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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...
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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
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The online version contains supplementary material available at 10.1007/s12298-022-01194-4.
PubMed: 35722517
DOI: 10.1007/s12298-022-01194-4 -
Methods in Molecular Biology (Clifton,... 2023Glycosphingolipids (GSLs) in the mammalian plasma membrane are essential for various biological events as they form glycolipid-rich membrane domains, such as lipid...
Glycosphingolipids (GSLs) in the mammalian plasma membrane are essential for various biological events as they form glycolipid-rich membrane domains, such as lipid rafts. GSLs consist of a certain oligosaccharide head group and a ceramide tail with various lengths of acyl chains. The structure of the head group as well as the carbon number and degree of the unsaturation of the acyl chain are known to regulate the membrane distributions and interleaflet couplings of GSLs by altering physicochemical properties, such as dynamics, interactions, and cluster sizes. This chapter provides the detailed use of time-resolved fluorescence measurement for investigating the membrane properties of lactosylceramide (LacCer)-enriched domains in bilayer membranes. LacCer belongs to the neutral GSLs and is believed in forming a highly ordered phase in model membranes and biological membranes, while the details of the domain remain unclear. Here, we suggest using trans-parinaric acid (tPA) and tPA-LacCer fluorescent probes to reveal the dynamics and size of the GSL domains since they prefer to be distributed in the GSL-rich ordered phase. The fluorescence lifetime in the nanosecond timescale reveals the difference in the surrounding membrane environments, which relates to hydrocarbon chain ordering, membrane hydration, and submicrometer domain size. The fluorescence lifetime of these probes can thus provide important information on submicron- to nano-scale small GSL domains not only in model membranes but also in biological membranes.
Topics: Animals; Liposomes; Glycolipids; Molecular Dynamics Simulation; Glycosphingolipids; Cell Membrane; Lactosylceramides; Mammals
PubMed: 36587084
DOI: 10.1007/978-1-0716-2910-9_19 -
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 -
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 -
Turkish Journal of Chemistry 2022In the present work, triacylglycerol and fatty acid compositions of . and . seed oils were determined using reverse phase high performance liquid chromatography with...
In the present work, triacylglycerol and fatty acid compositions of . and . seed oils were determined using reverse phase high performance liquid chromatography with both refractive index and spectrophotometric detections. The presence of conjugated octadecatetraenoic moieties was confirmed by UV and IR spectroscopy. Triacylglycerol (TAG) compositions were performed using an incremental approach and confirmed by the results of MS and electronic spectra. The quantitative analysis of TAG was achieved by careful calibration, introducing correction factors for the sensitivity of each compound. The results showed that both seed oils contain the same 23 TAGs. The mole fraction of 15 TAGs containing conjugated moieties was more significant than 88% (for .) and 81% (for .). Seed oils of and contain 43.44% and 36.12% mole of conjugated octadecatetraenoic fatty acids, respectively. These conjugated fatty acids were determined to be α-parinaric (C18:4) and β-parinaric (C18:4), in which isomer β-parinaric represents 23.21% and 26.27% of conjugated octadecatetraenoic acids for and seed oils, respectively. In addition, the mole fraction of -linolenic acid in both seed oils was also abundant at 24.5% and 28.2% for and . Therefore, .and seed oils are potential sources of polyunsaturated fatty acids, especially conjugated octadecatetraenoic acids.
PubMed: 37538780
DOI: 10.55730/1300-0527.3440 -
Biophysical Journal Apr 2022Lactosylceramide (LacCer) in the plasma membranes of immune cells is an important lipid for signaling in innate immunity through the formation of LacCer-rich domains...
Lactosylceramide (LacCer) in the plasma membranes of immune cells is an important lipid for signaling in innate immunity through the formation of LacCer-rich domains together with cholesterol (Cho). However, the properties of the LacCer domains formed in multicomponent membranes remain unclear. In this study, we examined the properties of the LacCer domains formed in Cho-containing 1-palmitoyl-2-oleoyl phosphatidylcholine (POPC) membranes by deuterium solid-state NMR and fluorescence lifetimes. The potent affinity of LacCer-LacCer (homophilic interaction) is known to induce a thermally stable gel phase in the unitary LacCer bilayer. In LacCer/Cho binary membranes, Cho gradually destabilized the LacCer gel phase to form the liquid-ordered phase by its potent order effect. In the LacCer/POPC binary systems without Cho, the H NMR spectra of 10',10'-d-LacCer and 18',18',18'-d-LacCer probes revealed that LacCer was poorly miscible with POPC in the membranes and formed stable gel phases without being distributed in the liquid crystalline domain. The lamellar structure of the LacCer/POPC membrane was gradually disrupted at around 60°C, whereas the addition of Cho increased the thermal stability of the lamellarity. Furthermore, the area of the LacCer gel phase and its chain order were decreased in the LacCer/POPC/Cho ternary membranes, whereas the liquid-ordered domain, which was observed in the LacCer/Cho binary membrane, was not observed. Cho surrounding the LacCer gel domain liberated LacCer and facilitated forming the submicron to nano-scale small domains in the liquid crystalline domain of the LacCer/POPC/Cho membranes, as revealed by the fluorescence lifetimes of trans-parinaric acid and trans-parinaric acid-LacCer. Our findings on the membrane properties of the LacCer domains, particularly in the presence of Cho, would help elucidate the properties of the LacCer domains in biological membranes.
