Reaction kinetics involving ground X2Π and excited A2Σ+hydroxyl radicals. Part 2.—Rate constants for reactions of OH X2Π with halogenomethanes and halogenoethanes

1979 ◽  
Vol 75 (0) ◽  
pp. 582-591 ◽  
Author(s):  
Michael A. A. Clyne ◽  
Pauline M. Holt
Keyword(s):  
Reaction Kinetics ◽  
Hydroxyl Radicals ◽  
Rate Constants

On the Chemical Reactivity of the Phytochrome Chromophore in the Pr and Pfr Form

1985 ◽  
Vol 40 (3-4) ◽  
pp. 215-218 ◽  
Author(s):  
Fritz Thümmler ◽  
Peter Eilfeld ◽  
Wolfhart Rüdiger ◽  
Doo-Khil Moon ◽  
Pill-Soon Song
Keyword(s):  
Reaction Kinetics ◽  
Rate Constants ◽  
Chemical Reactivity ◽  
Order Reaction ◽  
First Order Reaction ◽  
Limiting Factor ◽  
Pseudo First Order Reaction ◽  
First Order ◽  
Pseudo First Order ◽  
The Difference

The reactivity of the phytochrome chromophore and related tetrapyrroles towards ozone and tetranitromethane was investigated. Both oxidizing reagents cause bleaching of the main absorp­tion band of the pigment. The rate constants for this bleaching were determined under conditions of pseudo first order reaction kinetics. The rate constants for the reaction with ozone are similar for native phytochrome and for freely accessible tetrapyrroles (biliverdin, small chromopeptides from phytochrome) indicating that accessibility is not the limiting factor for the reaction with ozone. Under a variety of conditions, the Pfr chromophore reacts by about 10% faster than the Pr chromophore. This may reflect the true difference in reactivity. The rate constants for the reaction with tetranitromethane are much larger for biliverdin, bilirubin and small chromopeptides from phytochrome than for native phytochrome. The limiting factor for this reaction in native phytochrome therefore is the accessibility of the chromophore by the reagent. Previous conclusions on the difference in exposure of the tetrapyrrole chromophore in Pr and Pfr are confirmed.

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