微过氧化物酶-8与Eu3+相互作用的机理

用紫外-可见(UV-Vis)吸收光谱和电化学方法研究Eu3+与微过氧化物酶-8(MP-8)相互作用的机理,发现Eu3+优先与MP-8中血红素基团的2个丙酸基的羧基氧发生强的配位作用,导致MP-8分子中血红素基团的非平面性、暴露程度和电化学可逆性的增加.过剩的Eu3+与MP-8分子中肽链上的含氧基团发生弱的相互作用,对血红素基团结构的影响较小.     

Determination of the Dissociation Constants of Urocanic Acid Isomers in Aqueous Solutions

Summary. (E)- and (Z)-Urocanic acids are endogenous chemicals in the normal mammalian skin. The first and the second thermodynamic dissociation constants (pK _a1 and pK _a2) of urocanic acid isomers were determined using UV spectrophotometry in aqueous solutions. The values with standard deviation (pK _a1 = 3.43 ± 0.12 and pK _a2 = 5.80 ± 0.04) and (pK _a1 = 2.7 ± 0.3 and pK _a2 = 6.65 ± 0.04) were obtained to (E)- and (Z)-urocanic acids, respectively. The second dissociations were studied also by potentiometric titration in aqueous sodium chloride solutions up to the isotonic salt concentration (0.154 mol dm⁻³), and the second thermodynamic dissociation constants as well as activity parameters for both isomers were determined at temperature 25°C and for (E)-urocanic acid also at 37°C. The obtained pK _a2 values were close to those found by UV spectrophotometry. The equations for the calculation of the second stoichiometric dissociation constants of urocanic acid isomers on molality and molarity scale in aqueous sodium chloride solutions were derived. The obtained pK _a1 and pK _a2 values for (Z)-urocanic acid appear to be essentially lower than some previously reported values in literature. An erratum to this article is available at .     

Molecular motion and interactions in aqueous carbohydrate solutions. I. Dielectric-relaxation studies

Dielectric-relaxation studies in the frequency range 200 kHz to 35 GHz are reported for a range of sugars (from mono- to trisaccharides) in aqueous solution. The complex dielectric spectra were analyzed using a weighted least-squares minimization method to resolve the various component relaxations, and the implications of the analyses in terms of the molecular dynamics of solute and solvent and the interactions between solute and solvent are discussed. For the highest concentration studied (ca. 2M), it was found that the most significant analysis required three discrete relaxation processes, whereas lower concentration samples could usually be satisfactorily fitted with two. Irrespective of any uncertainty in model selection, a number of conclusions regarding the solute-solvent interactions can be made, and it is shown how final quantification of the extents of hydration can be made using the input of information from other techniques.     

Review of recent UV–Vis and infrared spectroscopy researches on wine detection and discrimination

Wine has become a commodity of significant commercial value, and the demand for high quality wine by consumers has been increasing. Suitable analytical techniques are needed for its quality control. Ultraviolet, Visible, Near-infrared and infrared spectroscopy is by far one of the most important techniques for determining the wine quality, including its components and characterization. This review will overview the available most recent applications of spectroscopic techniques in the past decade for wine quality prediction and discrimination both quantitatively and qualitatively. The fundamental principles of these techniques will be introduced briefly, and some innovative setups/instrumentations will also be illustrated. At last the limitations and prospects of spectroscopic techniques for wine industry will be discussed.     

黑米花色苷酰化修饰红外光谱分析

黑米花色苷易受外部环境影响发生降解致使局部分子结构破坏而使营养价值和保健功能有所下降。利用有机酸提供酰基对黑米花色苷进行修饰来提高花色苷结构的稳定性。利用红外光谱分析经咖啡酸酰化修饰黑米花色苷的结构变化。结果表明：黑米花色苷酰化修饰前后于官能团区3 650~3 200和1 680~1 620 cm-1处均有吸收峰，且其于指纹区1 282.68和1 277.51 cm-1处出现酚羟基吸收峰，于1 056.07和1 054.03 cm-1处出现醇羟基吸收峰，719.90和719.71 cm-1处出现苯环上C-H面外弯曲振动吸收峰。由此可见，黑米花色苷酰化修饰后主要结构框架仍为花色苷的芳环结构。此外，黑米花色苷酰化修饰前后于1 900~1 650 cm-1间1 714.28和1 728.13 cm-1处均出现共轭羰基的特征吸收峰，对应于可直接连接在苯环上的α-羰基结构，由此说明黑米花色苷结构中存在着酰基基团。黑米花色苷经酰化修饰后红外图谱于1 517.20 cm-1处出现新吸收峰，其正好处于1 800~900 cm-1双键(不含氢)伸缩振动区，指纹区876.65 cm-1处亦出现了苯环上的C-H面外弯曲振动吸收峰。与之相呼应在经二阶导数处理后红外光谱图中在2 500～2 000 cm-1间出现了新的波动，此波段为累积双键伸缩振动区，而官能团区3 650~3 200 cm-1间3 370.20 cm-1处的吸收峰正好处于多分子缔合区。由此可见，在咖啡酸作为酰基供体，酰化修饰黑米花色苷时由于分子间的重新缔合于结构中引入了新的酰基基团而呈现出一种双酰化的空间结构。黑米花色苷酰化结构中有机酸与糖链相连，将有机酸置于2-苯基苯并吡喃骨架的表面，这种堆积作用模式可以较好地抵抗水的亲核攻击和其他降解反应进而提高黑米花色苷结构的稳定性。     

