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Ionic reactions relative stabilities

Next we evaluate the PDLD + EVB surface for the enzymatic reaction using eq. (5.17). The resulting surface is shown in Fig. 5.6. As seen from the ligure, the protein can reduce Aby stabilizing the ionic state more than water. In fact, in the specific case of papain the protein inverts the stabilization of the covalent and ionic states relative to their order in solution. [Pg.145]

The results of an EVB/FEP for proton transfer from Cys to His were presented by Warshel (1991), based on a calibration of the protein reaction surface with solution results, which amount to 6 kcal/mol difference (in favor of SH relative to ImH+) due to the pKa values of the two conjugate acids. The protein is found to invert the stabilization of covalent and ionic state relative to their order in solution. This is a result of the stronger solvation in the enzyme, compared to water, and due to the orientation of protein dipoles. [Pg.315]

Inclusion of the ionic structures in the three-electron model made it possible to take into account the effects of polarization upon the mechanism of free-radical reactions and to arrive at the following conclusion addition of a free radical to a bond attacked by polar groups occurs in such a position for which the new bond that forms in the transition state possesses the most ionic character. If the reaction occurs under thermodynamic control, then the polarization effects stabilize the product thereby facilitating the development of reaction. Otherwise, products may form that are not thermodynamically the most stable. These qualitative conclusions have been supported [7] by ab initio calculations of the relative stability of reactants and products as well as the activation barriers for a series of the reactions ... [Pg.194]

Phase-transfer catalysis is a special type of catalysis. It is based on the addition of an ionic (sometimes non-ionic like PEG400) catalyst to a two-phase system consisting of a combination of aqueous and organic phases. The ionic species bind with the reactant in one phase, forcing transfer of this reactant to the second (reactive) phase in which the reactant is only sparingly soluble without the phase-transfer catalyst (PTC). Its concentration increases because of the transfer, which results in an increased reaction rate. Quaternary amines are effective PTCs. Specialists involved in process development should pay special attention to the problem of removal of phase-transfer catalysts from effluents and the recovery of the catalysts. Solid PTCs could diminish environmental problems. The problem of using solid supported PTCs seems not to have been successfully solved so far, due to relatively small activity and/or due to poor stability. [Pg.8]

Some of the reports are as follows. Mizukoshi et al. [31] reported ultrasound assisted reduction processes of Pt(IV) ions in the presence of anionic, cationic and non-ionic surfactant. They found that radicals formed from the reaction of the surfactants with primary radicals sonolysis of water and direct thermal decomposition of surfactants during collapsing of cavities contribute to reduction of metal ions. Fujimoto et al. [32] reported metal and alloy nanoparticles of Au, Pd and ft, and Mn02 prepared by reduction method in presence of surfactant and sonication environment. They found that surfactant shows stabilization of metal particles and has impact on narrow particle size distribution during sonication process. Abbas et al. [33] carried out the effects of different operational parameters in sodium chloride sonocrystallisation, namely temperature, ultrasonic power and concentration sodium. They found that the sonocrystallization is effective method for preparation of small NaCl crystals for pharmaceutical aerosol preparation. The crystal growth then occurs in supersaturated solution. Mersmann et al. (2001) [21] and Guo et al. [34] reported that the relative supersaturation in reactive crystallization is decisive for the crystal size and depends on the following factors. [Pg.176]


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See also in sourсe #XX -- [ Pg.249 , Pg.250 ]




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Relative stability

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