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Probing multiscale factors affecting the reactivity of nanoparticle-bound molecules
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dc.contributor.author | Mati, Ioulia | |
dc.contributor.author | Edwards, William | |
dc.contributor.author | Marson, Domenico | |
dc.contributor.author | Howe, Edward James | |
dc.contributor.author | Stinson, Scott | |
dc.contributor.author | Posocco, Paola | |
dc.contributor.author | Kay, Euan R. | |
dc.date.accessioned | 2022-05-02T23:51:55Z | |
dc.date.available | 2022-05-02T23:51:55Z | |
dc.date.issued | 2021-05-03 | |
dc.identifier | 273874572 | |
dc.identifier | 48894beb-fd8b-4cdf-8688-1918ebec421d | |
dc.identifier | 85106523729 | |
dc.identifier | 000656994100032 | |
dc.identifier.citation | Mati , I , Edwards , W , Marson , D , Howe , E J , Stinson , S , Posocco , P & Kay , E R 2021 , ' Probing multiscale factors affecting the reactivity of nanoparticle-bound molecules ' , ACS Nano , vol. Articles ASAP . https://doi.org/10.1021/acsnano.0c09190 | en |
dc.identifier.issn | 1936-0851 | |
dc.identifier.other | ORCID: /0000-0001-8177-6393/work/92775297 | |
dc.identifier.uri | https://hdl.handle.net/10023/25267 | |
dc.description | I. K. M., W. E., E. J. H, S. S. and E. R. K. are grateful for funding from the Leverhulme Trust [RPG-2015-042], the Engineering and Physical Sciences Research Council [EP/K016342/1], the University of St Andrews, and the EPSRC Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT) [Ph.D. studentship to SS: EP/L016419/1]. D. M. and P.P thank the Italian Ministry of University Research (MIUR) for funding [RBSI14PBC6]. | en |
dc.description.abstract | The structures and physicochemical properties of surface-stabilizing molecules play a critical role in defining the properties, interactions, and functionality of hybrid nanomaterials such as monolayer-stabilized nanoparticles. Concurrently, the distinct surface-bound interfacial environment imposes very specific conditions on molecular reactivity and behavior in this setting. Our ability to probe hybrid nanoscale systems experimentally remains limited, yet understanding the consequences of surface confinement on molecular reactivity is crucial for enabling predictive nanoparticle synthon approaches for postsynthesis engineering of nanoparticle surface chemistry and construction of devices and materials from nanoparticle components. Here, we have undertaken an integrated experimental and computational study of the reaction kinetics for nanoparticle-bound hydrazones, which provide a prototypical platform for understanding chemical reactivity in a nanoconfined setting. Systematic variation of just one molecular-scale structural parameter—the distance between reactive site and nanoparticle surface—showed that the surface-bound reactivity is influenced by multiscale effects. Nanoparticle-bound reactions were tracked in situ using 19F NMR spectroscopy, allowing direct comparison to the reactions of analogous substrates in bulk solution. The surface-confined reactions proceed more slowly than their solution-phase counterparts, and kinetic inhibition becomes more significant for reactive sites positioned closer to the nanoparticle surface. Molecular dynamics simulations allowed us to identify distinct supramolecular architectures and unexpected dynamic features of the surface-bound molecules that underpin the experimentally observed trends in reactivity. This study allows us to draw general conclusions regarding interlinked structural and dynamical features across several length scales that influence interfacial reactivity in monolayer-confined environments. | |
dc.format.extent | 1145977 | |
dc.language.iso | eng | |
dc.relation.ispartof | ACS Nano | en |
dc.subject | Self-assembled monolayers | en |
dc.subject | Reaction kinetics | en |
dc.subject | Dynamic covalent chemistry | en |
dc.subject | Gold nanoparticles | en |
dc.subject | Dissipative particle dynamics | en |
dc.subject | Nanoconfined chemistry | en |
dc.subject | Molecular dynamics | en |
dc.subject | QD Chemistry | en |
dc.subject | DAS | en |
dc.subject.lcc | QD | en |
dc.title | Probing multiscale factors affecting the reactivity of nanoparticle-bound molecules | en |
dc.type | Journal article | en |
dc.contributor.sponsor | The Leverhulme Trust | en |
dc.contributor.sponsor | EPSRC | en |
dc.contributor.sponsor | EPSRC | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.identifier.doi | 10.1021/acsnano.0c09190 | |
dc.description.status | Peer reviewed | en |
dc.date.embargoedUntil | 2022-05-03 | |
dc.identifier.grantnumber | ORPG-3419 | en |
dc.identifier.grantnumber | EP/K016342/1 | en |
dc.identifier.grantnumber | EP/L016419/1 | en |
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