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  • Articles  (2,588)
  • Analytical Chemistry and Spectroscopy  (2,588)
  • ENERGY PRODUCTION AND CONVERSION
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  • 11
    Electronic Resource
    Electronic Resource
    Ultrafast infrared spectroscopy in biomolecules: Active site dynamics of heme proteins (1996)
    New York, NY [u.a.] : Wiley-Blackwell
    Biospectroscopy 2 (1996), S. 277-299 
    Details
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Rapid advances in the generation of intense tunable ultrashort mid-infrared (IR) laser pulses allow the use of ultrafast IR pump-probe and vibrational echo experiments to investigate the dynamics of the fundamental vibrational transition of CO bound to the active site of heme proteins. The studies were performed using a free-electron laser (FEL) and an experimental set up at the Stanford University FEL Center. These novel techniques are discussed in some detail. Pump-probe experiments on myoglobin-CO (MbCO) measure CO vibrational relaxation (VR). The VR process involves loss of vibrational excitation from CO to the protein and solvent. Infrared vibrational echoes measure CO vibrational dephasing. The quantum mechanical treatment of the force-correlation function description of vibrational dynamics in condensed phases is described briefly. A quantum mechanical treatment is needed to explain the temperature dependence of VR in Mb-CO from 10 to 300 K. A molecular-level description including elements of heme protein structure in the treatment of vibrational dynamics is also discussed. Vibrational relaxation of CO in Mb occurs on the 10-11-s time scale. VR was studied in proteins with single-site mutations, proteins from different species, and model heme compounds. A roughly linear relationship between carbonyl stretching frequency and VR rate has been observed. The dominant VR pathway is shown to involve anharmonic coupling from CO through the π-bonded network of the porphyrin, to porphyrin vibrations with frequencies 〉 400 cm-1. The heme protein influences VR of bound ligands at the active site primarily via altering the through π-bond coupling between CO and heme. Preliminary vibrational echo studies of the effects of protein conformational relaxation dynamics on ligand dephasing are also reported. © 1996 John Wiley & Sons, Inc.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    15N and 13C NMR study of the effects of hydrogen bonding and protonation in linear schiff bases: Models for structural studies of rhodopsin and bacteriorhodopsinPart 4 of the series ‘Spectral Studies of Visual Pigments and Related Systems.’ For part 5, see Ref. 9. Dedicated to the memory of Professor Margaret Avram. (1984)
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 22 (1984), S. 121-124 
    Details
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of protonation and hydrogen bonding in linear Schiff bases obtained from n-butylamine with butyraldehyde, crotonaldehyde, sorbaldehyde and all-trans-retinal were studied by means of 15N and 13C NMR. The protonation-induced chemical shifts (Δδ) are an order of magnitude larger for 15N than for 13C. For 15N, this effect was found to increase with the extent of conjugation, culminating in the retinylideneimine (Δδ = -146 ppm), which constitutes a model for the study of the structure of the Schiff base linkage in visual pigments and related systems. Theoretical calculations of protonation-induced Δδ values based on MINDO/ 3 are in agreement with experimental results.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/mrc.1270220214
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  • 13
    Electronic Resource
    Electronic Resource
    NQR investigations of 35Cl in crystalline 2,5-dichloro-4-nitroaniline (1981)
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 16 (1981), S. 123-125 
    Details
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two NQR lines were observed for 35Cl in 2,5-dichloro-4-nitroaniline at room temperature, using a self-quenched super-regenerative spectrometer. Analysis of the Zeeman effect on the two lines using a cylindrical single crystal reveals that the crystal belongs to the monoclinic system. The principal field gradient Z axes enclose an angle of 35° and 28° in the cases of the low and high frequency resonance lines, respectively. The b axis is parallel to 81°, 280°. The unit cell contains either two or a multiple of two molecules. The molecules in the crystal can be arranged into two sets, with the molecular planes in each set being parallel among each other. The angle subtended between the two planes is 159° and each of the planes is inclined to the b axis at an angle of 79.5°. There is an in-plane bending of the two C—Cl bonds by 5.5°. The ionic, single bond and double bond characters of the C—Cl bonds for both chlorines are almost equal, and are in the ratio 24:73:3.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/mrc.1270160212
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  • 14
    Electronic Resource
    Electronic Resource
    Determination of metals in oil using total reflection X-ray fluorescence spectrometry (1987)
    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 16 (1987), S. 161-165 
