Hydrophobic complexation

For some systems the value of Kp may be made more favorable by adjusting pH to prevent ionisation of acids or bases, by forming ion pairs with ionisable solutes, by forming hydrophobic complexes with metal ions, or adding neutral salts to the aqueous... 

The photocurrent action spectra of these complexes show broad features covering a large part of visible spectrum, and display a maximum at around 550 nm, where the incident monochromatic IPCE exceeds 85%. These hydrophobic complexes show excellent stability towards water-induced desorption when used as CT photosensitizers in nanocrystalline Ti02-based solar cells.62... 

In any case, exceptions to the FIAM have been pointed out [2,11,38,44,74,76,78]. For example, the uptake has been shown to depend on the Cj M or rMI (e.g. in the case of siderophores [11] or hydrophobic complexes [43,50]), rather than on the free c M. Several authors [11,12,15] showed that a scheme taking into account the kinetics of parallel transfer of M from several solution complexes to the internalisation transporter ( ligand exchange ) can lead to exceptions to the FIAM, even if there is no diffusion limitation. Adsorption equilibrium has been assumed in all the models discussed so far in this chapter, and the consideration of adsorption kinetics is kept for Section 4. Within the framework of the usual hypotheses in this Section 3, we would expect that the FIAM is less likely to apply for larger radii and smaller diffusion coefficients (perhaps arising from D due to the labile complexation of M with a large macromolecule or a colloid particle, see Section 3.3). 

On the other hand, the presence of hydrophobic complexes is a prerequisite for partitioning and diffusion of metals into the lipid bilayer. In the following paragraphs, various types of metal complexes will be discussed, which are relevant to the interactions of metals in aquatic systems. The role of these various types of metal complexes with respect to interactions at the biological interphases will be systematically examined. 

The same relationships between free metal ions and total metal concentrations hold as above. Equation (4) may include the concentration of hydrophobic ligands. However, the occurrence of hydrophobic complexes is particularly relevant to the interactions with membranes. 

In the following section, the role of the various types of complexes mentioned above will be discussed with regard to various mechanisms of interactions at biological interphases. It is clear that metal ions and hydrophilic complexes cannot distribute into the membrane lipid bilayer or cross it. The role of hydrophilic ligands has thus to be discussed in relation to binding of metals by biological ligands. In contrast, hydrophobic complexes may partition into the lipid bilayer of membranes (see below, Section 6). 

Indirect evidence of hydrophobic complex formation in biological membranes is also given by the modulation of the toxicity of catechol and chlor-ocatechol by Cu2+ [78], Whereas toxicity of higher chlorocatechols was decreased by the addition of Cu2+, it was increased in the case of catechol and monochlorocatechol. Tentative models to explain these findings include complex formation between mono-and di-deprotonated catechols and Cu2+, both in the aqueous and in the membrane phase. 

There is an abundant research on the interactions of HIOCs and metals with biological interphases, in which organic chemicals and metals are treated independently. However, few studies have considered the role of combinations of HIOCs with metals. There is a particular lack of mechanistic approaches. With regard to the metals, the FIAM has been very successful, but it remains to be shown under which conditions additional interactions, such as partitioning of hydrophobic complexes and uptake of specific complexes, are important for metal uptake and toxic effects. In particular, the role of hydrophobic complexes with both natural and pollutant compounds in natural waters has not yet been fully elucidated, since neither their abundance nor their behaviour at biological interphases are known in detail. 

Dithizone (diphenylthiocarbazone) is a green compound that is soluble in nonpolar organic solvents and insoluble in water below pH 7. It forms red, hydrophobic complexes with most di- and trivalent metal ions. 

An ion-pair derived from the substrate and solid NaOH forms a cation-assisted dimeric hydrophobic complex with catalyst 39c, and the deprotonated substrate occupies the apical coordination site of one of the Cu(II) ions of the complexes. Alkylation proceeds preferentially on the re-face of the enolate to produce amino acid derivatives with high enantioselectivity. However, amino ester enolates derived from amino acids other than glycine and alanine with R1 side chains are likely to hinder the re-face of enolate, resulting in a diminishing reaction rate and enantioselectivity (Table 7.5). The salen-Cu(II) complex helps to transfer the ion-pair in organic solvents, and at the same time fixes the orientation of the coordinated carbanion in the transition state which, on alkylation, releases the catalyst to continue the cycle. 

For benzene hydroxylation an analytical system [37] was successfully used at the interface. This system contains Fe3+ hydrophobic complexes, which promote the process intensification. It is shown [38, 39] that compared with hydrophobic complexes, Fe3+ complexes with the phase transfer—tertiary ammonium salts and crown ethers—display more effective action. At 20-50 °C, owing to the use of trimethylacetylammonium bromide as the phase transferring agent, benzene is successfully hydroxylated in the two-phase water-benzene system in the presence of Fe3+ ions [40], Hence, it is Shilov s opinion [41] that in the case of cytochrome P-450 a radical reaction is probable. It produces radicals, which then transform in the cell, as follows ... 

The other important aspect in dye-sensitized solar cells is water-induced desorption of the sensitizer from the TiC>2 surface. Extensive efforts have been made in our laboratory to overcome this problem by introducing hydrophobic properties in the ligands 13-17. The absorption spectra of these complexes show broad features in the visible region and display maxima around 530 nm. The performance of these hydrophobic complexes as charge transfer photosensitizers in nanocrystalline TiC>2-based solar cells shows excellent stability towards water-induced desorption [36]. 

It is expected from the above considerations that the true ET can be obtained when a sufficiently hydrophobic redox species is used in the O phase. From this perspective, the previously reported ET systems involving highly hydrophobic complexes such as LuPc2 [4-6] might be considered as heterogeneous ETs. However, the rate of the heterogeneous... 

Molecular structure/biospecific adsorption Surface charge/ionic binding Metals complex formation/coordination complex Molecular size and shape/size exclusion Hydrophobicity/hydrophobic complex formation... 

---