Hydrophobic/hydrophilic effects

In this chapter, approaches to estimates of (1) the polyelectrolyte (electrostatic) effect, (2) the hydrophobicity/hydrophilicity effect, and (3) the multicoordination effect, specified for metal ion/polyelectrolyte systems are described. As weak acidic polyelectrolytes, polyacrylic acid, PAA, as well as polymethacrylic acid, PMA, are exemplified as an example of weak basic polyelectrolyte, poI y(/V-vinyI i m idazoIc), PVIm, is chosen all the chemical structures of the polymer ligands are illustrated in Figure 1. Precise poten-tiometric titration studies by the use of a glass electrode as well as respective metal ion selective electrodes have been performed for the complexation equilibrium analyses. All the equilibrium constants reported in this chapter were obtained at 298 K unless otherwise stated. 

Tian Y, Fendler J FI, Flungerbuhler FI, Guldi D M and Asmus K-D 1999 Effects of hydrophobic-hydrophilic balance and stereochemistry on the supramolecular assembly of functionalized fullerenes Supramol. Sc/. C 7 67-73... 

Partially hydrolyzed poly(vinyl alcohol) grades are preferred because they have a hydrophobic /hydrophilic balance that make them uniquely suited for emulsion polymerization. The compatibUity of the residual acetate units with the poly(vinyl acetate) latex particles partly explains the observed stabilization effect. The amount of PVA employed is normally 4—10% on the weight of vinyl acetate monomer. The viscosity of the resulting latex increases with increasing molecular weight and decreasing hydrolysis of the PVA (318). 

One of the most promising applications of enzyme-immobilized mesoporous materials is as microscopic reactors. Galameau et al. investigated the effect of mesoporous silica structures and their surface natures on the activity of immobilized lipases [199]. Too hydrophilic (pure silica) or too hydrophobic (butyl-grafted silica) supports are not appropriate for the development of high activity for lipases. An adequate hydrophobic/hydrophilic balance of the support, such as a supported-micelle, provides the best route to enhance lipase activity. They also encapsulated the lipases in sponge mesoporous silicates, a new procedure based on the addition of a mixture of lecithin and amines to a sol-gel synthesis to provide pore-size control. 

The concept of zeolite action was tested in a particular reaction where the enzyme is exposed from the beginning to an acidic environment the esterification of geraniol with acetic acid catalyzed by Candida antarctica lipase B immobilized on zeolite NaA [219]. Lipases have been used for the hydrolysis of triglycerides and due to their ambivalent hydrophobic/hydrophilic properties they are effective biocatalysts for the hydrolysis of hydrophobic substrates [220]. When water-soluble lipases are used in organic media they have to be immobilized on solid supports in order to exhibit significant catalytic activity. 

Recently, Porter et al. (1986b, 1988) have reported the synthesis of both meso- and ( )-forms of a series of two-chain carbonyl diacids made by joining two pentadecanoic acid units by a carbonyl group at the 3,3, 6,6, 9,9 and 12,12 positions, 3,5-didodecyl-4-oxoheptanedioic acid (C-15 3,3 ), 6,8-dinonyl-7-oxotridecanedioic acid (C-15 6,6 ), 9,11-dihexyl-10-oxononadecanedioic acid (C-15 9,9 ) and 12,14-dipropyl-13-oxopentacosanedioic acid (C-15 12,12 ), respectively. The diacids were used to probe further the question of stereochemical preference in two-chain amphiphiles. The method used for examining the diastereomeric preference was equilibration by base-catalyzed epimerization in homogeneous, bilayer and micellar media. This method allows for stereoselection based on hydrophobic/hydrophilic considerations rather than classic steric size effects. 

The chelate effect in proteins is also important, since the three-dimensional (3-D) structure of the protein can impose particular coordination geometry on the metal ion. This determines the ligands available for coordination, their stereochemistry and the local environment, through local hydrophobicity/hydrophilicity, hydrogen bonding by nearby residues with bound and non-bound residues in the metal ion s coordination sphere, etc. A good example is illustrated by the Zn2+-binding site of Cu/Zn superoxide dismutase, which has an affinity for Zn2+, such that the non-metallated protein can extract Zn2+ from solution into the site and can displace Cu2+ from the Zn2+ site when the di-Cu2+ protein is treated with excess Zn2+. 

