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Analytical Chemistry May 2021Cerebrosides (n-HexCer) and glycosphingosines (n-HexSph) constitute two sphingolipid subclasses. Both are comprised of a monosaccharide headgroup (glucose or galactose...
Cerebrosides (n-HexCer) and glycosphingosines (n-HexSph) constitute two sphingolipid subclasses. Both are comprised of a monosaccharide headgroup (glucose or galactose in mammalian cells) linked via either an α- or β-glycosidic linkage to the sphingoid backbone (n = α or β, depending upon the nature of the linkage to the anomeric carbon of the sugar). Cerebrosides have an additional amide-bonded fatty acyl chain linked to the sphingoid backbone. While differentiating the multiple isomers (i.e. glucose vs galactose, α- vs β-linkage) is difficult, it is crucial for understanding their specific biological roles in health and disease states. Shotgun tandem mass spectrometry has been a powerful tool in both lipidomics and glycomics analysis but is often limited in its ability to distinguish isomeric species. This work describes a new strategy combining shotgun tandem mass spectrometry with gas-phase ion chemistry to achieve both differentiation and quantification of isomeric cerebrosides and glycosphingosines. Briefly, deprotonated cerebrosides, [n-HexCer-H], or glycosphingosines, [n-HexSph-H], are reacted with terpyridine (Terpy) magnesium complex dications, [Mg(Terpy)], in the gas phase to produce a charge-inverted complex cation, [n-HexCer-H+MgTerpy] or [n-HexSph-H+MgTerpy]. The collision-induced dissociation (CID) of the charge-inverted complex cations leads to significant spectral differences between the two groups of isomers, α-GalCer, β-GlcCer, and β-GalCer for cerebrosides and α-GlcSph, α-GalSph, β-GlcSph, and β-GalSph for glycosphingosines, which allows for isomer distinction. Moreover, we describe a quantification strategy with the normalized percent area extracted from selected diagnostic ions that quantify either three isomeric cerebroside or four isomeric glycosphingosine mixtures. The analytical performance was also evaluated in terms of accuracy, repeatability, and interday precision. Furthermore, CID of the product ions resulting from 443 Da loss from the charge-inverted complex cations ([n-HexCer-H+MgTerpy]) has been performed and demonstrated for localization of the double-bond position on the amide-bonded monounsaturated fatty acyl chain in the cerebroside structure. The proposed strategy was successfully applied to the analysis of total cerebroside extracts from the porcine brain, providing in-depth structural information on cerebrosides from a biological mixture.
Topics: Animals; Cerebrosides; Glucosylceramides; Isomerism; Lipidomics; Swine; Tandem Mass Spectrometry
PubMed: 33957046
DOI: 10.1021/acs.analchem.1c01021 -
Marine Drugs Oct 2022Three new ceramides (1−3) and three new cerebrosides (4, 8, and 9), along with three previously known cerebrosides (ophidiocerebrosides C (5), D (6), and CE-3-2 (7)),...
Three new ceramides (1−3) and three new cerebrosides (4, 8, and 9), along with three previously known cerebrosides (ophidiocerebrosides C (5), D (6), and CE-3-2 (7)), were isolated from a deep-sea starfish species, the orange cookie starfish Ceramaster patagonicus. The structures of 1−4, 8, and 9 were determined by the NMR and ESIMS techniques and also through chemical transformations. Ceramides 1−3 contain iso-C21 or C23 Δ9-phytosphingosine as a long-chain base and have C16 or C17 (2R)-2-hydroxy-fatty acids of the normal type. Cerebroside 4 contains C22 Δ9-sphingosine anteiso-type as a long-chain base and (2R)-2-hydroxyheptadecanoic acid of the normal type, while compounds 8 and 9 contain saturated C-17 phytosphingosine anteiso-type as a long-chain base and differ from each other in the length of the polymethylene chain of (2R)-2-hydroxy-fatty acids of the normal type: C23 in 8 and C24 in 9. All the new cerebrosides (4, 8, and 9) have β-D-glucopyranose as a monosaccharide residue. The composition of neutral sphingolipids from C. patagonicus was described for the first time. The investigated compounds 1−3, 5−7, and 9 exhibit slight to moderate cytotoxic activity against human cancer cells (HT-29, SK-MEL-28, and MDA-MB-231) and normal embryonic kidney cells HEK293. Compounds 2, 5, and 6 at a concentration of 20 µM inhibit colony formation of MDA-MB-231 cells by 68%, 54%, and 68%, respectively. The colony-inhibiting activity of compounds 2, 5, and 6 is comparable to the effect of doxorubicin, which reduces the number of colonies by 70% at the same concentration.
