具有三维交叉孔道的新型亚磷酸锌的合成与结构

本文报道了一种新型三维亚磷酸锌[HO(CH₂)₂NH₃]₂•[Zn₃(HPO₃)₄]的合成和晶体结构。在它的结构中，ZnO₄和HPO₃严格按照顶点连接的方式交替相连。骨架结构存在两个沿着不同方向无限延伸的由ZnO₄和HPO₃组成的四元环链，在[0 1 0]、[0 4 15]和[0 -4 15]三个方向形成了三个交叉8元环孔道，有机胺阳离子起着平衡电荷和稳定骨架的结构。它的晶体数据为：[HO(CH₂)₂NH₃]₂•[Zn₃(HPO₃)₄],M=640.21, 正交晶系, Fdd2空间群, a=2.8528, b=0.8426, c=1.6159nm, Z=8, V=3.884nm³, R₁=0.0219, wR₂=0.0544。     

A Novel Polyoxovanadium Cluster Shell: β‐As8V14O42

The hydrothermal reaction of VOSO₄, As₂O₅, piperazine and H₂O produces [H₂N(CH₂)₄NH₂]₄[β‐As₈V₁₄O₄₂(SO₄)]·2HSO₄ ( 1 ), which is the first arsenic‐vanadium cluster containing a spherical β‐As₈V₁₄O₄₂ shell. The structure of this compound was characterized by single crystal X‐ray diffraction, elemental analysis, TG, and IR spectrum. Crystal data for 1 : Orthorhombic, Cmcm, a = 15.369(1) Å, b = 16.404(1) Å, c = 25.772(1) Å, V = 6497.4(9) ų, Z = 4.     

Baeyer-Villiger oxidation of ketones with hydrogen peroxide catalyzed by Sn-aniline complex

Sn-aniline complex was prepared by a simple procedure.Cyclic and acyclic ketones were oxidized into lactones or esters with very high selectivity and yield with 30% hydrogen peroxide in the presence of Sn-aniline complex.     

Study on the Interaction between Gatifloxacin Mesylate and Salmon Sperm DNA by Fluorescence Method

The interaction between gatifloxacin mesylate (GM) and salmon sperm DNA was studied by fluorescence spectrometry and ultra‐violet (UV) spectrometry. Additions of salmon sperm DNA to GM solution resulted in its strong fluorescence quenching and UV absorbance decrease due to the strong interaction between GM and salmon sperm DNA. Both the maximum fluorescence emission wavelength and the maximum UV absorbance wavelength of GM did not change with the increasing concentration of salmon sperm DNA, indicating no intercalative binding existed between them. The Stern‐Volmer plot indicated that the fluorescence‐quenching constant at different temperatures or different salmon sperm DNA concentration ranges was different. Effects of ionic strength and I^? on the fluorescence quenching of GM by salmon sperm DNA indicated that electrostatic interaction and groove binding coexisted between them.     

C NMR spectra of cyclomercurated ferrocenylimines: Substituent effects and conformations in the ferrocenes

Three series of cyclomercurated ferrocenylimines (2-chloromercurio-ferrocenylimines) have been studied using ¹³C NMR spectroscopy. Good to excellent linear relationships have been found to exist between the chemical shifts of the carbon atoms in the ferrocenyl moiety and normal Hammett substituent constants σ_m and σ_p. The δ values of the iminyl carbon atoms show excellent linear correlations with the σ values. In three series of the ferrocenes, the sensitivity of the carbon atoms to the substituent effect is different, which is discussed in terms of the twist angle between the N-phenyl ring and the C---C=N---C plane. The relative sensitivity of the chemical shifts on different positions in ferrocenyl moiety to the substituent effect has also been presented.     

