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  • Analytical Chemistry and Spectroscopy  (16)
  • Wiley-Blackwell  (16)
  • American Meteorological Society (AMS)
  • Cell Press
  • 1
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thirty seven of the thirty eight isomers of tetrachlorodibenzofuran (TCDF) have been synthesized by unambiguous routes, and purified. The 1,2,8,9-TCDF isomer could not be thus prepared, and attempts to make it by pyrolysis of appropriate precursors also failed. Retention characteristics of TCDFs under gas chromatographic conditions were determined, and found to agree well with those predicted by an existing mathematical model derived from data obtained for TCDF isomers prepared by more ambiguous procedures. Mass spectral characteristics were also obtained, particularly relative response factors for the molecular ions of the TCDF isomers under electron ionization (EI) conditions. A discussion of the likely transferability of these relative response factors between mass spectrometers of different types is included. Chemical ionization (CI) mass spectra were also obtained, for both positive and negative ions. These CI spectra yielded little structural information not available from the EI data, and problems of lack of sensitivity and of reproducibility render them less suitable for trace analysis of TCDFs. Some unusual ion chemistry was observed under CI conditions, which can be rationalized in terms of pre-ionization attack on the TCDF molecule by free radicals in the source.
    Additional Material: 5 Ill.
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  • 2
    ISSN: 0935-6304
    Keywords: Gas chromatography / electron impact (EI) and chemical ionization (CI) / mass spectrometry ; N,N-diethyl-m-toluamide ; Characterization of urinary metabolites of DEET in man ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies of the pharmacology and toxicology of the popular insect repellant, N,N-diethyl-m-toluamide (DEET), have largely been done in animal models using radioactive tracing without the structural elucidation of its metabolites.This paper describes a high resolution gas chromatography/mass spectrometry (GC/MS) technique and reports the results of the preliminary characterization of the metabolites of DEET in the urine of a 30-year-old man who had been exposed to DEET contained in a commercial product. The metabolites were extracted and separated with an OV-101 glass capillary column, 30 m × 0.3 mm, and mass spectrometric elucidations were carried out with both Electron Impact (EI) and Chemical Ionization-Methane (MCI) modes.Oxidation of the benzylic moiety and hydroxylation of the sidechain of DEET molecules appeared to be the predominate routes of metabolism in man. The artifacts were also proposed.
    Additional Material: 4 Ill.
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  • 3
    ISSN: 0935-6304
    Keywords: Capillary GC ; Cold on-column injection ; Splitless injection ; Automatic liquid sampler ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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  • 4
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A high performance liquid chromatographic/atmospheric pressure chemical ionization-mass spectrometric (HPLC/APCI-MS) method has been developed for the determination of the pesticides diflubenzuron (1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea) and clofentezine (3,6-bis(2-chlorophenyl)-1,2,4,5-tetrazine) in plums, strawberries and blackcurrant-based fruit drinks. Samples were homogenized with acetone, extracted into dichloromethane + cyclohexane and cleaned-up by high performance gel permeation chromatography. HPLC was performed on an ODS column with methanol + water at 1 mL/min. Detection was by negative-ion selected-ion monitoring APCI-MS. Comparison of response with solvent and matrix-matched standards showed some ehancement of response for the latter, and these standards were consequently used for quantification. The calibration was linear over the range 0.05-0.50 ng/μL in all three matrices. The mean overall recovery of diflubenzuron and clofentezine from spiked extracts (0.086 mg/kg) in all three matrices was 76% and 70% respectively with relative standard deviations of 15% and 12% respectively (n = 12). The limit of detection was both compound and commodity dependent and ranged from 0.01-0.05 ng/μL, equivalent to 0.003-0.014 mg/kg in the crop.
