Beiträge zur chemischen Kenntnis der Echinodermen.

Glyceryl-ether monooxygenase [EC 1.14.16.5]. A microsomal enzyme of ether lipid metabolism

“…31 Enantiomerically pure glyceryl ethers (12, chiral at C2) were prepared from the corresponding chiral 1,2-isopropylidene glycerols, 13,26,31,139 and by using radiolabeled ( 14 C and/or 3 H) reactive alkyl derivatives and/or radioactive isopropylidene glycerol appropriately labeled, radiolabeled ␣-alkyl glycerols have been prepared. 136 No inversion of configuration occurs at the prochiral carbon atom C3 in (10) or (11) in this reaction, but inversion at the ␣-carbon atom of the reactive alkyl derivative does take place. We have shown this by condensing the sodium salt (9, 2RS) with R-[1-2 H]-hexadecyl tosylate which gave (1ЈS)-[1Ј-2 H]-3-hexadecyloxy-(2RS)-propane-1,2-diol, whereas condensation of (2RS)-isopropylidene tosylate with the sodi-…”

“…It is imperative that the reactive metal in the first step is in stoichiometric amounts otherwise extensive hydrolysis of the active alkyl derivative can occur with formation of the respective alkanol. For best results the isopropylidene ether (11) should be purified by chromatography (e.g., through an alumina column and elution with hexane) and the fractions monitored by TLC or HPLC to ensure the removal of small amounts of any alkanol formed. The major pitfall in this synthesis is the formation of large amounts of the latter fatty alcohols as their properties can be very similar to those of the respective ethers (11) and (12).…”

“…For best results the isopropylidene ether (11) should be purified by chromatography (e.g., through an alumina column and elution with hexane) and the fractions monitored by TLC or HPLC to ensure the removal of small amounts of any alkanol formed. The major pitfall in this synthesis is the formation of large amounts of the latter fatty alcohols as their properties can be very similar to those of the respective ethers (11) and (12). It is therefore better to have slight excess of the salt (10) because its hydrolysis products (9) or glycerol can be readily removed from the respective desired ether.…”

Ether lipids

“…This can be seen in the isolation of alkylglycerols from the starfish Asterias rubens (Kossel and Edlbacher, 1915) and the coral related gorgonian Plexaura flexuosa (Kind and Bergmann, 1942). were the first to apply periodic acid to estimate the amount of alkylglycerols in unsaponifiable fractions based on the specific reaction of periodic acid with 1,2-diols assuming alkylglycerols were the only 1,2-diol, present in the unsaponifiable matter.…”

“…Archaeal ether lipids have found a variety of applications, including serving as antigencarrying liposomes (due to their adjuvant properties) (Krishnan et al, 2000;Sprott et al, 2008), as boundary lubricants and in biomedical nano-coatings (Bode et al, 2008). Kossel and Edlbacher (1915) were the first to isolate an alkylglycerol from the unsaponifiable fraction of the starfish Asterias rubens that much later was assigned as batyl alcohol 3 (Bergmann and Stansbury-Jr, 1943). Tsujimoto and Toyama (Heilbron and Owen, 1928), working with the unsaponifiable fractions from cartilaginous fish, isolated and recorded the chemical properties of the 1-O-alkyl-sn-glycerols comprising stearyl (C18:0), palmityl (C16:0), and oleyl (C18:1) alkyl chains and gave them the trivial names batyl 3, chimyl 4, and selachyl 5 alcohols in accordance with the chondrichthyans they were isolated from i.e.…”