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Contents Vol 64(6)

Monitoring Supramolecular Self-Assembly using Time-Resolved Fluorescence Spectroscopy

Scott C. McLean A , Colin A. Scholes A B , Trevor A. Smith A and Michelle L. Gee C
+ Author Affiliations
- Author Affiliations

A School of Chemistry, The University of Melbourne, Vic. 3010, Australia.

B Current address: Department of Chemical and Biomolecular Engineering, The University of Melbourne, Vic. 3010, Australia.

C Corresponding author. Email: mlgee@unimelb.edu.au




Michelle Gee is Head of the Soft Condensed Matter labs at the University of Melbourne. Her research is focussed on the molecular level behaviour of bio-macromolecules. In particular lipid–protein interactions in membranes and live cells, and the role of the glycocalyx in bacterial colonisation are studied using multidimensional fluorescence spectroscopies and direct nanomechanical force measurements. Michelle has held external appointments that include visiting chairs in the Departments of Physics and Chemical Engineering at Carnegie Mellon University and at CNRS. She currently serves on the editorial board of Soft Materials and is an elected member of council to the International Association of Colloid and Interface Scientists. She has a Ph.D. from the University of Melbourne in Chemistry and has held Post Doctoral Fellowships at the University of California Santa Barbara and Princeton University.

Australian Journal of Chemistry 64(6) 825-832 https://doi.org/10.1071/CH11066
Submitted: 10 February 2011  Accepted: 28 March 2011   Published: 27 June 2011

Abstract

Time-resolved fluorescence spectroscopy is used to observe subtleties in supramolecular structure during the self-assembly of polymers in solution. Lifetime distribution analysis of the fluorescence decay kinetics of the solvent-sensitive fluorescent probe 1-anilino-8-naphthalene sulfonic acid associated with the di-block copolymer poly(2-vinylpyridine)41–poly(ethylene oxide)204 (P2VP-PEO) as it self-assembles enabled identification of three microdomains, distinguishable on the basis of micropolarity. These microdomains can be assigned to different supramolecular substructures: the micelle corona (high polarity), the micelle core and the P2VP globule (both low polarity), and the core–corona interface and the globule–PEO junction (both intermediate polarity). Changes in the relative population distributions of these sub-structures as a function of P2VP-PEO pinpoint the onset of micellization corresponding to the critical micelle concentration (CMC) of the copolymer, but indicate significant variation in supramolecular structure, including micelle formation, well below the CMC. This suggests that supramolecular self-assembly in polymeric systems has characteristics of a second order phase transition.


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