有机官能团对硅基MSU-X织构性能的影响

采用有机硅氧烷(RTES)与硅氧烷(TEOS)共水解缩聚合成了有机官能化的MSU-1中孔材料(R=甲基,苯基,乙烯基,脲丙基)。当前驱体中RTES与TO64EOS的摩尔比为0.1:0.9时合成R10-MSU-1分子筛,通过现化分析技术证明BA所选有机官能团均能进入分子筛骨架,而且在相同摩尔数的各数有机硅氧烷存在下,由于其反应速率、空间位阻的不同使其对骨架的缩聚程度、孔道和表面性质有不同的影响。利用SAXS实验技术对所合成R10-MSU-1材料结构表面以及由于有机官能团的存在对无机骨架产生的影响进行了研究。SAXS较强的散射强度分布对Porod定理形成负偏离,表明孔和基体之间有明显的界而层存在,并求得界面层的平均厚度。实验证明有机基团的均匀分布于孔道表面而形成有机界面层。SAXS测试还显示上述分子筛呈质量分形特征,其形成过程可能为非平衡非线性的聚集机制。     

双冠醚化合物的合成研究 III. 一类新的双冠醚的合成

邻苯二酚、3,5-二叔丁基邻苯二酚分别与1,5-二氯-3-氧(杂)戊烷在碱性条件下反应, 合成了开链冠醚化合物(1a-b)。1a-b与环氧氯丙烷在氢氧化钠正丁醇中缩合, 得到相应的6-羟基二苯并-16-冠-5(2a-b)。化合物2a-b分虽与丁二酰氯、壬二酰氯在无水苯中反应, 生成了两种新的酯型双冠醚化合物3a-b; 2a-b分别与1,3-二溴丙烷、1,4-二溴丁烷、1,5-二溴戊烷、1,8-二氯-3,6-二氧(杂)辛烷及1,11-二氯-3,6,9-三氧(杂)十一烷在无水二氧六环中反应, 得到了四种新的醚型双冠醚化合物4a-e。     

Closed and open-shell atomic oxygen on silver: two distinct patterns of the O<Subscript>1s</Subscript> binding energy and X-ray absorption O <Emphasis Type="Italic">K</Emphasis>-edge spectra as revealed by density functional theory

The electronic structure of atomic oxygen adsorbed species is studied by means of the density functional theory in the context of the ethylene epoxidation on the silver surface. The adsorbed oxygen species are modeled by the Ag₂O molecule either in its closed (¹A₁) or open-shell states (³B₁ and ¹B₁). In both open-shell states the 1s level appears to be lower than that in ¹A₁ by about 2 eV. This is apparently a sequence of the separation of electron pair, occupying the *-type highest occupied molecular orbital (HOMO), decreasing the electron density at the oxygen center. Such variation of the O_1s level for closed and open-shell Ag₂O states seems to explain the X-ray photoelectron spectroscopy (XPS) data concerning two distinct atomic oxygen species on silver surface having the O_1s binding energy of about 528 and 530 eV, called nucleophilic and electrophilic oxygen, respectively. The X-ray absorption O K-edge spectra (XANES) calculated for two types of the Ag₂O states by means of multiple-scattered-X-based approach appears to be in a qualitative agreement with those experimentally recorded for nucleophilic and electrophilic oxygen.     

多功能聚合物合成有机化学之进展

我们探索了利用钯催化反应合成新型多功能聚合物, 实验结果显示这类反应能与甚多官能团相容, 从而为聚合物化学家提供若干实用之合成方法。     

SYNTHESES AND ADSORPTION PROPERTIES OF PHENOL-FORMALDEHYDE-TYPE CHELATING RESINS BEARING THE FUNCTIONAL GROUP OF TARTARIC ACID

Several kinds of novel chelating resins bearing the functional group of tartaric acid (TTA-FQ-12, TTA-FQ-23, and TTA-FQ-34) were synthesized by reacting epoxy maleic anhydride, which was prepared through the oxidization reaction of maleic anhydride by hydrogen peroxide, with phenol-formaldehyde resin containing polyamine (FQ resins series). The effects of such factors as reaction time, reaction temperature and pH value on the loading capacity of TTA in resins were investigated. The results showed that the optimum reaction conditions are as follows: time 9-12h; temperature 90-105℃;pH value 6-10. The loading capacities of TTA can reach 0.15, 0.14, and 0.11 mmol/g^-1 when the functional group of FQ resin was -OCH2CH2NHC2H4NH2, -O(CH2CH2NH)2C2H4NH2 and -O(CH2CH2NH)3C2H4NH2), respectively. The structures of resins were characterized by FTIR spectra. The primary study on the adsorption properties of the resins for metal ions showed that there are two kinds of adsorption mechanisms i.e. ion exchange and chelate in the adsorption process. TTA-FQ resins have much higher adsorption selectivity for Pb^2 and Zn^2 than for Cu^2 and Ni^2 . These resins can probably be used for separating Pb^2 or Zn^2 in the mixture of metal ions or for treating wastewater containing heavy metal ions.     

具有生物活性的磷杂环化合物研究: XIV. Lawesson试剂与 含活泼氢的双官能团 化合物的环化反应

研究Lawesson试剂与含活泼氢的双官能团化合物的环化反应,合成了O-P-O,N-P-O,N-P-N型五元、六元及七元磷杂环。探讨了其成环可能性及其环化机理。初步的生物活性测定结果表明,应用Lawesson试剂所合成的磷杂环具有较好的选择性除草活性。     

一种新的聚合物固载的1,3-二醇的合成及其对二醛的单保护性能

聚合物固载的1,2-二醇和1,3-二醇作为醛或酮的保护基团, 已有广泛研究。聚合物固载的保护试剂的重要特性是能够对双功能基化合物进行单保护。本文合成了二醇功能基直接与聚苯乙烯链的苯环相接的1,3-二醇树脂─1-聚苯乙烯基-2,2-二甲基-1,3-丙二醇。二醇功能基2位上的两个氢原子均被甲基所取代, 减少了被保护的醛解脱过程中二醇功能基脱水失活的可能性, 以增加功能的可再生性。     

基式原子诱导电负性指数的简易计算

有关基团电负性的研究,曾进行了大量的工作. 运用电负性指数对物质性能进行定量化研究可避免复杂的计算工作,笔者在前人工作的基础上导出一种简易的计算方法.     

应用荧光偏振技术研究双官能团分子的分子内能量迁移

分子间或分子内的电子激发态能量转移是重要的初级光化学过程之一。本工作利用荧光偏振技术研究了双-β-萘甲酸多次甲基二醇酯(B_n,n=2,3,4,5,10)在玻璃态异戊烷(77K)和聚甲基丙烯酸甲酯薄膜中的分子内能量迁移,发现能量迁移效率随多次甲基链长度的增加依次降低;测定了β-萘甲酸酯发色团能量迁移的临界距离约为30(?);讨论了分子内和分子间能量迁移对荧光去偏振的影响。B_n的分子结构式为:     

Thermodynamic Classifications and Dilatonic Black Holes

We analyze the thermodynamics of systems which have entropy functions of the type S(m) = am + b, where m is an extensive variable and a, b, and are constants. Such functions apply to dilatonic black holes whose mass is m. This analysis continues our earlier treatment of the general classification of the thermodynamics of systems by whether they exhibit entropy functions which may or may not be either superadditive, homogeneous or concave in the extensive variables on which the entropy depends. This leads to a classification into 8 types of thermodynamics (with several subtypes). We show that only five of these are available for systems having the entropy given above, and these are in fact realized if the constants are given appropriate values.