Projects per year
Abstract
Nanoparticle-based devices, materials and technologies will demand a new era of synthetic chemistry where predictive principles familiar in the molecular regime are extended to nanoscale building blocks. Typical covalent strategies for modifying nanoparticle-bound species rely on kinetically controlled reactions optimised for efficiency but with limited capacity for selective and divergent access to a range of product constitutions. In this work, monolayer-stabilized nanoparticles displaying complementary dynamic covalent hydrazone exchange reactivity undergo distinct chemospecific transformations by selecting appropriate combinations of ‘nucleophilic’ or ‘electrophilic’ nanoparticle-bound monolayers with nucleophilic or electrophilic molecular modifiers. Thermodynamically governed reactions allow modulation of product compositions, spanning mixed-ligand monolayers to exhaustive exchange. High-density nanoparticle-stabilizing monolayers facilitate in situ reaction monitoring by quantitative 19F NMR spectroscopy. Kinetic analysis reveals that hydrazone exchange rates are moderately diminished by surface confinement, and that the magnitude of this effect is dependent on mechanistic details: surface-bound electrophiles react intrinsically faster, but are more significantly affected by surface immobilization than nucleophiles. Complementary nanoparticles react with each other to form robust covalently connected binary aggregates. Endowed with the adaptive characteristics of the dynamic covalent linking process, the nanoscale assemblies can be tuned from extended aggregates to colloidally stable clusters of equilibrium sizes that depend on the concentration of a monofunctional capping agent. Just two ‘dynamic covalent nanoparticles’ with complementary thermodynamically governed reactivities therefore institute a programmable toolkit offering flexible control over nanoparticle surface functionalization, and construction of adaptive assemblies that selectively combine several nanoscale building blocks.
Original language | English |
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Pages (from-to) | 372-383 |
Number of pages | 12 |
Journal | Chemical Science |
Volume | 11 |
Issue number | 2 |
Early online date | 14 Nov 2019 |
DOIs | |
Publication status | Published - 14 Jan 2020 |
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Dive into the research topics of 'Programmable dynamic covalent nanoparticle building blocks with complementary reactivity'. Together they form a unique fingerprint.Projects
- 3 Finished
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Collaidal Catalysts: Switching on Colloidal Catalysts with Rotaxane Nanoparticle Monolayers
Kay, E. R. (PI)
1/07/15 → 31/07/19
Project: Standard
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Dynamic Covalent Nanocrystal: Dynamic Covalent Nanocrystal Building Blocks
Kay, E. R. (PI)
1/07/13 → 30/06/15
Project: Standard
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RSE Personal Research Fellowship: Metamaterials through self assembly across multiple size scales
Kay, E. R. (PI)
The Royal Society of Edinburgh
1/01/11 → 31/12/15
Project: Fellowship
Profiles
Datasets
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Programmable dynamic covalent nanoparticle building blocks with complementary reactivity (dataset)
Kay, E. R. (Creator), Marro, N. (Creator) & della Sala, F. (Creator), University of St Andrews, 14 Nov 2019
DOI: 10.17630/184e09e0-2192-44f0-936f-6acbabc3ab7b
Dataset
File