新颖双核钐硫酚化合物[(THF)3I2Sm(m-SAr)]2 (Ar = Ph, 4-Me2NC6H4)的合成与化合物[(THF)3I2Sm(m-S-4-Me2NC6H4)]2的晶体结构

Reactions of SmI2 in THF with ArSSAr produced two binuclear samarium thiolate complexes [（THF）3I2- Sm（μ-SAr）]2 [Ar=Ph （1）, 4-Me2NC6H4 （2）] in high yields. The structure of 2 was characterized by single crystal X-ray crystallography. The crystal of 2 belongs to the triclinic system with space group P 1 and a=0.95705（13） nm, b= 1.22287（14） nm, c= 1.26450（14） nm, a=64.194（11）°, B=78.491（13）°, y=76.176（12）°, V= 1.2860（3） nm^3, Z= 1,μ=4.783 mm^-1, Dc= 1.964 Mg/m^3, M= 1521.19, S= 1.046, R1=0.0358, wR2=0.0910. X-ray analysis revealed that 2 is a thiolate-bridged dimer in which each Sm atom adopts a distorted pentagonal bipyramidal coordi- nation geometry.     

具有岩兰烷基本结构的螺[4,5]癸多烯的合成

利用1,5-二甲基-6-亚甲基环己烯和2,4-二氧代戊酸甲酯的deMayo反应,经加成产物retro-benzilic acid重排,一步构成岩兰烷属螺环倍半萜类天然产物的基本碳架,通过对螺环上的多种官能团进行化学修饰,合成一系列螺[4,5]癸多烯化合物.所合成的新化合物的化学结构均经IR,1H NMR及元素分析予以证实.     

Hydrothermal Synthesis and Thermal Stability of Natural Mineral Lindgrenite

IntroductionSynthesis of natural minerals is helpful for tracingthe geological origin of mineral formation and forverifying the quality of minerals. The investigations onthe conditions for mineral formation, such as pressure,temperature, and starting mate…     

Dawson结构(NH4)6P2Mo18O62·12H2O纳米粉体的室温固相合成及形成机理

以H₆P₂Mo₁₈O₆₂·23H₂O和(NH₄)₂C₂O₄·H₂O为原料，首次采用室温固相反应合成出(NH₄)₆P₂Mo₁₈O₆₂·12H₂O纳米粉体，并运用元素分析、FTIR、XRD、TEM、TG-DTA和BET等技术对其组成、结构和性能进行了表征。发现(NH₄)₆P₂Mo₁₈O₆₂·12H₂O纳米粉体平均粒径为40 nm，保留着杂多阴离子的Dawson结构，具有Dawson结构的特征衍射峰，比表面积为143.9 m²·g^-1，在445 ℃以下杂多阴离子有良好的热稳定性。在该固相反应中，研磨和放热反应热能可加速反应物分子的扩散速率和生成物分子的成核速率，使产物粒径减小；反应物含有结晶水和生成物H₂C₂O₄·2H₂O对形成小粒径的(NH₄)₆P₂Mo₁₈O₆₂·12H₂O纳米粉体起关键作用。     

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).     

微环境影响下的乙酰基香豆素与吲哚的固相光反应

本文研究了乙酰基香豆素及其衍生物与吲哚的混晶在微环境影响下的固相光反应，并用固体紫外光谱、固体荧光光谱和X-射线粉末衍射技术考察了混晶的特征。实验结果表明，3-乙酰基香豆素及其7-乙酰氧基、7-苯甲酰氧基、5,6-苯并和6-溴衍生物与吲哚的固相光反应分别得到1:2缩合产物1～5，而6-硝基衍生物与吲哚的固相光反应却得到开环脱羰加成产物6。通过IR、MS、^1H NMR和元素分析结果确定了这六个新产物的结构。固体光谱的测试结果表明，取代乙酰基香豆素与吲哚间混晶的形成，分子间存在相互作用，使分子所处的微环境条件发生了变化。     

咪唑-金属配合物的合成、性质及其与DNA的作用机理

Three hexakis（imidazole）metallo complexes of Co, Cd and Ni were synthesized and spectroscopically characterized. The crystal and molecular structures have been determined by X-ray crystallography analysis. The metal ions have an octahedral geometry with the MN6 chromophore. The electrochemical experimental results indicate that both [Co（Im）6]C12·2HCl·2H2O （1） and [Ni（Im）6]C12·4H2O （3） [Im=imidazole] could interact with DNA mainly by intercalation.     

邻氨基酚电聚合膜的研究

在酸性溶液中, 邻氨基酚(OAP)可电聚合成均匀的活性聚邻氮基酚膜(POAP), 膜有致密结构和“张开”结构。POAP膜的主要结构形式为: 与Ni~(2+)络合后, 形成POAP—Ni~(2+)膜, 其主要结构形式为:     

美登素族生物碱的质谱-裂介机制研究与美登素合成中间物的结构测定

对天然美登素及其合成中间物1～9进行了电子轰击质谱研究,阐明了它们的裂解方式及谱与结构的关系,并据此对合成类似物作了结构鉴定。