Copolymerization of carbon dioxide and cyclohexene oxide catalyzed by aluminum porphyrin-quaternary ammonium salt in the presence of bulky lewis acid

Chloro( 5,10,15,20-tetraphenyl-porphyrinato)-aluminum/tetraethylammonium bromide ( Et4NBr) in combination with bulky Lewis acid was used for the copolymerization of CO2 and cyclohexene oxide ( CHO). Bulky Lewis acid having substituents at the ortho positions of the phenolate ligands, like methylaluminum bis(2,6-di-tert-butyl-4-methylphenolate), significantly shortened the induction period and raised the catalytic activity, the corresponding turnover frequency reached 44.9 h(-1) in 9 h, which was 23.8% higher than that from ( TPP)AlCl/Et4NBr binary catalyst. The resulting polycarbonate has carbonate linkage over 93% with number average molecular weight of ( 4.5-6.5) x 10(3) and polydispersity index below 1.10.

Alternating copolymerization of carbon dioxide and propylene oxide catalyzed by (R,R)-SalenCo(III)-(2,4-dinitrophenoxy) and Lewis-basic cocatalyst

A binary catalyst system of a chiral (R,R)-SalenCo(III)(2,4-dinitrophenoxy) (salen = N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-diphenylethylenediimine) in conjunction with (4-dimethylamino)pyridine (DMAP) was developed to generate the copolymerization of carbon dioxide (CO2) and racemic propylene oxide (rac-PO). The influence of the molar ratio of catalyst components, the operating temperature, and reaction pressure on the yield as well as the molecular weight of polycarbonate were systematically investigated. High yield of turnover frequency (TOF) 501.2 h(-1) and high molecular weight of 70,400 were achieved at an appropriate combination of all variables. The structures of as-prepared products were characterized by the IR, H-1 NMR, C-13 NMR measurements. The linear carbonate linkage, highly regionselectivity and almost 100% carbonate content of the resulting polycarbonate were obtained with the help of these effective catalyst systems under facile conditions.

Co-expression of CD173 (H2) and CD174 (Lewis Y) with CD44 suggests that fucosylated histo-blood group antigens are markers of breast cancer-initiating cells

Histo-blood group antigens CD173 (H2) and CD174 (Lewis Y) are known to be developmentally regulated carbohydrate antigens which are expressed to a varying degree on many human carcinomas. We hypothesized that they might represent markers of cancer-initiating cells (or cancer stem cells, CSC). In order to test this hypothesis, we examined the co-expression of CD173 and CD174 with stem cell markers CD44 and CD133 by flow cytometry analysis, immunocytochemistry, and immunohistochemistry on cell lines and tissue sections from breast cancer. In three breast cancer cell lines, the percentage of CD173(+)/CD44(+) cells ranged from 17% to > 60% and of CD174(+)/CD44(+) from 21% to 57%. In breast cancer tissue sections from 15 patients, up to 50% of tumor cells simultaneously expressed CD173, CD174, and CD44 antigens. Co-expression of CD173 and CD174 with CD133 was also observed, but to a lesser percentage. Co-immunoprecipitation and sandwich ELISA experiments on breast cancer cell lines suggested that CD173 and CD174 are carried on the CD44 molecule. The results show that in these tissues CD173 (H2) and CD174 (LeY) are associated with CD44 expression, suggesting that these carbohydrate antigens are markers of cancer-initiating cells or of early progenitors of breast carcinomas.

Enzymatic activities in constructed wetlands and di-n-butyl phthalate (DBP) biodegradation

