The alkyl and alk-1-enyl glycerols in the liver of rats fed long-chain alcohols or alkyl glycerols

Dietary long-chain alcohols and alkyl glycerols, including polyunsaturated compounds, are incorporated into the alkyl and alk-1-enyl moieties of the ionic alkoxylipids of rat liver, whereas polyunsaturated fatty acids are not.     

Autoxidation of mono-, di-, and trilinoleoyl glycerols at different concentrations

Mono-, di-, and trilinoleoyl glycerols were diluted with 1-undecanol or hexadecane to produce specific concentrations, and their oxidation processes were measured at 65 degrees C at 12% relative humidity. The rate constants for oxidation of the linoleoyl residue were proportional to the concentration for all substrates. This fact suggests that no intramolecular radical chain reaction between the linoleoyl residues occurred.     

Incorporation of labelled glycerols into ether lipids in Caldariella acidophila

The lipids of Caldariella acidophila, an extreme thermophile member of the new archaebacteria group, are macrocyclic tetraethers. They are made up of two glycerol molecules (or one glycerol and one nonitol) bridged through ether linkages by two C₄₀16,16′-biphytanyl chains. To elucidate the biosynthesis of the glycerol moiety of these tetraethers and the mechanism of glycerol ether assembly, labelled [U-¹⁴C, 1(3)-³H]glycerol and [U-¹⁴C, 2-³H]glycerol, were fed to C. acidophila. Both precursors were selectively incorporated with high efficiency, and without any change in the ³H/¹⁴C ratio, in the glycerol moiety of tetraethers. These results suggest that the ether forming step in the biosynthesis of tetraether lipids of C. acidophila, occurs without any loss of hydrogen from any of the glycerol carbons which in turn could be directly alkylated by geranylgeranyl pyrophosphate. The incorporation of radioactivity in the isoprenoid chains and into nonitol is also analysed.     

The alkyl moieties in wax esters and alkyl diacyl glycerols of sharks

The alkyl moieties in wax esters and alkyl diacyl glycerols from the liver of the dogfish, soupfin shark, and silky shark are almost exclusively saturated and monounsaturated, the main alkyl moieties being the C(16) and C(18) chains in both lipid classes. However, the alkyl moieties in wax esters occur in a wider range of chain lengths. The unsaturated alkyl moieties in the two classes of lipids are mixtures of isomers. The distribution of isomeric octadecenyl moieties in wax esters and alkyl diacyl glycerols is almost the same.     

Lp-PLA2 inhibitory activities of fatty acid glycerols isolated from Saururus chinensis roots

(R)-Glycerol-monolinoleate 4 and (R)-glycerol-monostearate 5 were isolated from the ethyl acetate extracts of Saururus chinensis roots and (R)- or (S)-fatty acid glycerols 4 and 5 were synthesized for confirming their structures and evaluating their inhibitory activities against Lp-PLA(2). The (R)-4 and (S)-4 exhibited Lp-PLA(2) inhibitory activities with IC(50) values of 45.0 and 52.0 microM, respectively.     

Heterogeneity of the sn-glycerol 3-phosphate pool in isolated hepatocytes, demonstrated by the use of deuterated glycerols and ethanol.

Hepatocytes were isolated from female rats and incubated with [1,1,3,3-2H4]glycerol or [2-2H]glycerol. The deuterium excess in phosphatidylcholines, sn-glycerol 3-phosphate and other organic acids was determined by g.l.c./mass spectrometry. The unlabelled fraction of the major phosphatidylcholines decreased exponentially, and the turnover was not changed by the presence of ethanol. The relative contribution of the two deuterated glycerols was about the same in the major phosphatidylcholine as in sn-glycerol 3-phosphate, indicating that formation by acylation of dihydroxyacetone phosphate is insignificant. [1,1,3,3-2H4]Glycerol had lost deuterium to a larger extent when it was incorporated in the phosphatidylcholine than when it was incorporated in sn-glycerol-3-phosphate, indicating that the phosphatidylcholines are formed from a separate pool of sn-glycerol 3-phosphate. Deuterium at C-2 was transferred between sn-glycerol 3-phosphate molecules to about 25%. Ethanol decreased the extent of deuterium transfer, the extent of glycerol uptake and the loss of deuterium at C-1 and C-3 in sn-glycerol 3-phosphate. The results indicate that the oxidation to dihydroxyacetone phosphate was inhibited by the NADH formed during ethanol oxidation. [2-2H]Glycerol also labelled an alcohol dehydrogenase substrate, malate and lactate, indicating oxidation of sn-glycerol 3-phosphate in the cytosol. The two acids appeared to be formed in reductions with different pools of NADH.     

