Proteinogenous amines

Another example of the ability of proteinogenic amino acids, small peptides, and amines to catalyse the formation of new C-C bonds has been demonstrated by Weber and Pizzarello they were able to carry out model reactions for the stereospecific synthesis of sugars (tetroses) using homochiral L-dipeptides. The authors achieved a D-enantiomeric excess (ee) of more than 80% using L-Val-L-Val as the peptide catalyst in sugar synthesis (in particular D-erythrose) via self-condensation of glycol aldehyde. 

In addition to the 20 proteinogenic amino acids (see p. 60), there are also many more compounds of the same type in nature. These arise during metabolic reactions (A) or as a result of enzymatic modifications of amino acid residues in peptides or proteins (B). The biogenic amines (C) are synthesized from a-amino acids by decarboxylation. 

Several proteinogenic amino acids (see p. 60) have neurotransmitter effects. A particularly important one is glutamate, which acts as a stimulatory transmitter in the CNS. More than half of the synapses in the brain are glutaminergic. The metabolism of glutamate and that of the amine GABA synthesized from it (see below) are discussed in more detail on p.356. Glycine is an inhibitory neurotransmitter with effects in the spinal cord and in parts of the brain. 

The proteinogenic amino acid glutamate (Glu) and the biogenic amine 4-aminobuty-rate derived from it are among the most important neurotransmitters in the brain (see p. 352). They are both synthesized in the brain itself In addition to the neurons, which use Glu or GABA as transmitters, neuroglia are also involved in the metabolism of these substances. 

Chiral intermediates (e.g., non-proteinogenic amino acids, alcohols, amines, polyols, aminoalcohols, and acids)... 

Recently a number of enzymatic systems have been developed at several chemical companies including Upases (synthesis of enantiotrope alcohols, R-amid, S-amin), nitrilases (R-mandehc acid), amidases (non-proteinogenic L-amino acids), aspartic acid ammonia lyase (L-aspartic add), penicilin acylase (6-Aminopenicilanic acid), acylases (semisynthetic penicillins), etc.( Koeller and Wong, 2001 and references therin). 

In a recent optimization study, an alternative coupling system has been developed [29 c], The chemical yield in the synthesis of two non-proteinogenic a-amino acids was remarkably improved by applying a coupled transamination process using additionally an ornithine co-aminotransferase to couple L-ornithine co-trans-amination to L-glutamate a-transamination [29 c],... 

Koessler, K. K. and Hanke, M. T., Studies on proteinogenous amines IV, the production of histamine from histidine by Bacillus coli communis, J. Biol. Chem. 39, 539 (1919). 

Cloetta, M. and Wunsche, F., tJber die Beziehungen chemischer Konstitution proteinogener Amine und ihrer Wirkung auf Korpertemperatur und Blutdruck, Arch. exp. Path. Pharmak. 96, 307 (1923). 

Guggenheim, M. and Loffler, W., Biologischer Nachweis proteinogener Amine in Organextrakten und Korperfliissigkeiten, Biochem. Z. 72, 303 (1916). 

Vanysek, F., Beitrage zur physiologischen Wirkung einiger proteinogener Amine, Biochem. Z. 67, 221 (1914). 

Franzen, Fr. (II), Untersuchungen zur Frage der Wirkung proteinogener Amine auf Sauerstoffversorgung und Sauerstoffverbrauch, Forschungsber. des Landes Nordrhein-Westfalen Nr. 1619, 1966. 

Classification of the Simpler Bases.—(1) Amines derived from natural amino acids. Proteinogenous amines. 

Proteinogenous Amines.— An a-amino acid can give rise to a corresponding amine by decarboxylation, in accordance with the type formula —... 

Physiological Properties of Histamine.— This amine is sharply differentiated from other proteinogenous amines by its powerful depressor effect. Intravenous injection is followed by a quick fall in blood pressure, which is not inhibited by atropine. This is due to a direct action on the capillary wall, causing paralysis, loss of tone, passive dilatation, and increased permeability. 

---