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Molecular and Cellular Biochemistry Nov 1980In this article, I review the current information concerning the partition of the fluorescent probes, cis-parinaric acid (9, 11, 13, 15-cis, trans, trans,... (Review)
Review
In this article, I review the current information concerning the partition of the fluorescent probes, cis-parinaric acid (9, 11, 13, 15-cis, trans, trans, cis-octadecatetraenoic acid) and trans-parinaric acid (9, 11, 13, 15-all trans-octadecatetraenoic acid) among aqueous, solid lipid, and fluid lipid phases. The association of these probes with lipid is described by a mole fraction partition coefficient whose value is trypically in the range of 1-5 x 10(6), a reasonable value in light of partition coefficients for other fatty acids between hydrophobic phases and water. The partition coefficient, in the absence of lipid phase changes, is relatively independent of temperature and only slightly dependent on the total aqueous probe concentration. In lipid samples which contain coexisting fluid and solid phases, trans-parinaric acid preferentially partitions into the solid phase, while cis-parinaric acid distributes nearly equally between fluid and solid phases. This partition behavior probably arises from the molecular shape of the cis and trans parinaric acid in mixed lipid systems or membranes it is possible to evaluate the proportion of lipid components involved in phase changes or phase separation. From fluorescence energy transfer between protein typtophan residues and the parinaric acid isomers it is possible to gain information about the organization of lipids and proteins in membranes and model systems. I close the review by considering some of the membrane research areas where these probes and their various lipid derivatives may be particularly useful.
Topics: Chemical Phenomena; Chemistry, Physical; Fatty Acids, Unsaturated; Fluorescence Polarization; Fluorescent Dyes; Isomerism; Lipids; Membrane Lipids; Surface Properties; Temperature
PubMed: 7007869
DOI: 10.1007/BF00227444 -
Physiology and Molecular Biology of... May 2022Parinaric and α-eleostearic acids are unusual conjugated fatty acids. Unusual fatty acids, in general, are known to have roles in defense response; however, the role of...
UNLABELLED
Parinaric and α-eleostearic acids are unusual conjugated fatty acids. Unusual fatty acids, in general, are known to have roles in defense response; however, the role of parinaric acid in is not known, nor is it known whether it occurs in different species of or its closest monotypic relative, (L.) Wight & Arn. The aim of the study was to (a) characterize the fatty acid composition of 21 species of and and (b) determine whether parinaric and α-eleostearic acids are present in these taxa and, if so, (c) whether there is interspecific and intraspecific variation in parinaric acid content. Fatty acid profiling was done using gas chromatography and mass spectrometry (GC-MS). To uncover taxonomic patterns of variation in fatty acids, principal component analysis and hierarchical cluster analysis were performed. The major fatty acids in were found to be palmitic (5.57-20.85%), stearic (2.86-21.61%), oleic (2.79-28.99%), linoleic (C18:2Δ, 2.04-26.64%), α-linolenic (C18:3∆; 11.07-53.99%), and four forms of parinaric acid (5.93-70.21%). Genus contains two unusual conjugated fatty acids- parinaric and α-eleostearic, however these are absent in closely related This study reports the presence of four different forms of parinaric acid in for the first time. Some species (, and ) were found to contain very high levels (> 50%) of parinaric acid and they might be useful for various biomedical and industrial applications. Apparently, the presence of parinaric acid is a characteristic of Significant variations were found in the amount and forms of parinaric acid. We propose the potential application of parinaric acid and α-eleostearic acid as chemotaxonomic markers for
SUPPLEMENTARY INFORMATION
The online version contains supplementary material available at 10.1007/s12298-022-01194-4.
PubMed: 35722517
DOI: 10.1007/s12298-022-01194-4 -
The Journal of Organic Chemistry Aug 2022A divergent formal synthesis of polyhydroxylated macrocyclic lactone (+)-aspicillin and polyene bioactive natural product β-parinaric acid and the total synthesis of...
