生物小分子与铜锌超氧化物歧化酶相互作用的波谱学研究及其应用

本工作以ESR和NMR为主要手段,并结合其它生化方法,考察了氨基酸、核酸碱基、糖等生命基本物质,和抗坏血酸等生命必需物质与钢锌超氧化物歧化酶的相互作用,实验观测到氨基酸、核酸碱基和抗坏血酸在水溶液中可以与酶中的Cu²⁺作用而使其脱离活性部位,以小分子络合物形式游离在溶液中,同时使酶失活,脱离活性部位的Cu²⁺的比例和酶的失活程度取决于小分子配体的加入量及其与Cu²⁺的络合能力。此外,首次尝试使用ESR方法,并借助氨基酸与酶的作用,考察了铜锌超氧化物歧化酶在盐酸胍变性和热变性过程中的构象变化行为,结果表明这一方法是直观而有效的。     

Hybrid organosilazane/organosilylamine telechelic oligomers—I. Two-dimensional NMR spectroscopy characterization of dimethylsilylethylenediamine oligomers

The detailed characterization of multifunctional hybrid organosilazane/organosilylamine telechelic oligomers by IR and ¹H, ¹³C and ²⁹Si NMR spectroscopy in one and two dimenions has been undertaken. The specific multifunctional oligomers, comprising NH/NH₂ or SiCl functionalities depending on the monomer feed-ratio, were prepared from mono- and di-functionally reacted dichlorodimethylsilane (DDS) and mono-, di-, tri- and tetra-functionally reacted ethylenediamine (EDA). Varying the feed-ratio afforded control of the microstructures of the oligomers and the preparation of oligomers with, in some cases, conterminously located silicon–chlorine (SiCl) groups. The combination of the NMR methods with the IR technique has enabled the detailed microstructural characterization of the oligomers and the identification of the functionalities therein. This approach and the knowledge gained from the DDS/EDA system has been applied to the microstructural characterization of other hybrid organosilazane/silylamine preceramic telechelic oligomers.     

Echo planar imaging of perfluorocarbons

Emulsions of perfluorotributylamine (FTBA) and perflubron were evaluated for their utility in ¹⁹F echo planar imaging. Fluorine images of the emulsions were obtained in a phantom and two mice that had been predosed. Both agents, but particularly perflubron, show potential for fluorine echo planar studies because of the long spin-spin relaxation times of the CF₃ resonances. High resolution thin slice images obtained in as little as 26.6 ms are presented.     

New developments in the field of piezothermal analysis

The solid transitions of C₂₁, C₂₃ and C₂₅ n-paraffins are examined from a piezothermal point of view. The paper is divided into two parts. The first is a report of the main features of a piezothermal analyzer when pressure scanning allows the continuous record of the expansivity as a function of pressure up to 5 Kilobars. Small samples are required and the scanning speeds vary from 0.3 to 16 Kilobars per hour. The second part describes the experimental procedure appropriate for solid state determinations. The resulting piezothermograms are presented and entropies of transformation are determined. A model allows a crude statistical approach giving the entropies of transformation with the correct order of magnitude. Problems related with phase transformations under a shearing stress are considered.

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Zusammenfassung Feststoffumwandlungen bei C₂₁, C₂₃ und C₂₅ n-Paraffinen wurden unter dem Gesichtspunkt der Piezowärme untersucht. Im ersten Teil vorliegender Arbeit werden die Haupteigenschaften eines piezothermischen Analysators beschrieben, bei dem durch Druck-Scanning die kontinuierliche Aufzeichnung des Ausdehnungsvermögens als Punktion des Druckes bis zu 5 kbar ermöglicht wird. Es werden nur kleine Proben benötigt, die Scanning-Geschwindigkeit variiert zwischen 0,3 und 16 kbar/h. Der zweite Teil beschreibt das geeignete experimentelle Verfahren zur Feststoffzustandsbestimmung. Die erhaltenen Piezothermogramme werden dargestellt und die Entropien der Umwandlung bestimmt. Ein Modell liefert eine grobe statistische Näherung, die die Entropien der Umwandlung in der richtigen Grö\enordnung liefert. Probleme in Zusammenhang mit Phasenumwandlungen bei Scherbeanspruchungen werden betrachtet.

