian origin except that the rare earths, Sc, Th, U, I, and Se were much higher in the former, other halogens, As and Na were lower. Values for elemental enrichment factors (EF) relative to normal crustal abundances indicated that only As(EF=13), Br(5.7), I(16), S(230), Sb(11) and Se(320) were appreciably enriched in coal. During static ashing at 750°C most of the halogens, S and Se were volatilized whereas most other inorganic constituents were highly retained and concentrated in the ash by factors of 6 to 11.