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Deep UV resonance Raman spectroscopy was used for characterizing ligand-metal ion complexes. The obtained results demonstrated a strong intrinsic sensitivity and selectivity of a Raman spectroscopic signature of a bicyclic diamide, a novel chelating agent for lanthanides and actinides (Lumetta, G. J.; Rapko, B. M.; Garza, P. A.; Hay, B. P.; Gilbertson, R. D.; Weakley, T. J. R.; Hutchison, J. E. J. Am. Chem. Soc. 2002, 124, 5644). Molecular modeling, which included structure optimization and calculation of Raman frequencies and resonance intensities, allowed for assigning all strong Raman bands of the bicyclic diamide as well as predicting the band shifts observed because of complex formation with metal ions. A comparative analysis of Raman spectra and the results of the molecular modeling could be used for elucidating the structure of complexes in solution.  相似文献   
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Extensive studies of the spectral-luminescent characteristics of four 8-azasteroids and a model compound 2-(3,3-dimethyl-1,2,3,4-tetrahydro-1-isoquinolidene)-5,5-dimethyl-1,3-cyclohexanedion in the gas phase have been made. From the analysis of the dependences of the absorption spectra on the vapor pressure (Tlow) and the fluorescence spectra on Tlow and the exciting radiation wavelength (exc) a conclusion on the presence in the vapors of the investigated 8-azasteroids of three absorption and fluorescence centers (S-, M-, and L-centers) has been drawn. The absorption spectra of these centers strongly overlap. Their long-wave absorption boundaries have been determined. The dependence of the fluorescence spectra of all three centers on exc, which is inherent in rarefied gases of individual organic molecules, is observed. The S-centers are the molecules of the initial steroids, and the M- and L-centers are the molecules of thermo- and phototransformations of the initial steroids. The model compound in the gas phase is characterized by the same dependences of the fluorescence spectra on Tlow and exc as those inherent in 8-azasteroids. Taking into account the additional data obtained as a result of investigation of the absorption and fluorescence spectra of solutions of the substances extracted from vacuum cells after the investigation of 8-azasteroids and the model compound in the gas phase, conclusions on the nature of the M- and L-centers have been drawn.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 48–57, January–February, 2005.  相似文献   
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We study a class of stationary transport equation with nonlocal low-order tems We obtain the existence and uniqueness of a solution in sobolev spaces  相似文献   
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非线性涡黏性系数模型和代数应力模型联系了线性涡黏性系数湍流模型和完整的微分 雷诺应力模型.随着它们受到日益关注,其形式也越来越多样化.本篇综述的目的是对这些模 型加以总结并比较它们之间的共同点及不同之处,指出它们与完整微分雷诺应力模型之间的 关系,以及相对于线性涡黏性系数模型而言它们在预报流场上所具有的优势.  相似文献   
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The early stages of hen egg white lysozyme (HEWL) fibrillation were quantitatively characterized by two-dimensional correlation deep UV resonance Raman spectroscopy (2D-DUVRR) in terms of the sequential order of events and their characteristic times. The evolution of individual secondary structural elements was established through the correlation between Amide I, Amide III, and Calpha-H bending Raman bands. The temporal order of tertiary and individual secondary structural changes was probed through the cross-correlation of phenylalanine and Amide Raman bands. Both the sequential order and the characteristic times of tertiary and secondary structural changes allowed for reconstructing the molecular mechanism of lysozyme structural changes at the early stages of fibrillation. The 2D-DUVRR analysis of our data indicated that melting of the alpha-helix happened after the formation of the disordered structure, which was termed as apparent inverse order of secondary structural changes. We demonstrated that this apparent inverse order of events is typical for all chemical reactions involving the formation of intermediate(s), which may lead to the serious misinterpretation of 2D correlation results. We proposed a new simulation-aided approach for reconstructing and quantitatively characterizing the reaction mechanism of a (bio)chemical reaction that accounts for the apparent inverse order of events.  相似文献   
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Since the initial introduction of the basic concept almost twenty years ago, two‐dimensional correlation spectroscopy (2DCoS) has become a popular analytical tool applicable to a broad range of science problems. Vibrational spectroscopy remains the major area of 2DCoS applications where infrared spectroscopy is the most popular technique followed by Raman and Near Infrared spectroscopies. An increasing number of publications over the past few years have established Raman 2DCoS as a powerful problem solving technique in protein studies. In this review we provide a critical survey of recent protein studies using the 2DCoS Raman approach. We also analyze common misconceptions and potential pitfalls in the interpretation of 2D correlation data. Over the past decade, there have been a number of publications pointing to artifacts associated with visualization and interpretation of 2D correlation maps. We demonstrate here how some of the ‘artifacts’ of the 2DCoS approach in ‐ reality turn into the strength of the method. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   
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Appearance energies of [M-H](-) ions from carbonyl compounds R-CO-R' (R,R' = H, CH(3), NH(2), OH) have been measured by means of negative ion mass spectrometry in resonant electron capture mode. Values of electron affinity of the corresponding radicals, CH(2)&dbond;C(X)O, NH&dbond;C(X)O and O&dbond;C(X)O, have been determined. Copyright 1999 John Wiley & Sons, Ltd.  相似文献   
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