Hydrophobic effect 1-14 INDEX

The hydrophobicity index is also suitable for correlating the cM values of various substituted sodium alkane 1-sulfonates [68]. The perfluoroalkyl substituent, e.g., 8 17 has a pronounced hydrophobic effect (/ = 1.66 at 75°C, sodium salt), whereas the hydrophilic disulfonates have values distinctly below 1 (for a-disulfonates, / = 0.75 was derived [70]). Further, it was somewhat surprisingly shown that substituents like 1-hydroxymethyl, 3-hydroxyethoxy, or even the hydroxyethoxyethoxy groups have hydrophobic effects. 

Gibbs energies of, table 294 of proteins 116-118 Hydropathy index 78, 79 Hydrophobic effect 50 Hydrophobic interaction chromatography 103... 

The effective carbon number neff is helpful in characterizing surfactants with an inner functional group. Surfactants with isomeric structures can be compared by means of the hydrophobicity index / [69], which indicates the influence of the effective length of the alkane chain on cM ... 

In the method by Schirmer and Cowan (1993), a kind of hydropho-bicity plot like the hydropathy plot of Kyte and Doolittle (1982) is used. The amino acid index representing hydrophobicity is modified to emphasize the effect of aromatic residues. Considering the structural feature of /3 strands, the averaged value of 4 positions (i — 2, i, i + 2, and i + 4 for position i) is taken, and the plot is drawn for both even- and odd-numbered positions. The peaks correspond well to the observed positions of the /3 strands. 

CONTENTS Preface, C. Allen Bush. Thermodynamic Solvent Isotope Effects and Molecular Hydrophobicity, Terrence G. Oas and Eric J. Toone. Membrane Interactions of Hemolytic and Antibacterial Peptides, Karl Lohner and Richard M. Epand. Spin-Labeled Metabolite Analogs as Probes of Enzyme Structure, Chakravarthy Narasimhan and Henry M. Miziorko. Current Perspectives on the Mechanism of Catalysis by the Enzyme Enolase, John M. Brewer and Lukasz Leb-ioda. Protein-DNA Interactions The Papillomavirus E2 Proteins as a Model System, Rashmi S. Hedge. NMR-Based Structure Determination for Unlabeled RNA and DNA, Philip N. Borer, Lucia Pappalardo, Deborah J. Kenwood, and Istvan Pelczer. Evolution of Mononuclear to Binuclear CuA An EPR Study, William E. Antholine. Index. 

The effect of zeolite porosity on the reaction rate was also well demonstrated in liquid-phase oxidation over titanium-containing molecular sieves. Indeed, the remarkable activity in many oxidations with aqueous H2O2 of titanium silicalite (TS-1) discovered by Enichem is claimed to be due to isolation of Ti(IV) active sites in the hydrophobic micropores of silicalite.[42,47,68 69] The hydrophobicity of this molecular sieve allows for the simultaneous adsorption within the micropores of both the hydrophobic substrate and the hydrophilic oxidant. The positive role of hydrophobicity in these oxidations, first demonstrated with titanium microporous glasses,[70] has been confirmed later with a series of titanium silicalites differing by their titanium content or their synthesis procedure.[71] The hydrophobicity index determined by the competitive adsorption of water and n-octane was shown to decrease linearly with the titanium content of the molecular sieve, hence with the content in polar Si-O-Ti bridges in the framework for Si/Al > 40.[71] This index can be correlated with the activity of the TS-1 samples in phenol hydroxylation with aqueous H2C>2.[71] The specific activity of Ti sites of Ti/Al-MOR[72] and BEA[73] molecular sieves in arene hydroxylation and olefin epoxidation, respectively, was also found to increase significantly with the Si/Al ratio and hence with the hydrophobicity of the framework. 

Abstract. Adsorption of antioxidants (vitamins C and E) from aqueous and ethanol solutions on unmodified and partially hydrophobized nanosilica A-200 was studied using UV spectroscopy and quantum chemical methods with consideration for the solvent effects. Antioxidant power of silica nanocomposites with immobilized vitamins was evaluated by measuring the total polyphenolic index following the Folin-Ciocalteu method. It has been shown that immobilization of vitamins on silica surface leads to their stabilization. Being released from the carrier molecules of vitamins do not lose their antioxidant properties... 