Topics: Antigens, CD; Cholesterol; Lactosylceramides; Lipid Bilayers; Phosphatidylcholines; Phospholipids
PubMed: 35218738
DOI: 10.1016/j.bpj.2022.02.037 -
Plant Physiology and Biochemistry : PPB Apr 2023This pilot study aimed at comparing zinc (Zn) and nickel (Ni) effects on the fatty acid (FA) profiles, oxidative stress and desaturase activity in the Zn...
This pilot study aimed at comparing zinc (Zn) and nickel (Ni) effects on the fatty acid (FA) profiles, oxidative stress and desaturase activity in the Zn hyperaccumulator Arabidopsis halleri and the excluder Arabidopsis lyrata to allow a better picture of the physiological mechanisms which may contribute to metal tolerance or acclimation. The most significant changes in the FA composition were observed in the shoots of the hyperaccumulator and in the roots of the excluder, and were not only metal-dependent, but also species-specific, since the most significant changes in the shoots of A. halleri were observed under Ni treatment, though Ni, in contrast to Zn, was accumulated mainly in its roots. Several FAs appeared in the roots and shoots of A. lyrata only upon metal exposure, whereas they were already found in control A. halleri. In both species, there was an increase in oleic acid under Ni treatment in both organs, whereas in Zn-treated plants the increase was shown only for the shoots. A rare conjugated α-parinaric acid was identified only in the shoots of metal-treated A. halleri. In the shoots of the hyperaccumulator, there was an increase in the content of saturated FAs and a decrease in the content of unsaturated FAs, while in the roots of the excluder, the opposite pattern was observed. These metal-induced changes in FA composition in the shoots of A. halleri can lead to a decrease in the fluidity of membranes, which could diminish the penetration of ROS into the membrane and thus maintain its stability.
Topics: Arabidopsis; Zinc; Nickel; Fatty Acids; Pilot Projects; Metals; Cadmium
PubMed: 36958152
DOI: 10.1016/j.plaphy.2023.107640 -
Langmuir : the ACS Journal of Surfaces... Sep 2019Lateral segregation of lipids in model and biological membranes has been studied intensively in the last decades using a comprehensive set of experimental techniques....
Lateral segregation of lipids in model and biological membranes has been studied intensively in the last decades using a comprehensive set of experimental techniques. Most methods require a probe to report on the biophysical properties of a specific molecule in the lipid bilayer. Because such probes can adversely affect the results of the measurement and perturb the local membrane structure and dynamics, a detailed understanding of probe behavior and its influence on the properties of its direct environment is important. Membrane phase-selective and lipid-mimicking molecules represent common types of probes. Here, we have studied how the fluorescent probes -parinaric acid (tPA), diphenylhexatriene (DPH), and 1-oleoyl-2-propionyl[DPH]--glycero-3-phosphocholine (O-DPH-PC) affect the membrane properties of 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine (POPC) bilayers using H and P NMR spectroscopy in the solid state. In addition, using 2D H magic-angle spinning (MAS) nuclear Overhauser enhancement spectroscopy (NOESY) NMR, we have determined the distribution of the probe moieties in the POPC membrane parallel to the membrane normal. We found that the different probes exhibit distinct membrane localizations and distributions, . tPA is located parallel to the membrane normal while DPH predominantly exist in two orientations. Further, tPA was conjugated to sphingomyelin (tPA-SM) as a substitute for the acyl chain in the SM. H NOESY NMR was used to probe the interaction of the tPA-SM with cholesterol as dominant in liquid ordered membrane domains in comparison to POPC-cholesterol interaction in membranes composed of ternary lipid mixtures. We could show that tPA-SM exhibited a strong favorable and very temperature-dependent interaction with cholesterol in comparison to POPC. In conclusion, the NMR techniques can explain probe behavior but also be used to measure lipid-specific affinities between different lipid segments and individual molecules in complex bilayers, relevant to understanding nanodomain formation in biological membranes.
