Abstract
The reaction of diazocarbonyl compounds with chymotrypsinogen and chymotrypsin in the presence of cupric ions was accompanied by the oxidative destruction of tryptophan and methionine residues and to a lesser extent of tyrosine and cystine residues of the proteins. Cu2+/diazoacetyl-DL-norleucine methyl ester complex was found to promote the oxidation of cystine residues of the proteins while the similar complex with the L-isomer of the diazocarbonyl compound was ineffective. Inclusion of α-aminocarbonyl compounds in the reaction medium not only prevented the Cu2+ ion mediated decomposition responsible for the diminution in the potency of the diazocarbonyl compound as a modifying agent, but also permitted the reaction to be accomplished over the pH range of 4.5 to 7.0. The side reactions, namely the oxidative destruction of amino acids could be minimized by exclusion of oxygen from the reaction medium.
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Abbreviations
- DAG:
-
α-diazoacetylglycine ethyl ester
- DI-DAN:
-
α-diazoacetyl-DL-norleucine methyl ester
- L-DAN:
-
α-diazoacetyl-L-norleucine methyl ester
- TLC:
-
thin layer chromatography
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All other abbreviations of amino acids, amino and derivatives and peptides are according to the guidelines of the IUPAC-IUB Commission on Biochemical Nomenclature (for a compilation see ref. 44).
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Widmer, F., Viswanatha, T. Possible side-reactions with diazocarbonyl dipeptide esters as protein modifying reagents. Carlsberg Res. Commun. 45, 149–159 (1980). https://doi.org/10.1007/BF02906516
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DOI: https://doi.org/10.1007/BF02906516