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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical ecology 24 (1998), S. 1845-1865 
    ISSN: 1573-1561
    Keywords: Hydrocarbons ; alkanes ; methyl-branched hydrocarbons ; cuticular hydrocarbons ; insects ; GC-MS data ; retention indices
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract A common and confusing problem in analyses of insect hydrocarbons is in making sense of complicated gas chromatograms and interpreting mass spectra since branched chain compounds differing by one or two carbons in backbone or chain length may elute from the column at nearly the same time. To address this confusing situation, relative gas chromatography (GC) retention times are presented for typical mono-, di-, tri-, and tetramethylalkanes comprising most of the commonly appearing series of homologous methyl-branched alkanes up to 53 carbons that are found in insect cuticular hydrocarbons. Typical insect-derived methylalkanes with backbones of 33 carbons were characterized by Kovats indices (KI); monomethyl alkanes elute between KI 3328 and 3374, dimethylalkanes elute between KI 3340 and 3410, trimethylalkanes elute between KI 3378 and 3437, and tetramethylalkanes elute between KI 3409 and 3459, depending upon the positions of substituents. A protocol is described for identification of methyl-branched hydrocarbons eluted from nonpolar polysiloxane DB-1 capillary GC columns. In this protocol, retention indices (KI values) are assigned to peaks, then the patterns in GC peaks that probably contain homologs are marked to assist subsequent GC-mass spectrometric (GC-MS) interpretation. Use of the KI allows assignment of likely structures and the elimination of others, with demonstrative consistency, as there are no known exceptions. Interpretation of electron ionization mass spectra can then proceed within narrowed structural possibilities without the necessity of chemical ionization GC-MS analysis. Also included are specific examples of insect hydrocarbons that were assembled from 30 years of the literature, and these are intended to help with confirmation of confusing or contradictory structures.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1076-5174
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A hydride Meisenheimer complex of 2,4,6-trinitrotoluene (TNT) (TNTH-) was synthesized using tetramethylammonium octahydroborate. TNT and TNTH- (as the tetramethylammonium salt) were analyzed by direct exposure probe mass spectrometry using electron impact (EI), chemical ionization (CI) and negative-ion chemical ionization (NCI). For further identification, the ions of the mass spectra were investigated using tandem mass spectrometry with collision-induced dissociation (CID). Although the EI mass spectra of both compounds were similar, the CID mass spectra of the ions at m/z 227 (M+ of TNT) of the two compounds showed large differences in daughter ion abundances. A major difference between the two compounds also appeared in their CI methane mass spectra. Two abundant ions, at m/z 183 and 198, appeared only in the CI mass spectrum of TNNH-. CID parent ion scans showed that the origin of these two ions was not the m/z 227 ion. We suggest that these ions are formed by chemical reactions of the complex on the surface of the heated probe tip, followed by ionization. These reactions, probably a reduction process forming m/z 198 and hydrolysis forming m/z 183, occur preferentially in TNTH-, the already reduced form of TNT. Formation of the ions at m/z 183 and 198 was also observed in the liquid chromatography particle beam CI mass spectrum of TNTH-.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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