氮杂冠醚研究：Ⅸ.双偶氮基开链冠醚的合成及紫外可见光谱研究

用邻硝基苯酚经过先桥接，还原，然后使生成的重氮盐分别与苯酚，取代苯酚和取代苯胺偶联的方法，合成了两类新型的双偶氮基于链有色冠醚，方法简便，产率高，在一定的酸性介质中，这类冠醚存在着铵醌互交异构。测定了它们在不同介质中的紫外可见光谱，并对最大吸收峰进行归属。     

氯磺化聚乙烯的γ—辐射交联

氯磺化聚乙烯(简称CSM)由于存在SO_2Cl基团很容易通过金属氧化物进行化学交联,但至今未见其辐射交联的详细报道.本文探讨氯含量对CSM辐射交联的影响. 所用CSM系吉林化工公司产品:20型(含氯量29～33％,下同),40型(33～37％)和30型(40～45％).将CSM和防老D按一定比例混炼均匀,再在140℃左右热压成形.试样用3.33×10~(15)Bg ~(60)Co于室温限量空气下进行辐照.辐照过的试样于80℃处理2小时以消除俘陷自由基.在氮气保护下先后用二甲苯和无水乙醇,加热回流48小时和8小时,测定凝胶含量.     

六次甲基四碲富瓦烯二碘盐的合成、晶体结构及其某些固态物性

在两相混合溶液中电解合成了HMTTeF·I_2盐的单晶。晶体属P2_1/n空间群,独立区里有一个HMTTeF分子,离子化发生在分子中的一个碲原子孤电子对上。粉末压片常温电导率为4.1×10~(-5)Scm~(-1)。喇曼光谱测定与电导率及X射线分析结果相符。     

Crystal Structure of Complex Tris（4,4,4—trifluoro—1—pheny1—1,3—butanedione）（1,10—phenanthroline）Europium（Ⅲ）

The complex Eu(btfa)₃ (phen) (btfa=4,4,4‐trifluoro‐1‐phenyl‐1, 3‐butanedione, phen = 1,10‐phenanthroline) has been prepared and characterized by elemental analysis, IR and UV spectroscopies. The crystal and molecular structures of the complex have been determined by X‐ray diffraction analysis. It belongs to the monoclinic crystal system, space group P2₁/c with a = 0.9700(2) nm, b = 3.7450(5) nm, c = 1.0917(3) nm, β = 92.51(2)°, V = 3.962(1) nm⁵, Z = 4, D_c = 1.639 g/cm³, μ = 1.676 mm^?1, F(000) = 1936, R₁, = 0.0388, wR₂ = 0.0775. Structure analysis shows that the europium(III) ion is coordinated to six oxygen atoms of β‐diketonate anions and two nitrogen atoms of phenanthroline molecule. The coordination polyhedron is an approximate square antiprism.     

2-噻吩乙醛酸-三苯基氧化膦-铕配合物的合成、结构表征及荧光性能的研究

用硝酸铕、2-噻吩乙醛酸(HL)和三苯基氧化膦(TPPO)合成了一种新型固体发光配合物;用元素分析、电导率、红外光谱和核磁共振确定了该配合物的分子式为EuL3TPPPO((H2O)2;在室温下测定了该配合物的荧光激发光谱和发射光谱;配合物中Eu(Ⅲ)离子的3个主要跃迁5D0→7F1,5D0→7F2和5D0→7F4分别位于593.4,618.8和699.4 nm.该固体配合物于室温下被紫外灯照射可以发出很强的红色荧光.IR光谱中2-噻吩乙醛酸在与稀土铕离子形成配合物后,vas(-COO-)由钠盐的1632 cm-1移至1612 cm-1,vs(-COO-)由1389 cm-1移至1409cm-1;vc=o(α-酮基)由HL的1654 cm-1移至1662 cm-1.配合物的vEu-o吸收峰出现在541 cm-1.在1HNMR谱图中,噻吩环上的3个氢原子的化学位移在形成配合物后移向高场;三苯基氧化膦中苯环上5种不同环境的质子的化学位移在形成配合物后向低场移动.TG分析证明,该固态配合物于空气中在常温至190℃以内是稳定的.     

气相反应C_(60)+O_3=C_(6O)(C_(2v))+O_2热力学函数的计算

计算了气相反应C60＋O3＝C6O（C2v）＋O2的热力学函数．得到了该反应Gibbs自由能的具体数值，结果表明在所研究的温度范围内Gibbs自由能为负值，从热力学角度来说，该反应可以自发进行,在计算该气相反应热力学函数的基础上，给出了气相C6O（C2v）的标准热力学函数     

表面增强拉曼光谱研究以4,4''''-联吡啶为标记分子的免疫检测

通过表面增强拉曼光谱(SERS)研究了标记分子4,4'-联吡啶在金溶胶上的吸附行为,并将其与山羊抗小鼠IgG结合,获得SERS标记免疫金溶胶.在固相基底上组装抗体,两者组装得到固相抗体-抗原-标记抗体“三明治”结构.在单组分和双组分体系中借助抗体上标记金纳米粒子所带的SERS信号达到免疫检测的目的.     

Synthesis of N—（4—Salicylideneiminoaryl）monoaza Crown Ethers and Dioxygen Affinities of Their Cobalt（Ⅱ）Complexes

The Schiff base‐containing pendant monoaza crown ether HL¹, HL², HL³ and HL⁴ have been synthesized by condensation of salicylaldehyde with N‐(4‐aminoaryl) monoaza crown ethers, which were prepared conveniently from 4‐nitro‐N, N‐di(hydroxyethyl) aniline or 4‐nitrobenzyl chloride via cyclization or condensation and reduction. The structures of HL¹—HL⁴ were verified by ¹H NMR, IR spectra, MS and elemental analysis. Moreover, the oxygenation constants (KO2) and thermodynamic parameters (δH⁰ and δS⁰) of their cobalt(II) complexes were determined in the range of ?5 °C to 25 °C, and the effect of crown ring bonded to a Schiff base on the dioxygen affinities of cobalt(II) complexes was also observed as compared to the uncrowned analogue (CoL).     

青霉素G钾盐在CTAB胶束中的水解及其抑制

以紫外光谱法研究了青霉素G钾盐(Pen-K)在十六烷基三甲基溴化铵（CTAB）胶束体系中的水解反应, 并探讨了水解反应机理.结果表明, CTAB胶束对Pen-K的水解具有抑制作用; Pen-K在CTAB胶束体系水解时,体系pH值的变化与在水中相似, 表明H＋浓度对这种抑制作用影响较小.红外光谱和微极性研究表明,部分Pen-K钾盐定位于CTAB胶束栅栏层中, 增加了其稳定性.     

Synthesis and Crystal Structure of Cubane—typeMolybdenum Cluster ComplexMo4S4（DTP）4[μ—SOP（OEt）2]2

1 INTRODUCTION Trinuclear molybdenum complexes with Mo3(3-S)(-O)n(-S)3n (n = 0~3) cores have been extensively studied on their diversified reactions towards various organic ligands and many metals. Many derivatives with Mo3S4 core have been rationally synthesized from the cation precursor [Mo3S4(H2O)9]4+ and its neutral derivative Mo3(3-S)(-S)3(DTP)4(H2O)[1]. However, due to their structural lability, complexes with Mo3(3-S)(-O)n(-S)3n (n = 1~3) cores have been reported limitedl…