Diacyl phosphate

The l,2-diacyl-l-/-butylhydrazines have been found to be effective as insect-growth regulators. Caged bicyclic phosphates have also shown promise as insecticides. Wang and Huang have combined these effects in the synthesis of compounds 266 and 267 <2000PS(161)173>. Compounds 268 and 269 have been synthesized for their potential... 

Glycerolipids are derivatives of glycerol and fatty acids. Most brain glycerolipids are derivatives of phos-phatidic acid (PtdOH), which is diacylated sn-glycerol-3-phosphate. The notation sn refers to stereochemical... 

Figure 12.11 Phosphoglyceride structure. The members of this group are derivatives of the parent compound, l,2-diacyl-src-glycerol-3-phosphate (phosphatidic acid) in which X is a hydrogen atom. This is replaced by either an amino alcohol or a polyhydroxy residue. In phosphoglycerides derived from animal tissues R1 is usually a saturated acyl chain of between 16 and 20 carbon atoms and R2 is usually unsaturated. Polyunsaturated acyl chains containing 16 or 18 carbon atoms predominate in leaf phosphoglycerides and those of bacterial origin are often more complex.

Table 12.5). Phosphoglycerides are derivatives of glycerophosphoric acid (l,2-diacyl-sn-3-phosphate) which is also called phosphatidic acid. 

The different phosphoglycerides are often named by placing the constituent attached to the phosphate group after phosphatidyl , e.g. phosphatidyl choline (3-in-phosphatidylcholine or l,2-diacyl-sn-glycero-3-phosphoryl-choline). There are many phosphoglycerides because of the possible variation in the fatty acid chains, and when the full chemical structure is known, it should be used (e.g. l-palmitoyl-2-oleoyl-phosphatidylcholine). Nomenclature that entails the use of the DL system should be avoided. 

This enzyme catalyzes the reaction of an acyl-CoA derivative with l-acyl-vn-glycerol 3-phosphate to generate coenzyme A and l,2-diacyl-5 n-glycerol 3-phosphate. The animal enzyme is reported to be specific for the transfer of unsaturated fatty acyl groups. Interestingly, the acyl-[acyl-carrier-protein] can also act as an acyl donor. 

Sodium bis(2-ethyl-l-hexyl) sulfosuccinate (Aerosol OT, AOT) sodium do-decylbenzene sulfonate (SDBS) sodium di-2-ethyl hexyl phosphate (NaDEHP) dioleyl phosphoric acid (DOLPA) di(tridecyl) phosphoric acid (DTDPA) sodium dodecyl sulfate (SDS) 1,3-dilauroyl glycerol-2-disodium phosphate (2-modified 1,3-diacyl glycerol)... 

The first steps of glycerophospholipid synthesis are shared with the pathway to triacylglycerols (Fig. 21-17) two fatty acyl groups are esterified to C-l and C-2 of L-glycerol 3-phosphate to form phosphatidic acid. Commonly but not invariably, the fatty acid at C-l is saturated and that at C-2 is unsaturated. A second route to phosphatidic acid is the phosphorylation of a diacyl-glycerol by a specific kinase. 

CH2li2 6rl5i ,w3.M+, or alkyl caboxylates H(Cih n W2-M+ withn typically 7-15 and M+ an alkali metal cation, generally sodium, or they may be anionic, such as H(CH2- 12 3+C1- or H(CH2 12 3 3+C1-. The alkyl chains need not be normal i.e., they may be branched, and may be fluorine-substituted. Some natural surfactants are also of importance e.g., lecithins such as 1,2-diacyl glycero-3-phosphate, with the acyl groups being H(CH2 an< n typica-Hy 12 18, the latter possibly oleyl, i.e., unsaturated. 

Takayama, K., Qureshi, N., Mascagni, P., Nashed, M.A., Anderson, L., Raetz, C.R.H. Fatty acyl derivatives of glucosamine 1-phosphate in Escherichia coli and their relation to lipid A. Complete structure of A diacyl GlcN-1-P found in a phosphatidylglycerol-deficient mutant. J Biol Chem 258 (1983) 7379-7385. 

Acid Treatment. This procedure, if applied to a sample containing all three species, would lead to release of a long-chain fatty aldehyde which could be isolated and analyzed as the dimethyl acetal. Subsequent thin-layer chromatography of the acid reaction mixture would allow recovery of the parent diacyl GPA and alkylacyl GPA. Then, using the chloroform soluble lipid phosphate as a guideline, base treatment of the original sample will lead to loss of chloroform-soluble phosphorus (representative of the diacyl GPA). The remaining chloroform-soluble phosphorus will represent the alkyl and alkenyl form. 

