二价氯化稀土催化丁二烯聚合的活性

<正> 稀土催化聚合双烯烃的研究表明,不同稀土元素的催化活性极不一样,对此虽有不同的解释,但通常公认Sm、Eu等活性骤低,可归之于它们在制备催化剂过程中极易被烷基铝从三价还原到二价,又根据大部分具活性的其它稀土元素在催化体系中总是三价的事实,进而推断:只有在体系中能保持三价的稀土化合物方有产生活性的可能,二价化合物则不具活性。然而,由于二价稀土化合物,特别是除Sm、Eu之外的二价化合物难以制得,迄今为止并无直接的实验事实来判断这些推断是否正确。     

Synthesis and in vivo study of metallofullerene based MRI contrast agent

Gd@C₈₂(OH)₄₀ has been developed as a new generation of MRI contrast agent. But recently, it was found that Gd@C₈₂(OH) _x with a larger number of OH (x>36) would lead to cage break and hence, release of highly toxic Gd ions. We synthesized the more stable Gd@C₈₂(OH) _x with less OH-number, Gd@C₈₂(OH)₁₆, and studied its proton relaxivity and MRI images. The results indicate that Gd@C₈₂(OH)₁₆ also gives high proton relaxivity, even higher than that of (NMG)₂-Gd-DTPA. The bio-distribution indicated that Gd@C₈₂(OH)₁₆ tends to be entrapped in the liver and kidney and remained in tissue for about 2 hours. The results suggest that the more stable metallofullerene derivative Gd@C₈₂(OH)₁₆ can be the potential candidate of the new MRI contrast agent.     

甲醇与乙醇一步合成异丁醛用CuO-ZnO/Al2O3催化剂

在ＣｕＯ－ＺｎＯ／Ａｌ２Ｏ３催化剂上，甲醇与乙醇在常压和２１０￣３６０℃温度下一步反应合成异丁醛。利用正交设计方法，研究了ＣｕＯ－ＺｎＯ／Ａｌ２Ｏ３体系催化剂组成和制备条件等因素对催化剂催化性能的影响。结果表明，催化剂中ＣｕＯ含量对催化剂的催化活性影响最大，而ＺｎＯ含量则主要影响催化剂对异丁醛的选择性。催化剂制备条件，如沉淀温度、陈化时间等，也不同程度也影响催化剂的催化性能。ＸＲＤ和ＢＥＴ表征结果     

1''-苯基-3''-甲基-5''-氧代吡唑-4''-基乙醛酸希土配合物的合成及性质研究

本文采用电导、pH滴定法研究了乙醇-水溶液中希土与1′-苯基-3′-甲基-5′-氧代吡唑-4′-基乙醛酸(简称H₂A)的配位反应.合成了15种新的希土固态配合物.通过元素分析、化学分析、水份分析确定了配合物的化学组成为RE(HA)₃·nH₂O(RE=Ce、Pr、Sm、Tm、Lu、n=1;RE=La、Nd、Eu、Gd、Tb、Dy、Ho、Er、Yb、Y,n=1-2).并对配合物的红外光谱、核磁共振谱、热稳定性、紫外光谱、溶解性及摩尔电导进行了测定.     

氮硫杂冠醚及其衍生物的合成

以噻吩、水杨醛、二胺、溴乙酸、烯丙基氯和丙烯腈为原料合成了 4,5 :14 ,15 二苯 3 ,16 二氧 2 1 硫 7,12 二氮双环[16.2 .1]二十一环 1( 2 0 ) ,18 二烯 (简称氮硫杂冠醚 )及其 5种衍生物 ,经元素分析 ,IR ,1 HNMR和MS谱表征了这些化合物的结构 .     

从头计算方法比较TiSi_2的C54相和C49相

采用平面波超软赝势描述多电子体系,利用密度泛函理论和广义梯度近似,计算出C54相和C49相TiSi2的晶格常数、体弹性模量、形成能、电子态密度(DOS)和Mulliken电荷布居等性质.通过比较这两种物质的性质,发现尽管两者形成能很相近,但C49相结构对称性差、体弹性模量小、熔点低,Ti原子d轨道的反键强、离子性弱.这些性质上的差异和C49相TiSi2在固相反应中优先形成有关.     

