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Fluorescence Correlation Spectroscopy in Dilute Polymer Solutions: Effects of Molar Mass Dispersity and the Type of Fluorescent Labeling

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Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany
Department of Chemistry, KU Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium
§ Institute for Physical Chemistry, University of Mainz, Jacob-Welder Weg 11, 55099 Mainz, Germany
Cite this: ACS Macro Lett. 2015, 4, 2, 171–176
Publication Date (Web):January 13, 2015
Copyright © 2015 American Chemical Society

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    Fluorescence correlation spectroscopy (FCS) has become an important tool in polymer science. Among various other applications the method is often applied to measure the hydrodynamic radius and the degree of fluorescent labeling of polymers in dilute solutions. Here we show that such measurements can be strongly affected by the molar mass dispersity of the studied polymers and the way of labeling. As model systems we used polystyrene and poly(methyl methacrylate) synthesized by atom transfer radical polymerization or free-radical polymerization. Thus, the polymers were either end-labeled bearing one fluorophore per chain or side-labeled with a number of fluorophores per chain proportional to the degree of polymerization.The experimentally measured autocorrelation curves were fitted with a newly derived theoretical model that uses the Schulz–Zimm distribution function to describe the dispersity in the degree of polymerization. For end-labeled polymers having a molecular weight distribution close to Schulz–Zimm, the fits yield values of the number-average degree of polymerization and the polydispersity index similar to those obtained by reference gel permeation chromatography. However, for the side-labeled polymers such fitting becomes unstable, especially for highly polydisperse systems. Brownian dynamic simulations showed that the effect is due to a mutual dependence between the fit parameters, namely, the polydispersity index and the number-average molecular weight. As a consequence, an increase of the polydispersity index can be easily misinterpreted as an increase of the molecular weight when the FCS autocorrelation curves are fitted with a standard single component model, as commonly done in the community.

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    Synthesis of the MMA-BODIPY monomers, synthesis of BODIPY ATRP initiator, synthesis of PS and PMMA polymers, FCS, NMR, and GPC characterizations. This material is available free of charge via the Internet at

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