Chemical sequence control of beta-sheet assembly in macromolecular crystals of periodic polypeptides.

A family of uniform periodic polypeptides has been prepared by bacterial expression of the corresponding artificial genes, with the objective of exploring the potential for control of supramolecular organization in genetically engineered protein-based polymeric materials. The repeating units of the polypeptides consist of oligomeric alanyl-glycine sequences interspersed with glutamic acid residues inserted at intervals of 8 to 14 amino acids. Crystallization of such materials from formic acid produces beta-sheet structures in the solid state, as shown by vibrational spectroscopy, nuclear magnetic resonance spectroscopy, and wide-angle x-ray diffraction. The diffraction results, together with observations from electron microscopy, are consistent with the formation of needle-shaped lamellar crystals whose thickness is controlled by the periodicity of the primary sequence. These results can be used to control solid-state structure in macromolecular materials.

[1]  Maurille J. Fournier,et al.  Protein engineering for materials applications , 1991 .

[2]  J. Bandekar,et al.  Vibrational spectroscopy and conformation of peptides, polypeptides, and proteins. , 1986, Advances in protein chemistry.

[3]  E. Atkins,et al.  “Cross-β” conformation in proteins☆ , 1968 .

[4]  G. Hinrichsen.  Untersuchungen zu struktur und eigenschaften der polyamide, 2. Einkristalle aus polyamid 6,6 , 1973 .

[5]  Maurille J. Fournier,et al.  Genetically directed syntheses of new polymeric materials. Expression of artificial genes encoding proteins with repeating -(AlaGly)3ProGluGly- elements , 1992 .

[6]  N. Morosoff,et al.  Drawing of nylon 6 fibers (bristles) , 1973 .

[7]  A. Keller,et al.  Crystallization and morphology of nylon-6,6 crystals: 1. Solution crystallization and solution annealing behaviour , 1981 .

[8]  G. Némethy,et al.  The γ Turn, a Possible Folded Conformation of the Polypeptide Chain. Comparison with the β Turn , 1972 .

[9]  P. Y. Chou,et al.  Prediction of protein conformation. , 1974, Biochemistry.

[10]  E. Blout,et al.  The Infrared Spectra of Polypeptides in Various Conformations: Amide I and II Bands1 , 1961 .

[11]  R. E. Marsh,et al.  An investigation of the structure of silk fibroin. , 1955, Biochimica et biophysica acta.

[12]  A. Keller,et al.  Electron microscope‐electron diffraction investigations of the crystalline texture of polyamides , 1959 .

[13]  T. Asakura,et al.  Solvent- and mechanical-treatment-induced conformational transition of silk fibroins studies by high-resolution solid-state carbon-13 NMR spectroscopy , 1990 .

[14]  C. Yanisch-Perron,et al.  Improved M13 phage cloning vectors and host strains: nucleotide sequences of the M13mp18 and pUC19 vectors. , 1985, Gene.

[15]  D. Tirrell,et al.  Determination of the chain-folding pattern in the crystalline domains of the repetitive polypeptide {(AlaGly)3GluGly(GlyAla)3GluGly}10 by FTIR studies of its blends with a carbon-13 enriched analog , 1993 .

[16]  H. Saitǒ,et al.  High-resolution carbon-13 NMR study of silk fibroin in the solid state by the cross-polarization-magic angle spinning method. Conformational characterization of silk I and silk II type forms of Bombyx mori fibroin by the conformation-dependent carbon-13 chemical shifts , 1984 .

[17]  R. Fraser,et al.  POLY-L-ALANYLGLYCINE. , 1965, Journal of molecular biology.

[18]  J. Koenig,et al.  Raman spectroscopic study of poly (β‐benzyl‐L‐aspartate) and sequential polypeptides , 1975 .

[19]  L. Brown,et al.  X-ray studies of poly-L-alanine , 1956 .

[20]  L. H. Bradley,et al.  Protein design by binary patterning of polar and nonpolar amino acids. , 1993, Methods in molecular biology.

[21]  S. G. Smith,et al.  Comparative studies of fibroins. I. The amino acid composition of various fibroins and its significance in relation to their crystal structure and taxonomy. , 1960, Journal of molecular biology.

[22]  H. D. Keith,et al.  Single crystals of poly(L‐glutamic acid) , 1969 .

[23]  F. Studier,et al.  Use of T7 RNA polymerase to direct expression of cloned genes. , 1990, Methods in enzymology.

[24]  J. Warwicker.  Comparative studies of fibroins. II. The crystal structures of various fibroins. , 1960, Journal of molecular biology.

[25]  M. J. Hill,et al.  Lamellar Structure and Morphology of Nylon 46 Crystals. A New Chain Folding Mechanism for Nylons , 1992 .

[26]  P. H. Till.  The growth of single crystals of linear polyethylene , 1957 .