The bioaccumulation of phthalate acid esters (PAEs) from industrial products and their mutagenic action has been suggested to be a potential threat to human health. The effects of the most frequently identified PAE, Di-n-butyl phthalate (DBP), and its biodegradation, were examined by comparison of two small scale plots (SSP) of integrated vertical-flow constructed wetlands. The influent DBP concentration was 9.84 mg l(-1) in the treatment plot and the control plot received no DBP. Soil enzymatic activities of dehydrogenase, catalase, protease, phosphatase, urease, cellulase, beta-glucosidase, were measured in the two SSP after DBP application for 1 month and 2 months, and 1 month after the final application. Both treatment and control had significantly higher enzyme activity in the surface soil than in the subsurface soil (P < 0.001) and greater enzyme activity in the down-flow chamber than in the up-flow chamber (P < 0.05). In the constructed wetlands, DBP enhanced the activities of dehydrogenase, catalase, protease, phosphatase and inhibited the activities of urease, cellulase and beta-glucosidase. However, urease, cellulase, beta-glucosidase activities were restored 1 month following the final DBP addition. Degradation of DBP was greater in the surface soil and was reduced in sterile soil, indicating that this process may be mediated by aerobic microorgansims. DBP degradation fitted a first-order model, and the kinetic equation showed that the rate constant was 0.50 and 0.17 d(-1), the half-life was 1.39 and 4.02 d, and the r(2) was 0.99 and 0.98, in surface and subsurface soil, respectively. These results indicate that constructed wetlands are able to biodegrade organic PA-Es such as DBP. (c) 2005 Elsevier Ltd. All rights reserved.

Lewis酸引发的LLDPE/PS共混体系的原位反应增容及其结构与性能研究

本文以单组分和双组分Lewis酸为催化剂，采用反应加工的方法，制备了原位反应增容的线性低密度聚乙烯/聚苯乙烯共混物（LLDPE/PS），并对原位反应增容的机理、增容体系的结构性能以及Lewis酸对共混组分的降解作用进行了系统研究。 以FTIR和NMR为手段、二甲苯为模拟化合物，确认LLDPE/PS共混体系在Lewis酸为催化剂作用下发生了LLDPE与PS的接枝反应，LLDPE接枝在PS苯环的对位上。形成的原位接枝共聚物对体系起增容作用。 使用溶剂抽提、SEM、DMA、流变和DSC等手段对以单组分Lewis酸AlCl3 为催化剂的LLDPE/PS共混物的结构性能进行了研究。从溶剂抽提前后的重量比计算了接枝物的含量。催化剂用量较低时体系中的接枝物含量随AlCl3的增加而提高，随着AlCl3进一步增加，接枝物含量不会增加反而下降，发现AlCl3导致均聚物的降解。研究结果表明，共混体系中加入适量的AlCl3催化剂后，分散相尺寸减小，分布均匀，储能模量增加，低频区的复数黏度升高。但AlCl3用量过高时使共混物的分散相尺寸增加，分布均匀度下降，储能模量和复数黏度降低。以GPC为手段研究了单组分 Lewis酸AlCl3对共混组分的降解作用，发现对PS的降解作用显著。 由于单组分Lewis酸催化剂会导致共混组分降解，使共混体系的物理机械性能变劣，为此，我们在LLDPE/PS共混物中引入了双组分Lewis酸催化剂（Me3SiCl、InCl3•4H2O）。结果表明双组分Lewis酸催化剂不但能够催化LLDPE和PS的原位接枝反应，获得高性能的LLDPE/PS合金材料，而且不会引发共混组分PS的降解。在催化剂用量固定时，采用双组分催化剂时共混物的拉伸强度随着LLDPE含量的增加几乎保持不变，但冲击强度有十分明显的提高。对比了加入催化剂前后共混物形貌的变化，增容后的共混物中分散相粒子尺寸显著降低，证明了双Lewis酸良好的催化性能。 对以双Lewis酸为催化剂的共混物的流变行为和结晶行为进行了研究。随着催化剂的加入，两相之间的相互作用增强，因此共混物的复数黏度，储能模量和损耗模量都有不同程度的提高。增容后的LLDPE相区变小，因而在冷却过程中出现不同程度的分步结晶现象。 对单组分和双组分Lewis酸催化剂原位反应增容LLDPE/PS共混体系的机理进行了探讨。机理为Friedel-Crafts烷基化反应。在采用单组分Lewis酸催化剂时， AlCl3与体系中含有的微量水等杂质发生反应，形成一个复合物，然后进一步与聚乙烯中的不饱和的双键发生反应形成碳正离子，并攻击LLDPE分子链从而形成大分子的碳正离子LLDPE+，而这些LLDPE+则通过电子的重排而发生剪切断裂。在催化剂的存在下，这些断裂的LLDPE片断取代PS中的苯环上的质子而发生接枝反应，从而形成LLDPE-g-PS共聚物。采用双组分Lewis酸催化剂时，首先发生双Lewis酸的耦合；耦合后的Lewis酸与水等杂质反应生成复合物，然后与非饱和的LLDPE分子反应生成初级碳正离子；初级碳正离子进攻LLDPE主链，生成较大的碳正离子；LLDPE+碳正离子取代PS苯环对位的质子而生成接枝共聚物。

