title: Sequence-Dependent Structure/Function Relationships of Catalytic Peptide-Enabled Gold Nanoparticles Generated under Ambient Synthetic Conditions.
abstract: Peptide-enabled nanoparticle (NP) synthesis routes can create and/or assemble functional nanomaterials under environmentally friendly conditions, with properties dictated by complex interactions at the biotic/abiotic interface. Manipulation of this interface through sequence modification can provide the capability for material properties to be tailored to create enhanced materials for energy, catalysis, and sensing applications. Fully realizing the potential of these materials requires a comprehensive understanding of sequence-dependent structure/function relationships that is presently lacking. In this work, the atomic-scale structures of a series of peptide-capped Au NPs are determined using a combination of atomic pair distribution function analysis of high-energy X-ray diffraction data and advanced molecular dynamics (MD) simulations. The Au NPs produced with different peptide sequences exhibit varying degrees of catalytic activity for the exemplar reaction 4-nitrophenol reduction. The experimentally derived atomic-scale NP configurations reveal sequence-dependent differences in structural order at the NP surface. Replica exchange with solute-tempering MD simulations are then used to predict the morphology of the peptide overlayer on these Au NPs and identify factors determining the structure/catalytic properties relationship. We show that the amount of exposed Au surface, the underlying surface structural disorder, and the interaction strength of the peptide with the Au surface all influence catalytic performance. A simplified computational prediction of catalytic performance is developed that can potentially serve as a screening tool for future studies. Our approach provides a platform for broadening the analysis of catalytic peptide-enabled metallic NP systems, potentially allowing for the development of rational design rules for property enhancement.
authors.affiliation: Applied Chemical and Materials Division, National Institute of Standards and Technology , Boulder, Colorado 80305, United States.|Materials and Manufacturing Directorate, Air Force Research Laboratory , Wright-Patterson AFB, Ohio 45433, United States.|Department of Chemistry, University of Miami , Coral Gables, Florida 33146, United States.
authors.forename: Nicholas M
authors.initials: NM
authors.lastname: Bedford
authors.affiliation: Institute for Frontier Materials, Deakin University , Geelong, Victoria 3216, Australia.
authors.forename: Zak E
authors.initials: ZE
authors.lastname: Hughes
authors.affiliation: Department of Chemistry, University of Miami , Coral Gables, Florida 33146, United States.|New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre , Guangzhou 510006, China.
authors.forename: Zhenghua
authors.initials: Z
authors.lastname: Tang
authors.affiliation: Chemical and Biological Engineering, State University of New York at Buffalo , Buffalo, New York 14260, United States.
authors.forename: Yue
authors.initials: Y
authors.lastname: Li
authors.affiliation: Department of Chemistry, University of Miami , Coral Gables, Florida 33146, United States.
authors.forename: Beverly D
authors.initials: BD
authors.lastname: Briggs
authors.affiliation: Advanced Photon Source, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Yang
authors.initials: Y
authors.lastname: Ren
authors.affiliation: Chemical and Biological Engineering, State University of New York at Buffalo , Buffalo, New York 14260, United States.
authors.forename: Mark T
authors.initials: MT
authors.lastname: Swihart
authors.affiliation: Department of Physics, Central Michigan University , Mt. Pleasant, Michigan 48858, United States.
authors.forename: Valeri G
authors.initials: VG
authors.lastname: Petkov
authors.affiliation: Materials and Manufacturing Directorate, Air Force Research Laboratory , Wright-Patterson AFB, Ohio 45433, United States.
authors.forename: Rajesh R
authors.initials: RR
authors.lastname: Naik
authors.affiliation: Department of Chemistry, University of Miami , Coral Gables, Florida 33146, United States.
authors.forename: Marc R
authors.initials: MR
authors.lastname: Knecht
authors.affiliation: Institute for Frontier Materials, Deakin University , Geelong, Victoria 3216, Australia.
authors.forename: Tiffany R
authors.initials: TR
authors.lastname: Walsh
mesh_terms: D002384:Catalysis; D006046:Gold / Q000737:chemistry*; D053768:Metal Nanoparticles; D046529:Microscopy, Electron, Transmission; D010455:Peptides / Q000737:chemistry*; D013329:Structure-Activity Relationship; D014961:X-Ray Diffraction
chemical_list: D010455:Peptides; D006046:Gold