Dehydrated amino acids

The lantibiotics differ extensively from the class II bacteriocins in that they contain post-translationally modified amino acids, as for example dehydrated amino acids and lanthionine residues, forming intramolecular thioether bridges [39, 184]. The chemical modification reactions leading to the typical lanthionines were first proposed by Ingram [185] and are assumed to be catalyzed by specific enzymes encoded in the lantibiotic gene cluster. In the lantibiotic lactocin S, p-alanine residues were discovered, probably by conversion of dehydrated serine residues via a dehydrogenation reaction [82]. In some... 

Kuipers OP, Rollema HS, Yap WM, Boot HJ, Sieten RJ, De Vos WM. Engineering dehydrated amino acid residues in the antimicrobial peptide nisin. J Biol Chem 1992 267 24340-24346. 

Crystalline solid m.p. 35-36 "C, b.p. 154--156 C, prepared by oxidizing A,A -dicycIo-hexylthiourea with HgO in carbon disulphide solution, also obtained from cyclohexylamine and phosgene at elevated temperatures. Used as a mild dehydrating agent, especially in the synthesis of p>eptides from amino-acids. Potent skin irritant. 

Milk and egg products are highly desired in pet foods since they supply the highest quaHty amino acid profiles with nearly 100% digestibiHty. Most milk protein concentrates are used for human foods, but some are available to pets (see Milk and milk products). An enormous quantity of whole eggs (qv) derived from egg graders, egg breakers, and hatchery operations are handled as dehydrated, Hquid, or frozen ingredients. 

FIGURE 1.9 (a) Amino acids build proteins by connecting the n-carboxyl C atom of one amino acid to the n-amino N atom of the next amino acid in line, (b) Polysaccharides are built by combining the C-1 of one sugar to the C-4 O of the next sugar in the polymer, (c) Nucleic acids are polymers of nucleotides linked by bonds between the 3 -OH of the ribose ring of one nucleotide to the 5 -P04 of its neighboring nucleotide. All three of these polymerization processes involve bond formations accompanied by the elimination of water (dehydration synthesis reactions). 

All three elimination reactions--E2, El, and ElcB—occur in biological pathways, but the ElcB mechanism is particularly common. The substrate is usually an alcohol, and the H atom removed is usually adjacent to a carbonyl group, just as in laboratory reactions. Thus, 3-hydroxy carbonyl compounds are frequently converted to unsaturated carbonyl compounds by elimination reactions. A typical example occurs during the biosynthesis of fats when a 3-hydroxybutyryl thioester is dehydrated to the corresponding unsaturated (crotonyl) thioester. The base in this reaction is a histidine amino acid in the enzyme, and loss of the OH group is assisted by simultaneous protonation. 

As noted previously in Section 11.10, biological dehydrations are also common and usually occur by an ElcB mechanism on a substrate in which the -OH group is two carbons away from a carbonyl group. An example occurs in the biosynthesis of the aromatic amino acid tyrosine. A base first abstracts a proton from the carbon adjacent to the carbonyl group, and the anion intermediate... 

The amino acid leucine is biosynthesized from n-ketoisocaproate, which is itself prepared from -ketoisovalerate by a multistep route that involves (1) reaction with acetyl CoA, (2) hydrolysis, (3) dehydration, (4) hydration. (5) oxidation, and (6) decarboxylation. Show lhe steps in the transformation, and propose a mechanism for each. 

The steric bulk of steroid structures prevents their use as the only organic side group present. However, mixed-substituent polymers that contain both steroidal side groups and amino acid ester or other cosubstituent units can be readily synthesized. If a saturated A ring is present in the steroid, linkage to the polymer chain is complicated by side reactions that result from dehydration of the steroid (chlorophosphazenes are powerful dehydrating agents). 

Later articles dealt with further elaboration of ideas on the driving forces which would have led to the formation of higher aggregates from RNA and amino acids. As had been suggested 20 years earlier, these processes could have taken place in rock pores and could have been driven by hydration and dehydration phases (Kuhn and Waser, 1994). The tiny pores in rocks act as minute test tubes, so optimal compositions could have been determined and replicated using many millions of systems. According to this model, none of the synthetic processes taking place would have required the presence of protein enzymes (see also Lahav, 1999). Just as other... 

Figure 19.1 A schematic view of the common formaldehyde-induced modifications in proteins. Reactive methylol adducts are formed in the initial reaction between formaldehyde and cysteine or the amino groups of basic amino acid residues. The methylol adduct can subsequently undergo a dehydration reaction to form a Schiff s base. Adducted residues can undergo a second reaction to form methylene bridges or can convert to the ethoxymethyl adduct after the ethanol dehydration step.

Thus, in a novel synthesis of hypoglycine A (96), hydroxycyclopropanation of ethenyl-acetaldehyde diethyl acetal (93) followed by formal dehydration of the cyclopropanol 94 via its tosylate intermediate gave the methylenecyclopropane species 95, a key precursor to the target amino acid (Scheme 11.26) [92]. 

Peptides are short chains of amino acids linked by peptide bonds. Most biologically active peptides contain two to ten amino acids. Peptide bonds are formed between the carboxyl carbon of one amino acid and the amino nitrogen of another. Since water is released, this is an example of dehydration synthesis. The bond forms as illustrated in Figure 16.7. 

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