     

三羟甲基甲胺、季戊四醇及其二元体系固-固相变的变温红外光谱研究

利用傅里叶变温红外光谱仪分别测定了三羟甲基甲胺（TAM）、季戊四醇（PE）及其二元体系变温红外谱。实验表明，多元醇分子中羟基吸收峰随温度升高耐发生位移向高波数移动，此结果既能反映多元醇及其二体系固－固相变的温度区间，又与转变热相对应，从而揭示了多元醇及其二元体系固－固相变贮热的机理。     

室温下压致铁钴镍合金的bcc→hcp相变

 本文采用高压X光衍射方法在金刚石对顶压砧中在位地（in situ）研究了Fe₆₈Co₂₄Ni₈（wt%）合金在室温下的压致bcc→hcp结构相变和直到40.5 GPa的等温压缩行为。实验结果表明该合金在常压下为bcc结构，晶格常数a₀=(0.287 0±0.000 1) nm，体积V₀=(7.119±0.007) cm³/mol，密度ρ₀=(7.981±0.008) g/cm³；在20.9 GPa附近出现bcc→hcp结构相变，两相共存压力区约10 GPa，在此区域内有晶面间距d(002)_hcp=d(110)_bcc，且原子平面(002)_hcp//(110)_bcc，hcp相比bcc相体积减小(0.33±0.02) cm³/mol；高压相hcp结构的晶格参数比值c/a=1.608±0.004；相变后原子配位数的增加使得hcp相(002)平面内及(002)平面间的最近邻原子间距比bcc相最近邻原子间距分别增大约1.6%和0.5%；用Murnaghan状态方程对实验数据进行最小二乘法拟合，得到bcc相B₀=(130±13) GPa，B₀'=12.6±0.5；hcp相V₀=(6.62±0.04) cm³/mol，B₀=(243±21) GPa，B₀'=6.8±0.3；对于该合金的bcc→fcp相变时的结构转变机制做了详细的讨论。     

Classical limit of relativistic quantal system with attractive Coulomb interaction

Using the appropriate harmonic oscillator states and reasonable approximations, we construct coherent wavepackets corresponding to the solutions of the Klein-Gordon equation for the attractive potentialV(r)=−k/r, k>0, in two and three space dimensions. We deduce the corresponding classical limit in two dimension by requiring that the expectation value 〈r〉 of the radial variable is large. In the case of three dimensions, besides the condition of large 〈r〉, we make the uncertainty Δr=[〈r ²〉 − 〈r〉²]^1/2 a minimum with respect to certain parameter of the wavepacket. We then investigate the trajectory traversed by the wavepacket in the classical limit. We find that the classical limit of this relativistic quantal problem gives, in the leading order, the same expression for the rate of motion of the perihelion as that given by the solution of the corresponding special relativistic classical dynamical problem. We also briefly discuss some of the subtle aspects of the classical limit of the relativistic quantal system, in general.     

高频单线圈双调谐NMR单晶探头的研制

本文报道了一种测角单晶NMR探头。该探头采用单线圃双调谐电路,工作频率在90MHz-110 MHz连续可调,可进行交叉极化大功率去耦实验。文中提出了一种简单而有效的测角装置,可使单晶绕三个互相垂直轴转动实现单晶的NMR测量。作为典型的应用例子,本文利用该探头实现了单晶DGO(2NH₂CH₂COOH·H₂C₂O₄)屏蔽张量的测量。     

苯对N,N-二甲基甲酰胺化合物~1H NMR的影响研究

本文研究了N,N-二甲基甲酰胺(DMF)在四氯化碳和苯混合溶剂中的~1H NMR。观察到N,N-二甲基甲酰胺(DMF)分子中两个甲基和混合溶剂中苯的共振吸收峰的化学位移随苯的摩尔分数增加而逐渐移向高场,而且两个甲基共振吸收峰向高场移动的程度不同,α甲基较β甲基为甚。DMF分子中两个甲基和混合溶剂中苯的化学位移可以用线性方程表示(δ=A+Bx),这里x是混合溶剂中苯的摩尔分数。相关系数R接近于-1。