title: Amino Acid Chirality and Ferrocene Conformation Guided Self-Assembly and Gelation of Ferrocene-Peptide Conjugates.
abstract: The self-assembly and gelation behavior of a series of mono- and disubstituted ferrocene (Fc)-peptide conjugates as a function of ferrocene conformation and amino acid chirality are described. The results reveal that ferrocene-peptide conjugates self-assemble into organogels by controlling the conformation of the central ferrocene core, through inter- versus intramolecular hydrogen bonding in the attached peptide chain(s). The chirality controlled assembling studies showed that two monosubstituted Fc conjugates FcCO-LFLFLA-OMe and FcCO-LFLFDA-OMe form gels with nanofibrillar network structures, whereas the other two diastereomers FcCO-DFLFLA-OMe and FcCO-LFDFLA-OMe exclusively produced straight nanorods and non-interconnected small fibers, respectively. This suggests the potential tuning of gelation behavior and nanoscale morphology by altering the chirality of constituted amino acids. The current study confirms the profound effect of diastereomerism and no influence of enantiomers on gelation. Correspondingly, the diastereomeric and enantiomeric Fc[CO-FFA-OMe]2 were constructed for the study of chirality-organized structures.
authors.affiliation: Department of Physical and Environmental Sciences, University of Toronto, 1265 Military Trail, Toronto, M1C 1A4 (Canada). bimalendu.adhikari@utoronto.ca.
authors.forename: Bimalendu
authors.initials: B
authors.lastname: Adhikari
authors.affiliation: Department of Physical and Environmental Sciences, University of Toronto, 1265 Military Trail, Toronto, M1C 1A4 (Canada).
authors.forename: Charanpreet
authors.initials: C
authors.lastname: Singh
authors.affiliation: Department of Physical and Environmental Sciences, University of Toronto, 1265 Military Trail, Toronto, M1C 1A4 (Canada).|Present address: Department of Chemistry, Quaid-i-Azam University, 45320 (Pakistan).
authors.forename: Afzal
authors.initials: A
authors.lastname: Shah
authors.affiliation: Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6 (Canada).
authors.forename: Alan J
authors.initials: AJ
authors.lastname: Lough
authors.affiliation: Department of Physical and Environmental Sciences, University of Toronto, 1265 Military Trail, Toronto, M1C 1A4 (Canada). bernie.kraatz@utoronto.ca.|Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6 (Canada). bernie.kraatz@utoronto.ca.
authors.forename: Heinz-Bernhard
authors.initials: HB
authors.lastname: Kraatz
mesh_terms: D000596:Amino Acids / Q000737:chemistry; D018360:Crystallography, X-Ray; D005296:Ferrous Compounds / Q000737:chemistry*; D005782:Gels / Q000737:chemistry*; D006860:Hydrogen Bonding; D000075163:Metallocenes; D008968:Molecular Conformation; D010455:Peptides / Q000737:chemistry* / Q000378:metabolism; D013237:Stereoisomerism
chemical_list: D000596:Amino Acids; D005296:Ferrous Compounds; D005782:Gels; D000075163:Metallocenes; D010455:Peptides; C004998:ferrocene
keywords: chirality; conformational analysis; ferrocene; gels; peptides