无机螺旋体超分子配合物的组装、应用和结构转化研究进展

简述了近年来报道的具有新颖结构和性能的无机螺旋体超分子配合物的组装、应用和结构转化方面的最新进展,并展望了无机螺旋体的发展前景及其开发应用潜力。     

大鼠肾组织的超低温快速冷冻固定和冷冻置换研究

超低温快速冷冻固定以极高的冷冻速率（１００００Ｋ／ｓ）对生物组织进行物理固定，可使生物组织结构、组织内可溶性离子及游离性物质得到保存，使被固定后的生物组织保持最接近于原自然状态，这种样品制备方法大大优于化学制备法，因而在Ｘ－射线微分析及免疫细胞化学中得到广泛应用。生物样品超低温快速冷冻后，利用冷冻置换法，在低温下将生物组织内的结晶水缓慢置换出来，而后常规包埋切片，可获得理想的组织结构及组织内待分析成分。本文应用超低温快速冷冻固定技术及冷冻置换法对大鼠肾皮质部的快速冷冻固定及损伤进行探讨。     

(4S)-4-羧基杂氮硅三环的合成

利用L-N,N-双(β-羟乙基)丝氨酸及L-N,N-双(β-羟乙基)苏氨酸与三乙氧基硅烷或氯烷基三乙氧基硅烷反应合成了具有手性的(4S)-4-羧基杂氮硅三环(1～5),并运用IR、~1HNMR、EI-MS等手段表征了结构。证据显示存在着贯穿笼状结构的N→Si配键。     

Hybrid inorganic-organic 1-D and 2-D frameworks with {As8V14O42} clusters as building blocks

Three novel hetero-polyoxovanadates, [Cd(2,2′-bpy)₃]{[Cd(dien)]As₈V₁₄O₄₂(H₂O)} (1, 2,2′-bpy=2,2′-bipyridine, and dien=diethylenetriamine), [Zn(2,2′-bpy)₂]₂[As₈V₁₄O₄₂(H₂O)]·H₂O (2) and [Ni(en)₂]₃[As₈V₁₄O₄₂(HPO₃)]·4H₂O (3, en=ethlenediamine), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Crystal data: 1 monoclinic, P2(1)/n, a=15.1728(5), b=19.2863(5), , β=96.005(2)°, Z=4. 2, orthorhombic, P2(1)2(1)2(1), a=12.1270(3), b=15.8678(8), , Z=4. 3, triclinic, , a=12.9340(3), b=13.4130(3), , α=87.170(3)°, β=77.517(3)°, γ=68.480(3)°, Z=2. Compounds 1-3 are all made of the {As₈V₁₄O₄₂} shells linked by corresponding transition metal complexes into extended structures. Compound 1 and 2 present 1-D wave-like and tubular structures, respectively, while compound 3 exhibits a novel 2-D structure containing interwinding puckery layers. Variable temperature susceptibility measurements demonstrate the presence of antiferromagnetic interaction between V^IV cations in 1 and 2.     

A novel three-dimensional coordination polymer [Cd2(C3H2O4)2(H2O)2(μ 2-hmt)] n (hmt = hexamethylenetetramine): synthesis and crystal structure

The self-assembly of the Cd^II ion, hexamethylenetetramine (hmt) and malonate ligand yields a three-dimensional (3D) coordination polymer [Cd₂(C₃H₂O₄)₂(H₂O)₂( ₂-hmt)] _n with channels. The Cd^II ion is located in a octahedral coordination environment, composed of four oxygen atoms from three malonates, one oxygen atom of water and one nitrogen atom of hmt. Two oxygen atoms of each malonate coordinate to the same Cd^II ion and the other two oxygen atoms connect to adjacent two Cd^II ions respectively to form a two-dimensional infinite network, these networks are bridged by ₂-hmt coordinated to Cd^II ions to product a 3D architecture.     

