Show simple item record

dc.contributor.authorFarhangi, Shiva
dc.contributor.authorCasier, Remi
dc.contributor.authorLi, Lu
dc.contributor.authorThoma, Janine Lydia
dc.contributor.authorDuhamel, Jean
dc.date.accessioned2018-12-17 14:48:35 (GMT)
dc.date.available2018-12-17 14:48:35 (GMT)
dc.date.issued2016-12
dc.identifier.urihttps://doi.org/10.1021/acs.macromol.6b02455
dc.identifier.urihttp://hdl.handle.net/10012/14250
dc.descriptionThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, copyright © American Chemical Society after peer review and technical editing by publisher. To access the final edited and published work see https://doi.org/10.1021/acs.macromol.6b02455en
dc.description.abstractThe long-range internal dynamics (LRID) of 74 pyrene-labeled macromolecules (PyLMs) were characterized in four solvents representing a broad range of dielectric constants equal to 2.4 (toluene), 7.6 (tetrahydrofuran, THF), 37.8 (N,N-dimethylformamide, DMF), and 46.7 (dimethyl sulfoxide, DMSO). The LRID of the PyLMs were quantified based on the parameters retrieved from the global model free analysis (MFA) of the time-resolved fluorescence (TRF) decays of the pyrene monomer and excimer. These parameters were combined to yield ⟨k⟩, the average rate constant of pyrene excimer formation in the PyLMs, and (IE/IM)TRF(ffree = 0), the ratio of excimer to monomer fluorescence intensity obtained in the absence of pyrene labels that do not form excimer. (IE/IM)TRF(ffree = 0) was found to increase linearly with increasing ⟨k⟩ values over 3 orders of magnitude in the four solvents studied with a slope that equaled the average lifetime of the pyrene excimer (τE). The ⟨k⟩ values obtained to build these master lines could be correlated back to the expected LRID of the macromolecules. The lowest ⟨k⟩ values were obtained for the end-labeled linear chains holding the pyrene groups far apart, whereas the branched macromolecules bringing the pyrene labels close to each other yielded the larger ⟨k⟩ values. Furthermore, the fact that these master curves were observed for so many different PyLMs in the four solvents covering such a broad range of solvent polarity suggests that this relationship represents a general physical phenomenon that applies to all PyLMs. Considering the importance of characterizing the LRID of macromolecules in solution, the (IE/IM)TRF(ffree = 0) vs ⟨k⟩ plots presented in this report can be viewed as calibration curves against which the LRID of any PyLM can now be compared. Thus, the 3 orders of magnitude range found for these master curves offers the scientific community an impressive analytical opportunity to gauge the LRID of macromolecules in solution.en
dc.description.sponsorshipNatural Sciences and Engineering Research Councilen
dc.language.isoenen
dc.publisherAmerican Chemical Societyen
dc.subjectpyreneen
dc.subjectmacromoleculesen
dc.titleCharacterization of the Long-Range Internal Dynamics of Pyrene-Labeled Macromolecules by Pyrene Excimer Fluorescenceen
dc.typeArticleen
dcterms.bibliographicCitationMacromolecules 2016, 49, 24, 9597-9604en
uws.contributor.affiliation1Faculty of Scienceen
uws.contributor.affiliation2Chemistryen
uws.contributor.affiliation2Institute of Polymer Research (IPR)en
uws.contributor.affiliation2Waterloo Institute for Nanotechnology (WIN)en
uws.typeOfResourceTexten
uws.peerReviewStatusRevieweden
uws.scholarLevelFacultyen
uws.scholarLevelGraduateen


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record


UWSpace

University of Waterloo Library
200 University Avenue West
Waterloo, Ontario, Canada N2L 3G1
519 888 4883

All items in UWSpace are protected by copyright, with all rights reserved.

DSpace software

Service outages