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  • 1
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Raman band of the ν1 vibrational mode of SO42- has been measured in aqueous solutions of Na2SO4 and (NH4)2SO4 at 5-80°C, and analysed from the stochastic point of view. The band shape is approximately symmetric, but cannot be reproduced by a Lorentzian curve. The vibrational relaxation is caused by a random modulation of very low frequency from surrounding water. The vibrational correlation time for the ions is not sufficiently long to make allowance for the Markovian process of relaxation, compared with the correlation time for the bath, that is water. The vibrational correlation function appropriate for these ions is proposed.
    Additional Material: 4 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 20 (1991), S. 493-497 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A sensitive and rapid method to analyse fuel components in blood from rats exposed to kerosene or light oil vapour was developed by making use of capillary gas chromatography/mass spectrometry. The aliphatic hydrocarbons with carbon numbers 8-10 and aromatics such as toluene, xylene, 3- and 4-ethyltoluene and trimethylbenzenes were clearly detected in blood from rats exposed to kerosene or light oil vapour, using the head-space method combined with the salting-out technique. The concentration ratio of pseudocumene to toluene in blood exposed to light oil was higher than that in the case of exposure to kerosene. The lower limits of detection were 50 pg and 1 ng in toluene and pseudocumene, respectively. Our suggestion is that this method is useful in forensic investigations to detect fuel components in blood and for the purposes of differentiating kerosene and light oil in blood tissues.
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  • 3
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman spectra were measured for five crystals containing N-deuterated histidinium and their C2-deuterated analogues. The spectra showed strong bands assignable to the C4=C5 stretching mode, ν(C4=C5), and the Nτ—C2—Nπ symmetric stretching mode, ν(NτC2Nπ), characteristic of the N-deuterated imidazolium ring. By comparison with the crystal structures, the ν(C4=C5) and ν(NτC2Nπ) frequencies are found to increase linearly with increase of the absolute value of the Cα—Cβ—C4=C5 torsional angle (χ2, 1), which determines the ring orientation relative to the amino acid backbone. Exceptionally, the ν(NτC2Nπ) frequency of the C2-deuterated imidazolium ring does not depend on the conformation but shows a correlation with the N—D stretching frequency of the ring, indicating that ν(NτC2Nπ) becomes a marker of hydrogen-bonding strength when the imidazolium ring is deuterated at C2. These marker bands may be useful in studying the conformation and hydrogen-bonding states of histidine residues in proteins and peptides.
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  • 4
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polarized Raman measurements have been made for the totally symmetric vibration bands of a series of halogen-substituted methanes in the liquid state at room temperature. The effect of polarization mixing due to divergence was examined experimentally and eliminated. The observed systematic variations in depolarization ratio are discussed in connection with the bond polarizability theory.
    Additional Material: 6 Ill.
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  • 5
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of temperature on the peak positions, the isotropic and reorientational band widths and the depolarization ratios of the Raman bands for the totally symmetric vibrations of CHCl3, CH2Cl2, CH2Br2, CH3Br, CH3I and CD3I has been measured in the liquid state. The isotropic band width for a C—X stretching vibration decreases with increasing temperature for molecule with only one C—X bond, whereas it increases for a molecule with two or three equivalent C—X bonds. The isotropic band width for the deformation vibrations decreases with increase in temperature. For all the bands, the depolarization ratios depend only slightly on temperature.
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 6 (1977), S. 89-91 
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ν1 Raman linewidths of SO42- in NH4HSO4, NH4HSO4 + HCl and H2SO4 aqueous solutions were estimated by resolving the observed bands into several components with a Voigt profile. From their concentration dependence, the rate constants of proton transfer were estimated to be 4.5 × 1011 M-1s-1 consistently for the three kinds of acidic solutions.
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  • 7
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Raman spectra of 14 positional isomers of carboxylic acids esters with 17 skeletal atoms, CH3(CH2)m-1COO(CH2)n-1CH3(CmCOOCn) with m + n = 15 and m = 1 - 14, have been measured in the crystalline state at liquid nitrogen temperature. The relationship between the observed wavenumbers of the characteristic bands and the positions of the  - C(=O) - O -  group in the molecular chain was examined. All of the positional isomers of CmCOOCn with m + n = 15 exhibit a strong LAM-1 band in the region between 147 and 136 cm-1. The LAM-1 wavenumbers for the isomers which have the  - C(=O) - O -  group almost in the middle of the molecular chain are slightly higher (147 - 143 cm-1) than those for the isomers which have the same group almost at the end of the chain. In order to elucidate the observed LAM-1 wavenumbers, the Raman spectra of two homologous series of esters, C5COOCn and C6COOCn, were examined. All isomers of CmCOOCn give a strong band at about 1135 cm-1 assignable to the k = 1 mode of the C - C stretching vibrations. Some of the isomers give an additional k = 1 band at about 1125 cm-1. The isomers of CmCOOCn, which exhibit the two k = 1 bands, have the  - C(=O) - O -  group almost in the middle of the molecular chain, and appear to give the LAM-1 band at the higher wavenumbers. In the crystalline state all of the esters examined take the all-trans conformation with the  - C(=O) - O -  group part incorporated.
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  • 8
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A band shape function for the isotropic Raman scattering described in terms of the band width in the weak coupling limit and the relaxation time of the bath mode has been proposed by summing the results of Berne et al. [J. Chem. Phys. 45, 1086 (1966)], Wang [Mol. Phys. 33, 207 (1977)] and Knauss [Mol. Phys. 36, 413 (1978)]. The results of band analyses with this function have been compared with those obtained from other conventionally used band shape and correlation functions. The present function is preferable for precise interpretation of vibrational relaxation mechanisms, particularly for those cases where temperature and concentration dependence of the band parameters are involved.
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  • 9
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The isotropic and anisotropic Raman band widths of the totally symmetric vibrations of halogen-substituted methanes have been measured in the liquid state at room temperature. The isotropic C—H and C—D stretching vibration bands broaden with increasing molecular weight and this is qualitatively explained by the Fischer-Laubereau dephasing model. The isotropic band widths of the deformation vibrations are correlated with the reorientational correlation times and are attributed to broadening due to interactions dependent on the orientation, such as the dipole-dipole interaction.
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  • 10
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aromatic solvent-induced shifts (ASIS) in 19F n.m.r. spectra of several organic fluoro compounds have been determined in several solvents. 19F n.m.r. signals of unsaturated fluoro compounds in C6F6 and C6H6 show excess high field shifts corresponding to the term σc (solvent shift caused by chemical interactions). The mechanism of this shift is discussed in connection with the presence of an F-π interaction. A thermal study also supports this idea.
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