Lipid catalysts

Yamashita, K., Sasaki, S.-i., Osaki, T., Nango, M., Tsuda, K. A holoenzyme model of thiamine dependent enzyme asymmetrical acyloin condensation using a lipid catalyst in a bilayer membrane. Tetrahedron Lett. 1995, 36, 4817-4820. 

The formation of nitrosamines in aprotic solvents has applicability to many practical lipophilic systems including foods (particularly bacon), cigarette smoke, cosmetics, and some drugs. The very rapid kinetics of nitrosation reactions in lipid solution indicates that the lipid phase of emulsions or analogous multiphase systems can act as "catalyst" to facilitate nitrosation reactions that may be far slower in purely aqueous media (41, 53, 54). This is apparently true in some cosmetic emulsion systems and may have important applicability to nitrosation reactions in vivo, particularly in the GI tract. In these multiphase systems, the pH of the aqueous phase may be poor for nitrosation in aqueous media (e.g., neutral or alkaline pH) because of the very small concentration of HONO or that can exist at these pH ranges. 

The membrane-bound catalyst for water oxidation to O2 can be prepared via oxidation of Mn(Il) and Co(ll) salts to Mn(IV) and Co(Ill) hydroxides, respectively, in the presence of lipid vesicles. Using these catalysts and photogenerated Ru(bipy)j complex as an oxidant, it is possible to oxidize water to O2 in vesicle systems. One of such systems for O2 evolution is schematically represented in Fig. 4. 

LOO, the peroxyl radical LH, the lipid substrate L, the lipid-derived alkyl radical AH, a chain-breaking antioxidant A, the antioxidant-derived radical. Copper is the catalyst in this reaction and would also form the alkoxy radical as shown in Reaction 2.9 (see text), which is omitted here for the sake of clarity. 

Copper salts such as CuS04 are potent catalysts of the oxidative modification of LDL in vitro (Esterbauer et al., 1990), although more than 95% of the copper in human serum is bound to caeruloplasmin. Cp is an acute-phase protein and a potent inhibitor of lipid peroxidation, but is susceptible to both proteolytic and oxidative attack with the consequent release of catalytic copper ions capable of inducing lipid peroxidation (Winyard and... 

Further research is required to establish whether free-radical-induced damage is a primary event in diabetes. Tissue damage, which is associated with inactivation of antioxidants and release of metal ions that are potent catalysts of free radical reactions, can lead to lipid peroxidation. This raises the possibility that the diabetic process itself or other frctors may increase free-radical activity following direct tissue damage. 

Most studies of ORR catalysis by metalloporphyrins have been carried out using water-insoluble catalysts absorbed on a graphite electrode in contact with aqueous solution. In a limited number of cases, four other approaches have been used catalysts imbedded in an inert film (i.e., Nafion or lipid) on the electrode surface self-assembled monolayers of catalysts catalysts in aqueous or mixed organic/aqueous solutions in contact with an electrode and catalysis in mixed aqueous/organic medium using... 

ORR catalysis by Fe or Co porphyrins in Nation [Shi and Anson, 1990 Anson et al., 1985 Buttry and Anson, 1984], polyp5rrolidone [Wan et al., 1984], a surfactant [Shi et al., 1995] or lipid films [CoUman and Boulatov, 2002] on electrode surfaces has been studied. The major advantages of diluting a metalloporphyrin in an inert film include the abUity to study the catalytic properties of isolated molecules and the potentially higher surface loading of the catalyst without mass transport Umit-ations. StabUity of catalysts may also improve upon incorporating them into a polymer. However, this setup requires that the catalyst have a reasonable mobUity in the matrix, and/or that a mobile electron carrier be incorporated in the film [Andrieux and Saveant, 1992]. The latter limits the accessible electrochemical potentials to that of the electron carrier. 

When dispersed in a lipid hhn on a surface of a graphite electrode, the FeCu catalysts ate clearly superior to the Fe-only forms in catal5Tic selectivity, stability, and turnover frequency. 

Now, this tentative description of the development of a correlation, later to become information from bases to the synthesis of proteins, by no means solves the problem of the origin of this code nor does it bring into focus the fact that the very proteins which were produced are responsible for the synthesis of the basic metabolic units, formaldehyde and acetic acid and then the amino acids and bases and finally the polymers by catalysts which are the polymers themselves. We do state, however, that the set of reactions quite probably give the most kinetically stable products. Now, the amounts of the different amino acids, lipids, saccharides... 

However, subsequent studies demonstrated that the formation of hydroxyl radicals, even if it takes place during lipid peroxidation, is of no real importance. Beloqui and Cederbaum [11] have found that although the glutathione-glutathione peroxidase system suppressed hydroxyl radical generation during the oxidation of 4-methylmercapto-2-oxo-butyrate, it exhibited a much smaller effect on microsomal lipid peroxidation. Therefore, hydroxyl radical formation is apparently unimportant in this process. Other authors also pointed out at an unimportant role of hydroxyl radicals in the initiation of microsomal lipid peroxidation [12 14], For example, it has been shown that Fe(EDTA), a most efficient catalyst of hydroxyl radical formation by the Fenton reaction, inhibited microsomal and liposomal lipid peroxidation, while the weak catalysts of this reaction Fe(ADP) and Fe(ATP) enhanced it [13]. 

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