A divergent formal synthesis of polyhydroxylated macrocyclic lactone (+)-aspicillin and polyene bioactive natural product β-parinaric acid and the total synthesis of non-terpenoid metabolite isolaurepan have been achieved using a ruthenium-catalyzed stereo- and chemoselective oxidative coupling reaction of easily accessible vinyl ketones and acrylates. The crucial transformation involves the efficient synthesis and functionalization of stereodefined ()-1,6-dioxo-2,4-dienes using simple reaction protocols, which enabled straightforward access to a diverse range of bioactive natural products.
Topics: Fatty Acids, Unsaturated; Oxepins; Polyenes; Ruthenium
PubMed: 35921130
DOI: 10.1021/acs.joc.2c01280 -
Biochimica Et Biophysica Acta Dec 1983The cis-isomer of parinaric acid, a naturally occurring C-18 polyene fatty acid, was incubated with brain subcellular fractions and the polarization of fluorescence...
The cis-isomer of parinaric acid, a naturally occurring C-18 polyene fatty acid, was incubated with brain subcellular fractions and the polarization of fluorescence increased in a time dependent manner. Greatest increases occurred in synaptosomal and microsomal membranes. This increase in polarization of fluorescence was found with the cis, but not the trans, isomer of parinaric acid and required Mg2+ or Ca2+ and was stimulated by coenzyme A and ATP. Synaptosomes were incubated with cis-parinaric acid and lipids were extracted and examined by high performance liquid chromatography. The highest incorporations of cis-parinaric acid were found in phosphatidylcholine (71%) and phosphatidylethanolamine (20%) while only traces were found in phosphatidylserine and phosphatidylinositol. [3H]Oleic acid was also incorporated into membrane phospholipids and unlabeled oleic acid blocked incorporation of cis-parinaric acid. It is proposed that cis-parinaric acid, like fatty acids normally found in brain, is incorporated into membrane phospholipids by an acyl-CoA acyltransferase. The presence of this enzyme in nervous tissue may make it possible to easily introduce fluorescent fatty acid probes into membrane phospholipids and to thereby facilitate study of membrane-mediated processes.
Topics: Animals; Chromatography, High Pressure Liquid; Coenzyme A-Transferases; Fatty Acids, Unsaturated; Fluorescence Polarization; Isomerism; Phospholipids; Rats; Sulfurtransferases; Synaptosomes
PubMed: 6580918
DOI: 10.1016/0005-2736(83)90172-4 -
Biochimica Et Biophysica Acta Sep 1987The decrease in fluorescence of conjugated polyenic acyl chains is used as a sensitive assay for lipid peroxidation. The fatty acid cis-trans-trans-cis-9,11,13,... (Comparative Study)
Comparative Study
The decrease in fluorescence of conjugated polyenic acyl chains is used as a sensitive assay for lipid peroxidation. The fatty acid cis-trans-trans-cis-9,11,13, 15-octadecatetraenoic acid (cis-parinaric acid) is introduced into liposomal membranes as free fatty acid or, by using the PC specific transfer protein from bovine liver, as 1-palmitoyl-2-cis-parinaroyl-sn-glycero-3-phosphocholine. The peroxidation process as monitored by the decrease in fluorescence intensity is compared with other peroxidation assay systems. Applications of the new assay system are discussed.
Topics: Androgen-Binding Protein; Carrier Proteins; Copper; Fatty Acids, Unsaturated; Fluorescent Dyes; Hydrogen Peroxide; Lipid Peroxides; Liposomes; Lysophosphatidylcholines; Phosphatidylcholines; Phospholipid Transfer Proteins; Spectrometry, Fluorescence
PubMed: 3651488
DOI: 10.1016/0005-2760(87)90027-0 -
Journal of Oleo Science 2024Conjugated fatty acids have anticancer effects. Therefore, the establishment of a synthetic method for conjugated fatty acids is important for overcoming cancer. Here,...
Conjugated fatty acids have anticancer effects. Therefore, the establishment of a synthetic method for conjugated fatty acids is important for overcoming cancer. Here, we attempted to synthesize conjugated fatty acids using enzymes extracted from seaweeds containing these fatty acids. Lipids from 12 species of seaweeds from the seas around Japan were analyzed, and Padina arborescens Holmes was found to contain conjugated fatty acids. Then, we synthesized parinaric acid, a conjugated tetraenoic acid, from α-linolenic acid using the enzyme of P. arborescens. This method is expected to have a variety of potential applications for overcoming cancer.
