On the quantitative molecular analysis of electronic energy transfer within donor-acceptor pairs.

An extended Förster theory (EFT) on electronic energy transfer is presented for the quantitative analysis of time-resolved fluorescence lifetime and depolarisation experiments. The EFT, which was derived from the stochastic Liouville equation, yields microscopic information concerning the reorientation correlation times, the order parameters, as well as inter chromophoric distances. Weakly interacting donor and acceptor groups, which reorient and interact in a pair wise fashion, are considered, under isotropic and anisotropic conditions. For the analysis of experiments it is shown that not only do we need to consider the orientational distributions of the transition dipoles, but the internal reorienting molecular dynamics within the pair which is of even greater importance. The latter determines the shape as well as the rate of the observed donor fluorescence and depolarisation decays, which are most often not mono-exponential functions. It is shown that the commonly used Förster theory is a special case of the EFT. Strategies are presented for applying the EFT, which makes use of Brownian dynamics simulation.

[1]  S. Kalinin,et al.  Partial donor–donor energy migration (PDDEM): A novel fluorescence method for internal protein distance measurements , 2004 .

[2]  D. D. Thomas,et al.  Mechanism of Ca-ATPase inhibition by melittin in skeletal sarcoplasmic reticulum. , 1995, Biochemistry.

[3]  I Munro,et al.  Subnanosecond motions of tryptophan residues in proteins. , 1979, Proceedings of the National Academy of Sciences of the United States of America.

[4]  J. Hughes,et al.  Dimerization and inter-chromophore distance of Cph1 phytochrome from Synechocystis, as monitored by fluorescence homo and hetero energy transfer. , 2003, Biochemistry.

[5]  J. Mestecky,et al.  Nanosecond fluorescence spectroscopy of human immunoglobulin A. , 1981, Biochemistry.

[6]  L. Johansson,et al.  Extended Förster Theory for Determining Intraprotein Distances. 1. The κ2-Dynamics and Fluorophore Reorientation , 2004 .

[7]  P. Håkansson,et al.  Extended Förster theory for determining intraprotein distances: 2. an accurate analysis of fluorescence depolarisation experiments. , 2007, Physical chemistry chemical physics : PCCP.

[8]  B. Nickel.  Orientation factor in Förster energy transfer with photoselection of donor and acceptor , 1995 .

[9]  J. Eisinger,et al.  The orientational freedom of molecular probes. The orientation factor in intramolecular energy transfer. , 1979, Biophysical journal.

[10]  Jay R. Knutson,et al.  Simultaneous analysis of multiple fluorescence decay curves: A global approach , 1983 .

[11]  M. P. Heyn.  Determination of lipid order parameters and rotational correlation times from fluorescence depolarization experiments , 1979, FEBS letters.

[12]  Th. Förster.  Zwischenmolekulare Energiewanderung und Fluoreszenz , 1948 .

[13]  L. Johansson,et al.  Extended Förster theory of donor-donor energy migration in bifluorophoric macromolecules. Part I. A new approach to quantitative analyses of the time-resolved fluorescence anisotropy , 2000 .

[14]  P. Bastiaens,et al.  Comparison of the dynamical structures of lipoamide dehydrogenase and glutathione reductase by time-resolved polarized flavin fluorescence. , 1992, Biochemistry.

[15]  L. Stryer,et al.  Energy transfer: a spectroscopic ruler. , 1967, Proceedings of the National Academy of Sciences of the United States of America.

[16]  L. Brand,et al.  Orientation factor in steady-state and time-resolved resonance energy transfer measurements. , 1992, Biochemistry.

[17]  C. Zannoni,et al.  Intensity deconvolution in fluorescence depolarization studies of liquids, liquid crystals and membranes , 1984 .

[18]  M. Fayer,et al.  Excitation transfer in disordered two‐dimensional and anisotropic three‐dimensional systems: Effects of spatial geometry on time‐resolved observables , 1986 .

[19]  B. Valeur,et al.  Fluorescence depolarization by electronic energy transfer in donor–acceptor pairs of like and unlike chromophores , 1991 .

[20]  Electronic energy transfer in liquids. The effect of molecular dynamics , 1993 .

[21]  I. Fedchenia,et al.  Brownian Dynamic Simulation of Restricted Molecular Diffusion. The Symmetric and Deformed Cone Models , 1993 .

[22]  L. Johansson,et al.  Energy migration and rotational motion within bichromophoric molecules. II. A derivation of the fluorescence anisotropy , 1996 .

[23]  C. Mateo,et al.  New fluorescent octadecapentaenoic acids as probes of lipid membranes and protein-lipid interactions. , 1996, Biophysical journal.

[24]  B. Valeur,et al.  Molecular Fluorescence: Principles and Applications , 2001 .

[25]  E. Katchalski‐Katzir,et al.  Distribution of end-to-end distances of oligopeptides in solution as estimated by energy transfer. , 1975, Proceedings of the National Academy of Sciences of the United States of America.

[26]  Zbigniew S. Kolber,et al.  Monte Carlo convolution method for simulation and analysis of fluorescence decay data , 1991 .

[27]  F. Tanaka.  Theory of time-resolved fluorescence under the interaction of energy transfer in a bichromophoric system: Effect of internal rotations of energy donor and acceptor , 1998 .

[28]  B. Meer,et al.  Resonance Energy Transfer: Theory and Data , 1994 .

[29]  M. Fayer,et al.  Effect of chromophore diffusion on electronic excitation transfer in micellar systems , 1997 .

[30]  T. Burghardt,et al.  Model-independent time-resolved fluorescence depolarization from ordered biological assemblies applied to restricted motion of myosin cross-bridges in muscle fibers. , 1986, Biochemistry.