The aminoacyl phosphatidyl glycerols of the plastid membrane system in the process of chloroplast biogenesis

The composition of aminoacyl phosphatidyl glycerols in maize plastids at different stages of chloroplast differentiation has been studied. In the course of incubation of 14C amino acids or 14CO2 with maize and bean seedlings in vivo the 14C amino acids were incorporated preferably into the acid phospholipid fraction, forming O-esters of amino acids with phosphatidylglycerols. The rate of lipoamino acid compounds formation increased with the chloroplast differentiation and reached its maximum in the seedlings containing chloroplasts with a developed lamellar system. Changes in the amino acid composition of 14C aminoacyl phosphatidyl glycerols were observed at all stages of chloroplast ultrastructure development.     

Characterization of hydroxycinnamoyltransferase from rice and its application for biological synthesis of hydroxycinnamoyl glycerols

Hydroxycinnamoyltransferases (HCTs) catalyze the transfer of the cinnamoyl moiety from hydroxycinnamoyl-CoA to various acceptors such as shikimic acid, quinic acid, hydroxylated acid, and glycerol. Four rice HCT homologues (OsHCT1–4) to tobacco HST were cloned, and OsHCT4 was expressed in Escherichia coli as a glutathione S-transferase fusion protein. Using the purified recombinant protein and biotransformation techniques, whether OsHCT4 shows hydroxycinnamoyltransferase activity with a variety of acyl group acceptors was investigated. The results of high performance liquid chromatography (HPLC) and mass spectrometry (MS) established that OsHCT4 mediated the trans-esterification of glycerol as well as shikimic acid in the presence of hydroxycinnamoyl-CoA. The structure of the reaction product was determined using nuclear magnetic resonance spectroscopy (NMR). E. coli cells co-expressing 4CL (4-coumarate:coenzyme A ligase) and OsHCT4 converted p-coumaric acid, ferulic acid, and caffeic acid into the corresponding glycerides. While this conversion is very efficient in vitro, the physiological significant in rice is currently unknown.     

Halo lipids, 8. Synthesis of O-alkyl-O-alkyl-O-(2,2,2-trifluoroethyl)glycerols and O-alkyl-O-(2,2,2-trifluoroethyl)glycero-phosphocholines

The syntheses and structure determination of 3 positional isomers of O-alkyl-O-(2,2,2,-trifluoroethyl)glycerols and their conversion into the corresponding O-alkyl-O-(2,2,2-trifluoroethyl)glycerophosphocholines via the [O-alkyl-O-(2,2,2-trifluoroethyl)glycero]-2-bromoethyl hydrogen phosphates are described.     

Identification of 1-alkyl-2-acyl-3-(2',3'-diacylglycerol)glycerols, a new type of lipid class, in harderian gland tumors of mice

A new class of alkyl glycerolipids, 1-alkyl-2-acyl-3-(2',3'-diacylglycerol)glycerols, was identified in lipid extracts prepared from harderian gland tumors of mice. After saponification, this lipid class yielded 1-alkyl-3-(1'-glycerol)glycerols. Identification was based on mass spectrometry, proton nuclear magnetic resonance spectroscopy, infrared spectroscopy, and chromatography of various derivatives and appropriate standards that were synthesized. The alkyl moieties of this unique lipid class consisted of saturated aliphatic chains with chain lengths of 14 to 20 carbon atoms. The acyl moieties were mostly saturated and monounsaturated aliphatic chains ranging from 14 to 24 carbon atoms. The alkyl and acyl moieties of 1-alkyl-2-acyl-3-(2',3'-diacylglycerol)glycerols were similar to those of alkyldiacylglycerols present in the same tissue, except for the presence of monounsaturated alkyl moieties in the latter. 1-Alkyl-2-acyl-3-(2', 3'-diacylglycerol)glycerols were only found in trace amounts in the normal harderian glands of mice. The total quantity of the alkyl and acyl moieties with a chain length greater than 20 carbon atoms in the alkyldiacylglycerols from tumors were considerably lower than those found in normal harderian glands of mice. This is the first report of the presence of bisglyceryl ether lipids in mammalian tissue; its unique chemical structure is consistent with the type of ether-linked lipid products that could be synthesized in the reaction catalyzed by alkyldihydroxyacetone-P synthase.     