Topics: alpha-Linolenic Acid; Seaweed; Fatty Acids, Unsaturated; Antineoplastic Agents
PubMed: 38692896
DOI: 10.5650/jos.ess23209 -
Preparative Biochemistry 1985Isolated guinea pig liver microsomal membranes catalyzed the incorporation of naturally occurring cis-parinaric acid into sn-3-[U-14C]glycerophosphate. This resulted in...
Isolated guinea pig liver microsomal membranes catalyzed the incorporation of naturally occurring cis-parinaric acid into sn-3-[U-14C]glycerophosphate. This resulted in the formation of sn-3-[14C](parinaroyl)phosphatidic acid, which was isolated by Chelex-100 and DEAE-cellulose column chromatography and further purified by Sephadex-G 25. The sn-3-[14C](parinaroyl)phosphatidic acid thus obtained exhibited absorption and fluorescence spectra substantially different from the cis-parinaric acid. Distribution of the incorporated cis-parinaric acid between the hydroxyl groups of biosynthesized sn-3-[14C]phosphatidic acid was determined by degradation with Crotalus adamanteus venom. This established that the major portion of the incorporated cis-parinaric acid esterified the secondary hydroxyl group in the sn-3-[14C]phosphatidic acid, while the primary hydroxyl group was esterified to a significantly lesser degree. The similarity between the biochemical incorporation of isomeric doxyl stearic acids into lipids of biological membranes and that of cis-parinaric acid into sn-3-phosphatidic acid described in this communication are discussed in relation to the possible use of these probes in studies of intact biological membranes.
Topics: Animals; Fatty Acids, Unsaturated; Guinea Pigs; Microsomes, Liver; Phosphatidic Acids; Spectrum Analysis
PubMed: 4034509
DOI: 10.1080/00327488508062432 -
Neurosurgery Sep 1995The cytotoxic effects of cis-parinaric acid, a plant-derived 18-carbon polyunsaturated fatty acid, were assessed in vitro on normal and neoplastic glia. After being...
The cytotoxic effects of cis-parinaric acid, a plant-derived 18-carbon polyunsaturated fatty acid, were assessed in vitro on normal and neoplastic glia. After being incubated for 24 hours in the presence of 12 mumol/L cis-parinaric acid, 36B10 glioma cultures demonstrated nearly 90% toxicity (unpaired Student's t test, P < 0.001). Similar results were obtained after the exposure of C6 rat glioma cultures, A172 human glioma cultures, and U-937 human monocytic leukemia cultures to cis-parinaric acid. In contrast, fetal rat astrocytes incubated with 12 mumol/L cis-parinaric acid demonstrated no significant toxicity (3% reduction, P = 0.12); fetal rat astrocytes showed only 20% toxicity after exposure to 40 mumol/L cis-parinaric acid (P = 0.001). The cytotoxic effects of cis-parinaric acid were antagonized with the addition of equimolar concentrations of alpha-tocopherol. Enzyme immunoassay of treated 36B10 glioma supernatant fluid for 8-isoprostane (a known oxidative metabolite) demonstrated a 10-fold increase of 8-isoprostane over 24 hours (123.0 +/- 10.3 versus 10.0 +/- 0.7 pg/ml for control, P < 0.001). These studies indicate that cis-parinaric acid may be significantly cytotoxic to malignant glioma cells in concentrations that spare normal astrocytes and that the mechanism of cytotoxicity is related to an oxidative process. The selective cytotoxic effect of cis-parinaric acid we describe represents the first step in the development of new chemotherapeutic agents for gliomas; these new agents act by preferentially enhancing lipid peroxidation in neoplastic cells.