Loss and recovery in hydrophobicity of silicone rubber exposed to corona discharge

This paper describes the loss and recovery in the hydrophobicity of unfilled high temperature vulcanized silicone rubber (HTV-SR) resulting from corona discharge. In this study, HTV-SR specimens were exposed to corona stress generated by a parallel needle-plane electrode system, and physicochemical analyses on the surface layer of SR before and after corona discharge treatment were carried out by using Fourier transform infra-red (FTIR) spectroscopy, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). It is demonstrated that hydrophilic OH groups that are by-products of ageing can be formed instead of hydrophobic CH₃ groups on the surface of aged SR and the corona discharge plays an important role on the temporary loss of hydrophobicity. After a substantial period of ‘rest’, the hydrophobic recovery of SR results from the diffusion of low-molecular weight (LMW) silicone fluid from the bulk onto the aged layer.     

ortho-Mercuration of ferrocenylimines

The mercuration of a series of aryliminomethylferrocenes occurred predominantly in an ortho-position of the substituted ferrocenyl ring to yield 2-mercurated ferrocenylimines. The regiospecificity of this reaction suggests that the mercury is directed into the ortho-position by coordination of the mercury to imino nitrogen with subsequent electrophilic substitution. The chromatographic and spectral properties of the 2-mercurated products show the presence of an intramolecular N → Hg coordination via the five-membered ring in these molecules, which was further confirmed by the single-crystal structure analysis of 2-chloromercuro-1-[(4-methoxyphenylimino)methyl]ferrocene.     

Synthesis and Characterization of Novel Organosoluble Methyl Substituted Poly(aryl Ether Ketone)s Containing Sulfone Linkage

Several new methyl substituted poly(aryl ether ketone)s containing sulfone linkage with inherent viscosities of 0.62–0.84 dL/g have been prepared from 4,4′‐bis(2‐methylphenoxy)diphenylsulfone and 4,4′‐bis(3‐methylphenoxy)diphenylsulfone with terephthaloyl chloride and isophthaloyl chloride by electrophilic Friedel‐Crafts acylation in the presence of DMF with anhydrous AlCl₃ as a catalyst in 1,2‐dichloroethane, respectively. These polymers having weight‐average molecular weight in the range of 71,000–49,000 are all amorphous and show high glass transition temperatures ranging from 167 °C to 191 °C, excellent thermal stability at temperatures over 400 °C in air or nitrogen, high char yields of 51–58% in nitrogen and good solubility in CHCl₃ and polar solvents such as DMF, DMSO and NMP at room temperature.     

Classificatin of chinese tea samples according to origin and quality by principal component techniques

Three categories of tea, black, green and oolong tea, with those varieties in each category were analyzed for their contents of cellulose, hemicellulose, lignin, polyphenols, caffeine and amino acids. The data were subjected to multivarige analysis. Principal component analysis and principal component classification provide discrimination between the different categories and varieties. The quality index, assigned to these tea standards by experts, could be predicted form the principal component scores.     

Direct Electrochemistry of Cytochrome c on EDTA-ZrO2 Organic-inorganic Hybrid Film Modified ElectrodesState Key Laborator3.＂ of Chemo／Biosensing and Chemometrics, Hunan Universit3; Changsha. Hunan 410082. China

A composite film of ethylenediamine tetraacetic acid (EDTA)‐ZrO₂ organic‐inorganic hybrid was prepared based on the chelation between Zr(IV) and EDTA. The direct electrochemical behavior of cytochrome c (cyt. c) at the hybrid film modified glassy carbon electrodes was investigated. The immobilized EDTA can promote the redox of heme in horse heart cyt. c which gives rise to a pair of reversible redox peaks with a formal potential of 40 mV (vs. SCE). The peak current increased linearly with the increase of cyt. c concentration in the range of 1.6 × 10^?6—8.0 × 10^?5 mol·L^?1 with the correlation coefficient of 0.996. Further investigation shows that metal ions can impede the electron transfer of cyt. c. The impediment capability of metal ions depends on their coordination capability with EDTA and their valence number.