    Details
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Oil was chosen as a new sampl type for total reflection XRF. A thin-film sample procedure is described which requires minimal sample preparation. This involves first bringing the oil into solution with a volatile solvent, then pipetting microliter amounts on to the reflector substrate followed by evaporation of the solvent. The linear dynamic range was found to extend to at least 5000 ppm. Detection limit measurements show that minute sample quantities are necessary for optimal detection limits of nanogram amounts. A maximum sample loading is required for the best detection limits in ppm. Using an Mo or Cu X-ray tube, limits were found to be a few ppm or sub-nanogram amounts. The spectrometer was calibrated by an internal standardization method and the results of determinations on sample solutions were typically within 10% relative accuracy.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/xrs.1300160405
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  • 15
    Electronic Resource
    Electronic Resource
    The Townes and Dailey approach to the interpretation of NQR parameters in the light of non-empirical calculations. Three-membered rings (1995)
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 33 (1995), S. 761-766 
    Details
    ISSN: 0749-1581
    Keywords: non-empirical calculations ; NQR parameters ; Townes and Dailey theory ; three-membered rings ; LMO approach ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nuclear and electronic contributions to the EFG tensor components eqii at 14N, 17O, 33S and 35Cl nuclei in aziridine, methylaziridine, chloroaziridine, oxirane and thiirane were determined. The nuclear contributions were calculated within classical representations, while electronic contributions were calculated non-empirically using a 6-31G* basis set within the framework of the LMO approach. On the basis of the analysis of the contributions to the EFG tensor components from definite bond and lone-pair orbitals, the main concepts of the Townes and Dailey approach were tested.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/mrc.1260331002
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  • 16
    Electronic Resource
    Electronic Resource
    Fourier transform Raman spectroscopy of superconducting YBa2Cu3O7-δ films on strontium titanate and magnesium oxide substrates (1991)
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 22 (1991), S. 639-643 
    Details
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thin sputtered films of the high-Tc material YBa2Cu3O7-Δ were investigated using 180° back-scattering geometry with Fourier transform (FT) Raman spectroscopy. It is established that the main bands in the spectra of a YBa2Cu3O7-Δ film on strontium titanate substrate exhibit similarity with those obtained for oriented untwinned crystallites of the superconductor having their c-axis perpendicular to the surface of the substrate. No degradation or excessive heating of the film was observed with 1.064 μm excitation for low laser powers. The film on a magnesium oxide substrate gives unique evidence of the isolated strong, featureless, almost flat continuum, producing a broad maximum near the region of the antiphase axial bending O(2)—Cu(2)—O(3) motions of planar oxygens at very low excitation energy. This appears to be the first application of FT-Raman spectroscopy using near-infrared excitation (1.064 μm) to the field of high-temperature superconducting films and their detailed characterization.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jrs.1250221108
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  • 17
    Electronic Resource
    Electronic Resource
    13C NMR assignments of the isoprenoid chain carbons of retinoids from empirical chemical shift differences (1987)
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 25 (1987), S. 1040-1045 
    Details
    ISSN: 0749-1581
    Keywords: α-retinal ; α-ethyl retinoate ; α-retinol ; α-retinoic acid ; 3,4-dehydroretinal ; 3,4-dehydroretinol ; ethyl 3,4-dehydroretinoate ; 3,4-dehydroretinoic acid ; 2D heteronuclear-correlated spectroscopy ; APT ; empirical chemical shift calculations ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C NMR assignments have been made for a series of 36 α- and 3,4-dehydroretinoids with different substituents (alcohol, ester, aldehyde and acid) and for their separated E and Z geometrical isomers. The assignments were made by using 2D heteronuclear-correlated NMR experiments. From the chemical shift data of 24 systematically related retinoids, empirical chemical shift changes due to four polar end groups (alcohol, aldehyde, carboxylic acids and esters), three chain configurations (all-E, 9Z and 13Z), and two ring substitutions (2,6,6-trimethyl-cyclohex-2-enyl and 2,6,6-trimethylcyclohexa-1,3-dienyl) were determined. All trends were found to be independent of each other, except for the dependence of the chemical shift change of the 13Z-isomers on the polar end groups. The chemical shift changes were used to predict the chemical shifts of other retinoids based on two different ring structures (2,6,6-trimethylcyclohexenyl and 4-methoxy-2,3,6-trimethylphenyl).