PubMed: 31424941
DOI: 10.1021/acs.langmuir.9b01202 -
Biophysical Journal Nov 2019Lateral segregation and the formation of lateral domains are well-known phenomena in ternary lipid bilayers composed of an unsaturated (low gel-to-liquid phase...
Lateral segregation and the formation of lateral domains are well-known phenomena in ternary lipid bilayers composed of an unsaturated (low gel-to-liquid phase transition temperature (T)) phospholipid, a saturated (high-T) phospholipid, and cholesterol. The formation of lateral domains has been shown to be influenced by differences in phospholipid acyl chain unsaturation and length. Recently, we also showed that differential interactions of cholesterol with low- and high-T phospholipids in the bilayer can facilitate phospholipid segregation. Now, we have investigated phospholipid-cholesterol interactions and their role in lateral segregation in ternary bilayers composed of different unsaturated phosphatidylcholines (PCs) with varying acyl chain lengths, N-palmitoyl-D-erythro-sphingomyelin (PSM), and cholesterol. Using deuterium NMR spectroscopy, we determined how PSM was influenced by the acyl chain composition in surrounding PC environments and correlated this with the affinity of cholestatrienol (a fluorescent cholesterol analog) for PSM in the different PC environments. Results from a combination of time-resolved fluorescence measurements of trans-parinaric acid and Förster resonance energy transfer experiments showed that the relative affinity of cholesterol for phospholipids determined the degree to which the sterol promoted domain formation. From Förster resonance energy transfer, deuterium NMR, and differential scanning calorimetry results, it was clear that cholesterol also influenced both the thermostability of the domains and the degree of order in and outside the PSM-rich domains. The results of this study have shown that the affinity of cholesterol for both low-T and high-T phospholipids and the effects of low- and high-T phospholipids on each other influence both lateral structure and domain properties in complex bilayers. We envision that similar effects also contribute to lateral heterogeneity in even more complex biological membranes.
Topics: Cholesterol; Deuterium; Fluorescence Resonance Energy Transfer; Lipid Bilayers; Magnetic Resonance Spectroscopy; Solubility; Sphingomyelins; Temperature; Unilamellar Liposomes
PubMed: 31610877
DOI: 10.1016/j.bpj.2019.09.025 -
Biophysical Journal Jul 2019Ceramide-1-phosphate is a minor sphingolipid with important functions in cell signaling. In this study, we examined the propensity of palmitoyl ceramide-1-phosphate...
Ceramide-1-phosphate is a minor sphingolipid with important functions in cell signaling. In this study, we examined the propensity of palmitoyl ceramide-1-phosphate (Cer-1P) to segregate laterally into ordered domains in different bilayer compositions at 23 and 37°C and compared this with segregation of palmitoyl ceramide (PCer) and palmitoyl sphingomyelin (PSM). The ordered-domain formation in the fluid phosphatidylcholine bilayers was determined using the emission lifetime changes of trans-parinaric acid and from differential scanning calorimetry thermograms. The lateral segregation of Cer-1P was examined when hydrated to bilayers in Tris buffer (50 mM Tris, 140 mM NaCl (pH 7.4)). At this pH, Cer-1P was negatively charged. The lateral segregation propensity of Cer-1P in 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) bilayers was intermediate between PCer and PSM. Based on differential scanning calorimetry analysis, we observed that the gel domains formed by Cer-1P in POPC bilayers (POPC:Cer-1P 70:30 by mol) were less stable (melting interval 16-37°C) than the corresponding POPC and PCer gel domains at equal composition (melting interval 20-55°C). The gel-phase melting enthalpy was also much lower in Cer-1P (1.5 kcal/mol) than in the PCer-containing POPC bilayers (9 kcal/mol). Cer-1P appeared to be at least partially miscible with PCer domains in POPC bilayers. Cer-1P domains were stabilized in the presence of PSM (POPC:PSM 85:15), similarly as seen with PCer-rich domains. In bilayers at 37°C, with an approximate outer-leaflet cell membrane composition (sphingomyelin and cholesterol enriched, aminophospholipid poor), Cer-1P segregation did not lead to the formation of ordered domains, at least when compared with PCer segregation. In bilayers with an approximate inner-leaflet composition (sphingomyelin poor, cholesterol and aminophospholipid enriched), Cer-1P also failed to form ordered domains. PCer segregated into ordered domains only after the PCer/cholesterol ratio exceeded an approximate equimolar ratio.
Topics: Ceramides; Cholesterol; Lipid Bilayers; Liposomes; Phosphatidylcholines; Thermodynamics
PubMed: 31133285
DOI: 10.1016/j.bpj.2019.05.015