Polyisoprenyl phosphates

A polyisoprenyl phosphate has been shown to act as an acceptor for D-mannose and 2-acetamido-2-deoxy-D-glucose in mung beans347 and peas.348 Similar polyisoprenyl phosphates that accept glycosyl groups have been reported in soy bean, wheat germ, and pea seedlings,349 Pha-... 

Pont Lezica355 speculated that the role of dolichyl phosphates, a-satu-rated polyisoprenyl phosphates of chain length between 80 and 105 carbon atoms, in glycosyl transfer during biosynthetic mechanisms is a general feature of eukaryotic cells, whereas, in prokaryotic cells, the lipids fulfilling this function are a-saturated polyisoprenyl phosphates of shorter chain-length, such as undecaprenyl phosphate (which contains 55 carbon atoms). 

Scher and coworkers showed that an alkali-stable, acid-labile lipoid material was synthesized from GDP-D-mannose and an endogenous lipid in crude, cell-free preparations of Micrococcus lysodeik-ticus. This compound has been shown to be a polyisoprenyl (d-mannosyl phosphate) it can serve as a D-mannosyl donor in the enzymic synthesis of a homopolysaccharide of D-mannose. The poly-isoprenol was found to be a C55 compound containing two internal, trans double bonds. It was shown that only the D-mannosyl group of GDP-d -mannose is transferred to the polyisoprenyl phosphate ( undecaprenyl 1-phosphate ), and that the reaction is readily reversible. 

Levy B. D., Fokin V. V., Clark J. M., Wakelam M. J. O., Petasis N. A., Serhan C. N. 1999. Polyisoprenyl phosphate (PIPP) signaling regulates phosphohpase D activity A stop signaling switch for aspirin-triggered UpoxinA4.751Sii B/oM/7ja/. 13(8) 903-911. 

Bonnans C., Fukunaga K., Keledjian R., Petasis N. A., Levy B. D. 2006. Regulation of phosphatidylinositol 3-kinase by polyisoprenyl phosphates in neutrophil-mediated tissue injury. Journal of Exnerime.ntal Medicine. 203(4) 857-863. 

Polyisoprenyl jff-D-mannopyranosyl phosphate (19),61 rather than the a-anomer, may be the naturally occurring compound in calf pancreas.52 Citronellol or dolichol were coupled with 2,3,4,6-tetra-0-acetyl-/ -D-mannopyranosyl phosphate with the aid of tri-isopropylbenzenesulphonyl chloride to give (19) after deacetylation and purifica-... 

Polyterpenoids.—Needles of Juniperus communis contain a range of polyprenols up to ca. Choj major component being the C95 alcohol (137). The series of syntheses of polyisoprenyl sugar phosphates has been extended to dolichyl /8-d-mannopyranosyl phosphate (138). A simple procedure for the preparation of... 

The biosynthesis and functions of the membrane glycoproteins of eukaryotic cells have been reviewed. The general features of the biosynthesis of these glycoproteins closely resemble those involved in the biosynthesis of complex bacterial glycans, especially the O-antigen of lipopolysaccharides. Syntheses of polyisoprenyl jS-o-mannopyranosyl phosphate and P -di-A-acetylchitobiosyl P -dolichyl pyrophosphate have been reported. A preparation from human-lymphocyte membranes was able to transfer D-mannose from GPD-o-mannose to the chitobiosyl derivative, whereas dolichyl D-mannosyl phosphate did not act as a D-mannosyl donor. It appears that D-mannosyl residues at various positions of the glycoprotein have different anomeric configurations, so that different D-mannosyl donors are required in their synthesis. 

Inhibition by 2-deoxy-D-arai>mn-hexose of the biosynthesis of the cell-wall mannan in Saccharomyces cerevisiae appears to involve a complex mechanism that disrupts the synthesis of protein rather than glycosylation. Studies using a particulate enzyme from Mycobacterium smegmatis have demonstrated that polyisoprenyl D-mannosyl phosphates are obligatory donors, while preparations obtained from Hansenula holstii have shown that a D-mannosyl-lipid is involved in the synthesis of mannosylated serine (or threonine) residues. ... 

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