Once the durability testing of the fuel cells is finalized, the internal components are then characterized. For diffusion layers, some of these characterization techniques include SEM to visualize surface changes, porosimetry measurements to analyze any changes in porosity within the DL and MPL, IGC (inverse gas chromatography) to identify relative humidity effects on the hydrophobic properties of the DLs, contact angle measurements to observe any changes in the hydrophobic/hydrophilic coatings of the DL, etc. [254,255]. 

A series of carboxyl containing bioerodible polymeric materials, characterized by modulated functionality and hydrophobic/hydrophilic balance, was prepared both on a lab-scale and in the pilot plant. Procedures were setup as amenable for scaled-up productions. Those materials displayed a high versatility to combine with proteins in different proportion and to provide hybrid bioerodible matrices without any adverse effect on protein structure and activity. 

Interfacial tension studies are particularly important because they can provide useful information on the interfacial concentration of the extractant. The simultaneous hydrophobic-hydrophilic nature of extracting reagents has the resulting effect of maximizing the reagent affinity for the interfacial zone, at which both the hydrophobic and hydrophilic parts of the molecules can minimize their free energy of solution. Moreover, as previously mentioned, a preferential orientation of the extractant groups takes place at the interface. Conse-... 

As illustrated by the examples, the eatalytie properties of POMs may benefit from the assoeiation with the matrix, and in some eases both enhanced activity and selectivity have resulted from immobilization. That is often the ease of POMs embedding in silica matrix and may be attributed to a eonstrained environment effect . However, it is still very difficult to predict the catalytic performance after immobilization, and only experiment ean clarify this matter. Meanwhile, a rational modification of acid-base and/or hydrophobic-hydrophilic properties of a support is possible in some cases and may tune the catalytic properties. 

SlogP VSA(. (10) intended to capture hydrophobic and hydrophilic effects ... 

Leo et al. indicated that the van der Waals volume is linearly related to hydro-phobicity for non-polar compounds expressed in terms of log P (octanol/water)66). Moriguchi et al. showed that the log P value is generally factored into two components attributable to hydrophilic effect of polar group and hydrophobic effect due to the net molar volume 67). Thus, the van der Waals volume could be a parameter related to solute-solvent interactions and partition coefficient. 

The medium may have a marked effect on the shape of receptor molecules itself. Shape modifications could strongly influence their substrate binding properties, for instance in the case of amphiphilic cyclophane receptors subjected to hydrophobic-hydrophilic factors in aqueous solution. Such medium effects in action are visualized by the solid state structures of two different forms of the water-soluble hexasodium salt of the macrobicyclic cyclophane 66, which could be crystallized in two very different shapes an inflated cage structure 71 building up cylinders disposed in a hexagonal array and a flattened structure 72 stacked in molecular layers separated by aqueous layers in a lamellar arrangement [4.73]. These two... 

We have examined two types of organized media that effectively control the charge separation and back reactions of the intermediate photoproducts. These include, (a) charged colloids i.e. SiC>2 and ZrC>2 colloids that introduce electrostatic interactions between the photoproducts and interface (7-10), and (b) water-in-oil microemulsions that provide aqueous-oil two phase systems capable of controlling the reactions by proper design of the hydrophobic-hydrophilic balance of the photoproducts ( 6). 

It is evident that a single electron transfer photoproduct is transformed into a doubly reduced charge relay in two phase systems. The primary processes in the natural photosynthetic apparatus involve single electron transfer reactions that proceed in hydrophobic-hydrophilic cellular microenvironment. Thus, we suggest similar induced disproportionation mechanisms as possible routes for the formation of multi-electron charge relays, effective in the fixation of CO2 or N2. 

The stability of the complex is proportional to the hydrophobic character of the substituents thus, a methyl or ethyl substituent will increase the stability. Hydroxyl groups hinder complex formation, and their hydrophilic effects decrease in the OKstthio> meta> para. In the case of amine groups, it is important whether they are present in their neutral form or ionized form. Ionic species usually do not form stable complexes (Szejtli, 1982). 

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