复合生物材料的研究进展

从力学性能的改善和降解速率的可调度等角度,总结了复合生物材料与单一组分的材料相比,在生物医学领域应用中所表现出的综合使用性能的优越性。综述了复合生物材料,特别是用于骨修复的各类有机／无机复合材料近年来的研究进展状况。提出将与人骨中磷灰石微晶类似的羟基磷灰石纳米粒子与可降解聚酯材料进行复合,能够得到具有优越骨诱导性能并且能够降解的新型骨修复材料。这方面的研究代表了有机／无机复合生物材料领域新的发展方向。     

The structure and magnetic properties of μ3-oxotriiron(III) complex [Fe3O(OBz)6(CH3OH)3](NO3)(CH3OH)2

A new μ₃-O triiron(III) complex [Fe₃O(OBz)₆(CH₃OH)₃](NO₃)(CH₃OH)₂ (HOBZ = benzoic acid) has been synthesized, its structure has been determined and variable temperature magnetic susceptility has also been measured. In the molecule, three iron atoms formed an equilateral triangle with μ₃-O in center. The fitting to the magnetic susceptibility showed that an intramolecular antiferromagnetic exchange interaction occurred between iron atoms with J=-25.51 cm^?1, and a weaker intermolecular autiferromagnetic exchange interaction occurred with zJ' = ?2.30 cm^?1.     

利用选择性激发核磁共振对混合物中的两种化合物进行结构解析

利用现代NMR的1D、2D技术对一个混合物进行了分析。结果表明：混合物由两种化合物组成。为了同时准确确定两种化合物的结构，本工作应用了1D-TOCSY技术，利用该技术选择性强的特点来补充常规的1D、2DHMR实验所提供的分子结构的信息。在没有进行预分离的条件下，顺利地完成了样品中两种化合物的核磁信号归属，并最终确定了它们的结构。     

Pulsed field gradient NMR on polybutylcyanoacrylate nanocapsules

The applicability of pulsed field gradient nuclear magnetic resonance spectroscopy to nanocapsule systems is demonstrated on dispersed poly-n-butylcyanoacrylate nanocapsules as a model system. Spectroscopic data are presented that allow for the structural characterization of the inner cavities, the observation of Brownian motion of the capsules and the detection of rapid molecular exchange through the capsule walls. An analytical formula is proposed that yields equilibrium populations and average residence times of a given tracer molecule, thus leading to crucial information regarding the permeability of the capsule walls. Based on these analytical methods, two varieties of nanocapsules are compared that derive from two different preparation procedures. It is found that thinner capsule walls obtained under acidic conditions of the organic phase during interfacial polymerization lead to correspondingly higher exchange rates of benzene as a tracer molecule.     

Magnetic Structure of CsPd2F5

The structure of CsPd₂F₅ has been confirmed from neutron diffraction data on powdered sample. CsPd₂F₅ crystallizes in the orthorhombic Imma space group. At 100 K, the unit-cell constants are a = 6.473(2) Å, b = 7.853(5) Å, c = 10.718(3) Å and the calculation carried out using the Rietveld method leads to R₁ = 0.020. The network is formed of PdF₆ octahedra chains containing half of Pd in high-spin configuration, connected one to each other by square planes containing the other half of Pd in low-spin configuration. CsPd₂F₅ orders antiferromagnetically below T_N = 38 K. In the ordered state a weak ferromagnetic component occurs (σ₀ = 0.098 μ_B at 2 K). The magnetic structure determined at 4 K is consistent with the magnetization data and can be described in the Im′m′a′ magnetic group without any doubling of the unit-cell parameters. Within the chains, Pd²⁺ are coupled antiparallel. The magnetic moments are located in the (x0z) plane, the angle between the moments and the z axis being 18°.     

触头用银合金粉末的氧化性能和氧化后的组织结构

通过热重实验和扫描电子显微等方法，研究了４种触头用银合金粉末的氧化性能及氧化后的组织结构。发现Ａｇ－Ｓｎ－ＲＥ合金粉末氧化以后，在粉末表层形成一层纯银层，其组织结构理想；它的氧化性能最好，适于制备触头材料。Ａｇ－Ｓｎ－ＲＥ合金粉末的优良氧化性能与其氧化后理想的组织结构有关。稀土元素可以降低合金粉末的氧化温度，其它影响作用有待于进一步研究。     

On the High Viscosity of Aqueous Solution of Lysozyme Induced by Some Organic Solvents

A remarkably high viscosity has been induced in protein aqueous solutions by the addition of certain structurally related organic solvents. The effect has been observed for lysozyme aqueous solutions containing tetramethylurea (TMU), dimethylsulfoxide (DMSO), dimethylformamide, and hexamethylphosphortriamide. The effect has also been induced in ferrocytochrome c aqueous solutions by TMU. Critical concentrations for both the protein and organic solvent were verified for the onset of the viscosity increase. A common feature of the solvents which were able to induce the effect is a dipolar moiety (C=O, S → O and P → O) and a nonpolar region represented by the methyl groups. The resulting fluids show an extremely restricted flow and a typical non-Newtonian, pseudoplastic behavior. Use was made of¹H nuclear magnetic resonance (NMR) and Raman spectroscopy to characterize protein structural modifications and of¹³C NMR to investigate changes in relaxation times and chemical shifts in the solvent/water solutions. A systematic rheological characterization of the systems was undertaken for some of the solvents, and unusual patterns of viscous effects were identified for the solvent/water systems both with and without protein. The process was found to be at least partially reversible, as concluded from the recovered original solution rheological characteristics and the original protein¹H NMR spectrum, after eliminating the organic solvent by ultrafiltration. The whole process was characterized as consisting of two mutually independent stages. The first involves an extensive conformational transition of the polypeptide backbone, from a predominantly α-helical to increased random coiled and β-sheet structures, with the occurrence of nonorthodox protein secondary structures at regions above the solvent critical point. The second stage consists of short-lived interchain contacts leading to an entanglement of the macromolecular system as a whole. A microphase reversion in the organic solvent/water mixture, supported by¹³C NMR and rheological results, is proposed as the driving force causing the observed behavior.     

A study of the formation of silica-supported mixed magnesium-manganese spinel oxides from multicomponent gels

The effects of thermal treatment on composite materials prepared by the gelation of sols comprising large concentrations of metal oxide precursor salts have been investigated, in order to determine the compositional and thermal requirements for forming spinel magnesium manganates in such systems. The preparative technique has been found to give rise to derived gel materials in which the metal oxide phase, in the form of regular spherical particles, is dispersed throughout a continuous silica matrix. Silica-supported mixed magnesium and manganese spinel oxide phases were obtained for systems comprising at least 30 wt% metal nitrate after heating to temperatures between 700 and 850°C, but not without concomitant formation of Mn₂O₃ and modification of the silica network by magnesium.     

Organic phase conversion of bulk (wurtzite) ZnO to nanophase (wurtzite and zinc blende) ZnO

We describe the all-organic phase conversion of bulk commercial ZnO in the wurtzite modification to sub-30 nm ZnO that we find to be partially in the zinc blende [, a=4.568(3) Å] modification. The conversion involves refluxing ZnO in 2,4-pentanedione (acetylacetone) at 413 K to form the zinc 2,4-pentanedionate, which is decomposed by heating at 573 K in an appropriate high-temperature solvent such as dibenzylether to form nanophase ZnO. This nanophase, partially zinc blende ZnO can also be obtained in a single step by heating commercial zinc 2,4-pentanedionate in refluxing dibenzylether. Thermodiffractometry suggests that the conversion of zinc blende ZnO to wurtzite ZnO commences near 650 K.