A RECONSIDERATION OF THE MEASUREMENT OF POLYMER INTERDIFFUSION BY FLUORESCENCE NONRADIATIVE ENERGY-TRANSFER

被引:60
作者
DHINOJWALA, A
TORKELSON, JM
机构
[1] NORTHWESTERN UNIV,DEPT CHEM ENGN,EVANSTON,IL 60208
[2] NORTHWESTERN UNIV,DEPT MAT SCI & ENGN,EVANSTON,IL 60208
关键词
D O I
10.1021/ma00095a024
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
A general formalism has been developed for quantitative determination of polymer self-diffusion coefficients, D(p), 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. D(p) 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/(16D(p)), 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 k(n)(D(p)t)1/2x, where k(n) is a function of the initial acceptor concentration. Similarly, the decrease in the normalized donor intensity with interdiffusion is proportional to (D(p)t)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 D(p).
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页码:4817 / 4824
页数:8
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