On the High Viscosity of Aqueous Solution of Lysozyme Induced by Some Organic Solvents

A remarkably high viscosity has been induced in protein aqueous solutions by the addition of certain structurally related organic solvents. The effect has been observed for lysozyme aqueous solutions containing tetramethylurea (TMU), dimethylsulfoxide (DMSO), dimethylformamide, and hexamethylphosphortriamide. The effect has also been induced in ferrocytochrome c aqueous solutions by TMU. Critical concentrations for both the protein and organic solvent were verified for the onset of the viscosity increase. A common feature of the solvents which were able to induce the effect is a dipolar moiety (C=O, S → O and P → O) and a nonpolar region represented by the methyl groups. The resulting fluids show an extremely restricted flow and a typical non-Newtonian, pseudoplastic behavior. Use was made of¹H nuclear magnetic resonance (NMR) and Raman spectroscopy to characterize protein structural modifications and of¹³C NMR to investigate changes in relaxation times and chemical shifts in the solvent/water solutions. A systematic rheological characterization of the systems was undertaken for some of the solvents, and unusual patterns of viscous effects were identified for the solvent/water systems both with and without protein. The process was found to be at least partially reversible, as concluded from the recovered original solution rheological characteristics and the original protein¹H NMR spectrum, after eliminating the organic solvent by ultrafiltration. The whole process was characterized as consisting of two mutually independent stages. The first involves an extensive conformational transition of the polypeptide backbone, from a predominantly α-helical to increased random coiled and β-sheet structures, with the occurrence of nonorthodox protein secondary structures at regions above the solvent critical point. The second stage consists of short-lived interchain contacts leading to an entanglement of the macromolecular system as a whole. A microphase reversion in the organic solvent/water mixture, supported by¹³C NMR and rheological results, is proposed as the driving force causing the observed behavior.     

Development of a universal Raman detector for microchromatography

Summary A detector for microchromatography in which Raman spectroscopy is used to identify the eluted species has been developed. The detector is designed to be applicable to a wide range of compounds without requiring the presence of a chromophore. Its use is illustrated in the analysis of nitro compounds on a 250 μm i.d. column. Raman spectra of each of the compounds could be identified as they passed the detector. The advatages of the use of fully deuterated solvents are demonstrated by the analysis of nitrobenzenes in methanol/water mobile phases. The detection limit for nitrobenzene using the Raman line at 1342 cm⁻¹ was 75ng.     

现场表面拉曼光谱研究Fe-Mo合金诱导共沉积

现场表面拉曼光谱结果显示，在0．2mol·L-1Na2MoO4,pH＝4．0的溶液中，电位正于0．5V（vsSCE）时只观察到多钼酸盐的拉曼峰（940、880和450cm-1）．负于-0．5V时，出现中心位于730cm-1的宽峰．同时电极表面有蓝色膜生成．表明混合氧化态（MO（Ⅳ），MO（Ⅴ））氧化膜的形成．730cm-1的峰在-1．9V时仍然存在，说明氧化膜没有被进一步还原．在钼酸钠溶液中同时含有0．1mol·L-1FeSO4和0．2mol·L-1柠檬酸时，中间态氧化膜的拉曼峰的中心移到740cm-1．且峰强度随着电位从-1．3V负移到-1．9V而逐渐减弱并最终消失．电极表面沉积层呈银白色，说明由于Fe2 的存在，钼的中间态氧化膜的结构发生了变化，能够被进一步还原形成Fe－Mo合金，表现出诱导共沉积的特征．     

CdS/SiO2复合材料的低频Raman散射研究

对用溶胶凝胶法制备的ＣｄＳ／ＳｉＯ２复合材料进行低频Ｒａｍａｎ散射研究，结果表明可从其低频Ｒａｍａｎ散射峰位计算出ＣｄＳ微晶的粒径，两种不同的低频振动模式由激发光的两种偏振方向加以区分，低频Ｒａｍａｎ散射射的二级散射峰根据实验结果加以指认，所得平均粒径结果与透射电镜观察结果有较好的对应关系，复合材料吸收光谱吸收边蓝移与ＣｄＳ纳米子粒径之间存在着密切的关系，实验证明，样品吸收边能量与ＣｄＳ平均粒径的     

I NQR and spectroscopic investigation of impurity-doped and mixed lithium iodate Li1−xHxIO3 crystals

The ¹²⁷I NQR, IR absorption and Raman spectra of impurity-doped and mixed lithium iodate Li_1−xH_xIO₃ crystals grown from water solutions with different LiIO₃/HIO₃ ratios were investigated depending on the content of the impurity hydrogen x. The NQR results suggested that, at small concentration of doping iodic acid x<0.22, the lattice dynamics of the crystal grown from water solution changes significantly though the crystal retains hexagonal symmetry. Spectroscopic studies are compatible with average hexagonal symmetry of the grown doped crystals. From the results of Raman studies at room temperature and 100 K, the concentration range of hydrogen dopant 0.22<x<0.36 was found where disordered solid solution crystals Li_1−xH_xIO₃ are formed.     

