Associative mechanism Occurrence

More recently, a new mode of cis-trans isomerization of a disilene has been suggested for the extremely hindered disilene 27. As will be detailed in Section VIII. B, 27 undergoes thermal dissociation into the corresponding silylenes. Monitoring the thermolysis of (Z)-27 at 50°C by H and 29Si NMR reveals a competitive formation of the isomerized ( >27 and benzosilacyclobutene 37, which is most likely formed by intramolecular insertion of silylene 36 into the C—H bond of the o-bis(trimethylsilyl)-methyl group (Scheme 3).22,59 This suggests the possible occurrence of cis-trans isomerization via a dissociation-association mechanism. 

This is not discussed in detail since mechanisms of resistance have been carefully reviewed (Ghannoum and Rice 1999). It was pointed out that resistance has not been associated with modification of the structure. For the 1,2,4-triazoles that have been widely used, their effect is due to inhibition of the synthesis of ergosterol that is the dominant component of fungal cell membranes. Resistance is generally associated with modification of the target enzymes, for example, the epoxidation of squalene (Terbinafine) or 14a-demethylase (Fluconazole). Resistance of Candida albicans to the azole antifungal agent fluconazole demonstrated, however, the simultaneous occurrence of several types of mechanism for resistance (Perea et al. 2001) ... 

Equation 28 states, that co is proportional to t. The effect of the thickness of the gel film on the frequency of the first resonance mode has been investigated. When the buoyancy is taken into account, the experimental results have quantitatively followed Eq. 28. It has been found that the buoyancy plays an important role in the occurrence of the electric field-associated vibration of gel film. The vibration of the gel film in an electric field has thus roughly analyzed as a mechanical bending vibration of a uniform cantilever beam. 

It may also happen that an association equilibrium exists between the luminescent indicator and the quencher. Non-associated indicator molecules will be quenched by a dynamic process however, the paired indicator dye will be instantaneously deactivated after absorption of light (static quenching). Equation 2 still holds provided static quenching is the only luminescence deactivation mechanism (i.e. no simultaneous dynamic quenching occurs) but, in this case, Ksv equals their association constant (Kas). However, if both mechanisms operate simultaneously (a common situation), the Stem-Volmer equation adopts more complicated forms, depending on the stoichiometry of the fluorophore quencher adduct, the occurrence of different complexes, and their different association constants. For instance, if the adduct has a 1 1 composition (the simplest case), the Stem-Volmer equation is given by equation 3 ... 

From the previously discussed studies, the oxidative burst response appears to integrate and/or orchestrate several defense responses. These provide an adaptive mechanism to counteract attacks on or injury to algal cells and thalli. As shown in Fig. 12.2, the occurrence of an oxidative burst associated with the perception of cell-free extracts of A. operculata was shown to play a crucial role in the natural resistance of C. crispus gametophytes (Bouarab et al. 1999). 

Hydrolytic degradation of polymers is still the main reason for the occurrence of faults in processing. This form of degradation commonly causes a reduction of the IV, associated with a deterioration in the mechanical properties, particularly the tensile strength. Therefore, it is important to ensure sufficient drying of the raw materials. Drying is a crucial prerequisite of any polyester processing... 

It has been shown that the interpretation of catalytic reactions involving group VIII transition metals in terms of n complex adsorption possesses considerable advantages over classical theories by providing a link between theoretical parameters and chemical properties of aromatic reagents and catalysts. The concept has led to the formulation of a number of reaction mechanisms. In heavy water exchange the dissociative tt complex substitution mechanism appears to predominate it could also play a major role when deuterium gas is used as the second reagent. The dissociative mechanism resolves the main difficulties of the classical associative and dissociative theories, in particular the occurrence... 

Brown, G. (1953) The occurrence of lepidocro-dte in British soils. J. Soil Sd. 4 220—228 Brown, G. (1980) Associated minerals. In Brindley, G.W. Brown, G. (eds.) Crystal structures of clay minerals and their X-ray identification. Min. Soc., London, 361-410 Brown, G.E.Jr. (1990) Spectroscopic studies of chemisorption reaction mechanisms at oxide/water interfaces. In Hochella, M.F.Jr. 

The amount of the products formed over the studied catalysts, in the presence and absence of molecular O2, are listed in Table III. It is evident that the formation of the oxidation products is associated with the gas phase oxygen supply. Then, as the reaction rates in the mixture of reactant and in separate steps differ (19), these data exclude the participation of lattice oxygen in the partial oxidation of methane via a two step redox mechanism as main reaction pathway proving the occurrence of a "concerted mechanism". 

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