title: Computational and Experimental Investigation of the Structure of Peptide Monolayers on Gold Nanoparticles.
abstract: The self-assembly and self-organization of small molecules on the surface of nanoparticles constitute a potential route toward the preparation of advanced proteinlike nanosystems. However, their structural characterization, critical to the design of bionanomaterials with well-defined biophysical and biochemical properties, remains highly challenging. Here, a computational model for peptide-capped gold nanoparticles (GNPs) is developed using experimentally characterized Cys-Ala-Leu-Asn-Asn (CALNN)- and Cys-Phe-Gly-Ala-Ile-Leu-Ser-Ser (CFGAILSS)-capped GNPs as a benchmark. The structure of CALNN and CFGAILSS monolayers is investigated using both structural biology techniques and molecular dynamics simulations. The calculations reproduce the experimentally observed dependence of the monolayer secondary structure on the peptide capping density and on the nanoparticle size, thus giving us confidence in the model. Furthermore, the computational results reveal a number of new features of peptide-capped monolayers, including the importance of sulfur movement for the formation of secondary structure motifs, the presence of water close to the gold surface even in tightly packed peptide monolayers, and the existence of extended 2D parallel β-sheet domains in CFGAILSS monolayers. The model developed here provides a predictive tool that may assist in the design of further bionanomaterials.
authors.affiliation: Institute of Integrative Biology, University of Liverpool , Crown Street, L69 7ZB Liverpool, U.K.|Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research) , 2 Fusionopolis Way, #08-03 Innovis, Singapore 138634.|Institute of High Performance Computing, A*STAR (Agency for Science, Technology and Research) , 1 Fusionopolis Way, #16-16 Connexis North, Singapore 138632.
authors.forename: Elena
authors.identifier: 0000-0001-5171-110X
authors.initials: E
authors.lastname: Colangelo
authors.affiliation: Institute of High Performance Computing, A*STAR (Agency for Science, Technology and Research) , 1 Fusionopolis Way, #16-16 Connexis North, Singapore 138632.
authors.forename: Qiubo
authors.initials: Q
authors.lastname: Chen
authors.affiliation: Department of Chemistry, University of Liverpool , Liverpool L69 7ZD, U.K.
authors.forename: Adam M
authors.initials: AM
authors.lastname: Davidson
authors.affiliation: Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research) , 2 Fusionopolis Way, #08-03 Innovis, Singapore 138634.
authors.forename: David
authors.initials: D
authors.lastname: Paramelle
authors.affiliation: Institute of High Performance Computing, A*STAR (Agency for Science, Technology and Research) , 1 Fusionopolis Way, #16-16 Connexis North, Singapore 138632.
authors.forename: Michael B
authors.initials: MB
authors.lastname: Sullivan
authors.affiliation: Department of Chemistry, University of Liverpool , Liverpool L69 7ZD, U.K.|Department of Chemistry, Surface Science Research Centre, University of Liverpool , Abercromby Square, Liverpool L69 3BX, U.K.
authors.forename: Martin
authors.initials: M
authors.lastname: Volk
authors.affiliation: Institute of Integrative Biology, University of Liverpool , Crown Street, L69 7ZB Liverpool, U.K.
authors.forename: Raphaël
authors.identifier: 0000-0001-5728-0531
authors.initials: R
authors.lastname: Lévy
mesh_terms: D000595:Amino Acid Sequence; D006046:Gold; D053758:Nanoparticles; D009842:Oligopeptides; D010446:Peptide Fragments / Q000737:chemistry*; D017433:Protein Structure, Secondary
chemical_list: D009842:Oligopeptides; D010446:Peptide Fragments; C070224:glycyl-alanyl-isoleucine; D006046:Gold