Constitutionally Selective Dynamic Covalent Nanoparticle Assembly.

Content Provider	Europe PMC
Author	Marro, Nicolas Suo, Rongtian Naden, Aaron B. Kay, Euan R.
Copyright Year	2022
Abstract	The future of materials chemistry will be defined byour abilityto precisely arrange components that have considerably larger dimensionsand more complex compositions than conventional molecular or macromolecularbuilding blocks. However, exerting structural and constitutional controlin the assembly of nanoscale entities presents a considerable challenge.Dynamic covalent nanoparticles are emerging as an attractive categoryof reaction-enabled solution-processable nanosized building blockthrough which the rational principles of molecular synthetic chemistrycan be extended into the nanoscale. From a mixture of two hydrazone-baseddynamic covalent nanoparticles with complementary reactivity, specificmolecular instructions trigger selective assembly of intimately mixedheteromaterial (Au–Pd) aggregates or materials highly enrichedin either one of the two core materials. In much the same way as complementaryreactivity is exploited in synthetic molecular chemistry, chemospecificnanoparticle-bound reactions dictate building block connectivity;meanwhile, kinetic regioselectivity on the nanoscale regulates thedetailed composition of the materials produced. Selectivity, and henceaggregate composition, is sensitive to several system parameters.By characterizing the nanoparticle-bound reactions in isolation, kineticmodels of the multiscale assembly network can be constructed. Despiteignoring heterogeneous physical processes such as aggregation andprecipitation, these simple kinetic models successfully link the underlyingmolecular events with the nanoscale assembly outcome, guiding rationaloptimization to maximize selectivity for each of the three assemblypathways. With such predictive construction strategies, we can anticipatethat reaction-enabled nanoparticles can become fully incorporatedin the lexicon of synthetic chemistry, ultimately establishing a syntheticscience that manipulates molecular and nanoscale components with equalproficiency.
ISSN	00027863
Volume Number	144
PubMed Central reference number	PMC9376925
Issue Number	31
PubMed reference number	35901233
Journal	Journal of the American Chemical Society [J. Am. Chem. Soc]
e-ISSN	15205126
DOI	10.1021/jacs.2c05446
Language	English
Publisher	American Chemical Society
Publisher Date	2022-07-28
Access Restriction	Open
Rights License	Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). © 2022 The Authors. Published by American Chemical Society
Content Type	Text
Resource Type	Article
Subject	Chemistry Colloid and Surface Chemistry Biochemistry Catalysis