Zur Kristallchemie der Oxoplatinate

On the Crystal Chemistry of Oxoplatinates Referring to the coordination of Pt²⁺ and Pt⁴⁺ by oxygen the crystal structures of oxoplatinates will be systemized. Pt²⁺ exclusively shows in solids a square and planar coordination well known and typical for Cu²⁺, Pd²⁺ and Ni²⁺ too. Often mixed valences (Pt²⁺/Pt⁴⁺) are observed in square planar oxygen surrounding. Some exceptionally rare coordination is the dumbbell like O—Pt²⁺—O. The crystal chemistry of Pt⁴⁺ resembles the countless metal ions showing octahedral coordination by oxygen. Despite different compositions the compounds BaLn₂PtO₅, Ba₃Cu₂Ln₂PtO₁₀, Ba₅Ln₈Zn₄O₂₁, Ba₁₃Ln₈Zn₄Pt₄O₃₇ and Ba₁₇Ln₁₆Zn₈Pt₄O₅₇ show amazing relationships of polyhedra connections. Additionally will be shown that Ba₄Sm₄Zn₃PtO₁₅ is isotypic to Ba₆Nd₂Al₄O₁₅ and Ba₄NaCu_{0, 5}Pt_{1, 5}O₈ to Ba₁₅Pt₆O₂₇. Oxoplatinates containing lone pair active elements show one side open polyhedra. The positions of the free (s²) electrons are calculated using the Coulomb terms of lattice energy.     

Consequence of assuming gamma-type distribution for characterizing structural heterogeneity of microporous solids

Extensive model studies were carried out for the gamma-type distribution, which was used to characterize structural heterogeneity of microporous solids. This distribution lead to a simple equation, which gave a good representation of many adsorption isotherms measured on microporous activated carbons. Assuming physically realistic values of the adsorption parameters, the gamma-type distribution curves were calculated together with curves of the adsorption isotherm, micropore distribution, adsorption potential distribution, enthalpy and entropy of adsorption.

---

Die Konsequenz der Annahme einer Gamma-Typ-Verteilung bei der Charakterisierung der strukturellen Heterogenität von mikroporösen Feststoffen

Zusammenfassung Es wurden für die Gamma-Typ-Verteilung, die zur Charakterisierung der strukturellen Heterogenität von mikroporösen Feststoffen genutzt wurde, ausgedchnte Modellrechnungen durchgeführt. Diese Verteilung führte zu einer einfachen Gleichung, die eine gute Darstellung vieler Adsorptionsisothermen an mikroporös-aktiviertem Kohlenstoff erlaubt. Unter der Annahme von physikalisch realistischen Werten für die Adsorptionsparameter wurden die Gamma-Typ-Verteilungskurven zusammen mit Kurven für die Adsorptionsisothermen, der Mikroporenverteilung, der Adsorptionspotentialverteilung und der Enthalphie und Entropie der Adsorption berechnet.

     

Hydrothermal synthesis and structural characterization of two organically templated zincophosphites with three-dimensional frameworks, (C6H14N2)·[Zn3(HPO3)4] and (C4H12N2)·[Zn3(HPO3)4]

Two organically templated zincophosphites, (C₆H₁₄N₂)·[Zn₃(HPO₃)₄] and (C₄H₁₄N₂)·[Zn₃(HPO₃)₄] have been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction. (C₆H₁₄N₂)·[Zn₃(HPO₃)₄] crystallizes in the triclinic space group , with cell parameters, a=9.363(4) Å, b=10.051(4) Å, c=10.051(4) Å, α=85.777(13)°, β=82.091(9)°, and γ=79.783(9)°. (C₄H₁₄N₂)·[Zn₃(HPO₃)₄] crystallizes in the monoclinic space group P2₁/c, with cell parameters, a=9.9512(3) Å, b=10.1508(3) Å, c=17.8105(5) Å, and β=95.6510(10)°. Although the two structures are different, they have the same anionic framework compositions of [Zn₃(HPO₃)₄]²⁻. Their frameworks are built up from strictly alternating ZnO₄ tetrahedra and HPO₃ pseudo pyramids by sharing vertexes. There exist channels with an eight-membered ring window along the a- and c-axis. Powder X-ray diffraction, IR spectroscopy, ³¹P MAS solid-state NMR, thermogravimetric and differential thermal analyses were also carried out.     

温州市1～13岁儿童血铅水平调查

随机抽取了温州市1~13岁的散居和集居儿童共2 038名,其中男1 404名,女634名,于2004年1月至2005年6月进行了静脉血铅测定。结果显示,温州市1~13岁儿童血铅为(60.30±29.57)μg/L,血铅含量≥100μg/L者,占总调查人数的10.99%,不同年龄的血铅水平及不同性别的血铅水平均存在差异。     

A framework for statistical modelling of plastic yielding initiated cleavage fracture of structural steels

The well established consensus that cleavage fracture is preceded by plastic deformation in structural steels implies that plastic yielding is the threshold stress state for a volume element to incur cleavage fracture. An accurate compliance with this consensus underlies the normalisation of cumulative cleavage fracture probability and the justification of constraint effect on cleavage fracture. These understandings lead to the proposal of a framework for statistical modelling of cleavage fracture in structural steels. The framework takes the spatial microcrack distribution into account to formulate the cumulative failure probability model that allows for a pertinent physical interpretation of Weibull statistics, and derives the fracture probability of an elemental volume in conformity with the yielding condition from a set of commonly adopted microcrack size or strength distributions. Alternative approaches to calibrating model parameters are suggested based on frequency analysis of brittle particles as cleavage initiators and on statistical analysis of cleavage fracture stress. The strict adherence to plastic yielding as a prerequisite to cleavage fracture also reveals the probabilistic nature of notch brittleness and ductile-to-brittle transition behaviour.     

