Physicochemical parameters, retention determination

The net retention volume and the specific retention volume, defined in Table 1.1, are important parameters for determining physicochemical constants from gas chromatographic data [9,10,32]. The free energy, enthalpy, and. entropy of nixing or solution, and the infinite dilution solute activity coefficients can be determined from retention measurements. Measurements are usually made at infinite dilution (Henry s law region) in which the value of the activity coefficient (also the gas-liquid partition coefficient) can be assumed to have a constant value. At infinite dilution the solute molecules are not sufficiently close to exert any mutual attractions, and the environment of each may be considered to consist entirely of solvent molecules. The activity... 

Quinones et al. (2000) reported the successful use of neural networks to predict the half-life of a series of 30 antihistamines. The input for the network was derived from the output of CODES, a routine that generates descriptors for a structure based on atom nature, bonding, and connectivity. Attempts to correlate the half-life with the physicochemical parameters log Kow, pKa, molecular weight, molar refractivity, molar volume, parachor, and polarity were unsuccessful. In a subsequent study by Quinones-Torrelo et al. (2001), the authors correlated the half-life of 18 antihistamines with their retention in a biopartitioning micellar chromatography system with a resultant correlation coefficient (R2adj) value of 0.89. The correlation is explained in that the retention in this system is dependent on hydrophobic, electronic, and steric properties, which are also important in determining half-life. 

The empirical physicochemical parameters have a good informative value for determining the mechanism of retention operating in a given chromatographic sy.stem. There are exhaustive compilations of such parameters like >/-octanol-water partition coefficients [45,46] or the LSER-based analyte parameters [47,48]. The problem is. however, that there is a lack of such descriptors for many analytes of interest in actual QSRR studies. 

Although the relationship between ordinary difiusion and molecular weight is well understood, we are still struggling to understand how composition affects thermal diffusion, and therefore ThFFF retention. Although we can relate retention to the phenomenological coefficient for thermal diffusion (Dt), Dt has not been successfully related to physicochemical parameters of the polymer and solvent. As a result, retention cannot be related to polymer composition unless Dt is first determined empirically. 

These methods allow not only the classification and clustering of any set of chromatographic systems but also exact determination of the relationship between the characteristics (physicochemical parameters or molecular substructures) of solutes and their retention behavior. It can be further concluded that chemometry considerably... 

The chromatographic characteristics of 14 peptides have been determined on a PGC column, using acetonitrile-water mixtures as eluents.The majority of peptides showed irregular retention behavior their retention decreased with increasing concentration of acetonitrile, reached a minimum, and increased again with increasing concentration of acetonitrile. For the elucidation of the relationship between the various physicochemical parameters and retention characteristics, principal component analysis (PCA) was employed. Calculations indicated that... 

The accuracy of this system is dependent on the correlation coefficient of a retention description obtained from studies of QSRR, therefore, the selection of descriptors is the most basic and important task to construct RPS. This selection could be done with statistical framework, even if such description is not clearly derived from theories. The retention description obtained from QSRR studies is more effective for a rapid and accurate prediction of retention than that derived from theoretical models, because the former is simple and does not require introduction of a number of physicochemical parameters (they are often not clearly known and are very difficult and time-consuming to determine) for the latter case. By contrast, the consideration of physical meanings of descriptors derived from QSRR studies gave the overview of retention mechanisms in reversed-phase LC (7-10). That is to say, hydrophobicity, size and shape of alkyl-benzenes and PAHs are dominate factors controlling their retention. 

In spite of widespread applications, the exact mechanism of retention in reversed-phase chromatography is still controversial. Various theoretical models of retention for RPC were suggested, such as the model using the Hildebrand solubility parameter theory [32,51-53], or the model supported by the concept of molecular connectivity [54], models based on the solvophobic theory [55,56) or on the molecular statistical theory [57j. Unfortunately, sophisticated models introduce a number of physicochemical constants, which are often not known or are difficult and time-consuming to determine, so that such models are not very suitable for rapid prediction of retention data. 

The accurate determination of the column void time, 0, is of fundamental importance in chromatography [1]. This is explained by the fact that a reliable estimation of this quantity is essential for the correct calculation of the retention factors (some refer to this as the capacity factor), k, which serves as the fundamental parameter for the comparison of retention data and for the interpretation of the physicochemical phenomena taking place within a chromatographic column. However, the determination of this parameter is very sensitive to the estimated value of the column void time, as can be seen from the equation... 

In spite of very diverse successful practical applications, the mechanism of com-plexation and the relationship between structure and selectivity are still at best only partly solved and remain open for discussion. Thermodynamic studies could supply some valuable information facilitating an understanding of the physicochemical basis of the complexation processes. The GC modified with CyDs is one of a variety of experimental methods employed in the determination of thermodynamic quantities for the formation of CyD inclusion complexes (see Chapters 8-10). The thermodynamic parameters for separation of the enantiomers were determined for various derivatives of CyDs dissolved in various stationary phases [63-65] or as a Uquid derivatized form [66]. Interesting observations were made by Armstrong et al. [66]. The authors postulated two different retention mechanisms. The first involved classical formation of the inclusion complex with high thermodynamic values of AH, AAH, and AAS and a relatively low column capacity and the second loose, probably external, multiple association with the CyD characterized by lower AH, AAH, and AAS values. The thermodynamic parameters of complexation processes obtained from liquid and gas chromatography measurements are collected in Table 5.2. It is clear from those data that for all the compounds presented the complexation processes are enthalpy-driven since in all cases AH is more negative than TAS. 

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