240 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS ENZYME BIOSYNTHESIS AND STRUCTURE A useiul review on enzymes as units of biological structure and function was published in 1956 as the result of a symposium held in 1955. TM In another brief review of induced synthesis of enzymes the enzyme-forming system was visualised as a complex between ribonucleic acid, inducer, and enzyme, with simple components, probably amino acids, being drawn from a metabolic pool for synthesis on the template, which may be ribonucleic acid. TM Liver cell nucleoli were isolated and found to have properties sug- gesting that they furnish the templates for synthesis of the enzymes which govern mitosis.• Cytochrome C was studied by isolating the portion of the apoenzyme bound to the porphyrin two cysteine residues were found to be joined to the porphyrin by sulphide bridges, and a histidine residue next to one of the cysteines was believed to be bound to the iron through its imidazole' ring. •2 ENZYME MECHANISM In a preliminary sketch of the principal features of a•theory of catalysis TM it was pointed out that all catalytic reactions are caused and directed by free valencies, with the catalyst playing a role not unlike that of a free radical. The fatty acid cycle was duplicated, using model compounds containing the structural elements considered important in coenzyme A activity. TM A possible analogue of enzyme action was seen in the "chain effect" of polysar- cosine ,dimethylamide in accelerating the polymerization of phenylalanine-N- carbonic anhydride the accelerating effect was proportional to the n amber of units in the polysarcosine molecules used. TM '. The transport of electrons over long chains of atoms appears to be involved in enzyme activity, and in macromolecules a distant transfer of ionisation is possible, not by a, small displacement of a, multitude of elementary charges,, but by a large displacement of relatively few charges along the molecules. m The electron transport systems of cell mitochondria are conceived to be quasi-conducting continua in which electrons originating in reduced diphosphopyridine nucleotide, and succinate are transferred ultimately to molecular oxygen. The various enzymes , of this semi~con- ductor system are linked to one another by bonds which permit resonance interaction throughout the entire structure in a manner not describable by classical kinetics. The many non-hem iron atoms present may act as conducting and structural links between the different oxidation-reduction units of the system. m Progress has been made in determining methods of attachment of enzymes to coenzymes and substrates. Kinetic studies supported the idea that primary amino groups of the old yellow enzyme serve as binding sites for the phosphoric acid residue of flavine mono-nucleotide. TM It was concluded that two carboxyl groups of glutamic acid combine with NH or NH radicals
SOME NEW KEYS TO COSMETIC CHEMISTRYm1956 241 of •glutamic dehydrogenase protei,n. TM The SH group •of mus'cle protein was shown to be essential for the action of acetylchol!ne, and in addition to the N atom of the latt, er, the ester group also reacted with active groups. of the protein molecule. •ø Methylat&ion of lysozyme did not inactivate it, showing that the groups active in catalysis are not those active in the enzyme-substrate unionß Molecular geometry was studied in connection with the cholinesteraso surface, and it was found that in the.• betdine amino alcohols, those with hydroxyl trans to the 9arboxyl inhibited the ester, but similar cis com- pound s showed no inhibition. TM Evidence was cited that precise orientation of catalytic groups at the point of bond formation and cleavage is critical for enzyme activity, implying that there is no necessity for high molecular weight in the enzyme molecule. TM In a brief review of mode of action of oxidation enzymes, Theorell TM pointed out that so far we know the structure of only the most easily accessible one-sixth of the smallest enzyme molecule, cytochrome C. An antidote for nerve gas was developed as a by-product of basic research ß . on cholinesterase the antidote, 2-pynd•ne aldoxime, fits into a specific active spot on the cholinesteras• surface, prever/ting the nerve gas from becoming attached there through its phosphorous-containing •group. •" The enzymatic activity of grain seeds was increased, and the germination and growth processes were stimulated, by ultrasonic' treatment of the seeds. STRUCTURE-ACTIVITY The edema producing potency, measured by increase in water content of a part of the conjunctiva of rabbits' 'eyes, increased with increasing molecular weight in the, normal alcohols methyl to amyl, and among the butyl alcohols the potency decreased in passing from primary to secondary to tertiary. TM A chemical model of drug action using diethylaminoethanol in a two-layer solvent system was selected because of its containing two active groups at the same distance, 5«A, as is typical of a striking number of drugs with a great variety of effects the tendencies of various amino acids to be•orne'b0und to this model were measured. The activities of 47 thyroxine analogues were correlated to the abilities of their side chains to' release electrons. TM A study of competitive photohalogenation of cyclo- hexane and toluene led to the conclusion that to account for the effect of structure on the selective rates of free radical reactions involving C-H bonds it is .necessary .to consider (1) bond dissociation energies, (2) the extent of bond breaking in the transition state, and (3) polar effects in both reacting m91ecules.• o A review of inclusion compounds suggested division of clathrates into three types: channel, like urea clathrates cage, like water molecules
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