Topics: Animals; Humans; Cerebrosides; Ceramides; Sphingosine; Starfish; HEK293 Cells; Sphingolipids; Fatty Acids; Monosaccharides; Doxorubicin
PubMed: 36286464
DOI: 10.3390/md20100641 -
Marine Drugs Jun 2021Sphingolipids are complex lipids widespread in nature as structural components of biomembranes. Commonly, the sphingolipids of marine organisms differ from those of... (Review)
Review
Sphingolipids are complex lipids widespread in nature as structural components of biomembranes. Commonly, the sphingolipids of marine organisms differ from those of terrestrial animals and plants. The gangliosides are the most complex sphingolipids characteristic of vertebrates that have been found in only the Echinodermata (echinoderms) phylum of invertebrates. Sphingolipids of the representatives of the Asteroidea and Holothuroidea classes are the most studied among all echinoderms. In this review, we have summarized the data on sphingolipids of these two classes of marine invertebrates over the past two decades. Recently established structures, properties, and peculiarities of biogenesis of ceramides, cerebrosides, and gangliosides from starfishes and holothurians are discussed. The purpose of this review is to provide the most complete information on the chemical structures, structural features, and biological activities of sphingolipids of the Asteroidea and Holothuroidea classes.
Topics: Animals; Aquatic Organisms; Ceramides; Cerebrosides; Echinodermata; Gangliosides; Molecular Structure; Sea Cucumbers; Sphingolipids; Starfish
PubMed: 34200995
DOI: 10.3390/md19060330 -
Oxidative Medicine and Cellular... 2022Linn. ( L.) has recently gained attention as a functional food due to the chemical composition of this plant regarding bioactive compounds. The special attention to the... (Review)
Review
Linn. ( L.) has recently gained attention as a functional food due to the chemical composition of this plant regarding bioactive compounds. The special attention to the use of as an ingredient in functional food products is also due to the promotion of sustainable food. It is an unconventional food plant, and its consumption may contribute to preserving biodiversity due to its cultivation in a polyculture system. Food sovereignty may be achieved, among other strategies, with the consumption of unconventional food plants that are more resistant in nature and easily cultivated in small places. grows spontaneously and may be found in streets and sidewalks, or it may be cultivated with seeds and cuttings propagation. The culinary versatility of opens up opportunities to explore the development of sustainable, functional food products. This mini-review shows that functional food products developed from are already available at the research level, but it is expected that more scientific literature focusing on the development of functional products with proven anticancer activities may be released in the near future. Polysaccharides, some phenolic compounds, alkaloids, and cerebrosides are associated with the inhibition and prevention of carcinogenesis through and investigations. The anticancer activities of , its bioactive compounds, and the involved molecular mechanisms have been reported in the literature. The importance of further elucidating the cancer inhibition mechanisms is in the interest of forthcoming applications in the development of food products with anticancer properties for implementation in the human diet.
Topics: Alkaloids; Cerebrosides; Functional Food; Humans; Plant Extracts; Portulaca
PubMed: 36193066
DOI: 10.1155/2022/7235412 -
Molecules (Basel, Switzerland) Mar 2020The detailed chemical analysis of the methanol extract of (Pers.) P. Karst. led to the isolation of two new cerebrosides, mericeramides A () and B () together with...
The detailed chemical analysis of the methanol extract of (Pers.) P. Karst. led to the isolation of two new cerebrosides, mericeramides A () and B () together with cerebroside B (), ergosterol (), 3β-hydroxyergosta-7,22-diene (), cerevisterol (), 3β-hydroxyergosta-6,8(14),22-triene (), 3β--glucopyranosyl-5,8-epidioxyergosta-6,22-diene () and (11,13)-9,10-dihydroxy-11,13-octadecadienoic acid (). The structures of the compounds were determined on the basis of NMR and MS spectroscopic analysis. Mericeramide A () is the first representative of halogenated natural cerebrosides. The isolated fungal metabolites - were evaluated for their antioxidant activity using the oxygen radical absorbance capacity (ORAC) assay. Compounds and proved to possess considerable antioxidant effects, with 2.50 ± 0.29, 4.94 ± 0.37 and 4.27 ± 0.05 mmol TE/g values, respectively. The result obtained gives a notable addition to the chemical and bioactivity profile of , highlighting the possible contribution of this species to a versatile and balanced diet.