Structural Dynamics of Phenyl Azide in Light-Absorbing Excited States:Resonance Raman and Quantum Mechanical Calculation Study

The excited state structural dynamics of phenyl azide (PhN₃) after excitation to the light absorbing S₂(A'), S₃(A'), and S₆(A') states were studied using the resonance Raman spectroscopy and complete active space self-consistent field calculations. The vibrational spectra and the UV absorption bands were assigned on the basis of the Fourier transform (FT)-Raman, FT-infrared measurements, the density-functional theory computations and the normal mode analysis. The A-, B-, and C-bands resonance Raman spectra in cyclohexane, acetonitrile, and methanol solvents were, respectively, obtained at 273.9, 252.7, 245.9, 228.7, 223.1, and 208.8 nm excitation wavelengths to probe the corresponding structural dynamics of PhN₃. The results indicated that the structural dynamics in the S₂(A'), S₃(A'), and S₆(A') states were significantly different. The crossing points of the potential energy surfaces, S₂S₁(1) and S₂S₁(2), were predicted to play a key role in the low-lying excited state decay dynamics, in accordance with Kasha's rule, and N7=N8 dissociation. Two decay channels initiated from the Franck-Condon region of the S₂(A') state were predicted: the radiative S_2,min→S₀ radiative decay and the S₂→S₁ internal conversion through the crossing points S₂S₁(1)/S₂S₁(2).     

Alloying Effect Study on Thermodynamic Stability of MgH2 by First-principles Calculation

First-principles calculations based on density functional theory were performed to study the effect of alloying on the thermodynamic stability of MgH₂ hydride (rutile and fluorite structures) with transitional metals (TM=Sc, Ti, Y) and group IIA elements (M=Ca, Sr, Ba). The results indicate that fluorite structure of these hydrides are more stable than its relative rutile structure at low alloying content (less 20%), structural destabilization of MgH₂ appears in the alloying cases of Ti, Sr and Ba respectively. The structure-transition point from rutile structure to fluorite structure is at around 20% for MgH₂-TM, and about 40% for MgH₂-M. The formation enthalpy of fluorite Mg_0.5Ba_0.52 is about 0.3 eV and higher than that of fluorite MgH₂, indicating that its hydrogen-desorption temperature at atmospheric pressure will be much lower than that of pure MgH₂. Good consistency between experimental and calculated data suggests that above-adopted method is useful to predict structural transition and properties of MgH₂ based hydrides for hydrogen storage.     

基于傅里叶红外光谱的SiO_2基相变储湿复合材料结构分析及性能优选预测

以SiO_2为载体材料、脂肪酸为相变材料制备具有相变调温性能与储湿调湿性能的SiO_2基相变储湿复合材料。采用等温吸放湿法和步冷曲线法测试不同脂肪酸用量的SiO_2基相变储湿复合材料相变调温性能与储湿调湿性能。利用傅里叶红外光谱测试SiO_2基相变储湿复合材料的结构组成,分析SiO_2与脂肪酸的嵌合机理。以SiO_2基相变储湿复合材料的傅里叶红外光谱特征吸收峰作为输入层,以SiO_2基相变储湿复合材料的脂肪酸用量、相对湿度52.89%下SiO_2基相变储湿复合材料吸湿平衡含湿量与放湿平衡含湿量的平均值、SiO_2基相变储湿复合材料从30~15℃降温所需的时间作为输出层,以S型激活函数作为隐含层,利用BE神经网络建立结构参数与综合相变储湿性能的SiO_2基相变储湿复合材料性能优选预测模型。结果表明,SiO_2基相变储湿复合材料中SiO_2与脂肪酸仅为物理嵌合,未发生化学作用;当脂肪酸用量0.079 mol时,所制备的SiO_2基相变储湿复合材料具有最优的综合相变储湿性能,即在相对湿度52.89%下的吸湿平衡含湿量为0.132 3 g·g~(-1)、放湿平衡含湿量0.147 5 g·g~(-1)、平衡含湿量的平均值为0.139 9 g·g~(-1),从30~15℃降温所需的时间为1 305 s;SiO_2基相变储湿复合材料的性能优选预测模型吻合性较好,具有较高的精确度,其预测值与实测值的相对误差为-2.07%和2.45%,可以用于优选预测SiO_2基相变储湿复合材料的储湿调湿性能和相变调温性能。     

On origin and evolution of carbonic anhydrase isozymes: A phylogenetic analysis from whole-enzyme to active site

Genetic evolution of carbonic anhydrase enzyme provides an interesting instance of functional similarity in spite of structural diversity of the members of a given family of enzymes. Phylogenetic analysis of α-, β- and γ-carbonic anhydrase was carried out to determine the evolutionary relationships among various members of the family with the enzyme marking its presence in a wide range of cellular and chromosomal locations. The presence of more than one class of enzymes in a particular organism was revealed by phylogenetic time tree. The evolutionary relationships among the members of animal, plant and microbial kingdom were developed. The study revises a long-established notion of kingdom-specificity of the different classes of carbonic anhydrases and provides a new version of the presence of multiple classes of carbonic anhydrases in a single organism and the presence of a given class of carbonic anhydrase across different kingdoms.