二苯基硅烷与二烯烃及炔烃的加成聚合

1.在氯鉑酸催化下,二苯基硅烷与二甲基二丙烯基硅烷聚合后,生成粘稠状的聚合物;而与乙炔、苯乙炔、二苯基二丙烯基硅烷、环戊二烯等以等克分子此聚合后,生成的聚合物都是在40—70℃軟化的脆性固体。对二苯基硅烷与环戊二烯之間的聚合进行了討論。 2.这些聚合物的热稳定性都相当高,并且以聚二苯基硅乙烷为最稳定。 3.合成了二氫化聚硅乙烷及二氫化聚硅丙烷。将它们在六氫吡啶中进行水解和縮聚后,軟化溫度都有一定程度的提高。     

发散法合成乙烯基封端的超支化聚碳硅烷

超支化聚碳硅烷具有耐高温、耐腐蚀、耐磨、良好流动性和溶解性,可望用于催化剂载体、陶瓷前驱体和发光材料等诸多领域.超支化聚碳硅烷合成方法有收敛法和发散法,其中收敛法通常仅用于合成较低代数的超支化聚碳硅烷.本文通过发散法,以廉价易得的甲基三氯硅烷与烯丙基溴格氏试剂反应,合成了超支化聚碳硅烷,并对所得产物进行了FT-IR、NMR、TGA和DSC等表征.     

有机硅树枝状化合物-硅胶键合固定相的制备及其在色谱中的应用

采用发散式合成法合成了末端为烯丙基的第一代（G1）与第二代（G2）硅碳烷树枝状大分子,通过硅氢加成反应使其进一步与球形硅胶反应,将硅碳烷树枝状大分子的两代分子分别键合于硅胶上,制备了有机硅树枝状大分子．硅胶键合固定相,对其进行了物理化学性能的表征及色谱性能的初步评价．G2-硅胶键合固定相的分离性能优于G1-硅胶键合固定相,对醇类,烷基取代苯类,N-取代苯类,甲基丙烯酸酯类,邻苯二甲酸酯类等具有良好的分离效果．     

樟脑型烯丙基硅烷的合成及在Sakurai反应中的应用

为发展新的手性烷基化试剂,从天然D-(+)-樟脑出发经过4步76%总产率合成了新型烯丙基硅烷2.烯丙基硅烷2和苯丙醛在路易斯酸作用下以84%的产率和20%的ee值生成高烯丙醇6.     

室温常压溶液法合成烯丙基功能化的正六边形硅纳米晶体

室温常压下,以氢化铝锂为还原剂在溶液中还原烯丙基三氯硅烷和四氯化硅体系,制备了烯丙基功能基团修饰的正六边形硅单晶.采用透射电子显微镜（Transmission Electron Microscopy,TEM）和傅里叶变换红外光谱（Fourier Transform Infrared,FTIR）对产物进行表征.研究了硅晶体的尺寸分布、晶面取向及表面组成,推测了可能的反应机理.结果表明,三氯硅烷与四氯化硅浓度比为1：3时经过还原可生成尺寸为20~50nm,表面有烯丙基基团的（111）晶向的单晶硅.     

新型有机硅化环氧树脂的合成与表征

以4,4′-二烯丙基双酚A(DABPA) 和环氧氯丙烷(ECH) 为原料经两步法合成了一种含烯丙基双键的环氧树脂二烯丙基双酚A二缩水甘油醚(DADGEBA),而后DADGEBA和三甲氧基硅烷经氯铂酸催化的硅氢加成反应制得了有机硅化环氧树脂(SEP)。采用红外光谱(FT-IR) 和核磁共振(¹³C-NMR、²⁹Si-NMR) 对所得树脂进行了结构表征,测定了环氧树脂的黏度、分子量和环氧值。结果表明,所合成树脂为含有三甲氧硅基的环 氧树脂,室温下可流动,溶于大部分常用溶剂,具有良好的使用性能。     

1,3-二羰基化合物烯丙基化构建季碳中心的反应研究

许多天然产物和药物活性分子往往因为季碳中心的存在而表现出更好的理化性质和生物活性.文章首先以氢化钠作碱,利用酮和酯反应得到了一系列的α-取代-1,3-二羰基化合物,收率50%～87%;然后进一步通过烯丙基化反应成功合成了具有3个官能团(2个羰基和1个烯基)的季碳砌块,产率为50%～93%.并对合成的α-取代-1,3-二羰基化合物和烯丙基化产物进行了1H NMR表征.     

