Synthesis and characterization of polyamides containing unnatural amino acids

We describe the synthesis of several polyamides that retain the secondary structure of proteins and contain derivatizable side chains. The derivatizable side chain allows for further reaction of the polymer chain (e.g., chain cross‐linking or addition of pendant groups). Polymers of α‐amino acids containing a terminal unsaturated bond on the side chain have been synthesized. Poly‐L‐pentenyl glycine, poly‐L‐propargyl glycine, and poly‐L‐allyl glycine were synthesized chemically via Leuchs' anhydrides and enzymatically using subtilisin Carlsberg. Poly‐L‐propargyl glycine and poly‐D,L‐allyl glycine folded into the β‐sheet configuration whereas poly‐L‐pentenyl glycine assumed a helical conformation. The secondary structure of poly‐L‐allyl glycine and poly‐D,L‐pentenylglycine could not be determined conclusively. Comparison of properties between the polymers obtained chemically and enzymatically is provided. © 1995 John Wiley & Sons, Inc.

[1]  E. Atkins,et al.  Chemical sequence control of beta-sheet assembly in macromolecular crystals of periodic polypeptides. , 1994, Science.

[2]  T. M. Parker,et al.  Biocompatibility of the Bioelastic Materials, Poly(GVGVP) and Its γ-Irradiation Cross-Linked Matrix: Summary of Generic Biological Test Results , 1991 .

[3]  D. Urry,et al.  Elastic protein-based polymers as cell attachment matrices. , 1991, Journal of vascular surgery.

[4]  Maurille J. Fournier,et al.  Genetically directed syntheses of new polymeric materials: efficient expression of a monodisperse copolypeptide containing fourteen tandemly repeated -(AlaGly)_4ProGluGly- elements , 1991 .

[5]  G. Whitesides,et al.  Kinetic resolution of unnatural and rarely occurring amino acids: enantioselective hydrolysis of N-acyl amino acids catalyzed by acylase I , 1989 .

[6]  E. Sonveaux,et al.  Crowned dopa's, their dimers, cyclodimers and polymers: Synthesis and cation complexation , 1986 .

[7]  C. Cantor,et al.  Biophysical Chemistry: Part II: Techniques for the Study of Biological Structure and Function , 1980 .

[8]  K. Itoh,et al.  Conformation of poly(DL-valine) obtained by the polymerization of the N-carboxy anhydride. , 1976, Biopolymers.

[9]  G. Fasman,et al.  Computed circular dichroism spectra for the evaluation of protein conformation. , 1969, Biochemistry.

[10]  S. Moore,et al.  Determination of D- and L-amino acids by ion exchange chromatography as L-D and L-L dipeptides. , 1968, The Journal of biological chemistry.

[11]  D. Veber,et al.  The Controlled Synthesis of Peptides in Aqueous Medium. I. The Use of α-Amino Acid N-Carboxyanhydrides , 1966 .

[12]  J. Greenstein,et al.  Chemistry of the Amino Acids , 1961 .

[13]  E. Blout,et al.  Polypeptides. V. The Infrared Spectra of Polypeptides Derived from γ-Benzyl-L-glutamate , 1956 .

[14]  A. Zilkha,et al.  Synthesis of Poly-S-Allylcysteine (Poly-Deoxo-Alliin) , 1955, Nature.

[15]  Professor Dr. Miklos Bodanszky,et al.  The Practice of Peptide Synthesis , 1994, Springer Lab Manual.

[16]  H. Kricheldorf.  α-Aminoacid-N-Carboxy-Anhydrides and Related Heterocycles , 1987 .