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 23 (1994), S. 71-74 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using gas chromatography/mass spectrometry we have observed six peaks in the single ion chromatograph at m/z 674 of the alkaline extract of barley straw cell walls. The breakdown pattern of these ions suggests that they could all be isomers of 5,5′-bis-dehydroferulic acid. Since only the 5,5′ linkage is reported to be present in plants this tentatively suggests that these compounds exhibit stable orientational isomerism about this bond. Plausible breakdown mechanisms are presented which allow for the complete assignment of structure to all the isomers. These mechanisms suggest that the two pairs of breakdown ions at m/z 556 and 467, and 265 and 193 are representative of trans and cis double bonds, respectively.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 6 (1992), S. 46-53 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Substituted cinnamic acids were dimerized, under fluorescent or UV light, as a glassy coating on a vial then subsequently analysed by GC/MS. Mass Spectrometric analysis of the dimers formed by each acid allowed the assignment of the dimer as a truxillic or truxinic structure since these structures had distinctive fragmentation patterns; the breakdown of the truxillic acids involves a McLafferty rearrangment before fragmentation occurs, whereas the truxinic acids, which have both carboxy groups on one side and both aromatic groups on the other, fragment asymmetrically to give characteristic stilbene and dicarboxylate fragments. It is apparent from the results of the dimerization of the lcinnamic acids that, under the conditions used here, if the monomeric acid had the capacity for hydrogen bonding using the ring substituent as well as the carboxy group, the dimerization products would be overshelmingly truxillic in structure. However, if only the carboxy group could hydrogen bond, the products would be almost exclusively traxinic in structure.
    Additional Material: 9 Ill.
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  • 7
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photoionization of a series of tricyclic geometric isomers has been studied at 1216 Å and 584 Å in a high resolution mass spectrometer. The fragmentations are discussed in terms of the molecular geometry and non-bonded steric interactions. Ionization potentials of all isomers are determined by electron-impact.
    Additional Material: 12 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 14 (1979), S. 265-272 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The origins and nature of the [C5H8]+⋅ ions which form the base peak in the electron impact spectrum of limonene, at nominal electron energies greater than 11 eV, have been investigated. Linked scan techniques were used to study unimolecular and collision induced fragmentation reactions. No fragmentation pathway leading to [C5H8]+⋅ could be found. Measurement of ionization efficiency curves indicated that the threshold for formation of C5H8[+⋅] lies above the range of internal energies deposited in incident ions by collisional activation. By a combination of comparisons of collisionally activated spectra and energetic considerations, the [C5H8]+⋅ ions formed from limonene were shown to resemble those of the molecular ion of isoprene, while the neutral fragment is most likely isoprene also. Deuterium labelling experiments yielded evidence of extensive scrambling prior to fragmentation. The most probable mechanism of formation of [C5H8]+⋅ appears to involve a retro Diels-Alder reaction of a structurally intact molecular ion of limonene.
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  • 9
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 11 (1978), S. 360-369 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbon-13 NMR spectra have been obtained for 27 aliphatic monosulphones and 13 aliphatic disulphones. Substitution rules have been formulated which allow the prediction of chemical shifts when a CH2 group in a hydrocarbon is replaced by an SO2 group, or when an H atom in a sulphone is replaced by an alkyl group. Carbon atoms β to a sulphone group show a marked upfield shift effect which is sensitive to the conformation about the C—S bond; atoms in the trans position experience an upfield shift (-9.39±1.64 ppm) compared with those in the gauche position. An assignment of the meso (m) and racemic (r) β-carbon peaks in di-sec-butyl sulphone was made by synthesis of the optically active compound. |δm-δLr| decreases with increasing temperature for both β-carbon atoms; this effect was interpreted in terms of two available conformers for each of the m and r compounds, those for the m form having the same energy and entropy, and those for the r form having ΔS=0.6 J K-1 mol-1 and ΔH=0.8 kJ mol-1. Observed chemical shifts for the disulphones were compared with those estimated by the application of the first set of substitution rules.
    Additional Material: 7 Ill.
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  • 10
    ISSN: 0749-1581
    Keywords: Long-range 13C—1H shift correlation ; Indirectly bonded carbon-hydrogen connectivities ; BIRD pulses ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several modifications of the basic 13C—1H shift correlation sequence as optimized for polarization transfer via long-range 13C—1H coupling constants are described and evaluated. Modifications involve incorporation of BIRD pulse(s) at the mid-point of the evolution period and/or at the mid-point of the fixed delay prior to polarization transfer, in addition to the previously discussed incorporation of a BIRD pulse during the final fixed delay. These modifications give significantly improved sensitivity for many cross-peaks, excellent suppression of one-bond peaks and, in the case of the sequence incorporating two additional BIRD pulses, some ability to distinguish two-bond and three-bond connectivity peaks. The latter sequence is, overall, comparable in sensitivity to the fixed time sequences XCORFE and COLOC. It is also easier to parameterize and gives better suppression of one-bond peaks and other artifacts.
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