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The analysis of volatile organic compounds (VOCs) as a tool for bacterial identification is reported. Headspace solid-phase microextraction (HS-SPME) coupled to gas chromatography-mass spectrometry (GC-MS) was applied to the analysis of bacterial VOCs with the aim of determining the impact of experimental parameters on the generated VOC profiles. The effect of culture medium, SPME fiber type and GC column were fully evaluated with the Gram-negative bacteria Escherichia coli and Klebsiella pneumoniae and the Gram-positive species Staphylococcus aureus. Multivariate analysis, including cluster analysis and principal component analysis, was applied to VOC data to determine whether the parameters under investigation significantly affected bacterial VOC profiles. Culture medium, and to a lesser extent, SPME fiber type, were found to significantly alter detected bacterial VOC profiles. The detected VOCs varied little with the polarity of the GC column. The results indicate that the generated bacterial VOC profiles need careful evaluation if they are to be used for clinical diagnostics. The whole process is limited by the need to grow the bacteria in broth (18 h) before extraction and analysis (63 min).

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This chapter extends the discussion to reactions between the Vilsmeier‐Haack reagent (subsequently referred to as the Vilsmeier reagent for brevity) and any other compounds in which a carbon‐carbon bond is formed. The discussion thus excludes reactions in which the Vilsmeier reagent acts as a chlorinating agent (for example in the preparation of acid chlorides), or in which it forms carbon‐oxygen or carbon‐nitrogen bonds, unless these are accompanied by formation of a carbon‐carbon bond. For a discussion of the nature of the reagent and of the mechanism of the reaction, the earlier chapter in vol. 49 should be consulted. There are also a number of reviews that deal at length with mechanisms of reactions involving the Vilsmeier reagent, notably those by Jutz and Marson, and hence this chapter will concentrate on applications, with brief mention of mechanisms when necessary. Wizinger has pointed out that alkenes could react with the Vilsmeier reagent, but his only examples were styrenes where the intermediate carbocation has considerable stability. Hydrolysis gives the cinnamaldehyde. In principle, any alkene which is not too sterically hindered can undergo this reaction, but the Vilsmeier reagent has low reactivity as an electrophile, and in practice activation is often necessary. The addition depends on the HOMO of the alkene, and anything increasing the HOMO energy will aid reaction, as for example further conjugation (dienes, trienes, etc.) or the presence of an electron‐donating substituent. Hence aldehydes and ketones are active in their enol forms, and enol ethers and enamines are good substrates. Indeed, all additions covered by this chapter can be regarded as alkene additions, even those on active methyl groups attached to electron‐deficient rings. As with any reaction involving carbocation intermediates, rearrangements are possible; the initial products are sometimes enamines, and this can give rise to polysubstitution. The substrates are grouped into eleven major subsections; references to reviews of particular relevance will be found in the appropriate subsection.

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