Though many open-chain diacyl peroxides have been described, very few cyclic compounds of this type are known. Monomeric cyclic phthaloyl peroxide (84) is prepared by treatment of phthaloyl chloride in chloroform with aqueous sodium peroxide solution in the presence of phosphate buffer, or by reaction of phthaloyl chloride with ethereal hydrogen peroxide in the presence of sodium carbonate.70-72 Russell71 has also obtained cyclic diacyl peroxides from the dichlorides of the C10, C12, and C14 dicarboxylic acids. Only polymeric diacyl peroxides were obtained from lower dicarboxylic acids. 

The phospholipid monolayers examined in this study were all saturated, symmetric, 1,2-diacyl-j -glycero-3-phosphate-based lipids. Four different lipid headgroups attached to the phosphate were examined choline, ethanolamine, glycerol and serine. Each lipid features a glycerol backbone, two saturated fatty acid chains and a phosphatidyl headgroup. 

Abbreviations used EMSA, electrophoretic mobility shift analysis IMPase 1, inositol monophosphatase 1 inositol synthase, A/vo-inositol 3-phosphate synthase NCBI, National Center for Biotechnology Information PCR, polymerase chain reaction Rb, retinoblastoma protein tss, transcriptional start site IP3, Inositol trisphosphate DAG, diacyl glycerol FISH, fluorescent in situ hybridization. 

Figure 1. Schematic representation of the brain inositol signaling system. The quantities of IMPase isoenzymes and IPPase are increased by chronic lithium treatment occurring at either the gene or protein levels. Inositol in this diagram indicates the myo-inositol isomer. Calbindin -calcium binding protein DAG- diacyl glycerol Gq-GTP binding protein IMPase 1 — inositol mono phosphatase 1 IPPase- inositol polyphosphate 1-phosphatase Ins(l)P, Ins(3)P, Ins(4)P-inos-itol monophosphates Ins(l,3)P2 - inositol 1,3-bisphosphate Ins( 1,4)/ 2 - inositol 1,4-bisphos-phate Ins(3,4)/)2- inositol 3,4-bisphosphate Ins (1,4,5)P3 - inositol 1,4,5-trisphosphate Ins( 1,3,4)/ 3 - inositol 1,3,4-trisphosphate Li+-lithium PA - phosphatidic acid PI- phosphatidyl inositol PIP- phosphatidyl inositol 4-phosphate PIP2- phosphatidyl inositol 4,5-bisphosphate PIP3- phosphatidyl inositol 3,4,5 trisphosphate PLC - phospholipase-C, VPA-valproate.

The structure of glycerophospholipids is characterized by a l,2-diacyl-3-phospho-5n-glycerol, or phosphatidyl moiety, and a variable headgroup linked to the phosphate. Major phosphoglycerides found in nature are phosphatidylcholine (PC), phosphatidylethanolamine (PE), phosphatidylglycerol (PG), phosphatidylserine, phosphatidylinositol (PI), and diphospha-... 

Phosphatidylcholine specific phospholipase C (PLC) can be used for the hydrolysis of PC (and PX) affording natural diacyl glycerol (DAG ) and chohne phosphate (CP) (or corresponding organic phosphate, OP). Transesterification has not been observed with this enzyme. The substrate specificity is less broad than desirable for the synthesis of OP that is otherwise... 

Figure 5. Biosynthetic pathways for diacyl, plasmalogen and alkyl-ether molecular subclasses of phospholipids. Monoacyl dihydroxyacetone phosphate is the key branch-point intermediate whose utilization determines the phospholipid subclass distribution of newly synthesized phospholipids. Reduction of monoacyl dihydroxyacetone phosphate leads to the biosynthesis of diacyl phospholipids. Fatty alcohol exchange, catalyzed by alkyl dihydroxyacetone phosphate synthase, is the first committed step in the biosynthesis of alkyl-ether and plasmalogen subclasses of phospholipids.

Fatty acids are not directly Incorporated Into phospholipids rather, they are first converted In eukaryotic cells Into CoA esters. The subsequent synthesis of many diacyl glycero phospholipids from fatty acyl CoAs, glycerol 3-phosphate, and polar head-group precursors Is carried out by enzymes associated with the cytosolic face of the ER membrane, usually the smooth ER, In animal cells (Figure 18-4). Mitochondria synthesize some of their own membrane lipids and Import others. In photosynthetic tissues, the chloroplast Is... 

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