新型功能化介孔材料CH3-MCM-41-NH2的合成和表征

以硅酸钠为硅源,十六烷基三甲基溴化铵（CTAB）为模板剂,合成介孔材料MCM-41．采用两步嫁接法,分别用三甲基氯化硅（TMSCL）和3-氨基三乙氧基硅烷（APTS）对合成的介孔分子筛进行化学修饰,首次将甲基和氨基同时嫁接到介孔材料MCM-41上,得到新型的介孔材料CH3-MCM-41-NH2．利用XRD和FT—IR对合成的新型功能化介孔材料进行表征．     

发散法合成超支化聚碳硅烷的研究进展

超支化聚碳硅烷是一种新型有机硅超支化聚合物,具有高流动性、化学惰性、热稳定性等优点,分子中存在纳米空腔和大量活性端基,因此具有广阔的应用前景.文章集中探讨了发散法合成超支化聚碳硅烷的研究进展,对这些方法的优缺点进行总结,并对超支化聚碳硅烷合成的新方法进行了展望.     

硅桥联有机锂化合物的合成及结构测定

以邻甲基苯胺为原料,经正丁基锂去氢后与二甲基二氯硅烷反应,硅烷化后再次与正丁基锂反应,合成了一种新型的有机锂化合物,并通过X-ray 单晶衍射、1H-NMR对该化合物进行了分析和表征.     

树枝形分子的合成及其对纳米硫化镉生长的控制

用发散法合成了以苯胺为核的不同代数的聚酰胺-胺(PAMAM)型树枝状分子,采用核磁共振仪(NMR)对它们的结构进行了鉴定。又以第4代PAMAM树形分子(G4.0)为模板,在树形分子空腔内原位合成了硫化镉(CdS)纳米粒子。通过改变Cd²⁺与G4.0树枝状分子的摩尔比可以得到不同粒径的CdS量子点,并对其光学性能进行了表征。探讨了溶剂对CdS半导体纳米粒子在PAMAM模板中生长的影响。用UV-visible分光光度计和TEM对CdS纳米簇的大小和形貌进行了表征。结果表明TEM 观测的CdS纳米簇粒径要大于用Brus公式估算的数值。     

聚酰胺-胺树状大分子的合成与荧光性质的研究

以乙二胺为核，合成了不同代数的树状大分子，用元素分析、红外光谱、核磁共振进行了结构表征．荧光分析表明，整代的树状大分子具有荧光发光性能，通过测定与不同金属离子(M=Cu^2 ，Ni^2 ，Zn^2 ，Fe^3 ，Cr^3 ，Eu^3 )配位后的荧光性质，发现少量金属离子的加入，荧光强度变化不大．但无论是一代(1．0G)还是二代(2．0G)树状大分子，Fe^3 和Cr^3 的加入均使荧光强度明显增加．     

以PAMAM树形分子为模板剂合成介孔磷酸铝

以4.0代聚酰胺-胺(PAMAM)树形分子为模板剂制备了介孔磷酸铝,运用红外光谱、X射线粉末衍射、透射电镜、N2吸附/脱附等技术对其结构及形貌进行了表征.结果表明所合成的化合物具有介孔结构特征,孔径分布为5-8 nm,并初步讨论了以树形分子为模板形成介孔结构的可能机理.关键词:聚酰胺-胺;介孔;磷酸铝     

低代数聚酰胺-胺树状高分子的合成

用发散法合成了0.5～4.0代聚酰胺-胺（PAMAM）树状高分子,以PAMAM G3.5,PAMAM G4.0树状高分子为例,采用傅里叶变换红外光谱仪、1H和13C超导核磁共振谱仪对其分子结构进行表征,并对聚酰胺-胺树状高分子合成的影响因素作了讨论.     

Determination of lead isotope compositions of geological samples using femtosecond laser ablation MC-ICPMS

Lead isotopic compositions of international silicate glasses, feldspar and copper-based samples are obtained using femtosecond laser ablation multiple collector inductively coupled plasma mass spectrometry (fLA-MC-ICPMS). Some international glass standards for the microanalysis are applied to evaluate the method reported here. The Pb isotopic composition of these NIST glasses (SRM 610, 612, 614), USGS (BHVO-2G, BCR-2G, BIR-1G and GSD-1G) and MPI-DING glasses (GOR132-G, KL2-G, T1-G, StHs60/80-G) agree well with recommended values in 2 s error. One of 15 copper-based metals is found to have homogenized Pb isotope data and can be used as an external calibration standard and quality control sample for chalcopyrite, ancient coins, etc., to trace the genesis of metal deposit and culture exchange among different dynasties (GBW02137, ²⁰⁸Pb/²⁰⁴Pb = 37.9661 ± 0.0005 (2 s), ²⁰⁷Pb/²⁰⁴Pb = 15.5770 ± 0.0002 (2 s), ²⁰⁶Pb/²⁰⁴Pb = 17.7462 ± 0.0002 (2 s)). We also prepared a feldspar glass to serve as the external calibration standard/QC for Pb isotope analysis using fLA-MC-ICPMS.     

