Raman Spectra of Pyridine Adsorbed on Supported Molybdate Catalysts

Pyridine adsorption was used as a probe of the surface structure of supported molybdate and cobalt molybdate catalysts. The catalysts consisted of a γ-Al₂O₃ support which had been impregnated with various molybdenum loadings ranging from 1.25% to 15% (MoO₃). The Raman spectra of the catalyst and of the adsorbed pyridine indicated that a considerable portion of the alumina surface was not covered by molybdenum even after molybdenum trioxide was formed. Brnsted acid site and Lewis acid site adsorption were observed for low     

Dynamical changes in hydration water accompanying lysozyme thermal denaturation

We study the dynamics of the first hydration shell of lysozyme to determine the role of hydration water that accompanies lysozyme thermal denaturation. We use nuclear magnetic resonance spectroscopy to investigate both the translational and rotational contributions. Data on proton self-diffusion and reorentational correlation time indicate that the kinetics of the lysozyme folding/unfolding process is controlled by the dynamics of the water molecules in the first hydration shell. When the hydration water dynamics change, because of the weakening of the hydrogen bond network, the three-dimensional structure of the lysozyme is lost and denaturation is triggered. Our data indicates that at temperatures above approximately 315 K, water behaves as a simple liquid and is no longer a good solvent.     

Multicomponent Rayleigh scattering from guanidine hydrochloride solutions

We present results of Brillouin light scattering studies of lysozyme and guanidine hydrochloride solutions in the temperature range 290–350 K. The Brillouin spectra of 6 M guanidine hydrochloride have been found to contain an additional component in Rayleigh scattering that manifests itself as a broad quasi‐elastic scattering line centered at the unshifted frequency and described by a Lorentz function (i.e. a Debye relaxor with relaxation time τ₁ ~ 25 ps at room temperature). The temperature dependence of τ₁ is described by the Arrhenius law with activation energy E_a = 0.11 ± 0.01 eV and prefactor τ₀= 0.33 ± 0.03 ps. The Brillouin spectra of lysozyme denatured by 6 M guanidine hydrochloride exhibit a more complicated structure of the additional contribution into Rayleigh scattering, which is fitted best of all by a sum of two Lorentzians centered at the unshifted frequency (with relaxation times τ₁ ~ 19 ps and τ₂ ~ 180 ps at 339 K). Possible origins of the quasi‐elastic scattering are discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

甲基橙在银镜上的表面增强拉曼光谱研究

利用表面增强拉曼光谱(SERS)技术研究了甲基橙的(MO)的SERS谱,对拉曼峰进行了指认,并给出了甲基橙在银镜上的吸附状态。     

钴铈复合氧化物在催化氧化中吸附氧的EPR研究

以溶胶-凝胶法制备了钴、铈及其复合氧化物,考察了其对对甲酚催化氧化的性能,复合氧化物表现出优良的活性和选择性.用EPR方法对3个催化剂样品表面吸附氧及其在可控气氛下与对甲酚的作用进行了研究,实验表明,O₂^-可能为活性氧物种,其吸附量及配位环境可与催化活性和选择性相关联。     

疏水表面上吸附态溶菌酶的DSC和FTIR研究

联合差示扫描量热 (DSC)和傅里叶变换红外吸收光谱(FTIR)分别研究了鸡蛋白溶菌酶(Lyz)在适度疏水吸附剂(PEG-600)表面上吸附和折叠时,不同盐(硫酸铵)浓度、表面覆盖度和变性剂(盐酸胍)浓度对无水环境的吸附态天然和变性溶菌酶构象变化及热稳定性的影响。研究发现：随着硫酸铵浓度和溶菌酶表面覆盖度的增加,吸附态天然和变性溶菌酶的吸热峰温度都逐渐降低,同时在较高温度下的微扰也增多。吸附发生后,α-螺旋结构减少,β-折叠和β-转角结构增多。在FTIR图谱中,吸附态变性溶菌酶在1 400～1 425 cm-1处的C—C拉伸振动峰和1 650～1 670 cm-1处的酰胺Ⅰ带特征峰都能明显观测到。但是,与之相比,相同条件下吸附态天然溶菌酶在1 650～1 670 cm-1处特征峰却几乎看不到。吸附态天然溶菌酶发生了结构丢失,表现得更加不稳定。     

Infrared Photothermal Deflection Spectroscopy of Carbon-Supported Metal Catalysts

The infrared (IR) study of surface species and reactions occurring on solids has contributed markedly to our understanding of surface chemistry and heterogeneous catalysis, and a wide variety of solids has been examined. However, an entire class of catalysts consisting of metal dispersed on carbon has never been studied because the carbon catalyst support absorbs IR radiation so strongly in even the thinnest practical layers that conventional IR techniques fail. As IR data would be helpful in understanding how such catalysts function, we have explored the feasibility of examining carbon-supported catalysts with photothermal beam deflection spectroscopy (PDS) and describe the first IR spectra ot surface species on a Ni-on-carbon catalyst.     

光谱法比较喜树碱与溶菌酶、过氧化氢酶的相互作用

采用紫外可见吸收、红外、荧光等多种光谱学方法研究了抗癌药物喜树碱和溶菌酶及过氧化氢酶两种蛋白之间的相互作用,结果表明,喜树碱与之均形成基态复合物并引起蛋白内源荧光猝灭。通过计算确定了喜树碱和蛋白相互作用的结合常数、结合位点数、主要作用力类型以及与蛋白中色氨酸的结合距离。喜树碱对过氧化氢酶具有较高的结合能力,这主要是由于喜树碱不仅与过氧化氢酶中的色氨酸存在相互作用,也与酶中的酪氨酸及血红素产生相互作用。喜树碱的存在可引起蛋白构象发生变化,使α-螺旋二级结构减少。     

电喷雾质谱法研究人参皂苷与溶菌酶的相互作用

用电喷雾质谱法研究了溶菌酶与人参皂苷Rg1和Re的非共价相互作用。非共价复合物的解离常数可以由溶菌酶和复合物的峰高直接计算得到。由各个体系得到的溶菌酶与Rg1和Re的一级解离常数KD, 1是一致的,但是二级解离常数KD, 2的差别较大。由此可以推断出复合物的峰高越强,结果的精密度越好。当固定溶菌酶的浓度不变时,复合物的解离常数会随着人参皂苷的浓度的增加而略微的增大。而当固定人参皂苷的浓度时,复合物的解离常数会随着溶菌酶的浓度的增加而减小。计算结果还证明了人参皂苷Rg1与溶菌酶的结合能力大于Re。     

The interaction of anionic azo dyes with hen egg-white lysozyme: 1

The interactions between seven anionic azo dyes and hen egg-white lysozyme were investigated by means of visible absorption spectroscopic and lytic activity measurements. The dyes, for which no report on the interaction has appeared so far, were bound with lysozyme to different extents as a result of the differences in their chemical structures. Although most of the dyes formed 11 complex with lysozyme, two of them behaved differently. From the measurements of the absorption, lytic inhibition toward cell walls and competitive binding with substrate analogues, it was concluded that a major binding site of these dyes on lysozyme is a charged lysine residue in the vicinity of the subsitesD, E andF, and, in the case of a dye that forms 21 complex with lysozyme, and additional binding site is in the vicinity of the subsite B.