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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 -
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 -
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 -
Journal of Oleo Science Sep 2020In this study, seed oils of Thladiantha nudiflora and Thladiantha dubia were found to contain 55.5 and 44.4% mole of conjugated octadecatrienoic fatty acids,...
In this study, seed oils of Thladiantha nudiflora and Thladiantha dubia were found to contain 55.5 and 44.4% mole of conjugated octadecatrienoic fatty acids, respectively. The presence of moieties of conjugated fatty acids was confirmed by a series from physical methods: UV, IR, H and C NMR. The triacylglycerols (TAGs) isolated of the seed oils were studied by RP-HPLC with diode array and mass spectrometric detections. It was shown that all 15 TAGs of Thladiantha dubia contain moieties of conjugated fatty acids - punicic, (9Z,11E,13Z)-octadeca-9,11,13-trienoic acid (35.6% mole) and 8.9% mole α-eleostearic, (9Z,11E,13E)-octadeca-9,11,13-trienoic acid. Meanwhile, 24 TAGs of Thladiantha nudiflora seed oil contain both acids in approximately equal proportions (27.4:28.2 % mole). The enrichment for polyunsaturated fatty acids of the hydrolysis product of the seed oils due to urea inclusion complex formation was discussed.
Topics: Chromatography, High Pressure Liquid; Cucurbitaceae; Fatty Acids, Unsaturated; Magnetic Resonance Spectroscopy; Mass Spectrometry; Plant Oils; Seeds; Triglycerides
PubMed: 32788518
DOI: 10.5650/jos.ess20075 -
Biophysical Journal Sep 2020The segregation of lipids into lateral membrane domains has been extensively studied. It is well established that the structural differences between phospholipids play...
The segregation of lipids into lateral membrane domains has been extensively studied. It is well established that the structural differences between phospholipids play an important role in lateral membrane organization. When a high enough cholesterol concentration is present in the bilayer, liquid-ordered (L) domains, which are enriched in cholesterol and saturated phospholipids such as sphingomyelin (SM), may form. We have recently shown that such a formation of domains can be facilitated by the affinity differences of cholesterol for the saturated and unsaturated phospholipids present in the bilayer. In mammalian membranes, the saturated phospholipids are usually SMs with different acyl chains, the abundance of which vary with cell type. In this study, we investigated how the acyl chain structure of SMs affects the formation of SM- and cholesterol-enriched domains. From the analysis of trans-parinaric acid fluorescence emission lifetimes, we could determine that cholesterol facilitated lateral segregation most with the SMs that had 16 carbon-long acyl chains. Using differential scanning calorimetry and Förster resonance energy transfer techniques, we observed that the SM- and cholesterol-enriched domains with 16 carbon-long SMs were most thermally stabilized by cholesterol. The Förster resonance energy transfer technique also suggested that the same SMs also form the largest L domains. In agreement with our previously published data, the extent of influence that cholesterol had on the propensity of lateral segregation and the properties of L domains correlated with the relative affinity of cholesterol for the phospholipids present in the bilayers. Therefore, the specific SM species present in the membranes, together with unsaturated phospholipids and cholesterol, can be used by the cell to fine-tune the lateral structure of the membranes.
Topics: Calorimetry, Differential Scanning; Cholesterol; Lipid Bilayers; Phospholipids; Sphingomyelins
PubMed: 32755561
DOI: 10.1016/j.bpj.2020.07.014 -
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 -
Biophysical Journal Apr 2019Ceramide is an important intermediate in sphingolipid homeostasis. We examined how colipids, with negative intrinsic curvature and which may induce curvature stress in...
Ceramide is an important intermediate in sphingolipid homeostasis. We examined how colipids, with negative intrinsic curvature and which may induce curvature stress in the bilayers, affected the segregation of palmitoyl ceramide (PCer). Such colipids include 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE), 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE), and tetra-linoleoyl cardiolipin (CL). In 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) bilayers, PCer formed ordered, gel-like domains at concentrations above 10 mol% at 23°C, as evidenced by the change in the average lifetime of the trans-parinaric acid emission. When POPE or DOPE were included in the DOPC bilayer (at 20:80 or 40:60 POPE or DOPE to DOPC, by mol), the lateral segregation of PCer was facilitated in a concentration-dependent manner, and less PCer was required for the formation of the ordered ceramide-rich domains. Inclusion of CL in the DOPE bilayer (at 10:90 or 20:80 CL to PC, by mol) also caused a similar facilitation of the lateral segregation of PCer. The PCer-rich domains formed in the presence of POPE, DOPE, or CL in DOPC bilayers were slightly more thermostable (by 2-10°C) when compared to PCer-rich domains in DOPC-only bilayers. Nonlamellar phases were not present in bilayers in which the effects of POPE or DOPE on PCer segregation were the largest, as verified by P NMR. When palmitoyl sphingomyelin was added to the different bilayer compositions at 5 mol%, relative to the phospholipids, PCer segregated into gel domains at lower concentrations (2-3 mol% PCer), and the effect of POPE on PCer segregation was eliminated. We suggest that the effects of POPE, DOPE, and CL on PCer segregation was in part influenced by their effects on membrane curvature stress and in part because of unfavorable interactions with PCer due to their unsaturated acyl chains. These lipids are abundant in mitochondrial membranes and are likely to affect functional properties of saturated ceramides in them.
Topics: Ceramides; Lipid Bilayers; Phospholipids
PubMed: 30940348
DOI: 10.1016/j.bpj.2019.03.004 -
Biophysical Journal Jan 2019Cholesterol is an essential molecule in the membranes of mammalian cells. It is known to be distributed heterogeneously within the cells, between the bilayer leaflets,...
Cholesterol is an essential molecule in the membranes of mammalian cells. It is known to be distributed heterogeneously within the cells, between the bilayer leaflets, as well as between lateral domains within the bilayer. However, we do not know exactly how cholesterol is distributed and what forces drive this sorting process because it extremely difficult to study using currently available methods. To further elucidate this distribution, we measured how cholesterol partitions between different phospholipid (PL) environments using different methods based on cholesterol, TopFluor-cholesterol, and cholesta-5,7,9(11)-triene-3-β-ol. Based on the obtained relative partition coefficients, we made predictions regarding how cholesterol would be distributed between lateral domains and between the inner and outer leaflets of the plasma membrane. In addition, using a trans-parinaric acid fluorescence-based method, we tested how cholesterol could influence lateral segregation through its interaction with unsaturated PLs with different headgroups. The results showed that the lower the affinity of cholesterol was for the different unsaturated PLs, the more cholesterol stimulated lateral segregation in a ternary bilayer of unsaturated PL/N-palmitoyl-D-erythro-sphingomyelin and cholesterol. Overall, the results indicate that both the distribution of cholesterol between different lipid environments and the impact of cholesterol on lateral segregation can be predicted relatively accurately from determined relative partition coefficients.
Topics: Animals; Cell Membrane; Cholesterol; Cyclodextrins; Humans; Lipid Bilayers
PubMed: 30583790
DOI: 10.1016/j.bpj.2018.11.3135