Self-assembling peptides: sequence, secondary structure in solution and film formation.

Peptides of alternating charge and hydrophobic amino acids have a tendency to adopt unusually stable beta-sheet structures that can form insoluble macroscopic aggregates under physiological conditions. In this study, analogues of a well-known self-assembling peptide, characterized by the same polar/nonpolar periodicity but with different residues, were designed to study the relationship between sequence, conformation in solution and film-forming capacity in saline solution. Peptide conformation, evaluated by circular dichroism, correlated with film forming capacity observed by inverted optical microscopy after addition of saline solution and subsequent drying. We found that polar/nonpolar periodicity of several analogues is not criterion enough to induce beta-sheet and thus film formation and that conformations different from beta-sheet also allow self-assemblage. Furthermore, addition of the short adhesive sequence RGD to a known self-assembling sequence was shown to not prevent the self-assembling process. This finding might prove useful for the design of biomimetic scaffolds.

[1]  A. Rich,et al.  Unusually stable β‐sheet formation in an ionic self‐complementary oligopeptide , 1994 .

[2]  C. Toniolo,et al.  Vacuum ultraviolet circular dichroism of beta-forming alkyl oligopeptides. , 1976, Journal of the American Chemical Society.

[3]  R D Kamm,et al.  Self-assembly of a beta-sheet protein governed by relief of electrostatic repulsion relative to van der Waals attraction. , 2000, Biomacromolecules.

[4]  Michael D. Altman,et al.  Peptide self-assembly in functional polymer science and engineering , 1999 .

[5]  R. Legge,et al.  Effect of amino acid sequence and pH on nanofiber formation of self-assembling peptides EAK16-II and EAK16-IV. , 2003, Biomacromolecules.

[6]  J. Duhamel,et al.  Concentration effect on the aggregation of a self-assembling oligopeptide. , 2003, Biophysical journal.

[7]  R. Hancock,et al.  Structure-activity relationships for the beta-hairpin cationic antimicrobial peptide polyphemusin I. , 2004, Biochimica et biophysica acta.

[8]  M. Illangasekare,et al.  Circular dichroism studies of distorted α-helices, twisted β-sheets, and β-turns , 1988 .

[9]  A. Rich,et al.  Spontaneous assembly of a self-complementary oligopeptide to form a stable macroscopic membrane. , 1993, Proceedings of the National Academy of Sciences of the United States of America.

[10]  T. Holmes,et al.  Novel peptide-based biomaterial scaffolds for tissue engineering. , 2002, Trends in biotechnology.

[11]  H A Scheraga,et al.  Origin of the right-handed twist of beta-sheets of poly(LVal) chains. , 1982, Proceedings of the National Academy of Sciences of the United States of America.

[12]  Shuguang Zhang,et al.  Conformational behavior of ionic self‐complementary peptides , 2000, Protein science : a publication of the Protein Society.

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

[14]  J. Hubbell,et al.  Synthetic biomaterials as instructive extracellular microenvironments for morphogenesis in tissue engineering , 2005, Nature Biotechnology.

[15]  A. Dunker,et al.  Aromatic and Cystine Side-Chain Circular Dichroism in Proteins , 1996 .

[16]  A. Rao,et al.  Conformation and antimicrobial activity of linear derivatives of tachyplesin lacking disulfide bonds. , 1999, Archives of biochemistry and biophysics.

[17]  Shuguang Zhang,et al.  Emerging biological materials through molecular self-assembly. , 2002, Biotechnology advances.

[18]  Richard T. Lee,et al.  Self-assembling short oligopeptides and the promotion of angiogenesis. , 2005, Biomaterials.

[19]  Hai-Meng Zhou,et al.  Conformational changes of lysozyme refolding intermediates and implications for aggregation and renaturation. , 2004, The international journal of biochemistry & cell biology.

[20]  A. Rich,et al.  Extensive neurite outgrowth and active synapse formation on self-assembling peptide scaffolds. , 2000, Proceedings of the National Academy of Sciences of the United States of America.

[21]  A. Rich,et al.  Direct conversion of an oligopeptide from a β-sheet to an α-helix: A model for amyloid formation , 1997, The Excitement of Discovery: Selected Papers of Alexander Rich.

[22]  A. Rich,et al.  Self-complementary oligopeptide matrices support mammalian cell attachment. , 1995, Biomaterials.

[23]  P. Y. Chou,et al.  Empirical predictions of protein conformation. , 1978, Annual review of biochemistry.

[24]  J. Bechhoefer,et al.  Self-assembly of the ionic peptide EAK16: the effect of charge distributions on self-assembly. , 2004, Biophysical journal.

[25]  Roger D Kamm,et al.  Control of self-assembling oligopeptide matrix formation through systematic variation of amino acid sequence. , 2002, Biomaterials.

[26]  N. Greenfield.  Methods to estimate the conformation of proteins and polypeptides from circular dichroism data. , 1996, Analytical biochemistry.

[27]  P. Y. Chou,et al.  Prediction of the secondary structure of proteins from their amino acid sequence. , 2006 .

[28]  S. Radford,et al.  Responsive gels formed by the spontaneous self-assembly of peptides into polymeric β-sheet tapes , 1997, Nature.

[29]  J. Brahms,et al.  Identification of β,β-turns and unordered conformations in polypeptide chains by vacuum ultraviolet circular dichroism , 1977 .

[30]  M. Hecht,et al.  Periodicity of polar and nonpolar amino acids is the major determinant of secondary structure in self-assembling oligomeric peptides. , 1995, Proceedings of the National Academy of Sciences of the United States of America.

[31]  G. Fasman.  Circular Dichroism and the Conformational Analysis of Biomolecules , 1996, Springer US.

[32]  Shuguang Zhang.  Fabrication of novel biomaterials through molecular self-assembly , 2003, Nature Biotechnology.

[33]  Pu Chen.  Self-assembly of ionic-complementary peptides : a physicochemical viewpoint , 2005 .

[34]  H. Wu,et al.  β‐turn formation by a six‐residue linear peptide in solution , 2002 .