title: Controlling Peptide Self-Assembly through a Native Chemical Ligation/Desulfurization Strategy.
abstract: Self-assembled peptides were synthesized by using a native chemical ligation (NCL)/desulfurization strategy that maintained the chemical diversity of the self-assembled peptides. Herein, we employed oxo-ester-mediated NCL reactions to incorporate cysteine, a cysteine-based dipeptide, and a sterically hindered unnatural amino acid (penicillamine) into peptides. Self-assembly of the peptides resulted in the formation of self-supporting gels. Microscopy analysis indicated the formation of helical nanofibers, which were responsible for the formation of gel matrices. The self-assembly of the ligated peptides was governed by covalent and non-covalent interactions, as confirmed by FTIR, CD, fluorescence spectroscopy, and MS (ESI) analyses. Peptide disassembly was induced by desulfurization reactions with tris(2-carboxyethyl)phosphine (TCEP) and glutathione at 80 °C. Desulfurization reactions of the ligated peptides converted the Cys and penicillamine functionalities into Ala and Val moieties, respectively. The self-supporting gels showed significant shear-thinning and thixotropic properties.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Indore, Khandwa Road, Indore, 452020, India.
authors.forename: Dnyaneshwar B
authors.initials: DB
authors.lastname: Rasale
authors.affiliation: Department of Chemistry, Indian Institute of Technology Indore, Khandwa Road, Indore, 452020, India.
authors.forename: Maruthi
authors.initials: M
authors.lastname: Konda
authors.affiliation: Department of Chemistry, Indian Institute of Technology Indore, Khandwa Road, Indore, 452020, India.
authors.forename: Sagar
authors.initials: S
authors.lastname: Biswas
authors.affiliation: Department of Chemistry, Indian Institute of Technology Indore, Khandwa Road, Indore, 452020, India. apurba.das@iiti.ac.in.
authors.forename: Apurba K
authors.initials: AK
authors.lastname: Das
mesh_terms: D002942:Circular Dichroism; D010455:Peptides / Q000737:chemistry*; D013050:Spectrometry, Fluorescence; D021241:Spectrometry, Mass, Electrospray Ionization; D013455:Sulfur / Q000737:chemistry*
chemical_list: D010455:Peptides; D013455:Sulfur
keywords: desulfurization; gels; native chemical ligation; peptides; self-assembly