Topics: Agaricales; Antioxidants; Cerebrosides; Chromatography, High Pressure Liquid; Magnetic Resonance Spectroscopy; Molecular Structure; Oxygen Radical Absorbance Capacity; Steroids
PubMed: 32204362
DOI: 10.3390/molecules25061395 -
Journal of Lipid Research Jul 1966The fatty acid composition of cerebrosides and sulfatides from frontal lobe gray and white matter was determined for five fresh and four formalinized adult brains and...
The fatty acid composition of cerebrosides and sulfatides from frontal lobe gray and white matter was determined for five fresh and four formalinized adult brains and for eight infants. Fatty acid patterns were unaffected by formalinization, but varied considerably from one another in the proportion of saturated to unsaturated fatty acids. The percentages of 24:0 and 24:1 increased with age. Cerebrosides obtained from areas such as the brainstem and cerebellum, where myelination was more advanced, tended to have a larger proportion of long-chain fatty acids than samples extracted from frontal or parietal lobe white matter. Hydroxy fatty acids showed an adult pattern in all instances in which amounts sufficient for accurate quantification could be isolated. Lipid hexose, cerebroside + sulfatide hexose, and methanoleluted hexose were measured in the brains of 12 infants ranging in age from a 4 month fetus to 2 yr. In the most immature, the majority of lipid hexose was in the form of glycolipids more polar than cerebrosides and sulfatides. These have tentatively been identified as hematosides and globosides. With maturation, cerebrosides and sulfatides increased progressively, but the amounts of the more polar glycolipids remained constant in relation to the total lipid content of tissue.
Topics: Adult; Aged; Brain Chemistry; Cerebrosides; Child, Preschool; Chromatography; Fatty Acids; Fetus; Glycolipids; Hexoses; Humans; Infant; Infant, Newborn; Middle Aged; Myelin Sheath
PubMed: 5965291
DOI: No ID Found -
The Biochemical Journal Nov 1976The synthesis and turnover of cerebrosides and phospholipids was followed in microsomal and myelin fractions of developing and adult rat brains after an intracerebral... (Comparative Study)
Comparative Study
The synthesis and turnover of cerebrosides and phospholipids was followed in microsomal and myelin fractions of developing and adult rat brains after an intracerebral injection of [U-14C]serine. The kinetics of incorporation of radioactivity into microsomal and myelin cerebrosides indicate the possibility of a precursor-product relationship between cerebrosides of these membranes. The specific radioactivity of myelin cerebrosides was corrected for the deposition of newly formed cerebrosides in myelin. Multiphasic curves were obtained for the decline in specific radioactivity of myelin and microsomal cerebrosides, suggesting different cerebroside pools in these membranes. The half-life of the fast turning-over pool of cerebrosides of myelin was 7 and 22 days for the developing and adult rat brain respectively. The half-life of the slowly turning-over pool of myelin cerebrosides was about 145 days for both groups of animals. The half-life of the rapidly turning-over microsomal cerebrosides was calculated to be 20 and 40 h for the developing and adult animals respectively. The half-life of the intermediate and slowly turning-over microsomal cerebrosides was 11 and 60 days respectively, for both groups of animals. The amount of incorporation of radioactivity into microsomal cerebrosides from L-serine was greatly decreased in the adult animals, and greater amounts of the precursor were directed towards the synthesis of phosphatidylserine. In the developing animals, considerable amounts of cerebrosides were synthesized from L-serine, besides phosphatidylserine. The time-course of incorporation indicated that a precursor-product relationship exists between microsomal and myelin phosphatidylserine. The half-life of microsomal phosphatidylserine was calculated to be about 8 h for the fast turning-over pool in both groups of animals.
