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Engineering topics

Smith, G. G.

Publications and source records attributed to Smith, G. G..

A critical evaluation of the application of amino acid racemization to geochronology and geothermometry

Attempts have been made to determine the age of biological samples by measuring the racemization of amino acids in protein samples. The pitfalls and inherent complications in diagenetic racemization studies are reviewed, and recent advances in improving techniques are outlined. Methodological topics include isolation of amino acids from geological samples, resolution of amino acid enantiomers, and the effects of acid hydrolysis. The theory and kinetics of amino acid racemization are discussed with attention to the derivation of the rate expression for amino acid racemization, isoleucine and the equilibrium constant, the mechanism of amino acid racemization, the racemization of 'bound' versus 'free' amino acids, and factors affecting the racemization rates of free amino acids in aqueous solution. Applications of amino acid racemization kinetics to geochronology is considered with reference to shells, marine sediments, and bones. Potential complications include heating and diagenesis, diagenetic formation of amino acids, the effect of clays, species effect, and contamination.

Williams, K. M.↗

Mass spectrometry in structural and stereochemical problems. CXCIX.

Electron-impact induced fragmentations of o-, m-, and p-hydroxyalkylphenones and their trimethylsilyl (TMS) ethers are studied by means of high-resolution mass spectrometry, metastable defocusing, and deuterium labeling of the TMS ether derivatives. A markedly increased methyl radical loss from the o-TMS ether is attributed to a proximity effect. Minor fragmentation was observed with m- and p-isomers. Significantly intense doubly-charged ions were formed from ketonic cleavage and by the loss of a TMS methyl radical. The sequence of fragmentation was found to depend on the size of the alkyl group attached to the ketone carbonyl.

Smith, G. G.↗