Abstract
In polymerization of N-carboxyanhydride-L-α-arginine (L-Arg-NCA) in H2O, nucleophilic reaction of guanidine group with the carbonyl group of L-Arg-NCA leads to quick intramolecular rearrangement, yielding a 6-membered ring intermediate 1-amidino-3-amino-2-piperidone, which is either elongated by another L-Arg-NCA yielding arginyl-1-amidino-3-amino-2-piperidone or hydrolyzed to L-α-arginine. The oligoarginines are formed mainly through hydrolysis of arginyl-1-amidino-3-amino-2-piperidones. This is a unique pathway in polymerization of L-Arg-NCA with regard to the usual pathway of elongations by reaction of N-carboxyanhydride-L-α-amino acid with L-α-amino acid or oligopeptides.
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References
Stahmann M. Polyamino Acids, Polypeptides and Proteins. Madison, Wisconsin: Univ Wisconsin Press, 1962
Katchelski E, Sela M, Silman H I, Berger A. Polyamino Acids as Protein Models. The Proteins. Vol II. 2nd ed. New York: Academic Press, 1964. 405–581
Kricheldorf H R. α-Aminoacid-N-Carboxy-Anhydrides and Related Heterocycles: Synthesis, Properties, Peptide Synthesis. Polymerization. Berlin: Springer-Verlag, 1987. 1–209
Kricheldorf H R. Polypeptides and 100 years of chemistry of α-amino acid N-carboxyanhydrides. Angew Chem Int Ed, 2006, 45: 5752–5784
Ehler K W. Reactions of carbamylimidazoles with nucleophiles-An example of an intramolecular acyl transfer reaction. J Org Chem, 1976, 41: 3041–3042
Brack A. Selective emergence and survival of early polypeptides in water. Orig Life Evol Biosph, 1987, 17: 367–379
Hill R., Orgel L E. Oligomerization of negative-charged amino acids by carbonyldiimidazole. Origins Life Evol Biosph, 1996, 26: 539–545
Blocher M, Liu D, Walde P, Luisi P L. Liposome-assisted selective polycondensation of α-amino acids and peptides. Macromolecules, 1999, 32: 7332–7334
Pascal R, Boiteau L, Commeyras A. From the prebiotic synthesis of α-amino acids towards a primitive translation apparatus for the synthesis of peptides. Top Curr Chem, 2005, 259: 69–122
Plasson R, Biron J P, Cottet H, Commeyras A, Taillades J. Kinetic study of the polymerization of α-aminoacid N-carboxyanhydrides in aqueous solution using capillary electrophoresis. J Chromatograph A, 2002, 952: 239–248
Hitz T, Luisi P L. Spontaneous onset of homochirality in oligopeptide chains generated in the polymerization of N-carboxyanhydride amino acids in water. Origins Life Evol Biosph, 2004, 34: 93–110
Kricheldorf H R. Polypeptides. In: Penczek S, ed. Models of Biopolymers by Ring-Opening Polymerization. Boca Raton, Florida: CRC Press, 1990. 1–132
Zervas L, Winitz M, Greenstein J P. Studies on arginine peptides. I. Intermediates in the synthesis of N-terminal and C-terminal arginine peptides. J Org Chem. 1957, 22: 1515–1521
Hayakawa T, Kondo Y, Yamamoto H, Murakami Y. The synthesis of poly-L-arginine hydrobromide and copolymers of L-arginine and other amino acids. Bull Chem Soc Jpn, 1969, 42: 479–482
Hayakawa T, Windsor C R, Fox S W. Copolymerization of the Leuchs anhydrides of the eighteen amino acids common to protein. Arch Biochem Biophys, 1967, 118: 265–272
Zhang L S, Tam J P. Lactone and lactam library synthesis by silver ion-assisted orthogonal cyclization of unpro-tected peptides. J Am Chem Soc, 1999, 121: 3311–3320
Xin L, Ma Y L, Liu Y N, Yan Q, Wang K J. Sodium chloride enhanced oligomerization of L-arginine. Biopolymers, 2006, 81: 1–7
Ren J, Xin L, Liu Y N, Wang K J. Copolymerization of mixed L-alpha-arginine with L-alpha-glutamic acid. Macromolecules, 2008, 41: 1996–2002
Bartlett P D, Jones R H. A kinetic study of the Leuchs anhydrides in aqueous solution. J Am Chem Soc, 1957, 79: 2153–2159
Ehler K W, Orgel L E. N,N′-carbonyldiimidazole-induced peptide formation in aqueous solution. Biochim Biophys Acta, 1976, 434: 233–243
Liu R H, Orgel L E. Polymerization of beta-amino acids in aqueous solution. Origins Life Evol Biosph, 1998, 28: 47–60
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Supported by the Special Research Project of Beijing Scientific and Technical Committee (Grant No. Z00063002040191) and the Natural Basic Research Program of China (Grant No. 2007CB935901)
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Xin, L., Ren, J., Xiang, J. et al. 6-Membered ring intermediates in polymerization of N-carboxyanhydride-L-α-arginine in H2O. Sci. China Ser. B-Chem. 52, 1220–1226 (2009). https://doi.org/10.1007/s11426-009-0112-1
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DOI: https://doi.org/10.1007/s11426-009-0112-1