Alkylating agents from sugars: synthesis of chlorambucil derivatives carried by chiral glycosyl glycerols derived from D-glucosamine

Chlorambucilamide derivatives involving chiral glycosyl glycerols derived from D-glucosamine were synthesized in good yield by coupling the chlorambucil moiety to the amino group of omega-amino-(omega-1)-hydroxyalkyl 2-acylamino-4,6-O-benzylidene-2-deoxy-beta-D-glucopyranosides, and subsequent hydrolysis of the benzylidene group. The starting material was easily available from 2-acetamido-2-deoxy-D-glucose. The bonding of 2,3,4,6-tetra-O-pivaloyl-beta-D-galactopyranosylamine to chlorambucil by formation of an amide function is also described.     

Cloning and expression of the Apa LI, Nsp I, Nsp HI, Sac I, Sca I, and Sap I restriction-modification systems in Escherichia coli

The genes encoding the ApaLI (5′-G^TGCAC-3′), NspI (5′-RCATG^Y-3′), NspHI (5′-RCATG^Y-3′), SacI (5′-GAGCT^C-3′), SapI (5′-GCTCTTCN1^-3′, 5′-^N4GAAGAGC-3′) and ScaI (5′-AGT^ACT-3′) restriction-modification systems have been cloned in E.?coli. Amino acid sequence comparison of M.ApaLI, M.NspI, M.NspHI, and M.SacI with known methylases indicated that they contain the ten conserved motifs characteristic of C5 cytosine methylases. NspI and NspHI restriction-modification systems are highly homologous in amino acid sequence. The C-termini of the NspI and NlaIII (5′-CATG-3′) restriction endonucleases share significant similarity. 5mC modification of the internal C in a SacI site renders it resistant to SacI digestion. External 5mC modification of a SacI site has no effect on SacI digestion. N4mC modification of the second base in the sequence 5′-GCTCTTC-3′ blocks SapI digestion. N4mC modification of the other cytosines in the SapI site does not affect SapI digestion. N4mC modification of ScaI site blocks ScaI digetion. A DNA invertase homolog was found adjacent to the ApaLI restriction-modification system. A DNA transposase subunit homolog was found upstream of the SapI restriction endonuclease gene.     

1-O-2′-hydroxyalkyl and 1-O-2′-ketoalkyl glycerols

1-O-2′-Hydroxyalkyl glycerols were synthesized from 1,2-alkanediols and, alternatively, from 1,2-epoxyalkanes. Their 2,3-isopropylidene derivatives, 2′-acetoxy-2,3-isopropylidene derivatives and 2′,2,3-triacetoxy derivatives were prepared. 1-O-2′-Ketoalkyl-2,3-isopropylidene glycerols were prepared from the corresponding 2′-hydroxy derivatives; they were hydrolyzed to 1-O-2′-ketoalkyl glycerols. The compounds were characterized by thin-layer and gas-liquid chromatography, by infrared spectroscopy and mass spectrometry.     

Juvenile hormone–stimulated synthesis of acyl‐glycerols and vitamin E in female accessory sexual glands of the fire bug,Pyrrhocoris apterus L.

Secretory cells of the female accessory sexual glands (AG) of P. apterus grow and produce yellow oily exocrine secretion in response to stimulation by endogenous juvenile hormone (JH) or exogenous treatments by JH analogues. The secretion determines the property of future egg shells by coating the chorion surface of the oocytes that are passing individually through the common uterus during oviposition. Diapausing females with a physiologically inhibited endocrine system or females with artificially removed hormonal sources show inactive ovaries and empty AG without the secretory products. Ovary‐ectomised females with the intact neuroendocrine system develop hypertrophic AG loaded with the oily secretion. This shows that there is no direct dependence between formation of the oily secretion in AG and ovarian growth. Chemical analysis of the secretory products revealed the presence of acetylated glycerols, with the most abundant stearoyl‐diacetyl‐glycerol, stearoyl‐acetyl‐propionyl‐glycerol, and the corresponding derivatives of arachidonic acid. In addition to this, the JH‐activated secretory cells of AG also produced γ‐ and δ‐tocopherols. The possible antioxidant or antimutagenic action of these vitamin E compounds in insect reproduction has been emphasized. © 2009 Wiley Periodicals, Inc.