Abstract
Many natural polymeric materials (particularly structural proteins) display a hierarchy of structure over several length scales. Block copolymers are able to self-assemble into ordered nanostructures1,2, but the random-coiled nature of their polymer chains usually suppresses any further levels of organization. The use of components with regular structures, such as rigid-rod polymers, can increase the extent of spatial organization in self-assembling materials3. But the synthesis of such polymeric components typically involves complicated reaction steps that are not suitable for large-scale production. Proteins form hierarchically organized structures in which the fundamental motifs are generally α-helical coils and β-sheets4. Attempts to synthesize polypeptides with well-defined amino-acid sequences, which might adopt similar organized structures, have been plagued by unwanted side reactions5 that give rise to products with a wide range of molecular weights6,7,8,9,10, hampering the formation of well-defined peptide block copolymers11,12,13,14,15,16,17. Here I describe a polymerization strategy that overcomes these difficulties by using organonickel initiators which suppress chain-transfer and termination side reactions. This approach allows the facile synthesis of block copolypeptides with well-defined sequences, which might provide new peptide-based biomaterials with potential applications in tissue engineering, drug delivery and biomimetic composite formation.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Rent or buy this article
Prices vary by article type
from$1.95
to$39.95
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Hillmyer, M. A. et al . Complex phase behavior in solvent-free nonionic surfactants. Science 271, 976–978 (1996).
Matsen, M. W. & Bates, F. S. Origins of complex self-assembly in block copolymers. Macromolecules 29, 7641–7644 (1996).
Stupp, S. I. et al . Supramolecular materials: self-organized nanostructurs. Science 276, 384–389 (1997).
Fasman, G. D. Prediction of Protein Structure and the Principles of Protein Conformation(Plenum, New York, (1989)).
Bamford, C. H., Elliot, A. & Hanby, W. E. Synthetic Polypeptides(Academic, New York, (1956)).
Cardinaux, F., Howard, J. C., Taylor, G. T. & Scheraga, H. A. Block copolymers of amino acids. I. Synthesis and structure of copolymers of l-alanine or l-phenylalanine with d,l-lysine- d 7or d,l-lysine. Biopolymers 16, 2005–2028 (1977).
Howard, J. C., Cardinaux, F. & Scheraga, H. A. Block copolymers of amino acids. II. Physicochemical data on copolymers containing l-alanine or l-phenylalanine. Biopolymers 16, 2029–2051 (1977).
Gratzer, W. B. & Doty, P. Aconformational examination of poly-l-alanine and poly-d,l-alanine in aqueous solution. J. Am. Chem. Soc. 85, 1193–1197 (1963).
Inoue, K. et al . Preparation and conformation of hexaarmed star poly(β-benzyl-l-aspartates) utilizing hexakis(4-aminophenoxy) cyclotriphosphazene. J. Am. Chem. Soc. 116, 10783–10784 (1994).
Kubota, S. & Fasman, G. D. The β conformation of polypeptides of valine, isoleucine, and threonine in solution and solid-state: optical and infrared studies. Biopolymers 14, 605–631 (1975).
Kricheldorf, H. R. α-Aminoacid-N-Carboxyanhydrides and Related Materials(Springer, New York, (1987)).
Kricheldorf, H. R. in Models of Biopolymers by Ring-Opening Polymerization(ed. Penczek, S.) (CRC, Boca Raton, (1990)).
Idelson, M. & Blout, E. R. Polypeptides XV. Infrared spectroscopy and the kinetics of the synthesis of polypeptides: primary amine initiated reactions. J. Am. Chem. Soc. 79, 3948–3957 (1957).
Idelson, M. & Blout, E. R. Polypeptides XVIII. A kinetic study of the polymerization of amino acid N -carboxyanhydrides initiated by strong bases. J. Am. Chem. Soc. 80, 2387–2393 (1958).
Lundberg, R. D. & Doty, P. Polypeptides XVII. A study of the kinetics of the primary amine-initiated polymerization of N -carboxyanydrides with special reference to configurational and stereochemical effects. J. Am. Chem. Soc. 79, 3961–3972 (1957).
Deming, T. J. Polypeptide materials: new synthetic methods and applications. Adv. Mater. 9, 299–311 (1997).
Deming, T. J. Transition metal–amine initators for preparation of well-defined poly(γ-benzyl-l-glutamate). J. Am. Chem. Soc. 119, 2759–2760 (1997).
Fetters, L. J. in Encyclopedia of Polymer Science and Engineering 2nd edn 19–25 (Wiley-Interscience, New York, (1987)).
Webster, O. Living polymerization methods. Science 251, 887–893 (1991).
Collman, J. P., Hegedus, L. S., Norton, J. R. & Finke, R. G. Principles and Applications of Organotransition Metal Chemistry 2nd edn(University Science, Mill Valley, (1987)).
Uhlig, E., Fehske, G. & Nestler, B. Z. Reaktionen cyclischer Carbonsaueureanhydride mit (α,α′-Dipyridyl)-(cyclooctadien-1,5)-nickel. Anorg. Allg. Chem. 465, 141–146 (1980).
Sano, K., Yamamoto, T. & Yamamoto, A. Preparation of Ni- or Pt-containing cyclic esters by oxidative addition of cyclic carboxylic anhydrides and their properties. Bull. Chem. Soc. Jpn 57, 2741–2747 (1984).
Castaño, A. M. & Echavarren, A. M. Reactivity of a nickelacycle derived from aspartic acid: alkylations, insertions, and oxidations. Organometalics 13, 2262–2268 (1994).
Block, H. Poly(γ-benzyl-l-glutamate) and Other Glutamic Acid Containing Polymers(Gordon and Breach, New York, (1983)).
Noshay, A. & McGrath, J. E. Block Copolymers(Academic, New York, (1977)).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Deming, T. Facile synthesis of block copolypeptides of defined architecture. Nature 390, 386–389 (1997). https://doi.org/10.1038/37084
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1038/37084
This article is cited by
-
A nanoscale MOF-based heterogeneous catalytic system for the polymerization of N-carboxyanhydrides enables direct routes toward both polypeptides and related hybrid materials
Nature Communications (2023)
-
Recent advances in enantioselective ring-opening polymerization and copolymerization
Communications Chemistry (2023)
-
Tunable, biodegradable grafting-from glycopolypeptide bottlebrush polymers
Nature Communications (2021)
-
Accelerated polymerization of N-carboxyanhydrides catalyzed by crown ether
Nature Communications (2021)
-
Facile Synthesis of High Molecular Weight Polypeptides via Fast and Moisture Insensitive Polymerization of α-Amino Acid N-Carboxyanhydrides
Chinese Journal of Polymer Science (2020)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.