Lipids, arsenic-containing

K. Hanaoka, W. Goessler, K. Yoshida, Y. Fujittaka, T. Raise, K. Irgolic, Arsenocho-line and dimehtylated arsenic containing lipids in starspotted shark Mustelus manazo, Appl. Organomet. Chem., 13 (1999), 765-770. 

Arsenolipids are naturally occurring arsenic-containing lipids that have been discovered in natural sources (1). The arsonolipids or 2,3-diacyloxypropylarsonic acids, are analogs of phosphonolipids (Fig. 1 - compound 1), in which P has been replaced by As (Fig. 1 -compound 2) and they have not been discovered in nature. The synthesis of arsonolipids [Ars] has been explored and a simple one-pot method with moderate yield (2) is currently available for the preparation of racemic or optically active arsonolipids. Recently, this method was reinvestigated (3). After being synthesized and characterized, it was anticipated that Ars may express selective anticancer activity, by being incorporated into the membranes of cancerous cells which may result in the modification of their... 

K Hanaoka, W Goessler, K Yoshida, Y Fujitaka, T Kaise, KJ Irgolic. Arseno-choline- and dimethylated arsenic-containing lipids in starspotted shark Mustelus manazo. Appl Organomet Chem 13 765-770, 1999. 

Work on the sulfoquinovosyldiacylglycerol continued in Andy s laboratories after he moved back to California, but his association with the Scripps Institute of Oceanography led to new discoveries, particularly in the lipids of marine organisms. The finding of arsenic containing lipids has been particularly interesting and impressive. 

Piperoudi S, Fatouros D, loannou PV, Frederik P, Antimisiaris SG (2006) Incorporation ofPEG-Upids in arsonoliposomes can produce highly stable arsenic-containing vesicles of specific Upid composition. Chem Phys Lipids 139 96-106... 

Biochemical effects of arsenic are caused by blocking the SH-groups of proteins, which is most serious in enzymes containing sulphur (mainly hydrolases) and also by a chemical similarity between arsenic and phosphorus. Arsenic disturbs the metabolism of glycides and lipids, with considerable damage to the oxidative phosphorylation, etc. 

The use of different combinations of solvents has been used to extract a variety of metal(loid) species from a range of different sample types. The majority of As species, including the two common oxidation states, are highly polar and very water soluble. The most popular extraction methods are therefore based on using water or mixtures of methanol and water in various proportions, and these have been applied to both marine and terrestrial samples. The extraction of arsenic species from biological and environmental samples has been reviewed. Research has focused mostly on the so-called water-soluble species, and very few methods have been developed for the other As-containing fraction termed lipid soluble. ... 

Marine algae also contain a considerable amount (up to 50%) of lipid-soluble arsenic (39). This arsenic has been rigorously identified on only one occasion, and shown to be a phospholipid derivative (see Fig. 2, compound 5) of an arsenosugar (82,83). 

Lipid arsenic compounds also occur in marine animals (34,110). The compounds originally present in the lipid fraction were subjected to base and/or acid hydrolysis, and the water-soluble products identified by HPLC-ICPMS. In this way, phosphatidylarsenocholine (see Fig. 2, compound 18) and a phosphatidyl-arsenosugar (see Fig. 2, compound 5) were identified in the digestive gland of lobster (34), and evidence was presented for the presence of lipids containing arsenocholine and dimethylated arsenic moieties in shark tissues (110). 

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