Homogeneous Epitaxial Growth of N,N '-di(n-butyl)quinacridone Thin Films on Ag(110)

The structural evolution of the ordered N-N' dibutyl-substituted quinacridone (QA4C) multilayers (3 MLs) has been monitored in situ and in real time at various substrate temperatures using low energy electron diffraction (LEED) during organic molecular beam epitaxy (MBE). Experimental results of LEED patterns clearly reveal that the structure of the multilayer strongly depends on the substrate temperature. Multilayer growth can be achieved at the substrate temperatures below 300 K, while at the higher temperatures we can only get one ordered monolayer of QA4C. Two kinds of structures, the commensurate and incommensurate one, often coexist in the QA4C multilayer. With a method of the two-step substrate temperatures, the incommensurate one can be suppressed, and the commensurate, on the other hand, more similar to the (001) plane of the QA4C bulk crystal, prevails with the layer of QA4C increasing to 3 MLs. The two structures in the multilayers are compressed slightly in comparison to the original ones in the first monolayer.

单细胞凝胶电泳技术检测碳离子束和X射线照射对Lewis肺癌细胞的DNA损伤

比较研究了89.63MeV/u的碳离子束和6MeV的X射线照射Lewis肺癌细胞所致的细胞克隆存活和DNA损伤效应,以探讨单细胞凝胶电泳检测细胞辐射敏感性及重离子束治疗肿瘤的优势。结果表明,在10%细胞存活水平上碳离子束的相对生物学效应(Relative biological effectiveness,RBE)值达到1.77。单细胞凝胶电泳检测损伤DNA尾部百分含量(Tail DNA,TD)和Olive尾矩(Olive tail moment,OTM)的剂量效应曲线表明,X射线的剂量效应曲线为线性,而碳离子束诱导出一个包含线性和指数项的双阶段效应曲线。碳离子束辐照剂量大于8Gy后TD和OTM都存在饱和效应。在2Gy的剂量点,高传能线密度(LET)碳离子束比X射线产生更低的存活分数和更高的初始OTM。本研究提示:在Lewis肺癌细胞中,碳离子束照射比X射线产生更为强烈的细胞致死和DNA损伤效应,可使肿瘤治疗具有更高效率。

重离子对小鼠移植性Lewis肺癌分次照射的生物效应

目的　研究重离子不同分次照射的生物效应。方法　除对照组外 ,选择了 2个剂量点 :低剂量为 12Gy,高剂量为 2 4Gy。每个剂量分单次、2和 3次照射组 ,观察Lewis肺癌的肿瘤体积变化、肿瘤生长延迟时间和荷瘤小鼠生存时间。结果　无论高剂量还是低剂量 ,分 3次照射的肿瘤生长延迟和生存时间都显著大于单次和分 2次照射。结论　采用分 3次照射的肿瘤生物效应优于单次和分 2次照射 ,低剂量又优于高剂量。此研究结果为我国重离子束治疗肿瘤的临床试验提供了实验依据。

~(12)C~(6+)离子辐照小鼠Lewis肿瘤的研究

研究了HIRFL提供的12C6+离子辐照C57BL/6J小鼠右后腿移植的Lewis肿瘤的生长延迟和碳离子辐照对Lewis肿瘤小鼠寿命的延长.结果表明,碳离子照射的小鼠肿瘤生长体积明显地小于对照的体积.在剂量相同、分次数辐照越多时,肿瘤生长就越缓慢,肿瘤抑制就越高.在辐照分次数相同时,不同剂量对受照肿瘤生长体积未产生差异.在4Gy×3,8Gy×3和12Gy×2组3种辐照剂量下,小鼠寿命的P值小于0.05;可知小鼠的寿命延长具有统计学意义.