Interaction solvophobic

Recently the solvent effect on the [4+2] cycloaddition of singlet oxygen to cyclic dienes has been subjected to a multiparameter analysis. A pre-equilibrium with charge-transfer character is involved, which is affected by the solvent through dipolarity-polarisability (n ) and solvophobic interactions ( Sjf and Another multiparameter analysis has been published by Gajewski, demonstrating the... 

In summary, solvents can influence Diels-Alder reactions through a multitude of different interactions, of which the contributions to fire overall rate uniquely depend on the particular solvent-diene-dienophile combination. Scientists usually feel uncomfortable about such a situation and try to extract generalities. When limited to the most extensively studied type A Diels-Alder reactions this approach seems feasible. These Diels-Alder reactions are dominated by hydrogen bonding interactions in combination with solvophobic interactions. This observation predicts a very special role of water as a solvent for type A Diels-Alder reactions, which is described in Section 1.4. 

Studies on solvent effects on the endo-exo selectivity of Diels-Alder reactions have revealed the importance of hydrogen bonding interactions besides the already mentioned solvophobic interactions and polarity effects. Further evidence of the significance of the former interactions comes from computer simulations" and the analogy with Lewis-acid catalysis which is known to enhance dramatically the endo-exo selectivity (Section 1.2.4). 

C. FJorvath, W. Melander and I. Molnar, Solvophobic interactions in liquid chromatography with non-polar stationaiy phases , 7. Chromatogr. 125 129 (1976). 

Polar, water-soluble analogs of these molecules (23 and 24) have also been studied and have been shown to form helical columns in a variety of polar solvents such as methanol, butanol, acetonitrile, and water, by virtue of solvophobic interactions between the large aromatic cores.82,83 A stepwise association process is observed when alcohol solutions of 24 are cooled. The... 

Horvath, C.S., Melander, W.R., and Molnar, L, Solvophobic interactions in liquid chromatography with nonpolar stationary phases, J. Chromatogr., 125, 129, 1976. 

Entropy-related adsorption, denoted hydrophobic sorption (or solvophobic interaction) is the partitioning of nonpolar organics out of the polar aqueous phase onto hydrophobic surfaces. Fig. 5.6 shows a schematic model of forces that contribute to the sorption of hydrophobic organics, relevant to the subsurface environment. 

If the retention enthalpies of the two sites differ, curvature may be observed in the plots. Moreover, if the enthalpies are opposite in sign, a minimum will occur in the van t Hoff plot at a temperature where the ratio of the retention foctors for the two mechanisms equals the absolute value of the reciprocal of the ratio of the corresponding enthalpies. Most frequently, however, less dramatic curvature would be expected. Such behavior may be anticipated in the RPC of amines with- arge nonpolar moieties which could be retained by silmiophilic interactions with surface silanols and by solvophobic interactions with nonpolar ligates of a reversed phase with low surface coverage. Recently an lihalysis of this behavior has been reported 93). 

The main reason for chromatographic retention on reversed phases is solvophobic interaction, but under certain conditions silanophilic interaction and additional effects contribute to, or even govern, the chromatographic process. A concise review of physicochemical phenomena contributing to retention in RPC has been recently given by Horvath54). 

The solubility of polymers is, for thermodynamic reasons, more restricted than the solubility of low-molecular compounds and, consequently, the choice of solvents is limited. Potential solvents for most synthetic polymers are of moderate polarity. Alcohols and liquids of similar polarity are precipitants for many synthetic polymers. The search for a mobile phase that enables RPC through solvophobic interactions between the polymer and the nonpolar stationary phase requires attempts to make the mobile phase an unfavorable environment for the solute. This easily conflicts with the narrow limits of solubility of the polymer under investigation. Solubility effects are known to occur even in low-molecular RPC 92 94), but in polymer RPC they even may govern retention. 

Ben-Naim (1972b, c) has examined hydrophobic association using statistical mechanical theories of the liquid state, e.g. the Percus-Yevick equations. He has also examined quantitative aspects of solvophobic interactions between solutes using solubility data for ethane and methane. The changes in thermodynamic parameters can be calculated when two methane molecules approach to a separation of, 1-533 x 10-8 cm, the C—C distance in ethane, and the solvophobic quantities 8SI/i, s 2 and 8SiS2 can be calculated. In water (solvophobic = hydrophobic) 5si/i is more negative than in other solvents and decreases as the temperature rises both 8s iH%... 

Secondary binding forces are mainly classified into Coulomb forces, hydro-gen-bonding forces, van der Waals forces, charge transfer forces, exchange repulsion and hydrophobic interactions (Table 1). Besides these forces, there are other interactions such as ion-dipole and solvophobic interactions. 

Similarly, attractive forces called solvophobic interaction"28 exist when the interaction forces between solvent molecules are stronger than those between solvent and solute molecules. 

Certain fundamental characteristics of MECC that influence retention have been investigated (5). The technique has been used in the analysis of a variety of samples including phenolic compounds (1), phenylthiohydantoin—amino acids (6), and metabolites of vitamin Bg (7). In related electrokinetic separation techniques, substituted benzene compounds have been separated based on the formation of inclusion complexes with an ionic cyclodextrin derivative in the mobile phase (8) and polyaromatic hydrocarbons have been separated based on solvophobic interactions with a tetraakyl— ammonium ion in the mobile phase (9). The effects of injection procedures on efficiency have also been studied (10). 

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