Non-covalent adsorption of amino acid analogues on noble-metal nanoparticles: influence of edges and vertices.
The operation of many nanostructured biomolecular sensors and catalysts critically hinges on the manipulation of non-covalent adsorption of biomolecules on unfunctionalised noble-metal nanoparticles (NMNPs). Molecular-level structural details of the aqueous biomolecule/NMNP interface are pivotal to the successful realisation of these technologies, but such experimental data are currently scarce and challenging to obtain. Molecular simulations can generate these details, but are limited by the assumption of non-preferential adsorption to NMNP features. Here, via first principles calculations using a vdW-DF functional, and based on nanoscale sized NMNPs, we demonstrate that adsorption preferences to NP features vary with adsorbate chemistry. These results show a clear distinction between hydrocarbons, that prefer adsorption to facets over edges/vertices, over heteroatomic molecules that favour adsorption onto vertices over facets. Our data indicate the inability of widely used force-fields to correctly capture the adsorption of biomolecules onto NMNP surfaces under aqueous conditions. Our findings introduce a rational basis for the development of new force-fields that will reliably capture these phenomena.
Institute for Frontier Materials, Deakin University, Geelong VIC 3216, Australia. tiffany.walsh@deakin.edu.au.
Zak E
ZE
Hughes
Tiffany R
TR
Walsh
D000327:Adsorption; D000596:Amino Acids / Q000737:chemistry*; D006046:Gold / Q000737:chemistry*; D057927:Hydrophobic and Hydrophilic Interactions; D053768:Metal Nanoparticles / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D010984:Platinum / Q000737:chemistry*; D013329:Structure-Activity Relationship; D013499:Surface Properties; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
D000596:Amino Acids; D014867:Water; D010984:Platinum; D006046:Gold