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Title: Elucidation of Peptide-Directed Palladium Surface Structure for Biologically Tunable Nanocatalysts

Abstract

Peptide-enabled synthesis of inorganic nanostructures represents an avenue to access catalytic materials with tunable and optimized properties. This is achieved via peptide complexity and programmability that is missing in traditional ligands for catalytic nanomaterials. Unfortunately, there is limited information available to correlate peptide sequence to particle structure and catalytic activity to date. As such, the application of peptide-enabled nanocatalysts remains limited to trial and error approaches. In this paper, a hybrid experimental and computational approach is introduced to systematically elucidate biomolecule-dependent structure/function relationships for peptide-capped Pd nanocatalysts. Synchrotron X-ray techniques were used to uncover substantial particle surface structural disorder, which was dependent upon the amino acid sequence of the peptide capping ligand. Nanocatalyst configurations were then determined directly from experimental data using reverse Monte Carlo methods and further refined using molecular dynamics simulation, obtaining thermodynamically stable peptide-Pd nanoparticle configurations. Sequence-dependent catalytic property differences for C-C coupling and olefin hydrogenation were then eluddated by identification of the catalytic active sites at the atomic level and quantitative prediction of relative reaction rates. This hybrid methodology provides a clear route to determine peptide-dependent structure/function relationships, enabling the generation of guidelines for catalyst design through rational tailoring of peptide sequences

Authors:
; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Argonne National Laboratory - Advanced Photon Source; US Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF); National Research Council; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1241352
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 9; Journal Issue: 5; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
atomic pair distribution function; bio-templating; catalysis; molecular dynamics simulations; peptides

Citation Formats

Bedford, Nicholas M., Ramezani-Dakhel, Hadi, Slocik, Joseph M., Briggs, Beverly D., Ren, Yang, Frenkel, Anatoly I., Petkov, Valeri, Heinz, Hendrik, Naik, Rajesh R., and Knecht, Mark R. Elucidation of Peptide-Directed Palladium Surface Structure for Biologically Tunable Nanocatalysts. United States: N. p., 2015. Web. doi:10.1021/acsnano.5b00168.
Bedford, Nicholas M., Ramezani-Dakhel, Hadi, Slocik, Joseph M., Briggs, Beverly D., Ren, Yang, Frenkel, Anatoly I., Petkov, Valeri, Heinz, Hendrik, Naik, Rajesh R., & Knecht, Mark R. Elucidation of Peptide-Directed Palladium Surface Structure for Biologically Tunable Nanocatalysts. United States. doi:10.1021/acsnano.5b00168.
Bedford, Nicholas M., Ramezani-Dakhel, Hadi, Slocik, Joseph M., Briggs, Beverly D., Ren, Yang, Frenkel, Anatoly I., Petkov, Valeri, Heinz, Hendrik, Naik, Rajesh R., and Knecht, Mark R. Fri . "Elucidation of Peptide-Directed Palladium Surface Structure for Biologically Tunable Nanocatalysts". United States. doi:10.1021/acsnano.5b00168.
@article{osti_1241352,
title = {Elucidation of Peptide-Directed Palladium Surface Structure for Biologically Tunable Nanocatalysts},
author = {Bedford, Nicholas M. and Ramezani-Dakhel, Hadi and Slocik, Joseph M. and Briggs, Beverly D. and Ren, Yang and Frenkel, Anatoly I. and Petkov, Valeri and Heinz, Hendrik and Naik, Rajesh R. and Knecht, Mark R.},
abstractNote = {Peptide-enabled synthesis of inorganic nanostructures represents an avenue to access catalytic materials with tunable and optimized properties. This is achieved via peptide complexity and programmability that is missing in traditional ligands for catalytic nanomaterials. Unfortunately, there is limited information available to correlate peptide sequence to particle structure and catalytic activity to date. As such, the application of peptide-enabled nanocatalysts remains limited to trial and error approaches. In this paper, a hybrid experimental and computational approach is introduced to systematically elucidate biomolecule-dependent structure/function relationships for peptide-capped Pd nanocatalysts. Synchrotron X-ray techniques were used to uncover substantial particle surface structural disorder, which was dependent upon the amino acid sequence of the peptide capping ligand. Nanocatalyst configurations were then determined directly from experimental data using reverse Monte Carlo methods and further refined using molecular dynamics simulation, obtaining thermodynamically stable peptide-Pd nanoparticle configurations. Sequence-dependent catalytic property differences for C-C coupling and olefin hydrogenation were then eluddated by identification of the catalytic active sites at the atomic level and quantitative prediction of relative reaction rates. This hybrid methodology provides a clear route to determine peptide-dependent structure/function relationships, enabling the generation of guidelines for catalyst design through rational tailoring of peptide sequences},
doi = {10.1021/acsnano.5b00168},
journal = {ACS Nano},
issn = {1936-0851},
number = 5,
volume = 9,
place = {United States},
year = {2015},
month = {5}
}