Topics: Animals; Antineoplastic Agents; Arachidonic Acids; Astrocytes; Brain Neoplasms; Cell Line; Cell Survival; Dinoprost; Dose-Response Relationship, Drug; F2-Isoprostanes; Fatty Acids, Unsaturated; Glioma; Humans; Lipid Peroxidation; Rats; Tumor Cells, Cultured
PubMed: 7501114
DOI: 10.1227/00006123-199509000-00017 -
Biochimica Et Biophysica Acta Nov 1987The effect of the fluorophore trans-parinaric acid on the structure of lipid bilayer was studied and compared with the effect of other 'perturbants'. These include... (Comparative Study)
Comparative Study
The effect of the fluorophore trans-parinaric acid on the structure of lipid bilayer was studied and compared with the effect of other 'perturbants'. These include commonly used fluorophores (diphenylhexatriene, heptadecylhydroxycoumarin, cis-parinaric acid and two fatty acids, palmitic and oleic acids). Differential scanning calorimetry (DSC) and proton nuclear magnetic resonance techniques were used to evaluate structural changes in the lipid bilayers. The thermodynamic parameters of dipalmitoylphosphatidylcholine multilamellar vesicles obtained from the DSC thermograms suggest that trans-parinaric acid differs from the other 'perturbants'. trans-Parinaric acid has the most pronounced impact on the Tm, the width (delta T1/2) and the index of asymmetry of the main gel to liquid crystalline phase transition without any effect on its transition, delta H. The presence of trans-parinaric acid in the lipid bilayer of dimyristoylphosphatidylcholine small unilamellar vesicles influences the chemical shift difference between the choline protons of phosphatidylcholine molecules present in the two leaflets of the vesicle bilayer (delta delta H). This suggests that trans-parinaric acid affects the head group packing in the bilayer. Its main effect is abolishing the major alterations in head group packing that occur through the phase transition. The above data indicate that trans-parinaric acid is concentrated in the gel phase domains, whereby it stabilizes the phase separation between the gel and liquid crystalline phases, probably by affecting lipid molecules present in the boundary regions between these two domain types.
Topics: 1,2-Dipalmitoylphosphatidylcholine; Calorimetry, Differential Scanning; Dimyristoylphosphatidylcholine; Diphenylhexatriene; Fatty Acids, Unsaturated; Fluorescent Dyes; Lipid Bilayers; Liposomes; Magnetic Resonance Spectroscopy; Oleic Acid; Oleic Acids; Palmitic Acid; Palmitic Acids; Phosphatidylcholines; Thermodynamics; Umbelliferones
PubMed: 3663661
DOI: 10.1016/0005-2736(87)90092-7 -
Chemistry and Physics of Lipids Sep 2004A simple and reliable method for synthesizing four isomers of parinaric acid from alpha-linolenic acid (ALA) in high yields is described. The methylene-interrupted, cis...
A simple and reliable method for synthesizing four isomers of parinaric acid from alpha-linolenic acid (ALA) in high yields is described. The methylene-interrupted, cis triene system (1,4,7-octatriene) of ALA and common to other naturally occurring polyunsaturated fatty acids was transformed to a conjugated tetraene system (1,3,5,7-octatetraene). The synthesis involves bromination of ALA using 0.l M Br(2) in a saturated solution of NaBr in methanol, esterification of the fatty acid dibromides, double dehydrobromination by 1,8-diazabicyclo[5.4.0]undec-7-ene and saponification of the conjugated esters to a mixture of free conjugated acids. Addition of one molecule of bromine to the 12,13-double bond of ALA and subsequent dehydrobromination produces alpha-parinaric acid (9Z,11E,13E,15Z-octadecatetraenoic acid); addition of Br(2) to the 9,10-double bond or 15,16-double bond and then dehydrobromination and rearrangement yields 9E,11E,13E,15Z-octadecatetraenoic or 9E,11E,13E,15Z-octadecatetraenoic acids, respectively. The mixture of parinaric acid isomers is obtained in 65% yield, and the isomers can be purified by preparative HPLC; alternatively, the isomers can be converted by base catalyzed cis-trans isomerization (or by treatment with I(2)) to exclusively beta-parinaric acid (9E,11E,13E,15E-octadecatetraenoic acid). The various parinaric acid isomers were characterized by (1)H NMR, (13)C NMR, UV, GLC, HPLC and mass spectrometry.
Topics: Fatty Acids; Fatty Acids, Unsaturated; Isomerism; alpha-Linolenic Acid
PubMed: 15351273
DOI: 10.1016/j.chemphyslip.2004.06.001