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- W2619102628 endingPage "597" @default.
- W2619102628 startingPage "586" @default.
- W2619102628 abstract "Hydrogels prepared from self-assembling peptides are promising materials for medical applications, and using both l- and d-peptide isomers in a gel’s formulation provides an intuitive way to control the proteolytic degradation of an implanted material. In the course of developing gels for delivery applications, we discovered that a racemic mixture of the mirror-image β-hairpin peptides, named MAX1 and DMAX1, provides a fibrillar hydrogel that is four times more rigid than gels formed by either peptide alone—a puzzling observation. Herein, we use transmission electron microscopy, small angle neutron scattering, solid state NMR, diffusing wave, infrared, and fluorescence spectroscopies, and modeling to determine the molecular basis for the increased mechanical rigidity of the racemic gel. We find that enantiomeric peptides coassemble in an alternating fashion along the fibril long axis, forming an extended heterochiral pleat-like β-sheet, a structure predicted by Pauling and Corey in 1953. Hydrogen bonding between enantiomers within the sheet dictates the placement of hydrophobic valine side chains in the fibrils’ dry interior in a manner that allows the formation of nested hydrophobic interactions between enantiomers, interactions not accessible within enantiomerically pure fibrils. Importantly, this unique molecular arrangement of valine side chains maximizes inter-residue contacts within the core of the fibrils resulting in their local stiffening, which in turn, gives rise to the significant increase in bulk mechanical rigidity observed for the racemic hydrogel." @default.
- W2619102628 created "2017-06-05" @default.
- W2619102628 creator A5005713509 @default.
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- W2619102628 creator A5065785217 @default.
- W2619102628 creator A5080844755 @default.
- W2619102628 creator A5082962021 @default.
- W2619102628 date "2017-05-31" @default.
- W2619102628 modified "2023-10-11" @default.
- W2619102628 title "Molecular, Local, and Network-Level Basis for the Enhanced Stiffness of Hydrogel Networks Formed from Coassembled Racemic Peptides: Predictions from Pauling and Corey" @default.
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- W2619102628 doi "https://doi.org/10.1021/acscentsci.7b00115" @default.
- W2619102628 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/5492410" @default.
- W2619102628 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/28691070" @default.
- W2619102628 hasPublicationYear "2017" @default.
- W2619102628 type Work @default.