Spectroscopic Studies on the Interaction of Tetramethylpyridylporphyrins and Cationic Clays

In the present work, the interaction between5,10,15,20-tetrakis(1-methyl-4-pyridyl)-21H,23H-porphine (TMPyP) and its metallated form(CoTMPyP) with three cationic clays was investigatedby X-ray diffraction (XRD), UV-VIS and resonance Ramanspectroscopies. Sodium montmorillonites K10 and KSFand a synthetic fluorohectorite (FHT) containingdifferent macrocycle loadings, were prepared by an ionexchange reaction. In nonsaturated KSF and FHT, theCoTMPyP molecule assumes a flat orientation, relativeto the host layers, giving rise to at least twoabsorption bands in the Soret region (ca. 445 and 465 nm)assigned to adsorbed and intercalated CoTMPyP,respectively. For the delaminated K10 sample, a broadband centered around 456 nm, indicates a majorcontribution from the metalloporphyrin on the clayexternal surfaces. The electronic spectra of FHTsamples containing increasing amounts of CoTMPyPshow bands red shifted even when a small amount ofporphyrin is used, suggesting that the electroniclevels of the macrocycle are more affected by theinteraction with the clay than by the metalloporphyrindistortion inside the galleries. The resonance Ramanspectra obtained for all CoTMPyP samples presentedonly minor shifts in peak positions and band width,with the exception of the FHT saturated sample, wherethe bands are clearly broader when compared to otherloadings, suggesting that porphyrin aggregation isoccurring. In the case of TMPyP, the bands at ca. 430and 468 nm were assigned to nonprotonated andprotonated molecules, respectively. This assignment issupported by resonance Raman spectroscopy, which alsoshowed the ₂ mode (ca. 1550 cm^-1) to bethe most sensitive peak to protonation.     

Dehydration and crystallization process in sol-gel zirconia

Sol-gel zirconia was characterized using high-resolution thermogravimetry (Hi-Res TG) and differential scanning calorimetry (DSC) and compared with X-ray diffraction, Raman scattering, and UV-Vis spectroscopy. ZrO_2-x(OH)_2x·yH₂O annealed below 400°C show typical behavior of amorphous material. As the annealing temperature is increased, the tetragonal and monoclinic phases crystallize. Typical Hi-Res TG curve shows that the samples are continuously dehydrated in a long temperature range, between room temperature and 600°C. The total mass loss relative to the initial mass is of about 29%. The DSC analysis coupled with TG and structural information, indicate that the exothermic processes about 355 and 447°C can be related to the nucleation process of the formation of tetragonal zirconia, with bulk crystallization at 447°C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation and Characterization of N-4-Nitrophenyl-L-prolinol Nanocrystals in Sol-Gel Matrices

Organic nanocrystals of N-4-nitrophenyl-l-prolinol (NPP) have been grown in sol-gel matrices prepared from silicon alkoxide precursors. Our process is based on the control of the nucleation and growth kinetics of the dye in the pores of dense gels. Nanocomposites gel-glasses are obtained with a high optical quality due to the small size of the nanocrystals (10-20 nm). Differential scanning calorimetry experiments evidenced clearly the melting point of NPP nanocrystals, which is registered 51°C above that of NPP powder. Micro-Raman and solid state NMR spectroscopies allowed us to demonstrate that our nanocrystallization process does not chemically modify NPP molecules. We specified also the nature of interactions existing between the NPP nanocrystals and the xerogels. These strong interactions, which explain the important increase of the melting point of the nanocrystals in comparison to the NPP powder, are hydrogen bonds between nitro groups of NPP and uncondensed silanol functions of the silicate network.     

Strategy for obtaining improved surface-enhanced Raman scattering by combining electrochemical and plasmas technologies

In this work, surface-enhanced Raman scattering (SERS)-active gold substrates were first developed by combining the technologies of oxidation–reduction cycles (ORCs) and plasmas treatments in roughening metal substrates. First, a gold substrate was treated by argon plasmas. Then the treated gold substrate was further roughened by triangular-wave ORCs in an aqueous solution containing 0.1 M HCl. Encouragingly, the SERS of Rhodamine 6G (R6G) adsorbed on this roughened gold substrate modified by argon plasmas pretreatment exhibits a higher intensity by 10-fold of magnitude and a better resolution, as compared with the SERS of R6G adsorbed on an unmodified roughened gold substrate. Meanwhile, the probing concentration of R6G adsorbed on the modified substrate can be reduced by one order. It was also found that the pretreatment of argon plasmas demonstrates a positive effect on the (2 2 0) face of Au partly changing into the (1 1 1) face with the lowest surface energy after the ORCs roughening, which is contributive to the improved SERS observed.     

激光拉曼光谱在高分子中的应用

论述了激光拉曼光谱对高分子结构、结晶形态和表征,反应动力学过程和取向的研究,还介绍了纵向声学模、共振、高温高压、光波导和付里叶拉曼光谱在高分子研究中的最新进展。