Topics: Animals; Brain; Cerebrosides; Female; Half-Life; Male; Microsomes; Myelin Sheath; Phosphatidylserines; Phospholipids; Rats; Serine; Sulfoglycosphingolipids; Time Factors
PubMed: 1008849
DOI: 10.1042/bj1600195 -
Journal of Lipid Research Jan 2019Cerebrosides, including glucosylceramides (GlcCers) and galactosylceramides (GalCers), are important membrane components of animal cells with deficiencies resulting in...
Cerebrosides, including glucosylceramides (GlcCers) and galactosylceramides (GalCers), are important membrane components of animal cells with deficiencies resulting in devastating lysosomal storage disorders. Their quantification is essential for disease diagnosis and a better understanding of disease mechanisms. The simultaneous quantification of GlcCer and GalCer isomers is, however, particularly challenging due to their virtually identical structures. To address this challenge, we developed a new LC/MS-based method using differential ion mobility spectrometry (DMS) capable of rapidly and reproducibly separating and quantifying isomeric cerebrosides in a single run. We show that this LC/ESI/DMS/MS/MS method exhibits robust quantitative performance within an analyte concentration range of 2.8-355 nM. We further report the simultaneous quantification of nine GlcCers (16:0, 18:0, 20:0, 22:0, 23:0, 24:1, 24:0, 25:0, and 26:0) and five GalCers (16:0, 22:0, 23:0, 24:1, and 24:0) molecular species in human plasma, as well as six GalCers (18:0, 22:0, 23:0, 24:1, 24:0 and 25:0) and two GlcCers (24:1 and 24:0) in human cerebrospinal fluid. Our method expands the potential of DMS technology in the field of glycosphingolipid analysis for both biomarker discovery and drug screening by enabling the unambiguous assignment and quantification of cerebroside lipid species in biological samples.
Topics: Cerebrosides; Chromatography, Liquid; Female; Humans; Ion Mobility Spectrometry; Isomerism; Middle Aged; Reference Standards; Spectrometry, Mass, Electrospray Ionization; Tandem Mass Spectrometry; Time Factors
PubMed: 30413651
DOI: 10.1194/jlr.D089797 -
The Journal of Biological Chemistry Dec 1955
Topics: Cerebrosides
PubMed: 13271440
DOI: No ID Found -
Journal of Oleo Science Feb 2021Sphingolipids, including ceramide (Cer) and glucosylceramide (GlcCer), have the characteristic structural units called sphingoid bases, and are constituents of cell and...
Sphingolipids, including ceramide (Cer) and glucosylceramide (GlcCer), have the characteristic structural units called sphingoid bases, and are constituents of cell and vacuole membranes. Plant sphingolipids bear highly diverse base structures and the base composition differs depending on the plant species. It is thought that the composition of sphingolipid classes and sphingoid bases is related to membrane fractions. However, there is little information about differences in sphingolipids among plant cultivars and the changes occurring in sphingolipids during food processing. This study investigated sphingolipids in sake rice (saka-mai) cultivars grown for sake (rice wine), and the changes in sphingolipids during polishing and brewing. In six brown rice samples, there were no large differences of the base composition among Cer or GlcCer of cultivars, whereas there were differences in their sphingolipid contents. When compared to brown rice, highly polished rice contained lower levels of sphingolipids, especially Cer. For three rice brans from different polishing steps, the Cer content was higher in the outer bran than in the inner bran. Sake and sake lees (sake-kasu) were produced by three different starter cultures (shubo preparations: the mixture of koji rice as an enzyme cocktail containing amylases, sake yeast, and adding rice as a carbohydrate source). The Cer/GlcCer ratio in sake and sake lees depended on the starter culture; Cer and GlcCer in sake lees possessed a fungi-specific base, 9-methyl-trans-4,trans-8- sphingadienine. In addition, sake lees had a higher Cer/GlcCer ratio when compared to highly polished rice as a sake source. These results suggest that the sphingolipid content of brown rice differs depending on the rice cultivar; further, the sphingolipids and the sphingolipid composition in sake and sake lees are affected by fungal sphingolipids and self-digestion during brewing.
Topics: Ceramides; Ethanolamines; Fermentation; Food Handling; Glucosylceramides; Oryza; Sphingolipids; Wine
PubMed: 33456006
DOI: 10.5650/jos.ess20234