Preparation,crystal structure,and physical characterization of a new hybrid material (C5H9N3)ZnCl4·H2O

An organic–inorganic hybrid compound (C₅H₉N₃)ZnCl₄ · H₂O was synthesized by slow evaporation and characterized by single-crystal X-ray diffraction, differential scanning calorimetry, thermogravimetry, temperature-dependent X-ray powder diffraction, infrared spectroscopy, and some preliminary theoretical calculations of non-linear optic activity. The compound crystallizes in the non-centrosymmetric space group Pca2₁ with unit cell parameters: a = 22.714(5), b = 7.313(5), c = 7.301(5) Å, Z = 4, and V = 1212.8(12) ų. The structure was solved using direct methods and refined by least-squares analysis [R ₁ = 0.0484 and wR ₂ = 0.1255]. It is built from isolated [ZnCl₄]^2? anions, 2,5-diaminopyridinediium [C₅H₉N₃]²⁺ cations, and water molecules which are connected by a 3-D hydrogen-bond network. Thermodiffractometry and thermogravimetric analyses indicate that its decomposition proceeds through four stages leading to a new crystalline anhydrous phases.     

由季戊四醇合成季戊四硫醇的新方法

以季戊四醇为原料,先合成四对甲苯磺酸季戊四醇酯,然后四对甲苯磺酸季戊四醇酯与硫氰酸钾在N,N-二甲基甲酰胺中加热反应,生成了2,3,7,8-四硫螺[4,4]壬烷,2,3,7,8-四硫螺[4,4]壬烷经四氢化铝锂还原、酸化,得到季戊四硫醇.产物结构经熔点、红外光谱、质子核磁共振谱、拉曼光谱鉴定.     

An investigation on visible luminescence of Ho activated LBTAF glasses

Different concentrations of Ho³⁺-doped lead borate titanate aluminum fluoride (LBTAFHo) glasses with chemical composition of PbO-H₃BO₃-TiO₂-AlF₃-Ho₂O₃ were prepared by the melt quenching method. The spectral properties were investigated using the absorption, emission and decay measurements. The experimental oscillator strengths were calculated from the area under the absorption bands. Applying Judd-Ofelt theory, the intensity parameters (Ω_{λ=2, 4, 6}) were calculated, by the least square fit approach from which the radiative transition rates, luminescence branching ratios and radiative decay times were determined. The photoluminescence spectra revealed the quenching of luminescence intensity beyond 1.0 mol% of Ho³⁺ ion concentration. To investigate the luminescence potentiality of ⁵F₄→⁵I₈ emission level, the effective bandwidth and the stimulated emission cross-section were determined. The quenching in experimental decay time is attributed to the resonance energy transfer among the excited Ho³⁺ ions.     

Raman Spectroscopic Studies of Methane Gas Hydrates

Abstract

A brief review of the Raman spectroscopic studies of methane gas hydrates is given, supported by some new measurements done in our laboratory.     

Synthesis and Rearrangement of P‐Nitroxyl‐Substituted PIII and PV Phosphanes: A Combined Experimental and Theoretical Case Study

Low‐temperature generation of P‐nitroxyl phosphane 2 (Ph₂POTEMP), which was obtained by the reaction of Ph₂PH ( 1 ) with two equivalents of TEMPO, is presented. Upon warming, phosphane 2 decomposed to give P‐nitroxyl phosphane P‐oxide 3 (Ph₂P(O)OTEMP) as one of the final products. This facile synthetic protocol also enabled access to P‐sulfide and P‐borane derivatives 7 and 13 , respectively, by using Ph₂P(S)H ( 6 ) or Ph₂P(BH₃)H ( 11 ) and TEMPO. Phosphane sulfide 7 revealed a rearrangement to phosphane oxide 8 (Ph₂P(O)STEMP) in CDCl₃ at ambient temperature, whereas in THF, thermal decomposition of sulfide 7 yielded salt 10 ([TEMP‐H₂][Ph₂P(S)O]). As well as EPR and detailed NMR kinetic studies, indepth theoretical studies provided an insight into the reaction pathways and spin‐density distributions of the reactive intermediates.