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Photoperturbation-relaxation approach to the kinetics of cooperative ligand binding by heme proteins

Technical Report ·
OSTI ID:6090429

A small perturbation technique for measuring the ligand photodissociation and recombination kinetics of heme proteins has been developed. The Photodissociation Perturbation Relaxation (PPR) method involves perturbing the photodissociation rates of ligand-heme systems maintained at photointensity-dependent, nonequilibrium photostationary states. The theoretical and experimental datails of the PPR method are presented herein. A formalism for computing PPR amplitudes and time constants for complex reaction mechanisms for the eigenvectors and eigenvalues of the appropriate linear rate equations is derived; a FORTRAN code embodying this formalism is presented. PPR kinetics measurements obtained for the carbon monoxide derivatives of sperm whale myoglobin and human hemoglobin are presented. CO-hemoglobin combination rate constants and photodissociation quantum efficiencies, determined via fitting model-derived relaxation eigenmodes to PPR transients are presented.

Research Organization:
Oak Ridge National Lab., TN (USA)
DOE Contract Number:
W-7405-ENG-26
OSTI ID:
6090429
Report Number(s):
ORNL/TM-8637; ON: DE83014601
Country of Publication:
United States
Language:
English