Biophysical Journal 59: 476-487 (1991)
© 1991 the Biophysical Society

This Article Full Text (PDF) Alert me when this article is cited Alert me if a correction is posted Services Similar articles in this journal Similar articles in PubMed Alert me to new issues of the journal Download to citation manager Citing Articles Citing Articles via HighWire Citing Articles via Google Scholar Google Scholar Articles by Nagle, J F Search for Related Content PubMed PubMed Citation Articles by Nagle, J F

Solving complex photocycle kinetics. Theory and direct method.

Department of Biological Sciences, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213.

ABSTRACT

A direct nonlinear least squares method is described that obtains the true kinetic rate constants and the temperature-independent spectra of n intermediates from spectroscopic data taken in the visible at three or more temperatures. A theoretical analysis, which is independent of implementation of the direct method, proves that well determined local solutions are not possible for fewer than three temperatures. This analysis also proves that measurements at more than n wavelengths are redundant, although the direct method indicates that convergence is faster if n + m wavelengths are measured, where m is of order one. This suggests that measurements should concentrate on high precision for a few measuring wavelengths, rather than lower precision for many wavelengths. Globally, false solutions occur, and the ability to reject these depends upon the precision of the data, as shown by explicit example. An optimized way to analyze vibrational spectroscopic data is also presented. Such data yield unique results, which are comparably accurate to those obtained from data taken in the visible with comparable noise. It is discussed how use of both kinds of data is advantageous if the data taken in the visible are significantly less noisy.

This article has been cited by other articles:

				B. U. Klink, R. Winter, M. Engelhard, and I. Chizhov Pressure Dependence of the Photocycle Kinetics of Bacteriorhodopsin Biophys. J., December 1, 2002; 83(6): 3490 - 3498. [Abstract] [Full Text] [PDF]

				L. Zimanyi, A. Kulcsar, J. K. Lanyi, D. F. Sears Jr., and J. Saltiel Singular value decomposition with self-modeling applied to determine bacteriorhodopsin intermediate spectra: Analysis of simulated data PNAS, April 13, 1999; 96(8): 4408 - 4413. [Abstract] [Full Text] [PDF]

				L. Zimanyi, A. Kulcsar, J. K. Lanyi, D. F. Sears Jr., and J. Saltiel Intermediate spectra and photocycle kinetics of the Asp96 right-arrow Asn mutant bacteriorhodopsin determined by singular value decomposition with self-modeling PNAS, April 13, 1999; 96(8): 4414 - 4419. [Abstract] [Full Text] [PDF]