Journal article
Selective Adsorption of Thiol-Containing Molecules on Copper Sulfide Surfaces via Molecule–Surface Disulfide Bridges
Journal of physical chemistry. C, Vol.129(4), pp.1976-1987
01/30/2025
DOI: 10.1021/acs.jpcc.4c06463
Abstract
Recent results in the fields of nanoenhanced agriculture and expanding interest in prebiotic chemistry have placed increased emphasis on understanding the chemically selective interaction of small molecules with the surfaces of metal sulfides. We present an integrated experimental and computational study of the interaction of thiol-containing molecules with copper sulfide (covellite) surfaces in aqueous media. In situ Fourier-transform infrared (FTIR) measurements and ex situ X-ray photoelectron spectroscopy (XPS) measurements show that molecules bearing free thiol groups, including glutathione and cysteine, bind strongly to CuS (covellite) nanoparticles and to CuS (001) single crystals, while control studies show that similar molecules lacking the free thiol group exhibit much less binding. Additional experiments show that these thiol-containing molecules interact transiently with CuO nanoparticle surfaces but are readily removed by rinsing. The FTIR and XPS experiments demonstrate that adsorption of molecular thiols to CuS surfaces occurs in a chemically selective manner. Further experimental studies and density functional calculations show that the preferred mode of binding is through the surface S atoms, forming a Solid–S–S–Molecule disulfide linkage. While the role of disulfide linkages in controlling structure and function of proteins and other biomolecules is widely known, the formation of surface disulfide linkages as a motif for covalent molecular binding at surfaces has not been established previously.
Details
- Title: Subtitle
- Selective Adsorption of Thiol-Containing Molecules on Copper Sulfide Surfaces via Molecule–Surface Disulfide Bridges
- Creators
- Connor R. Protter - University of Wisconsin–MadisonJennifer L. Bjorklund - Brookhaven National LaboratorySara E. Mason - Brookhaven National LaboratoryRobert J. Hamers - University of Wisconsin–Madison
- Resource Type
- Journal article
- Publication Details
- Journal of physical chemistry. C, Vol.129(4), pp.1976-1987
- DOI
- 10.1021/acs.jpcc.4c06463
- ISSN
- 1932-7447
- eISSN
- 1932-7455
- Publisher
- AMER CHEMICAL SOC
- Grant note
- Division of Chemistry: CHE-2001611 National Science FoundationNSF Center for Sustainable Nanotechnology: DE-SC0012704 U.S. Department of Energy Office of Science User Facility, at Brookhaven National Laboratory
This work was supported by the National Science Foundation under Grant No. CHE-2001611, the NSF Center for Sustainable Nanotechnology. This research used the Theory and Computation Facility of the Center for Functional Nanomaterials (CFN), which is a U.S. Department of Energy Office of Science User Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704.
- Language
- English
- Electronic publication date
- 01/17/2025
- Date published
- 01/30/2025
- Academic Unit
- Chemistry
- Record Identifier
- 9984775015602771
Metrics
8 Record Views