Assembly of Linked Nanocrystal Colloids by Reversible Covalent Bonds

dc.creatorDominguez, Manuel N.
dc.creatorHoward, Michael P.
dc.creatorMaier, Josef M.
dc.creatorValenzuela, Stephanie
dc.creatorSherman, Zachary M.
dc.creatorReimnitz, Lauren C.
dc.creatorKang, Jiho
dc.creatorCho, Shin Hum
dc.creatorGibbs, Stephen L.
dc.creatorMenta, Arjun K.
dc.creatorZhuang, Deborah L.
dc.creatorvan der Stok, Aevi
dc.creatorKline, Sarah J.
dc.creatorAnslyn, Eric V.
dc.creatorTruskett, Thomas M.
dc.creatorMilliron, Delia J.
dc.description.abstractThe use of dynamically bonding molecules designed to reversibly link solvent-dispersed nanocrystals (NCs) is a promising strategy to form colloidal assemblies with controlled structure and macroscopic properties. In this work, tin-doped indium oxide NCs are functionalized with ligands that form reversible covalent bonds with linking molecules to drive assembly of NC gels. We monitor gelation using small angle X-ray scattering and characterize how changes in the gel structure affect infrared optical properties arising from the localized surface plasmon resonance of the NCs. The assembly is reversible because of the designed linking chemistry, and we disassemble the gels using two strategies: addition of excess NCs to change the ratio of linking molecules to NCs and addition of a capping molecule that displaces the linking molecules. The assembly behavior is rationalized using a thermodynamic perturbation theory to compute the phase diagram of the NC–linking molecule mixture. Coarse-grained molecular dynamics simulations reveal the competition between loop and bridge linking motifs essential for understanding NC gelation. This combined experimental, computational, and theoretical work provides a platform for controlling and designing the properties of reversible colloidal assemblies that incorporate NC and solvent compositions beyond those compatible with other contemporary (e.g, DNA-based) linking strategies.
dc.description.departmentCenter for Dynamics and Control of Materials
dc.description.sponsorshipWe would like to acknowledge the UT Mass Spectrometry Facility for their instrumental help and the UT NMR facilities for equipment use and assistance: NIH Grant Number 1 S10 OD021508-01. This work was primarily supported by the National Science Foundation through the Center for Dynamics and Control of Materials: an NSF Materials Research Science and Engineering Center (NSF MRSEC) under Cooperative Agreement DMR-1720595. This work was also supported by NSF Graduate Research Fellowships DGE-1610403 (M.N.D. and S.V.), an Arnold O. Beckman Postdoctoral Fellowship (Z.M.S.), NSF (CHE- 1905263), and the Welch Foundation (F-1848 and F-1696). E.V.A. acknowledges support from the Welch Regents Chair (F-0046). We acknowledge the Texas Advanced Computing Center (TACC) at The University of Texas at Austin for providing HPC resources.
dc.identifier.citationDominguez M, Howard M, Maier J, Valenzuela S, Sherman Z, Reimnitz L, et al. Assembly of Linked Nanocrystal Colloids by Reversible Covalent Bonds. ChemRxiv. 2020; doi:10.26434/chemrxiv.12943508.v1
dc.relation.ispartofCenter for Dynamics and Control of Materials Publications
dc.titleAssembly of Linked Nanocrystal Colloids by Reversible Covalent Bonds

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