    Additional Material: 8 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/mrc.1260251204
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  • 18
    Electronic Resource
    Electronic Resource
    Vibrational spectra and normal coordinate analysis of CF3OF and CF3OCl (1980)
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 9 (1980), S. 230-238 
    Details
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The IR spectra (1400 cm-1 to 160 cm-1) of the gases at ambient temperature and the Raman spectra (below 1400 cm-1) of the liquids near -196°C are reported for CF3OF and CF3OCl. All fundamentals are assigned under Cs symmetry and the results of a normal coordinate analysis are presented. The assignments of Smardzewski and Fox are adopted with one exception for both CF3OF and CF3OCl: the CF3 rock of A″ symmetry is assigned near 430 cm-1 and the two bands between 200 cm-1 and 300 cm-1 are assigned to an A′ fundamental, involving CF3 rocking and COX bending and a Δν=2 transition in the CF3 torsion. An extra band at 548 cm-1 in the Raman spectrum of liquid CF3 COl near -196°C is assigned to a CF3OCl⃛Cl2 complex. The values of the force constants d(OX) for CF3OX molecules are suggested to be near those for X2O molecules. More than half the normal modes of A′ symmetry show extensive mixing of symmetry coordinates. In some of these cases the symmetry coordinate for which the normal mode is named is the largest but not the dominant contributor to the potential energy distribution, while in others this symmetry coordinate is not even the largest contributor to the potential energy distribution. No normal modes of A′ symmetry are present in which ν(CO), δs(CF3), δ(COX), or δ(CF3) symmetry coordinates are dominant, and the mode conventionally labeled as v(CO) should be labeled as νs(CF3). For the remaining A′ normal modes and all the A″ normal modes, the symmetry coordinate for which the normal mode is named is dominant in the potential energy distribution.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jrs.1250090406
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  • 19
    Electronic Resource
    Electronic Resource
    Vibrational spectroscopy at high pressures: 44 - thallous carbonate (1983)
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 14 (1983), S. 144-149 
    Details
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman spectra of thallous carbonate have been studied to c. 52 kbar and mid-IR spectra to 36 kbar. Details of the assignment have also been established using single-crystal IR reflectance and Raman spectroscopy. Phase transitions were found near 13 and 38 kbar on the basis of the Raman evidence, thus supporting the earlier conclusions of Meisalo and Kalliomaki based on x-ray powder and optical results. Analysis of possible space group relations between phases III (ambient) and IV showed that IV must be orthorhombic and adopt one of the D2hn groups, where n = 17, 19, 21, 25 or 28. Structural relationships between the phases are discussed.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jrs.1250140304
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  • 20
    Electronic Resource
    Electronic Resource
    A gas chromatographic/mass spectrometric assay for catechol estrogens in microsomal incubations: Comparison with a radiometric assay (1988)
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 15 (1988), S. 157-161 
    Details
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A gas chromatographic/mass spectrometric assay for quantifying two catechol estrogens, 2-hydroxyestradiol and 4-hydroxyestradiol, in microsomal preparations is described. The assay employs deuterium-labeled analogs of the catechol estrogens as internal standards and permits quantification of catechol estrogens, in microsomal incubations, at low (1-2) μM concentrations. The compounds are analyzed as their trimethylsilyl derivatives following separation by capillary gas chromatography.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bms.1200150307
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