Kutter and Hansch have analyzed the monoamine oxidase inhibition of phenoxyethylcyclopropylamines (46). Equation 24 shows that specific steric effects as well as electron-attracting and hydrophobic properties of substituents are responsible to the activity. Recently, it has been shown that the E8 value can be used as an index for intermolecular steric effects (46). In Equation 24, E8mm is the sum of E8 values of substituents at the two meta positions. The positive sign of the coefficient of this term means that the corresponding positions on the receptor site cannot accommodate larger substituents because of steric restraint. 

Surfactant surface activity is most completely presented in the form of the Gibbs adsorption isotherm, the plot of solution surface tension versus the logarithm of surfactant concentration. For many pure surfactants, the critical micelle concentration (CMC) defines the limit above which surface tension does not change with concentration, because at this stage, the surface is saturated with surfactant molecules. The CMC is a measure of surfactant efficiency, and the surface tension at or above the CMC (the low-surface-tension plateau) is an index of surfactant effectiveness (Table XIII). A surfactant concentration of 1% was chosen where possible from these various dissimilar studies to ensure a surface tension value above the CMC. Surfactants with hydrophobes based on methylsiloxanes can achieve a low surface tension plateau for aqueous solutions of —21-22 mN/m. There is ample confirmation of this fact in the literature (86, 87). 

Two of the hydrophihcity scales in Table 2 were derived from experimental measures of the behavior of amino acids in various solvents, namely partitioning coefficients [K-D index of Kyte and Doolittle (30)] or mobility in paper chromatography [Rf index of Zimmerman et al. (31)]. By contrast, the Hp index was obtained from quantum mechanics (QM) calculations of electron densities of side chain atoms in comparison with water (32). The Hp index is correlated highly with these two established hydrophobicity scales (Table 4). Therefore, like the polarizability index, it is possible to represent fundamental chemical properties of amino acids (hydrophUicity, Hp) with parameters derived from ab initio calculations of electronic properties. However, in contrast to polarizabihty (steric effects), hydrophihcity shows significant correlation with preference for secondary structure. Thus, hydrophobic amino acids prefer fi-strands (and fi-sheet conformations) and typically are buried in protein structures, whereas hydrophilic residues are found commonly in turns (coil structure) at the protein surface. 

IlMei et al. (39) derived the VHSE5 composite index of electronic effects. This scale (Vectors of Hydrophobic, Steric, and Electronic properties) was derived from principal components analysis of 50 different physico-chemical variables. 

The Z3 electronic index was taken from Hellberg et al. (25). This scale was derived from principal components analysis of 29 variables. The Z3 index was completely independent from hydrophobic (zl scale) and steric (z2 scale) effects. 

MR is generally scaled by 0.1 and used in biological QSAR, where intermolecular effects are of primary importance. The refractive index of the molecule is represented by n. With alkyl substituents, there is a high degree of collinearity with hydrophobicity hence, care... 

Referring once more to the effect of the aqueous medium composition upon the relative hydrophobicity of biological solutes, the correlation relationship establish-ecj io3,u6) between the effects of the medium ionic composition on the relative hydrophobicity of serum albumins of various origin and on that of erythrocytes from the same species should be noted. The ionic strength value of the medium in the aqueous ficoll-dextran biphasic system has been used as a quantitative index of the ionic composition of the system, and the ionic composition was varied from 0.11 M phosphate buffer to 0.15 M NaCl in 0.01 M buffer at pH 7.4 116). Partition coefficients of cells in an aqueous polymeric biphasic system are determined as the ratio of a number of the cells in the phase to that of the cells present at the interphase 90). Specific features of the partition behavior of cells in aqueous biphasic systems are discussed in detail elsewhere (see, e.g., Ref. 90 91). It has been established 116) that erythrocytes of different species are distributed in the aqueous ficoll-dextran biphasic system according to the following equation ... 

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