Synthesis and photoluminescence properties of 8-hydroxyquinoline derivatives and their metallic complexes

Three new 8-hydroxyquinoline derivatives, i.e. 5-[(4-styryl-benzylidene)-amino]-quinolin-8-ol (1), 5-[(4-bromo-2-fluoro-benzylidene)-amino]-quinoline-8-ol (2) and 2-[2-(9-ethyl-9H-carbazol-2yl)-vinyl]-quinolin-8-ol (3), and their metallic complexes were synthesized and identified by ultraviolet-visible (UV-Vis), ¹H nuclear magnetic resonance (¹H NMR), Fourier transform infrared spectrometer (FTIR), mass spectrometry (MS) spectra and elemental analyses. Their fluorescence properties were studied by photoluminescence, which indicated that the luminescence wavelength of 5-and 2-substitued-8-hydroxyquinoline derivatives shifted to red in comparison with that of 8-hydroxyquinoline. Meanwhile, the fluorescence lifetime of 2-[2-(9-ethyl-9H-carbazol-2yl)-vinyl]-quinolin-8-ol and its zinc complex showed long lifetime in benzene solution. __________ Translated from Chinese Journal of Organic Chemistry, 2007, 27(3): 402–408 [译自: 有机化学]     

Design of coordination polymer as stable catalytic systems

Here we report the first example of catalytic metallogels, which are formed irreversibly in dimethylsulfoxide via the creation of cross-linked, three-dimensional coordination polymer networks by using transition-metal ions with multiple sites available for coordination and multidentate ligands. Conformational flexibility of the ligands and slow formation of the coordination polymers apparently favor the gelation. These metallogels are stable in water and most organic solvents and can catalyze the oxidation of benzyl alcohol to benzaldehyde by using their PdII moieties as the catalytic centers. The best catalytic turnover of the metallogel is twice that of [Pd(OAc)2] under similar reaction conditions.     

Needlelike and spherical polyelectrolyte complex nanoparticles of poly(l-lysine) and copolymers of maleic acid

We report on the bulk and surface properties of dispersions consisting of nonstoichiometric polyelectrolyte complex (PEC) nanoparticles. PEC nanoparticles were prepared by mixing poly(l-lysine) (PLL) or poly(diallyldimethylammonium chloride) (PDADMAC) with poly(maleic acid-co-alpha-methylstyrene) (PMA-MS) or poly(maleic acid-co-propylene) (PMA-P). The monomolar mixing ratio was n-/n+ = 0.6, and the concentration ranged from 1 to 6 mmol/L. Subsequent centrifugation enabled the separation of the excess polycation, resulting in a stable coacervate phase further used in the experiments. The bulk phase parameters turbidity and hydrodynamic radius (R(h)) of the PEC nanoparticles showed a linear dependence on the total polymer content independently of the mixed polyelectrolytes. This can be interpreted by the increased collision probability of the polyelectrolyte chains when the overlap concentration is approached or exceeded. Different morphologies of the cationic PEC nanoparticles, which were solution-cast onto Si supports, were obtained by atomic force microscopy (AFM). The combinations of PLL/PMA-MS and PDADMAC/PMA-MS revealed more or less hemispherical particle shapes, whereas that of PLL/PMA-P revealed an elongated needlelike particle shape. Circular dichroism and attenuated total reflection Fourier transform infrared (ATR-FTIR) measurements proved the alpha-helical conformation for the PEC PLL/PMA-P and the random coil conformation for the PEC PLL/PMA-MS. We conclude that stiff alpha-helical PLL induces anisotropic elongated PEC nanoparticles, whereas randomly coiled PLL forms isotropic spherical PEC nanoparticles.     

酸性品红与蛋白质结合反应的研究及应用

在pH1.4的Clark-Lubs缓冲介质中，蛋白质与酸性品红反应形成结合物，该结合物的最大吸收波长为576nm，与酸性品红相比，红移了34nm。据此拟定了分析方法，制定了牛血清白蛋白(BSA)、人血清白蛋白(HAS)、γ-球蛋白(γ-G)和酪蛋白的工作曲线，测定的摩尔吸光系数均在10^5数量级，用于人血清中总蛋白的测定，结果与溴甲酚绿(BCG)法基本一致。