Amphiphilic activation

Knoller, S., Shpungin, S., and Pick, E. (1991) The membrane-associated component of the amphiphile-activated, cytosol-dependent superoxide-forming NADPH oxidase of macrophages is identical to cytochrome b559./. Biol. Chem. 266, 2795-2804. 

Proteins, like other macromolecules, can be made into monolayers at the air-water interface either by spreading, adsorption, or specific binding. Proteins, while complex polymers, are interesting because of their inherent surface activity and amphiphilicity. There is an increasing body of literature on proteins at liquid interfaces, and here we only briefly discuss a few highlights. 

Forbes M D E, Schulz G R and Avdievich N I 1996 Unusual dynamics of micellized radical pairs generated from photochemically active amphiphiles J. Am. Chem. Soc. 118 10 652-3... 

The study on micellar models is still at the beginning. An amphiphilic ligand which can form micelles by itself has not yet been prepared. It is necessary to obtain complexes of higher stability in order to activate the hydroxyl group strong enough in the reactions of inactive esters or amides. Enantioselectivity must reach higher specifity. Nevertheless it seems to be clear that many features or some important clues have already been disclosed for further refinements of this micellar systems. More details about the present micellar reactions will be reported elsewhere in near future. 

The formation of a microphase structure leads to a surface-active effect [31]. The surface tension of water is considerably lowered when amphiphilic copolymers are dissolved. The surface-active effect appears more significantly in the copolymers with more hydrophobic units. 

Phosphorus-containing surfactants are amphiphilic molecules, exhibiting the same surface-active properties as other surfactants. That means that they reduce the surface tension of water and aqueous solutions, are adsorbed at interfaces, form foam, and are able to build micelles in the bulk phase. On account of the many possibilities for alteration of molecular structure, the surface-active properties of phosphorus-containing surfactants cover a wide field of effects. Of main interest are those properties which can only be realized with difficulty or in some cases not at all by other surfactants. Often even quantitative differences are highly useful. 

Adsorption on solid matrices, which improves (at optimal protein/support ratios) enzyme dispersion, reduces diffusion limitations and favors substrate access to individual enzyme molecules. Immobilized lipases with excellent activity and stability were obtained by entrapping the enzymes in hydrophobic sol-gel materials [20]. Finally, in order to minimize substrate diffusion limitations and maximize enzyme dispersion, various approaches have been attempted to solubilize the biocatalysts in organic solvents. The most widespread method is the one based on the covalent linking of the amphiphilic polymer polyethylene glycol (PEG) to enzyme molecules [21]. 

Kozubek, A., Tyman, J. Resorcinolic lipids, the natural non-isoprenoid phenolic amphiphiles and their biological activity. Chemical Reviews, Vol.99, No.l. Qanuary 1999), pp. 1-31, ISSN 0009-2665... 

Tab. 2.9 Antibacterial activities of [Ala ]-magainin II amide and amphiphilic 3i4-helical ent-157b, 83-85) and 2.5,2-helical (158, 159) yS-peptides [175, 234, 248]...

Fig. 2.40 Sequences and helical wheel representation of amphiphilic 2.5,2-helical jS-pep-tide 17-mers evaluated for antimicrobial activity [234, 248]. These peptides are exclusively composed of hydrophobic trans-ACPC...

Meanwhile we have shown that the excision activation of ICOR channels is due to disinhibition [72]. The respective inhibitor, operationally named cytosolic inhibitor (Cl), is present in the cytosol of placenta trophoblast cells HT29- and Tg4-colonic carcinoma cells and RE cells of normal and CF patients. The molecule has an apparent molecular weight of 700-1 500 Da it is amphiphilic heat stable and not digested by trypsin, proteases, nucleotidases, lipases or amylase [72]. Burc-khardt, Fromter and their collaborators [114] have confirmed our results and extracted a similar or identical Cl from kidney cortex. 

At the present time, "interest in reversed micelles is intense for several reasons. The rates of several types of reactions in apolar solvents are strongly enhanced by certain amphiphiles, and this "micellar catalysis" has been regarded as a model for enzyme activity (. Aside from such "biomimetic" features, rate enhancement by these surfactants may be important for applications in synthetic chemistry. Lastly, the aqueous "pools" solubilized within reversed micelles may be spectrally probed to provide structural information on the otherwise elusive state of water in small clusters. 

The combination of hydrophilic and hydrophobic parts of a molecule defines its amphiphilicity. A program has been described to calculate this property and calibrated against experimental values obtained from surface activity measurements [133]. These values can possibly be used to predict effect on membranes leading to cytotoxicity or phospholipidosis, but may also contain information, not yet unraveled, on permeability. Surface activity measurements have also been used to make eshmates of oral absorphon [126]. 

Phospholipids are amphiphilic compoimds with high surface activity. They can significantly influence the physical properties of emulsions and foams used in the food industry. Rodriguez Patino et al. (2007) investigated structural, morphological, and surface rheology of dipalmitoylpho-sphatidylcholine (DPPC) and dioleoyl phosphatidylcholine (DOPC) monolayers at air-water interface. DPPC monolayers showed structural polymorphisms at the air-water interface as a function of surface pressure and the pH of the aqueous phase (Fig. 6.18). DOPC monolayers showed a... 

One can further elaborate a model to have a concrete form of /(ft), depending on which aspect of the adsorption one wants to describe more precisely, e.g., a more rigorous treatment of intermolecular interactions between adsorbed species, the activity instead of the concentration of adsorbates, the competitive adsorption of multiple species, or the difference in the size of the molecule between the solvent and the adsorbate. An extension that may be particularly pertinent to liquid interfaces has been made by Markin and Volkov, who allowed for the replacement of solvent molecules and adsorbate molecules based on the surface solution model [33,34]. Their isotherm, the amphiphilic isotherm takes the form... 

Surface active agents (surfactants) are active (adsorb) at surfaces and reduce surface tensions. Surfactants work because they are amphiphilic they have opposing solubility tendencies in one molecule, such as a hydrocarbon chain and a polar end. Because of this disparity in solubility, they tend to form concentration gradients at dissimilar phase interfaces. Surfactant additives are classified according to the interface at which they are active. 

This subject can be considered in terms of five different types of molecules or materials (a) biologically inert, water-insoluble polymers (b) water-insoluble polymers that bear biologically active surface groups (c) water-swellable polymeric gels, or amphiphilic polymers that function as membranes (d) water-insoluble but bioerodable polymers that erode in aqueous media with concurrent release of a linked or entrapped bioactive molecule and (e) water-soluble polymers that bear bioactive agents as side groups. 

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