Thermodynamic discrimination

Analysis of thermodynamical parameters of LGICR have revealed that five out of six receptors are thermodynamically discriminated (Table 2.5, Fig. 2.3b). As for the glycine receptor, the agonist binding has to be classified as entropy-driven (2 < AH0... 

Both the prokaryotic and the eukaryotic excision nucleases employ thermodynamic discrimination and kinetic proofreading to achieve high specificity. However, despite these elaborate discriminatory mechanisms, excision nucleases do not have absolute specificity and gratuitous repair of undamaged DNA occurs at a low but potentially deleterious level (23-25). 

FIGURE 9.1 The difference in relative Gibbs free energy (AG) of association, for the formation of diastereomeric complexes, provides the fnndamental basis for thermodynamic discrimination of enantiomers based on their complexation with a chiral selector. 

The positive values obtained in practically all cases indicate that all these models may be plausible representations of the data and indeed, the correlation coefBcients, R, are greater than 0.9. Thus, statistical compliance is not a sufficient basis for model discrimination. Specifically, the thermodynamic consistency of the estimates, as proposed by Boudart et al. [3], is appropriate further scrutinizing criterion during kinetic modelling and has been gainfully employed in other reactions [4-6]. 

Estimation of parameters. Model parameters in the selected model are then estimated. If available, some model parameters (e.g. thermodynamic properties, heat- and mass-transfer coefficient, etc.) are taken from literature. This is usually not possible for kinetic parameters. These should be estimated based on data obtained from laboratory expieriments, if possible carried out isothermal ly and not falsified by heat- and mass-transport phenomena. The methods for parameter estimation, also the kinetic parameters in complex organic systems, and for discrimination between models are discussed in more detail in Section 5.4.4. More information on parameter estimation the reader will find in review papers by Kittrell (1970), or Froment and Hosten (1981) or in the book by Froment and Bischoff (1990). 

It seems also meaningful to recall that, for both PVL and iPP, the metastable chiral modification is not obtained from solution. This fact is hard to rationalize if polymorphic discrimination occurs on the basis of the secondary nucleation site which should exist also in the presence of the solution it rather points to diffusion and to transport problems in the melt, or thermodynamic control in solution. 

The implications for films cast from mixtures of enantiomers is that diagrams similar to those obtained for phase changes (i.e., melting point, etc.) versus composition for the bulk surfactant may be obtained if a film property is plotted as a function of composition. In the case of enantiomeric mixtures, these monolayer properties should be symmetric about the racemic mixture, and may help to determine whether the associations in the racemic film are homochiral, heterochiral, or ideal. Monolayers cast from non-enantiomeric chiral surfactant mixtures normally will not exhibit this feature. In addition, a systematic study of binary films cast from a mixture of chiral and achiral surfactants may help to determine the limits for chiral discrimination in monolayers doped with an achiral diluent. However, to our knowledge, there has never been any other systematic investigation of the thermodynamic, rheological and mixing properties of chiral monolayers than those reported below from this laboratory. 

Polar-substituted alkenes where the functionality is not attached to a strained ring are considerably more discriminating in their compatibility with metathesis catalysts and as a rule require relatively high catalyst charges. In the aliphatic series, unsaturated esters have received the most attention. Boelhouwer reported in 1972 the metathesis of the ester methyl oleate and its trans isomer, methyl elaidate, with a homogeneous catalyst based on a 1/1.4 molar combination of WCl6/(CH3)4Sn (23). At 70°C and an ester/W molar ratio of 33, near-thermodynamic equilibrium was attained, and 49 and 52% of the respective esters were converted to equal amounts of 9-octadecene and the dimethyl ester of 9-octadecene-1,18-dioic acid. 

Selectivity in the hydrogenation reaction of dienes to monoenes can be achieved by two types of catalytic system (i) those which are completely inert with respect to the hydrogenation of the resulting monoenes and (ii) those for which the selectivity is due to the discrimination based on thermodynamic and/ or kinetic factors that suppress the rate of formation of the saturated hydrocarbon. The latter approach is the most common way of achieving selectivity for these hydrogenations. 

Mass discrimination with distillation effects. Let us assume that the isotope composition of an element is being measured by thermal ionization. This method consists in ionizing the sample atoms by evaporation on a metal filament. Statistical thermodynamics (e.g., Denbigh, 1968) tells us that, while vapor pressure is a function... 

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