title: Emergent Catalytic Behavior of Self-Assembled Low Molecular Weight Peptide-Based Aggregates and Hydrogels.
abstract: We report a series of short peptides possessing the sequence (FE)n or (EF)n and bearing l-proline at their N-terminus that self-assemble into high aspect ratio aggregates and hydrogels. We show that these aggregates are able to catalyze the aldol reaction, whereas non-aggregated analogues are catalytically inactive. We have undertaken an analysis of the results, considering the accessibility of catalytic sites, pKa value shifts, and the presence of hydrophobic pockets. We conclude that the presence of hydrophobic regions is indeed relevant for substrate solubilization, but that the active site accessibility is the key factor for the observed differences in reaction rates. The results presented here provide an example of the emergence of a new chemical property caused by self-assembly, and support the relevant role played by self-assembled peptides in prebiotic scenarios. In this sense, the reported systems can be seen as primitive aldolase I mimics, and have been successfully tested for the synthesis of simple carbohydrate precursors.
authors.affiliation: Departament de Química Inorgànica i Orgànica, Universitat Jaume I, 12071, Castelló, Spain.
authors.forename: Marta
authors.initials: M
authors.lastname: Tena-Solsona
authors.affiliation: Department of Chemistry, Ben-Gurion University of the Negev, Be'er Sheva, Israel.
authors.forename: Jayanta
authors.initials: J
authors.lastname: Nanda
authors.affiliation: Departament de Química Inorgànica i Orgànica, Universitat Jaume I, 12071, Castelló, Spain.
authors.forename: Santiago
authors.initials: S
authors.lastname: Díaz-Oltra
authors.affiliation: Department of Chemistry, Ben-Gurion University of the Negev, Be'er Sheva, Israel.
authors.forename: Agata
authors.initials: A
authors.lastname: Chotera
authors.affiliation: Department of Chemistry, Ben-Gurion University of the Negev, Be'er Sheva, Israel. gonenash@bgu.ac.il.
authors.forename: Gonen
authors.initials: G
authors.lastname: Ashkenasy
authors.affiliation: Departament de Química Inorgànica i Orgànica, Universitat Jaume I, 12071, Castelló, Spain. escuder@uji.es.
authors.forename: Beatriu
authors.initials: B
authors.lastname: Escuder
mesh_terms: D002384:Catalysis; D005634:Fructose-Bisphosphate Aldolase / Q000737:chemistry* / Q000378:metabolism; D020100:Hydrogels / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D057927:Hydrophobic and Hydrophilic Interactions; D015394:Molecular Structure; D008970:Molecular Weight; D010455:Peptides / Q000737:chemistry* / Q000378:metabolism; D056692:Prebiotics; D011392:Proline / Q000737:chemistry*
chemical_list: D020100:Hydrogels; D010455:Peptides; D056692:Prebiotics; D011392:Proline; D005634:Fructose-Bisphosphate Aldolase
keywords: aldol reaction; gels; peptides; self-assembly; supramolecular chemistry