The thiyl radical derived from glutathione (GSH) is shown to decay rapidly in aqueous solution by intramolecular rearrangement reactions into the non-sulphur-centred radical 1. The reaction is induced by OH- with a rate constant of 5 x 10(9) dm3 mol-1 and is also observable at near-neutral conditions (at physiological pH values around 7.5 the rate of formation of 1 amounts to approximately 1 x 10(3) s-1). The activation enthalpy and entropy at pH 8.4 and 20 degrees C were found to be 26.7 kJ mol-1 and -77 J mol-1 K-1, respectively. Radical 1 was unequivocally identified by EPR as the alpha-amino radical at the glutamyl residue of GSH. It is relatively long-lived with typical bimolecular decay rate constants of the order of (2-20) x 10(6) dm3 mol-1 s-1. At higher GSH concentrations the formation of 1 is retarded but not inhibited. All radicals, sulphur- as well as non-sulphur-centred ones are connected via equilibria, partly under the action of 'repair' processes of GSH. These repair processes, however, are slow (k much less than 1.4 x 10(5) dm3 mol-1 s-1). The equilibria are established quite rapidly and were found to be far on the side of the non-sulphur-centred radical under all conditions employed. Radical 1 possesses reducing properties as evidenced by its fast reaction with 4-nitro-acetophenone (PNAP) to yield PNAP.- (k = 7 x 10(8) dm3 mol-1 s-1).

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Cocoa butterfat and cocoa powder are key economic products from the seeds of the cacao tree (Theobroma cacao L.). In this study, 323 accessions (comprised mainly of Upper Amazon Forasteros and Refractarios) from the International Cocoa Genebank, Trinidad were characterized for one biochemical and five morphological seed-derived traits. The data were analysed using non-parametric statistics including correlation analysis to identify promising parental candidates for future cacao breeding programmes. The Upper Amazon Forastero group had the greatest proportion of accessions with high butterfat content in cotyledons, whereas Refractario and Trinitario groups tended to contain more accessions with high butterfat content per fruit. The correlation of butterfat content of cotyledons with the dry mass of cotyledons was inconsistent in significance and direction. However, consistent significant positive correlations between butterfat content per fruit, cotyledon size and dry mass of cotyledons were found. The results suggested that butterfat content is a likely trait for independent selection but that selection for increased cotyledon size could lead to the selection of genotypes for high butterfat yield. Several promising accessions exhibited favourable levels of multiple traits and MATINA 1/7, CRU 51, AM 2/91 [POU], CRU 133, EET 58 [ECU] and POUND 18/A [POU] could be recommended as good choices for parental stock in breeding programmes for improving cacao butterfat content.

Abstract

In vitro kinetic studies with DFT computations to explain the potential of acrylamide metabolism/toxicity with thiols in vivo.