Synthesis,crystal structure and property of a novel azide-bridged one-dimensional chain copper(II) complex with a dinucleating macrocyclic polyamine

An azide-bridged polymeric cationic chain complex, [LCu₂(N₃)₂]n(ClO₄)_2n ·n(H₂O)**, where L=the dinucleating macrocyclic ligand bis-p-xylylBISDIEN, has been prepared and characterized by x-ray crystallography, u.v.-vis and i.r. spectra, and by magnetic measurements. The structure consists of cationic azide-bridged [LCu₂(N₃)₂]²⁺ (unit) chains, non-coordinated perchlorate anions and crystallized water molecules. The azide anion is bound to two copper atoms in neighboring units with an end-to-end bridging mode. In each unit, the copper atoms have a different coordination geometry; Cu(1) is a four-coordinated, distorted square-planar geometry, whereas Cu(2) is a five-coordinated, distorted square-pyramid. The electronic spectra of the title complex differ in anhydrous and in aqueous MeCN solutions, indicating that dissociation and solvation occur in aqueous solutions. The characteristic i.r. absorptions of azides and perchlorates are described. Magnetic moments vary from 2.05 (B.M.) at 300K to2.01 (B.M.) at 80K, which suggests that very weak interactions exist between the metals.     

电子自旋共振准三维图象的重建方法

根据投影切片原理, 设计了一个简单而有效的ESR图象重建算法和程序, 可利用样品的一集ESR谱, 方便地绘制出样品在某截面的自旋密度立体轮廓图、等值图和散点密度分布图等, 为分析和研究自旋密度的分布及其性质, 提供了直观依据。作为应用, 文中给出了石英杜瓦受紫外光辐照后产生的局部晶格缺陷——F心的空间分布图, 图中清楚表明, F心的浓度与辐照方向和辐照强度的密切关系, 与试验结果完全相符。     

高含量钒的钼钒磷杂多化合物的合成和性质研究

本工作改进了文献[4]报导的几种原料同时混合、加热煮沸合成的方法采用分步加入原料,控制反应温度、多次重结晶的方法合成了6、7、8个钒原子取代的钼钒磷杂多酸铵;并以铵盐为原料,用离子交换、冷冻分离和真空抽吸相结合的提纯方法制备了未见文献报导的相应的固体杂多酸;H₅[PMo₅V₇O_37.5]·xH₂O,H₆[PMo₄V₈O_37.5]·xH₂O。通过元素组成分析确定了它们的组成。这些杂多酸在水溶液、非水溶液中的电位滴定表明,杂多阴离子在分解前没有发生自电离、水解等情况,它们在水溶液中是稳定的。酸的碱度分别为5、5、6。通过纸上色谱实验,讨论了杂多酸的分解过程。由热重分析和溶解性实验得到它们的分解温度,本文还讨论了这些化合物的红外、紫外光谱,x光粉末衍射及极谱性质。光谱结果表明,它们可能具有Keggin结构,由导数脉冲极谱得到它们的峰电位。     

Synthesis and crystal structure of a new one-dimensional system with end-to-end single dicyanamide bridges between nickel(II) centres

The complex [Ni(tn)₂{N(CN)₂}]ClO₄ (tn=trimethylenediamine) has been synthesized and the structure has been determined. The complex forms a one-dimensional chain structure via the bidentate bridging ligand dicyanamide. A two-dimensional networks is formed via interchain hydrogen bond interactions.     

非线性光学材料──水草酸铵

一水草酸铵（简称ＡＯＭ）是一种优良的电光晶体￣［１］。文献￣［１，２］报道了该晶体的晶体结构，化学式为（ＮＨ＿４）＿２Ｃ＿２Ｏ＿２·Ｈ＿２Ｏ，属正交晶系，Ｐ２２２空间群，晶胞参数ａ＝０．８０３５ｎｍ，ｂ＝１。０３１ｎｍ，ｃ＝０．３８０１ｎｍ，ｚ＝２。本文拟报道ＡＯＭ单晶生长，热化学分析，透过波段以及非线性光学性质的初步研究。