树状分子接枝壳聚糖的合成与热致液晶性

甲壳素/壳聚糖是拥有多个反应性官能团的天然多糖,而树状分子则是一类可以在分子水平上控制和设计大小、形状、结构和功能基团的化合物,将其作为侧链通过接枝反应引入到壳聚糖主链上有望获得新型的天然高分子液晶材料.我们利用经典的收敛法合成了DOBOB酸(3,4,5-三[对-(十二烷氧基)苄氧基]苯甲酸)树枝状分子,并且以对甲苯磺酰氯为催化剂,在吡啶/无水氯化锂的溶剂体系中将其接枝到壳聚糖分子链上,产物的化学结构经红外1、H-NMR1、3C-NMR以及元素分析表征验证.通过DSC和热台偏光显微镜研究表明,这种树枝状分子接枝壳聚糖化合物同时具有热致和溶致液晶性,是一种全新的壳聚糖衍生物液晶.     

末端带苯并噁嗪环的树枝状高分子的合成

采用溶剂法,以1.0GPAMAM和2.0GPAMAM为原料,与苯酚、多聚甲醛反应分别制备了2种新型的树枝状苯并噁嗪:1.0G苯并噁嗪(1.0GBZ)和2.0G苯并噁嗪(2.0GBZ).利用1 H NMR,FT-IR和DSC对其结构和固化行为进行了表征.通过TGA考察了所得聚合物的耐热性能.     

Human endothelial senescence induced by IL-1α in vitro

Interleukin 1(IL-1) is an important proinflammatory cytokine that causes pleiotropic effects. Vascular endothelial cells stimulated by IL-1α can lead to the inflammatory response. Reactive oxygen species (ROS) are also generated at the site of inflammation and serve as an important factor against foreign invader. Here we report that long-term stimulation of human vein endothelial cells with IL-1α can accelerate their senescence associated with β-galactosidase activity. The flow cytometric analyses showed that most of the induced cells entered G0-G1 phase. DNA damage was more severe in senescent cells by comet assay. The induced cells by IL-1α had higher levels of ROS and malonyldialdehyde (MDA), lower activity of antioxidant enzymes and lower capacity of total antioxidant systems than control, which led to cell damage and cell degeneration, that is to say, which contributed to cellular senescence. Our results gave a direct proof to a new hypothesis-"the inflammation hypothesis of aging" on cellular level, and also provided a basis for the study on anti-aging and aging-related diseases.     

Fluorescence study on the interactions of PAMAM dendrimers and their derivatives with bovine serum albumin

The interactions of amino-terminated, and ethylenediamine core poly（amidoamine） （PAMAM） dendrimers and their derivatives with bovine serum albumin （BSA） were investigated by fluorescence spectroscopy. Experimental results showed that the fluorescence intensity of BSA decreased after the addition of different modified dendrimers, and the extent of the fluorescence quenching caused by various modified dendrimers strongly depends upon the different functional groups on their surfaces. We also investigated the influence of pH and ionic strength on the interaction between various modified dendrimers and BSA. Circular dichroism （CD） spectroscopic measurements showed that the content of α-helix structure of BSA decreased after the addition of different modified dendrimers, which indicated that dendrimers induced changes in the secondary structure of BSA.     

Mouse p53 inhibits SV40 origin-dependent DNA replication

p53 is a cellular phosphoprotein that is present at elevated concentrations in cells transformed by different agents. p53 complementary DNA expression-constructs immortalize primary cells in vitro and co-operate with an activated ras oncogene in malignant transformation. Several reports have implicated p53 in mammalian cell cycle control and specifically with events occurring at the G0-G1 boundary. p53 forms specific complexes with simian virus 40 (SV40) large-T antigen, and such complexes are found associated with both replicating and mature SV40 DNA in lytically infected cells. In an accompanying paper Gannon and Lane report that in in vitro plate-binding assays, mouse p53 can displace polymerase alpha from complex with T-antigen. We have examined the in vivo consequences of expressing wild-type and mutant p53 proteins from other species in SV40-transformed monkey cells. We report here that expression of mouse p53 results in a substantial and selective inhibition of SV40 origin-dependent DNA replication. In addition to any function in the G0-G1 transition, the data presented suggest that p53 may affect directly the initiation or maintenance of replicative DNA synthesis.