Skip navigation
Skip navigation

Computational design of pH-switchable control agents for nitroxide mediated polymerization

Gryn'ova, Ganna; Smith, Leesa; Coote, Michelle

Description

In the present work we use accurate quantum chemistry to evaluate several known and novel nitroxides bearing acid–base groups as pH-switchable control agents for room temperature NMP. Based on G3(MP2,CC)(+)//M06-2X/6-31+G(d) calculations with UAKS-CPCM/M06-2X/6-31+G(d) solvation corrections, a number of novel nitroxides are predicted to be suitable for controlled polymerization of bulk styrene at room temperature when deprotonated (i.e. negatively charged), while remaining inert when...[Show more]

dc.contributor.authorGryn'ova, Ganna
dc.contributor.authorSmith, Leesa
dc.contributor.authorCoote, Michelle
dc.date.accessioned2020-09-02T01:35:28Z
dc.date.available2020-09-02T01:35:28Z
dc.identifier.issn1463-9076
dc.identifier.urihttp://hdl.handle.net/1885/209212
dc.description.abstractIn the present work we use accurate quantum chemistry to evaluate several known and novel nitroxides bearing acid–base groups as pH-switchable control agents for room temperature NMP. Based on G3(MP2,CC)(+)//M06-2X/6-31+G(d) calculations with UAKS-CPCM/M06-2X/6-31+G(d) solvation corrections, a number of novel nitroxides are predicted to be suitable for controlled polymerization of bulk styrene at room temperature when deprotonated (i.e. negatively charged), while remaining inert when neutral. These include an a-ethyl analogue of 3-carboxy-PROXYL and novel derivatives of 2,2,5-trimethyl-4-phenyl-3- azahexane-3-nitroxide (TIPNO) that have been modified to include acidic groups. Among the other species evaluated, 3,4-dicarboxy-PROXYL, a-carboxylated PROXYL and the phosphoric acid derivative of N-(2-methylpropyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl (SG1) are predicted to undergo suitable pH-switching at around 60 1C, and may also be fitting for some applications.
dc.description.sponsorshipThe authors acknowledge financial support from the Australian Research Council (CE140100012), and generous allocations of computing time on the National Facility of the Australian National Computational Infrastructure. G. G. also acknowledges support from the Laboratory for Computational Molecular Design at EPFL.
dc.format.mimetypeapplication/pdf
dc.language.isoen_AU
dc.publisherRoyal Society of Chemistry
dc.rights© the Owner Societies 2017
dc.sourcePhysical Chemistry Chemical Physics
dc.titleComputational design of pH-switchable control agents for nitroxide mediated polymerization
dc.typeJournal article
local.identifier.citationvolume19
dc.date.issued2017
local.publisher.urlhttp://pubs.rsc.org/en/Journals/JournalIssues/CP
local.type.statusAccepted Version
local.contributor.affiliationGryn'ova, A., Research School of Chemistry, The Australian National University
local.contributor.affiliationSmith, Leesa M., Research School of Chemistry, The Australian National University
local.contributor.affiliationCoote, Michelle, Research School of Chemistry, The Australian National University
dc.relationhttp://purl.org/au-research/grants/arc/CE140100012
local.bibliographicCitation.issue34
local.bibliographicCitation.startpage22678
local.bibliographicCitation.lastpage22683
local.identifier.doi10.1039/C7CP04337F
dcterms.accessRightsOpen Access
dc.provenancehttps://v2.sherpa.ac.uk/id/publication/18031..."The Accepted Version can be archived in a Non-Commercial Repository. 12 months embargo" from SHERPA/RoMEO site (as at 2/09/2020).
CollectionsANU Research Publications



Items in Open Research are protected by copyright, with all rights reserved, unless otherwise indicated.

Updated:  19 May 2020/ Responsible Officer:  University Librarian/ Page Contact:  Library Systems & Web Coordinator