A Reconsideration of the Measurement of Polymer Interdiffusion by Fluorescence Nonradiative Energy Transfer

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Abstract

A general formalism has been developed for quantitative determination of polymer self-diffusion coefficients, Dp, using fluorescence nonradiative energy transfer (NRET). The experimental geometry consists of a “sandwich” of two thin polymer films, one labeled with NRET donor chromophores and the other with NRET acceptor chromophores. Dp can be characterized self-consistently by steady-state fluorescence intensity measurements of donors or acceptors or by transient donor fluorescence intensity decay measurements as a function of interdiffusion time, t. For t < x2/(16Dp), where x is the thickness of the donor-labeled polymer layer, increases in the normalized acceptor intensity and normalized energy transfer efficiency with interdiffusion are the same and equal to kn(Dpt)1/2/x, where kn is a function of the initial acceptor concentration. Similarly, the decrease in the normalized donor intensity with interdiffusion is proportional to (Dpt)1/2/x. The general formalism presented here has been compared to earlier approaches, revealing that a previous method of analyzing the steady-state acceptor intensity in terms of polymer diffusion is merely a limiting case of the present formalism while a previous method of analyzing the donor intensity decays results in underestimates of Dp.

Original languageEnglish (US)
Pages (from-to)4817-4824
Number of pages8
JournalMacromolecules
Volume27
Issue number17
DOIs
StatePublished - Aug 1 1994

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

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