St Andrews Research Repository

St Andrews University Home
View Item 
  •   St Andrews Research Repository
  • University of St Andrews Research
  • University of St Andrews Research
  • University of St Andrews Research
  • View Item
  •   St Andrews Research Repository
  • University of St Andrews Research
  • University of St Andrews Research
  • University of St Andrews Research
  • View Item
  •   St Andrews Research Repository
  • University of St Andrews Research
  • University of St Andrews Research
  • University of St Andrews Research
  • View Item
  • Register / Login
JavaScript is disabled for your browser. Some features of this site may not work without it.

Programmable dynamic covalent nanoparticle building blocks with complementary reactivity

Thumbnail
View/Open
Marro_2019_CS_Programmable_CC.pdf (1.329Mb)
Date
14/01/2020
Author
Marro, Nicolas
della Sala, Flavio
Kay, Euan Robert
Funder
The Royal Society of Edinburgh
The Leverhulme Trust
EPSRC
Grant ID
n/a
ORPG-3419
EP/K016342/1
Keywords
QD Chemistry
DAS
BDC
R2C
Metadata
Show full item record
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.
Citation
Marro , N , della Sala , F & Kay , E R 2020 , ' Programmable dynamic covalent nanoparticle building blocks with complementary reactivity ' , Chemical Science , vol. 11 , no. 2 , pp. 372-383 . https://doi.org/10.1039/C9SC04195H
Publication
Chemical Science
Status
Peer reviewed
DOI
https://doi.org/10.1039/C9SC04195H
ISSN
2041-6520
Type
Journal article
Rights
Copyright © 2019 The Author(s). Open Access Article. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Description
This work was supported by the EPSRC (EP/K016342/1, EP/P505097/1, EP/M506631/1) and the Leverhulme Trust (RPG-2015-042). ERK thanks the Royal Society of Edinburgh and Scottish Government for a Personal Research Fellowsh
Collections
  • University of St Andrews Research
URI
http://hdl.handle.net/10023/18986

Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.

Advanced Search

Browse

All of RepositoryCommunities & CollectionsBy Issue DateNamesTitlesSubjectsClassificationTypeFunderThis CollectionBy Issue DateNamesTitlesSubjectsClassificationTypeFunder

My Account

Login

Open Access

To find out how you can benefit from open access to research, see our library web pages and Open Access blog. For open access help contact: openaccess@st-andrews.ac.uk.

Accessibility

Read our Accessibility statement.

How to submit research papers

The full text of research papers can be submitted to the repository via Pure, the University's research information system. For help see our guide: How to deposit in Pure.

Electronic thesis deposit

Help with deposit.

Repository help

For repository help contact: Digital-Repository@st-andrews.ac.uk.

Give Feedback

Cookie policy

This site may use cookies. Please see Terms and Conditions.

Usage statistics

COUNTER-compliant statistics on downloads from the repository are available from the IRUS-UK Service. Contact us for information.

© University of St Andrews Library

University of St Andrews is a charity registered in Scotland, No SC013532.

  • Facebook
  • Twitter