Kinetics of bimolecular reactions in model bilayers and biological membranes. A critical review

2006 ◽  
Vol 123 (2-3) ◽  
pp. 77-94 ◽  
Author(s):  
Eurico Melo ◽  
Jorge Martins
2018 ◽  
Vol 43 (1) ◽  
pp. 1-20 ◽  
Author(s):  
Mohammad Niyaz Khan ◽  
Ibrahim Isah Fagge

The aqueous surfactant (Surf) solution at [Surf] > cmc (critical micelle concentration) contains flexible micelles/nanoparticles. These particles form a pseudophase of different shapes and sizes where the medium polarity decreases as the distance increases from the exterior region of the interface of the Surf/H2O particle towards its furthest interior region. Flexible nanoparticles (FNs) catalyse a variety of chemical and biochemical reactions. FN catalysis involves both positive catalysis ( i.e. rate increase) and negative catalysis ( i.e. rate decrease). This article describes the mechanistic details of these catalyses at the molecular level, which reveals the molecular origin of these catalyses. Effects of inert counterionic salts (MX) on the rates of bimolecular reactions (with one of the reactants as reactive counterion) in the presence of ionic FNs/micelles may result in either positive or negative catalysis. The kinetics of cationic FN (Surf/MX/H2O)-catalysed bimolecular reactions (with nonionic and anionic reactants) provide kinetic parameters which can be used to determine an ion exchange constant or the ratio of the binding constants of counterions.


2006 ◽  
Vol 106 (11) ◽  
pp. 4518-4584 ◽  
Author(s):  
Antonio Fernández-Ramos ◽  
James A. Miller ◽  
Stephen J. Klippenstein ◽  
Donald G. Truhlar

Homogeneous thermal gas reactions were at one time tacitly assumed to possess a definite order, unimolecular and bimolecular reactions, for example, being sharply distinguished. The kinetics of the decomposition of acetalde­ hyde, CH 3 CHO = CH 4 + CO, over the pressure range of 100 to 400 mm. were found to satisfy the criterion of a bimolecular reaction, namely, that the reciprocal of the time for half change (1/ t 1/2 ) )plotted against the initial pressure ( p 0 ) gave a straight line inclined to the axes. The line, however, did not pass through the origin, as may be seen in fig. 1 of the present paper. This indicated the presence of some first order reaction, the nature of which was not determined. Subsequently, in accordance with the collision theory of activation and deactivation, it was shown that certain reactions, sometimes called quasiummolecular, change their order from the second at low pressures to the first at high pressures. This apparently was the reverse of the behaviour shown by acetaldehyde.


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