Factors substrate reflectance

Enantioselective enzyme-catalyzed reactions may involve the transformation of a prochiral substrate into a chiral product, in which case the selectivity is measured by the enantiomeric excess (ee). The transformations can also involve kinetic resolution of racemic substrates, in which case enantioselectivity is measured by the selectivity factor E reflecting the relative rates of reaction of the R)- and (5)-enantiomer. 

The birefringence of substrate materials for optical data storage devices requires special attention, especially in the case of EOD(MOR) disks. Birefringence has no importance for glass substrates (glass does not exhibit any significant birefringence) and is only a subordinate factor for polymeric protective layers of aluminum substrates because of their reflective read/write technique. 

The single mutation Asp 32-Ala reduces the catalytic reaction rate by a factor of about lO compared with wild type. This rate reduction reflects the role of Asp 32 in stabilizing the positive charge that His 64 acquires in the transition state. A similar reduction of kcat and kcat/ m (2.5 x 10 ) is obtained for the single mutant Asn 155-Thr. Asn 155 provides one of the two hydrogen bonds to the substrate transition state in the oxyanion hole of subtilisin. 

The hydrogen abstraction addition ratio is generally greater in reactions of heteroatom-centered radicals than it is with carbon-centered radicals. One factor is the relative strengths of the bonds being formed and broken in the two reactions (Table 1.6). The difference in exothermicity (A) between abstraction and addition reactions is much greater for heteroatom-centered radicals than it is for carbon-centered radicals. For example, for an alkoxy as opposed to an alkyl radical, abstraction is favored over addition by ca 30 kJ mol"1. The extent to which this is reflected in the rates of addition and abstraction will, however, depend on the particular substrate and the other influences discussed above. 

The constant s, characteristic of the substrate complex, reflects its sensitivity to variation in nucleophilicity as assessed by the Ptpy2Cl2 reaction. It is called the nucleophilic discrimination factor (ndf). The intercept log k turns out to be related to the value of the k term in the rate law for the solvent in question. Some representative ligands involved in attack on Pt(II) complexes may be listed in order of decreasing as follows ... 

Some of the transition metal macrocycles adsorbed on electrode surfaces are of special Interest because of their high catalytic activity for dloxygen reduction. The Interaction of the adsorbed macrocycles with the substrate and their orientation are of Importance In understanding the factors controlling their catalytic activity. In situ spectroscopic techniques which have been used to examine these electrocatalytlc layers Include visible reflectance spectroscopy surface enhanced and resonant Raman and Mossbauer effect spectroscopy. This paper Is focused principally on the cobalt and Iron phthalocyanlnes on silver and carbon electrode substrates. 

The factors that promote unimolecular, as opposed to bimolecular (E2), elimination are very much the same as those that promote SN1 with respect to Sw2, namely (a) an alkyl group in the substrate that can give rise to a relatively stable carbocation, and (b) a good ionising, ion-solvating medium. Thus (a) is reflected in the fact that with halides, increasing El elimination occurs along the series,... 

It is contended that the renal slice technique measures primarily basolateral uptake of substrates or nephrotoxins, based on histological evidence of collapsed tubular lumens. This results in the inaccessibility of brush-border surfaces for reabsorptive transport (Burg and Orloff, 1969 Cohen and Kamm, 1976). This observation limits the ability of this model to accurately reflect reactions to nephrotoxins that occur as the result of brush-border accumulation of an injurious agent. Ultrastructurally, a number of alterations, particularly in the plasma membrane and mitochondrial compartments, have been shown to occur over a 2-h incubation period (Martel-Pelletier et al., 1977). This deterioration in morphology is very likely a consequence of the insufficient diffusion of oxygen, metabolic substrates, and waste products in the innermost regions of the kidney slice (Cohen and Kamm, 1976). Such factors also limit the use of slices in studying renal metabolism and transport functions. 

The rate at which the substrate is converted to the product by the action of an enzyme is dependent upon the concentrations of both the enzyme and the substrate. The initial rate of such a reaction is maximal and it is this initial rate of reaction that reflects the enzyme activity (Figure 8.12). The major factor in this decline is the depletion of the substrate but the increasing amount of product competing for the enzyme also reduces the rate of the forward reaction. Additionally, inactivation of the enzyme may occur, particularly if an appreciable reaction time is involved. 

The secondary deuterium KIEs obtained by converting the secondary tritium KIEs found for the E2 reactions of several different 2-arylethyl substrates into secondary deuterium KIEs with the Swain-Schaad equation (Swain et al., 1958) are in Table 36. As discussed above, one would expect the secondary deuterium isotope effect to reflect the extent to which rehybridization of the /3-carbon from sp3 of the reactant to sp2 in the product has taken place in the transition state. According to this reasoning, the secondary tritium EIE should be a good estimate of the maximum secondary tritium KIE. Because these reactions were not reversible, the EIE could not be measured. However, one can estimate the EIE (the maximum expected secondary KIE) using Hartshorn and Shiner s (1972) fractionation factors. The predicted EIE (Kh/Kd) values were 1.117 at 40°C and 1.113 at 50°C. Seven of the reactions... 

While in the ideal case S(g) according to Eq. (57) clearly reflects the singular behavior at T due to substrate inhomogeneity and/or limited resolution the actual behavior of scattering data is quite smooth see Fig. 13b for an example. A detailed analysis of finite resolution effects on the structure factor of two-dimensional lattice gas models has been presented by Bartelt et af. If the... 

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