Dataset Information

The electronic structure of the metal-organic interface of isolated ligand coated gold nanoparticles.

ABSTRACT: Light induced electron transfer reactions of molecules on the surface of noble metal nanoparticles (NPs) depend significantly on the electronic properties of the metal-organic interface. Hybridized metal-molecule states and dipoles at the interface alter the work function and facilitate or hinder electron transfer between the NPs and ligand. X-ray photoelectron spectroscopy (XPS) measurements of isolated AuNPs coated with thiolated ligands in a vacuum have been performed as a function of photon energy, and the depth dependent information of the metal-organic interface has been obtained. The role of surface dipoles in the XPS measurements of isolated ligand coated NPs is discussed and the binding energy of the Au 4f states is shifted by around 0.8 eV in the outer atomic layers of 4-nitrothiophenol coated AuNPs, facilitating electron transport towards the molecules. Moreover, the influence of the interface dipole depends significantly on the adsorbed ligand molecules. The present study paves the way towards the engineering of the electronic properties of the nanoparticle surface, which is of utmost importance for the application of plasmonic nanoparticles in the fields of heterogeneous catalysis and solar energy conversion.

SUBMITTER: Schurmann R

PROVIDER: S-EPMC8922996 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

The electronic structure of the metal-organic interface of isolated ligand coated gold nanoparticles.

Schürmann Robin R Titov Evgenii E Ebel Kenny K Kogikoski Sergio S Mostafa Amr A Saalfrank Peter P Milosavljević Aleksandar R AR Bald Ilko I

Nanoscale advances 20220202 6

Light induced electron transfer reactions of molecules on the surface of noble metal nanoparticles (NPs) depend significantly on the electronic properties of the metal-organic interface. Hybridized metal-molecule states and dipoles at the interface alter the work function and facilitate or hinder electron transfer between the NPs and ligand. X-ray photoelectron spectroscopy (XPS) measurements of isolated AuNPs coated with thiolated ligands in a vacuum have been performed as a function of photon ...[more]

PMID: 35399325

Similar Datasets

Project description:Glutathione (GSH) plays a pivotal role in numerous physiological and metabolic processes, including the defense of cells against free radicals and metal toxicity. This tripeptide has been combined with several metal nanoparticles to form a metal-organic interface with unique properties. Here, we implement a one-step, high-yield synthesis method to produce ultrasmall gold, silver, and copper nanoparticles in the intermediate size regime between size-selected nanoclusters and plasmonic nanoparticles to be functionalized with l- and d-glutathione, and study the chirality transfer evidenced by the emergent optical activity observed for each case. The distinctive interactions that take place at the metal-ligand interface for each metal are primarily accountable for establishing the properties of this system. In its protonated state, glutathione anchors only by its thiol group to the surface of gold and copper nanoparticles, whilst for silver nanoparticles an additional binding site through the nitrogen atom of the amide group was indicated by XPS data, albeit with a relatively low proportion. This may contribute to the higher anisotropy factor observed in silver-glutathione nanoparticles. Such slight variations in adsorption configuration generate different chiroptical activity, which has been analyzed per energy region using time-dependent DFT calculations, revealing that metal-to-ligand transitions dominate most of the spectra while ligand-to-ligand are also present in the higher energy regime. Moreover, FTIR and CD data together suggest that those dissimilarities also propitiate particular peptide self-assemblies through intermolecular GSH interactions for each metal, which result in supramolecular structures with properties of beta-sheet arrays. This study offers a parallel examination of the chirality of glutathione-functionalized coinage metals, allowing to establish decisive differences that can be tailored to benefit developments in chiral biomedicine and other diverse applications.

Dataset Information

The electronic structure of the metal-organic interface of isolated ligand coated gold nanoparticles.

Publications

The electronic structure of the metal-organic interface of isolated ligand coated gold nanoparticles.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets