Show legend Show as text

Structure type: oligomer
Trivial name: S-GalCer
Contained glycoepitopes: IEDB_136044,IEDB_136095,IEDB_137472,IEDB_141794,IEDB_190606,SB_1,SB_118,SB_139,SB_165,SB_166,SB_187,SB_195,SB_7,SB_82,SB_88

• Article ID: 4262
  Diaz-Valencia JD, Almaraz-Barrera MJ, Arias-Romero LE, Hernandez-Rivas R, Rojo-Dominguez A, Guillen N, Vargas M "The ABP-120 C-end region from Entamoeba histolytica interacts with sulfatide, a new lipid target" - Biochemical and Biophysical Research Communications 338(3) (2005) 1527-1536
  

  EhABP-120 is the first filamin identified in the parasitic protozoan Entamoeba histolytica. Filamins are a family of cross-linking actin-binding proteins that promote a dynamic orthogonal web. They have been reported to interact directly with more than 30 cellular proteins and some phosphoinositides. The biochemical consequences of these interactions may have either positive or negative effects on the cross-linking function and also form a link between the cytoskeleton and plasma membrane. In this study, the EhABP-120 carboxy-terminal domain (END) was biochemically characterized. This domain was able to associate to 3-sulfate galactosyl ceramide, a new lipid target for a member of the filamin family. Also, the END domain was able to dimerize 'in vitro.' Molecular modeling analysis showed that the dimeric region is stabilized by a disulfide bond. Electrostatic and docking studies suggest that an electropositive concave pocket at the dimeric END domain interacts simultaneously with several sulfogalactose moieties of the sulfatide.

  chemistry, genetics, metabolism, Non-U.S.Gov't, analysis, molecular, lipid, Molecular Sequence Data, molecular modeling, Substrate Specificity, glycolipid, Cell Membrane, proteins, protein structure, models, amino acid sequence, ceramide, Sequence Alignment, Animals, Research Support, Tertiary, ABP-120, Filamin, Entamoeba histolytica, Sulfatide, Dimer, Contractile Proteins, Cytoskeleton, Family, Microfilament Proteins, Sulfoglycosphingolipids, Transfection

  NCBI PubMed ID: 16274663
  Journal NLM ID: 0372516
  Publisher: Academic Press
  Institutions: Departamento de Biomedicina Molecular, Centro de Investigacion y de Estudios Avanzados del IPN, Mexico, DF, Mexico
  Methods: molecular modeling, 32P labeling, Confocal laser scanning microscopy
  
   
  
  Entamoeba histolytica
  CSDB ID 11423 (all data & tools)

Show legend Show as text

Structure type: oligomer ; 776 [M+Na]+
Contained glycoepitopes: IEDB_136044,IEDB_137472,IEDB_141794,IEDB_190606,SB_1,SB_165,SB_166,SB_187,SB_195,SB_7,SB_88

• Article ID: 6696
  Toledo MS, Levery SB, Straus AH, Suzuki E, Momany M, Glushka J, Moulton JM, Takahashi HK "Characterization of sphingolipids from mycopathogens: factors correlating with expression of 2-hydroxy fatty acyl (E)-Delta 3-unsaturation in cerebrosides of Paracoccidioides brasiliensis and Aspergillus fumigatus" - Biochemistry 38 (1999) 7294-7306
  

  Significant differences exist between mammals and fungi with respect to glycosphingolipid (GSL) structure and biosynthesis. Thus, these compounds, as well as the cellular machinery regulating their expression, have considerable potential as targets for the diagnosis and treatment of fungal diseases. In this study, the major neutral GSL components extracted from both yeast and mycelium forms of the thermally dimorphic mycopathogen Paracoccidioides brasiliensis were purified and characterized by 1H and 13C NMR spectroscopy, ESI-MS and ESI-MS/CID-MS, and GC-MS. The major GSLs of both forms were identified as beta-glucopyranosylceramides (GlcCer) having (4E, 8E)-9-methyl-4,8-sphingadienine as long chain base in combination with either N-2'-hydroxyoctadecanoate or N-2'-hydroxy-(E)-3'-octadecenoate. The mycelium form GlcCer had both fatty acids in a approximately 1:1 ratio, while that of the yeast form had on average only approximately 15% of the (E)-Delta 3-unsaturated fatty acid. Cerebrosides from two strains of Aspergillus fumigatus (237 and ATCC 9197) expressing both GalCer and GlcCer were also purified and characterized by similar methods. The GalCer fractions were found to have approximately 70% and approximately 90% N-2'-hydroxy-(E)-3'-octadecenoate, respectively, in the two strains. In contrast, the GlcCer fractions had N-2'-hydroxy-(E)-3'-octadecenoate at only approximately 20 and approximately 50%, respectively. The remainder in all cases was the saturated 2-OH fatty acid, which has not been previously reported in cerebrosides from A. fumigatus. The availability of detailed structures of both glycosylinositol phosphorylceramides [Levery, S. B., Toledo, M. S., Straus, A. H., and Takahashi, H. K. (1998) Biochemistry 37, 8764-8775] and cerebrosides from P. brasiliensis revealed parallel quantitative differences in expression between yeast and mycelium forms, as well as a striking general partitioning of ceramide structure between the two classes of GSLs. These results are discussed with respect to possible functional roles for fungal sphingolipids, particularly as they relate to the morphological transitions exhibited by P. brasiliensis.

  Publication DOI: 10.1021/bi982898z
  Journal NLM ID: 0370623
  Publisher: American Chemical Society
  Correspondence: leverysb@ccrc.uga.edu, takahashi.bioq@epm.br
  Institutions: Department of Biochemistry, Universidade Federal de São Paulo/Escola Paulista de Medicina, Rua Botucatu 862, 04023-900, São Paulo, SP, Brasil, Departments of Biochemistry and Molecular Biology and of Botany, and The Complex Carbohydrate Research Center, University of Georgia, 220 Riverbend Road, Athens, GA, USA
  Methods: 13C NMR, 1H NMR, GC-MS, ESI-MS, HPTLC, ion exchange chromatography, ESI-MS/CID-MS, silica gel chromatography, 2-D 1H-1H TOCSY, 13C-1H HSQC, 13C-1H HMBC
  
   
  
  Aspergillus fumigatus ATCC 9197, Aspergillus fumigatus strain 237
  CSDB ID 40560 (all data & tools)

Show legend Show as text

Structure type: monomer
Contained glycoepitopes: IEDB_136044,IEDB_137472,IEDB_141794,IEDB_190606,SB_1,SB_165,SB_166,SB_187,SB_195,SB_7,SB_88

• Article ID: 6751
  Toledo MS, Levery SB, Straus AH, Takahashi HK "Dimorphic expression of cerebrosides in the mycopathogen Sporothrix schenckii" - Journal of Lipid Research 41 (2000) 797-806
  

  Major neutral glycosphingolipid components were extracted from Sporothrix schenckii, a dimorphic fungus exhibiting a hyphal saprophytic phase and a yeast parasitic phase responsible for chronic mycotic infections in mammalian hosts. These components, one from the mycelial form and two from the yeast form, were purified and their structures were elucidated by 1H nuclear magnetic resonance (NMR) spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and tandem ESI-MS/MS. All three were characterized as cerebrosides (monohexosylceramides) containing (4E, 8E)-9-methyl-4,8-sphingadienine as the long-chain base attached to N-2′-hydroxyoctadecanoate and N-2′-hydroxy-(E)-Δ3-octadecenoate as the fatty acyl components. However, while the mycelial form expressed only β-glucopyranosylceramide, the yeast form expressed both β-gluco- and β-galactopyranosylceramides in approximately equal amounts. In addition, while the glucosylceramides of both mycelial and yeast forms had similar proportions of saturated and (E)-Δ3 unsaturated 2-hydroxy fatty acid, the galactocerebroside of the yeast form had significantly higher levels of (E)-Δ3 unsaturation. The differences in cerebroside hexose structure represent a novel type of glycosphingolipid dimorphism not previously reported in fungi. Possible implications of these findings with respect to regulation of morphological transitions in S. schenckii and other dimorphic fungi are discussed.

  NMR, mass spectrometry, nuclear magnetic resonance spectroscopy, ESI-MS, tandem mass spectrometry, Electrospray Ionization, collision-induced dissociation, yeast, fungus, mycosis

  Journal NLM ID: 0376606
  WWW link: http://www.jlr.org/content/41/5/797.long
  Publisher: ASBMB
  Institutions: Department of Biochemistry, Universidade Federal de São Paulo/Escola Paulista de Medicina, Rua Botucatu 862, 04023-900, São Paulo, SP, Brasil, The Complex Carbohydrate Research Center and Department of Biochemistry and Molecular Biology, University of Georgia, 220 Riverbend Road, Athens, GA 30602-7229
  Methods: 1H NMR, ESI-MS, HPTLC, ESI-MS/CID-MS
  
   
  
  Sporothrix schenckii 65
  CSDB ID 40709 (all data & tools)

Show legend Show as text

Structure type: monomer
Contained glycoepitopes: IEDB_136044,IEDB_137472,IEDB_141794,IEDB_190606,SB_1,SB_165,SB_166,SB_187,SB_195,SB_7,SB_88

• Article ID: 6751
  Toledo MS, Levery SB, Straus AH, Takahashi HK "Dimorphic expression of cerebrosides in the mycopathogen Sporothrix schenckii" - Journal of Lipid Research 41 (2000) 797-806
  

  Major neutral glycosphingolipid components were extracted from Sporothrix schenckii, a dimorphic fungus exhibiting a hyphal saprophytic phase and a yeast parasitic phase responsible for chronic mycotic infections in mammalian hosts. These components, one from the mycelial form and two from the yeast form, were purified and their structures were elucidated by 1H nuclear magnetic resonance (NMR) spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and tandem ESI-MS/MS. All three were characterized as cerebrosides (monohexosylceramides) containing (4E, 8E)-9-methyl-4,8-sphingadienine as the long-chain base attached to N-2′-hydroxyoctadecanoate and N-2′-hydroxy-(E)-Δ3-octadecenoate as the fatty acyl components. However, while the mycelial form expressed only β-glucopyranosylceramide, the yeast form expressed both β-gluco- and β-galactopyranosylceramides in approximately equal amounts. In addition, while the glucosylceramides of both mycelial and yeast forms had similar proportions of saturated and (E)-Δ3 unsaturated 2-hydroxy fatty acid, the galactocerebroside of the yeast form had significantly higher levels of (E)-Δ3 unsaturation. The differences in cerebroside hexose structure represent a novel type of glycosphingolipid dimorphism not previously reported in fungi. Possible implications of these findings with respect to regulation of morphological transitions in S. schenckii and other dimorphic fungi are discussed.

  NMR, mass spectrometry, nuclear magnetic resonance spectroscopy, ESI-MS, tandem mass spectrometry, Electrospray Ionization, collision-induced dissociation, yeast, fungus, mycosis

  Journal NLM ID: 0376606
  WWW link: http://www.jlr.org/content/41/5/797.long
  Publisher: ASBMB
  Institutions: Department of Biochemistry, Universidade Federal de São Paulo/Escola Paulista de Medicina, Rua Botucatu 862, 04023-900, São Paulo, SP, Brasil, The Complex Carbohydrate Research Center and Department of Biochemistry and Molecular Biology, University of Georgia, 220 Riverbend Road, Athens, GA 30602-7229
  Methods: 1H NMR, ESI-MS, HPTLC, ESI-MS/CID-MS
  
   
  
  Sporothrix schenckii 65
  CSDB ID 40710 (all data & tools)

Show legend Show as text

Structure type: monomer ; 760 [M+Li]+
Contained glycoepitopes: IEDB_136044,IEDB_137472,IEDB_141794,IEDB_190606,SB_1,SB_165,SB_166,SB_187,SB_195,SB_7,SB_88

• Article ID: 6788
  Levery SB, Toledo MS, Doong RL, Straus AH, Takahashi HK "Comparative analysis of ceramide structural modification found in fungal cerebrosides by electrospray tandem mass spectrometry with low energy collision-induced dissociation of Li+ adduct ions" - Rapid Communications in Mass Spectrometry 14 (2000) 551-563
  

  Fungal cerebrosides (monohexosylceramides, or CMHs) exhibit a number of ceramide structural modifications not found in mammalian glycosphingolipids, which present additional challenges for their complete characterization. The use of Li+ cationization, in conjunction with electrospray ionization mass spectrometry and low energy collision-induced dissociation tandem mass spectrometry (ESI-MS/CID-MS), was found to be particularly effective for detailed structural analysis of complex fungal CMHs, especially minor components present in mixtures at extremely low abundance. A substantial increase in both sensitivity and fragmentation was observed on collision-induced dissociation of [M+Li]+versus [M+Na]+ of the same CMH components analyzed under similar conditions. The effects of particular modifications on fragmentation were first systematically evaluated by analysis of a wide variety of standard CMHs expressing progressively more functionalized ceramides. These included bovine brain galactocerebrosides with non-hydroxy and 2-hydroxy fatty N-acylation; a plant glucocerebroside having (E/Z)-Δ8 in addition to (E)-Δ4 unsaturation of the sphingoid base; and a pair of fungal cerebrosides known to be further modified by a branching 9-methyl group on the sphingoid moiety, and to have a 2-hydroxy fatty N-acyl moiety either fully saturated or (E)-Δ3 unsaturated. The method was then applied to characterization of both major and minor components in CMH fractions from a non-pathogenic mycelial fungus, Aspergillus niger; and from pathogenic strains of Candida albicans (yeast form); three Cryptococcus spp. (all yeast forms); and Paracoccidioides brasiliensis (both yeast and mycelium forms). The major components of all species examined differed primarily (and widely) in the level of 2-hydroxy fatty N-acyl Δ3 unsaturation, but among the minor components a significant degree of additional structural diversity was observed, based on differences in sphingoid or N-acyl chain length, as well as on the presence or absence of the sphingoid Δ8 unsaturation or 9-methyl group. Some variants were isobaric, and were not uniformly present in all species, affirming the need for MS/CID-MS analysis for full characterization of all components in a fungal CMH fraction. The diversity in ceramide distribution observed may reflect significant species-specific differences among fungi with respect to cerebroside biosynthesis and function.

  Publication DOI: 10.1002/(SICI)1097-0231(20000415)14:7<551::AID-RCM909>3.0.CO;2-L
  Journal NLM ID: 8802365
  Publisher: John Wiley And Sons Ltd
  Correspondence: leverysb@ccrc.uga.edu
  Institutions: Department of Biochemistry, Universidade Federal de São Paulo/Escola Paulista de Medicina, Rua Botucatu 862, 04023-900, São Paulo, SP, Brasil, The Complex Carbohydrate Research Center and Department of Biochemistry and Molecular Biology, University of Georgia, 220 Riverbend Road, Athens, GA 30602-7229, USA
  Methods: ESI-MS, ESI-MS/CID-MS
  
   
  
  Aspergillus fumigatus ATCC strain 9197
  CSDB ID 40809 (all data & tools)

Show legend Show as text

Structure type: monomer
Trivial name: glucosylceramide
Compound class: glycolipid
Contained glycoepitopes: IEDB_136044,IEDB_137472,IEDB_141794,IEDB_190606,SB_1,SB_165,SB_166,SB_187,SB_195,SB_7,SB_88

• Article ID: 6824
  Park C, Bennion B, Francois IEJA, Ferket KKA, Cammue BPA, Thevissen K, Levery SB "Neutral glycolipids of the filamentous fungus Neurospora crassa: altered expression in plant defensin-resistant mutants" - Journal of Lipid Research 46(4) (2005) 759-768
  

  To defend themselves against fungal pathogens, plants produce numerous antifungal proteins and peptides, including defensins, some of which have been proposed to interact with fungal cell surface glycosphingolipid components. Although not known as a phytopathogen, the filamentous fungus Neurospora crassa possesses numerous genes similar to those required for plant pathogenesis identified in fungal pathogens (Galagan, J. E., et al. 2003. Nature 422: 859-868), and it has been used as a model for studying plant-phytopathogen interactions targeting fungal membrane components (Thevissen, K., et al. 2003. Peptides. 24: 1705 1712). For this study, neutral glycolipid components were extracted from wild-type and plant defensin-resistant mutant strains of N. crassa. The structures of purified components were elucidated by NMR spectroscopy and mass spectrometry. Neutral glycosphingolipids of both wild-type and mutant strains were characterized as beta-glucopyranosylceramides, but those of the mutants were found with structurally altered ceramides. Although the wild type expressed a preponderance of N-2'-hydroxy-(E)-Delta(3)-octadecenoate as the fatty-N-acyl component attached to the long-chain base (4E,8E)-9-methyl-4,8-sphingadienine, the mutant ceramides were found with mainly N-2'-hydroxyhexadecanoate instead. In addition, the mutant strains expressed highly increased levels of a sterol glucoside identified as ergosterol-beta-glucoside. The potential implications of these findings with respect to defensin resistance in the N. crassa mutants are discussed.

  mass spectrometry, nuclear magnetic resonance spectroscopy, ceramide, tandem mass spectrometry, Electrospray Ionization, collision-induced dissociation, glucoside, Aspergillus fumigatus, sphingolipid, cerebroside, ergosterol, sterol

  NCBI PubMed ID: 15654124
  Publication DOI: 10.1194/jlr.M400457-JLR200
  Journal NLM ID: 0376606
  Publisher: ASBMB
  Correspondence: slevery@cisunix.unh.edu
  Institutions: Department of Chemistry, University of New Hampshire, Durham, NH 03824-3598, Complex Carbohydrate Research Center and Department of Biochemistry and Molecular Biology, University of Georgia, Athens, GA 30602-7229, Center of Microbial and Plant Genetics, Katholieke Universiteit Leuven, B-3001 Heverlee-Leuven, Belgium
  Methods: 13C NMR, 1H NMR, NMR-2D, ESI-MS, ion-exchange chromatography, extraction, HPTLC, ESI-QTOF-MS
  
   
  
  Neurospora crassa 74-OR23-1A
  CSDB ID 41384 (all data & tools)

Show legend Show as text

Structure type: monomer ; 778 [M+Na]+
C₄₃H₈₁NO₉
Trivial name: flavicerebroside A
Compound class: glycosphingolipid
Contained glycoepitopes: IEDB_136044,IEDB_137472,IEDB_141794,IEDB_190606,SB_1,SB_165,SB_166,SB_187,SB_195,SB_7,SB_88

• Article ID: 6834
  Jiang T, Li T, Li J, Fu HZ, Pei YH, Lin WH "Cerebroside analogues from marine-derived fungus Aspergillus flavipes" - Journal of Asian Natural Products Research 6(4) (2004) 249-257
  

  From the mycelium of the marine-derived fungus Aspergillus flavipes, isolated from the sea anemone Anthopleura xanthogrammica, two new cerebroside analogues, namely flavicerebrosides A (1): [(2S,2'R,3R,4E,8E)-N-2'-hydroxyoctadecanoyl-1-O-beta-D-galactopyranosyl-9-methyl-4,8-sphingadienine], and B (2): [(2S,2'R,3R,3'E,4E,8E)-N-2'-hydroxy-3'-octadecenoyl-1-O-beta-D-galactopyranosyl-9-methyl-4,8-sphingadienine], together with two known glycosphingolipids cerebrosides D (3) and C (4), were isolated. Their structures were identified by means of extensive spectroscopic analysis (IR, UV, 2D NMR, MS, CD) and chemical degradation. All four compounds showed cytotoxic activity against the KB cell line.

  fungus, Aspergillus flavipes, flavicerebrosides A and B

  Publication DOI: 10.1080/1028602031000147384
  Journal NLM ID: 100888334
  Publisher: Harwood Academic Publishers; London: Informa Healthcare
  Correspondence: whlin@bjmu.edu.cn
  Institutions: State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Beijing, 100083, China, Shangdong Key Laboratory of Marine Biological Active Substance, SOA, Qingdao, 266061, China, Department of Phytochemistry, Shenyang Pharmaceutical University, Shenyang, 110015, China
  Methods: 13C NMR, 1H NMR, NMR-2D, IR, FAB-MS, GC-MS, sugar analysis, TLC, acid hydrolysis, ESI-MS/MS, methanolysis, HPLC, UV, extraction, CD, HR-FAB-MS
  
   
  
  Aspergillus flavipes
  CSDB ID 41291 (all data & tools)

Show legend Show as text

Structure type: monomer ; 776 [M+Na]+
C₄₃H₇₉NO₉
Trivial name: flavicerebroside B
Compound class: glycosphingolipid
Contained glycoepitopes: IEDB_136044,IEDB_137472,IEDB_141794,IEDB_190606,SB_1,SB_165,SB_166,SB_187,SB_195,SB_7,SB_88

• Article ID: 6834
  Jiang T, Li T, Li J, Fu HZ, Pei YH, Lin WH "Cerebroside analogues from marine-derived fungus Aspergillus flavipes" - Journal of Asian Natural Products Research 6(4) (2004) 249-257
  

  From the mycelium of the marine-derived fungus Aspergillus flavipes, isolated from the sea anemone Anthopleura xanthogrammica, two new cerebroside analogues, namely flavicerebrosides A (1): [(2S,2'R,3R,4E,8E)-N-2'-hydroxyoctadecanoyl-1-O-beta-D-galactopyranosyl-9-methyl-4,8-sphingadienine], and B (2): [(2S,2'R,3R,3'E,4E,8E)-N-2'-hydroxy-3'-octadecenoyl-1-O-beta-D-galactopyranosyl-9-methyl-4,8-sphingadienine], together with two known glycosphingolipids cerebrosides D (3) and C (4), were isolated. Their structures were identified by means of extensive spectroscopic analysis (IR, UV, 2D NMR, MS, CD) and chemical degradation. All four compounds showed cytotoxic activity against the KB cell line.

  fungus, Aspergillus flavipes, flavicerebrosides A and B

  Publication DOI: 10.1080/1028602031000147384
  Journal NLM ID: 100888334
  Publisher: Harwood Academic Publishers; London: Informa Healthcare
  Correspondence: whlin@bjmu.edu.cn
  Institutions: State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Beijing, 100083, China, Shangdong Key Laboratory of Marine Biological Active Substance, SOA, Qingdao, 266061, China, Department of Phytochemistry, Shenyang Pharmaceutical University, Shenyang, 110015, China
  Methods: 13C NMR, 1H NMR, NMR-2D, IR, FAB-MS, GC-MS, sugar analysis, TLC, acid hydrolysis, ESI-MS/MS, methanolysis, HPLC, UV, extraction, CD, HR-FAB-MS
  
   
  
  Aspergillus flavipes
  CSDB ID 41292 (all data & tools)

Show legend Show as text

Structure type: oligomer
Trivial name: CDS
Compound class: glycosphingolipid
Contained glycoepitopes: IEDB_136044,IEDB_137472,IEDB_141794,IEDB_153201,IEDB_156493,IEDB_190606,SB_1,SB_165,SB_166,SB_187,SB_195,SB_7,SB_88

• Article ID: 6838
  Aoki K, Uchiyama R, Yamauchi S, Katayama T, Itonori S, Sugita M, Hada N, Yamada-Hada J, Takeda T, Kumagai H, Yamamoto K "Newly discovered neutral glycosphingolipids in Aureobasidin A-resistant Zygomycetes - Identification of a novel family of gala-series glycolipids with core Gal alpha 1-6Gal beta 1-6Gal beta sequences" - Journal of Biological Chemistry 279(31) (2004) 32028-32034
  

  We found for the first time that Zygomycetes species showed resistance to Aureobasidin A, an antifungal agent. A novel family of neutral glycosphingolipids (GSLs) was found in these fungi and isolated from Mucor hiemalis, which is a typical Zygomycetes species. Their structures were completely determined by compositional sugar, fatty acid, and sphingoid analyses, methylation analysis, matrix-assisted laser desorption ionization time-of-flight/mass spectrometry, and H-1 NMR spectroscopy. They were as follows: Galbeta1-6Galbeta1-1Cer (CDS), Galalpha1-6Galbeta1-6Galbeta1-1Cer (CTS), Galalpha1-6Galalpha1-6Galbeta1-6Galbeta1-1Cer (CTeS), and Galalpha1-6Galalpha1-6Galalpha1-6Galbeta1-6Galbeta1-1Cer (CPS). The ceramide moieties of these GSLs consist of 24: 0, 25: 0, and 26: 0 2-hydroxy acids as major fatty acids and 4-hydroxyoctadecasphinganine ( phytosphingosine) as the sole sphingoid. However, the glycosylinositolphosphoceramide families that are the major GSLs components in fungi were not detected in Zygomycetes at all. This seems to be the reason that Aureobasidin A is not effective for Zygomycetes as an antifungal agent. Our results indicate that the biosynthetic pathway for GSLs in Zygomycetes is significantly different from those in other fungi and suggest that any inhibitor of this pathway may be effective for mucormycosis, which is a serious pathogenic disease for humans.

  glycosphingolipid, Aureobasidin A, Mucor hiemalis, sphingolipid biosynthesis, mucormycosis

  Publication DOI: 10.1074/jbc.M312918200
  Journal NLM ID: 2985121R
  Publisher: Baltimore, MD: American Society for Biochemistry and Molecular Biology
  Correspondence: kaoki@lif.kyoto-u.ac.jp
  Institutions: Graduate School of Biostudies, Kyoto University, Kyoto, Japan, Faculty of Liberal Arts and Education, Shiga University, 2-5-1, Hiratsu, Otsu, Shiga 520-0862, Japan, Kyoritsu University of Pharmacy, 1-5-30, Shibakoen, Minato-ku, Tokyo 105-8512, Japan
  Methods: 1H NMR, methylation, GLC-MS, TLC, enzymatic hydrolysis, GLC, MALDI-TOF MS, composition analysis, extraction
  
   
  
  Mucor hiemalis 314
  CSDB ID 41304 (all data & tools)

Show legend Show as text

Structure type: oligomer
Trivial name: CTS
Compound class: glycosphingolipid
Contained glycoepitopes: IEDB_134624,IEDB_136044,IEDB_136906,IEDB_137472,IEDB_141794,IEDB_151528,IEDB_153201,IEDB_156493,IEDB_190606,IEDB_742248,SB_1,SB_163,SB_165,SB_166,SB_187,SB_195,SB_7,SB_88

• Article ID: 6838
  Aoki K, Uchiyama R, Yamauchi S, Katayama T, Itonori S, Sugita M, Hada N, Yamada-Hada J, Takeda T, Kumagai H, Yamamoto K "Newly discovered neutral glycosphingolipids in Aureobasidin A-resistant Zygomycetes - Identification of a novel family of gala-series glycolipids with core Gal alpha 1-6Gal beta 1-6Gal beta sequences" - Journal of Biological Chemistry 279(31) (2004) 32028-32034
  

  We found for the first time that Zygomycetes species showed resistance to Aureobasidin A, an antifungal agent. A novel family of neutral glycosphingolipids (GSLs) was found in these fungi and isolated from Mucor hiemalis, which is a typical Zygomycetes species. Their structures were completely determined by compositional sugar, fatty acid, and sphingoid analyses, methylation analysis, matrix-assisted laser desorption ionization time-of-flight/mass spectrometry, and H-1 NMR spectroscopy. They were as follows: Galbeta1-6Galbeta1-1Cer (CDS), Galalpha1-6Galbeta1-6Galbeta1-1Cer (CTS), Galalpha1-6Galalpha1-6Galbeta1-6Galbeta1-1Cer (CTeS), and Galalpha1-6Galalpha1-6Galalpha1-6Galbeta1-6Galbeta1-1Cer (CPS). The ceramide moieties of these GSLs consist of 24: 0, 25: 0, and 26: 0 2-hydroxy acids as major fatty acids and 4-hydroxyoctadecasphinganine ( phytosphingosine) as the sole sphingoid. However, the glycosylinositolphosphoceramide families that are the major GSLs components in fungi were not detected in Zygomycetes at all. This seems to be the reason that Aureobasidin A is not effective for Zygomycetes as an antifungal agent. Our results indicate that the biosynthetic pathway for GSLs in Zygomycetes is significantly different from those in other fungi and suggest that any inhibitor of this pathway may be effective for mucormycosis, which is a serious pathogenic disease for humans.

  glycosphingolipid, Aureobasidin A, Mucor hiemalis, sphingolipid biosynthesis, mucormycosis

  Publication DOI: 10.1074/jbc.M312918200
  Journal NLM ID: 2985121R
  Publisher: Baltimore, MD: American Society for Biochemistry and Molecular Biology
  Correspondence: kaoki@lif.kyoto-u.ac.jp
  Institutions: Graduate School of Biostudies, Kyoto University, Kyoto, Japan, Faculty of Liberal Arts and Education, Shiga University, 2-5-1, Hiratsu, Otsu, Shiga 520-0862, Japan, Kyoritsu University of Pharmacy, 1-5-30, Shibakoen, Minato-ku, Tokyo 105-8512, Japan
  Methods: 1H NMR, methylation, GLC-MS, TLC, enzymatic hydrolysis, GLC, MALDI-TOF MS, composition analysis, extraction
  
   
  
  Mucor hiemalis 314
  CSDB ID 41305 (all data & tools)

Show legend Show as text

Structure type: oligomer
Trivial name: CTeS
Compound class: glycosphingolipid
Contained glycoepitopes: IEDB_134624,IEDB_136044,IEDB_136906,IEDB_137472,IEDB_141794,IEDB_151528,IEDB_153201,IEDB_156493,IEDB_190606,IEDB_742248,SB_1,SB_163,SB_165,SB_166,SB_187,SB_195,SB_7,SB_88

• Article ID: 6838
  Aoki K, Uchiyama R, Yamauchi S, Katayama T, Itonori S, Sugita M, Hada N, Yamada-Hada J, Takeda T, Kumagai H, Yamamoto K "Newly discovered neutral glycosphingolipids in Aureobasidin A-resistant Zygomycetes - Identification of a novel family of gala-series glycolipids with core Gal alpha 1-6Gal beta 1-6Gal beta sequences" - Journal of Biological Chemistry 279(31) (2004) 32028-32034
  

  We found for the first time that Zygomycetes species showed resistance to Aureobasidin A, an antifungal agent. A novel family of neutral glycosphingolipids (GSLs) was found in these fungi and isolated from Mucor hiemalis, which is a typical Zygomycetes species. Their structures were completely determined by compositional sugar, fatty acid, and sphingoid analyses, methylation analysis, matrix-assisted laser desorption ionization time-of-flight/mass spectrometry, and H-1 NMR spectroscopy. They were as follows: Galbeta1-6Galbeta1-1Cer (CDS), Galalpha1-6Galbeta1-6Galbeta1-1Cer (CTS), Galalpha1-6Galalpha1-6Galbeta1-6Galbeta1-1Cer (CTeS), and Galalpha1-6Galalpha1-6Galalpha1-6Galbeta1-6Galbeta1-1Cer (CPS). The ceramide moieties of these GSLs consist of 24: 0, 25: 0, and 26: 0 2-hydroxy acids as major fatty acids and 4-hydroxyoctadecasphinganine ( phytosphingosine) as the sole sphingoid. However, the glycosylinositolphosphoceramide families that are the major GSLs components in fungi were not detected in Zygomycetes at all. This seems to be the reason that Aureobasidin A is not effective for Zygomycetes as an antifungal agent. Our results indicate that the biosynthetic pathway for GSLs in Zygomycetes is significantly different from those in other fungi and suggest that any inhibitor of this pathway may be effective for mucormycosis, which is a serious pathogenic disease for humans.

  glycosphingolipid, Aureobasidin A, Mucor hiemalis, sphingolipid biosynthesis, mucormycosis

  Publication DOI: 10.1074/jbc.M312918200
  Journal NLM ID: 2985121R
  Publisher: Baltimore, MD: American Society for Biochemistry and Molecular Biology
  Correspondence: kaoki@lif.kyoto-u.ac.jp
  Institutions: Graduate School of Biostudies, Kyoto University, Kyoto, Japan, Faculty of Liberal Arts and Education, Shiga University, 2-5-1, Hiratsu, Otsu, Shiga 520-0862, Japan, Kyoritsu University of Pharmacy, 1-5-30, Shibakoen, Minato-ku, Tokyo 105-8512, Japan
  Methods: 1H NMR, methylation, GLC-MS, TLC, enzymatic hydrolysis, GLC, MALDI-TOF MS, composition analysis, extraction
  
   
  
  Mucor hiemalis 314
  CSDB ID 41306 (all data & tools)

Show legend Show as text

Structure type: oligomer
Trivial name: CPS
Compound class: glycosphingolipid
Contained glycoepitopes: IEDB_134624,IEDB_136044,IEDB_136906,IEDB_137472,IEDB_141794,IEDB_151528,IEDB_153201,IEDB_156493,IEDB_190606,IEDB_742248,SB_1,SB_163,SB_165,SB_166,SB_187,SB_195,SB_7,SB_88

• Article ID: 6838
  Aoki K, Uchiyama R, Yamauchi S, Katayama T, Itonori S, Sugita M, Hada N, Yamada-Hada J, Takeda T, Kumagai H, Yamamoto K "Newly discovered neutral glycosphingolipids in Aureobasidin A-resistant Zygomycetes - Identification of a novel family of gala-series glycolipids with core Gal alpha 1-6Gal beta 1-6Gal beta sequences" - Journal of Biological Chemistry 279(31) (2004) 32028-32034
  

  We found for the first time that Zygomycetes species showed resistance to Aureobasidin A, an antifungal agent. A novel family of neutral glycosphingolipids (GSLs) was found in these fungi and isolated from Mucor hiemalis, which is a typical Zygomycetes species. Their structures were completely determined by compositional sugar, fatty acid, and sphingoid analyses, methylation analysis, matrix-assisted laser desorption ionization time-of-flight/mass spectrometry, and H-1 NMR spectroscopy. They were as follows: Galbeta1-6Galbeta1-1Cer (CDS), Galalpha1-6Galbeta1-6Galbeta1-1Cer (CTS), Galalpha1-6Galalpha1-6Galbeta1-6Galbeta1-1Cer (CTeS), and Galalpha1-6Galalpha1-6Galalpha1-6Galbeta1-6Galbeta1-1Cer (CPS). The ceramide moieties of these GSLs consist of 24: 0, 25: 0, and 26: 0 2-hydroxy acids as major fatty acids and 4-hydroxyoctadecasphinganine ( phytosphingosine) as the sole sphingoid. However, the glycosylinositolphosphoceramide families that are the major GSLs components in fungi were not detected in Zygomycetes at all. This seems to be the reason that Aureobasidin A is not effective for Zygomycetes as an antifungal agent. Our results indicate that the biosynthetic pathway for GSLs in Zygomycetes is significantly different from those in other fungi and suggest that any inhibitor of this pathway may be effective for mucormycosis, which is a serious pathogenic disease for humans.

  glycosphingolipid, Aureobasidin A, Mucor hiemalis, sphingolipid biosynthesis, mucormycosis

  Publication DOI: 10.1074/jbc.M312918200
  Journal NLM ID: 2985121R
  Publisher: Baltimore, MD: American Society for Biochemistry and Molecular Biology
  Correspondence: kaoki@lif.kyoto-u.ac.jp
  Institutions: Graduate School of Biostudies, Kyoto University, Kyoto, Japan, Faculty of Liberal Arts and Education, Shiga University, 2-5-1, Hiratsu, Otsu, Shiga 520-0862, Japan, Kyoritsu University of Pharmacy, 1-5-30, Shibakoen, Minato-ku, Tokyo 105-8512, Japan
  Methods: 1H NMR, methylation, GLC-MS, TLC, enzymatic hydrolysis, GLC, MALDI-TOF MS, composition analysis, extraction
  
   
  
  Mucor hiemalis 314
  CSDB ID 41307 (all data & tools)

Show legend Show as text

Structure type: oligomer ; 1028.8 [M+Na]+
Trivial name: neogala sphingolipid, NGL2
Compound class: glycosphingolipid
Contained glycoepitopes: IEDB_136044,IEDB_136095,IEDB_137472,IEDB_141794,IEDB_149176,IEDB_153201,IEDB_156493,IEDB_190606,SB_1,SB_165,SB_166,SB_187,SB_195,SB_7,SB_88

• Article ID: 6876
  Tani Y, Funatsu T, Ashida H, Ito M, Itonori S, Sugita M, Yamamoto K "Novel neogala-series glycosphingolipids with terminal mannose and glucose residues from Hirsutella rhossiliensis, an aureobasidin A-resistant ascomycete fungus" - Glycobiology 20(4) (2010) 433-441
  

  Hirsutella rhossiliensis, a nematophagous fungus belonging to the Ascomycota, is resistant to aureobasidin A (AbA). In this fungus, the biosynthetic pathway leading to mannosylinositolphosphoceramides, which is inhibited by AbA, was not detected. Instead, this fungus contains neutral complex glycosphingolipids (GSLs) and monoglycosylceramides. Except for monoglycosylceramides, neutral GSLs share a neogala-series core structure, Galbeta1-6Galbeta1-Cer. Among the GSLs of H. rhossiliensis, three novel GSLs with terminal Man and Glc residues on the sugar chain were elucidated. We analyzed GSL structure using compositional sugar, fatty acid, and sphingoid analyses, methylation analysis, matrix-assisted laser desorption ionization time-of-flight/mass spectrometry (MALDI-TOF MS), and (1)H nuclear magnetic resonance spectroscopy (NMR). The following structures were determined: Manalpha1-3Galbeta1-6Galbeta1-6Galbeta1-Cer; Glcalpha1-2Galbeta1-6Galbeta1-6Galbeta1-Cer; and Manalpha1-3Galbeta1-6(Glcalpha1-4)Galbeta1-6Galbeta1-Cer. In the ceramides, the fatty acids were predominantly saturated h24:0-acids and the sphingoids were predominately t18:0- or t18:1-sphingoids. In contrast, the ceramides of Glcbeta1-Cer contained d18:2- and d19:2-sphingoids. These findings indicate the presence of a novel biosynthetic pathway of neogala-series GSLs in fungi.

  glycosphingolipid, Aureobasidin A, Ascomycota, Hirsutella rhossiliensis, neogalatriaosylceramide

  NCBI PubMed ID: 20007186
  Publication DOI: 10.1093/glycob/cwp190
  Journal NLM ID: 9104124
  Publisher: IRL Press at Oxford University Press
  Correspondence: yasu-t@lif.kyoto-u.ac.jp
  Institutions: Graduate School of Biostudies, Kyoto University, Kyoto 606-8502, Japan, Department of Bioscience and Bioinformatics, Ritsumeikan University, Kusatsu, Shiga 525-8577, and Faculty of Liberal Arts and Education, Shiga University, Otsu, Shiga 520-0862, Japan
  Methods: 1H NMR, GC-MS, sugar analysis, TLC, GC, MALDI-TOF MS, enzymatic digestion, mild alkaline hydrolysis, methylation analysis
  
   
  
  Hirsutella rhossiliensis JCM 23109
  CSDB ID 41936 (all data & tools)

Show legend Show as text

Structure type: oligomer ; 1030.8 [M+Na]+
Trivial name: neogala sphingolipid, NGL2
Compound class: glycosphingolipid
Contained glycoepitopes: IEDB_136044,IEDB_136095,IEDB_137472,IEDB_141794,IEDB_149176,IEDB_153201,IEDB_156493,IEDB_190606,SB_1,SB_165,SB_166,SB_187,SB_195,SB_7,SB_88

• Article ID: 6876
  Tani Y, Funatsu T, Ashida H, Ito M, Itonori S, Sugita M, Yamamoto K "Novel neogala-series glycosphingolipids with terminal mannose and glucose residues from Hirsutella rhossiliensis, an aureobasidin A-resistant ascomycete fungus" - Glycobiology 20(4) (2010) 433-441
  

  Hirsutella rhossiliensis, a nematophagous fungus belonging to the Ascomycota, is resistant to aureobasidin A (AbA). In this fungus, the biosynthetic pathway leading to mannosylinositolphosphoceramides, which is inhibited by AbA, was not detected. Instead, this fungus contains neutral complex glycosphingolipids (GSLs) and monoglycosylceramides. Except for monoglycosylceramides, neutral GSLs share a neogala-series core structure, Galbeta1-6Galbeta1-Cer. Among the GSLs of H. rhossiliensis, three novel GSLs with terminal Man and Glc residues on the sugar chain were elucidated. We analyzed GSL structure using compositional sugar, fatty acid, and sphingoid analyses, methylation analysis, matrix-assisted laser desorption ionization time-of-flight/mass spectrometry (MALDI-TOF MS), and (1)H nuclear magnetic resonance spectroscopy (NMR). The following structures were determined: Manalpha1-3Galbeta1-6Galbeta1-6Galbeta1-Cer; Glcalpha1-2Galbeta1-6Galbeta1-6Galbeta1-Cer; and Manalpha1-3Galbeta1-6(Glcalpha1-4)Galbeta1-6Galbeta1-Cer. In the ceramides, the fatty acids were predominantly saturated h24:0-acids and the sphingoids were predominately t18:0- or t18:1-sphingoids. In contrast, the ceramides of Glcbeta1-Cer contained d18:2- and d19:2-sphingoids. These findings indicate the presence of a novel biosynthetic pathway of neogala-series GSLs in fungi.

  glycosphingolipid, Aureobasidin A, Ascomycota, Hirsutella rhossiliensis, neogalatriaosylceramide

  NCBI PubMed ID: 20007186
  Publication DOI: 10.1093/glycob/cwp190
  Journal NLM ID: 9104124
  Publisher: IRL Press at Oxford University Press
  Correspondence: yasu-t@lif.kyoto-u.ac.jp
  Institutions: Graduate School of Biostudies, Kyoto University, Kyoto 606-8502, Japan, Department of Bioscience and Bioinformatics, Ritsumeikan University, Kusatsu, Shiga 525-8577, and Faculty of Liberal Arts and Education, Shiga University, Otsu, Shiga 520-0862, Japan
  Methods: 1H NMR, GC-MS, sugar analysis, TLC, GC, MALDI-TOF MS, enzymatic digestion, mild alkaline hydrolysis, methylation analysis
  
   
  
  Hirsutella rhossiliensis JCM 23109
  CSDB ID 42150 (all data & tools)

Show legend Show as text

Structure type: oligomer ; 1190.6 [M+Na]+
Trivial name: neogala sphingolipid, sNGL3
Compound class: glycosphingolipid
Contained glycoepitopes: IEDB_136044,IEDB_136095,IEDB_137472,IEDB_141794,IEDB_149176,IEDB_153201,IEDB_156489,IEDB_156493,IEDB_190606,SB_1,SB_165,SB_166,SB_187,SB_195,SB_7,SB_88

• Article ID: 6876
  Tani Y, Funatsu T, Ashida H, Ito M, Itonori S, Sugita M, Yamamoto K "Novel neogala-series glycosphingolipids with terminal mannose and glucose residues from Hirsutella rhossiliensis, an aureobasidin A-resistant ascomycete fungus" - Glycobiology 20(4) (2010) 433-441
  

  Hirsutella rhossiliensis, a nematophagous fungus belonging to the Ascomycota, is resistant to aureobasidin A (AbA). In this fungus, the biosynthetic pathway leading to mannosylinositolphosphoceramides, which is inhibited by AbA, was not detected. Instead, this fungus contains neutral complex glycosphingolipids (GSLs) and monoglycosylceramides. Except for monoglycosylceramides, neutral GSLs share a neogala-series core structure, Galbeta1-6Galbeta1-Cer. Among the GSLs of H. rhossiliensis, three novel GSLs with terminal Man and Glc residues on the sugar chain were elucidated. We analyzed GSL structure using compositional sugar, fatty acid, and sphingoid analyses, methylation analysis, matrix-assisted laser desorption ionization time-of-flight/mass spectrometry (MALDI-TOF MS), and (1)H nuclear magnetic resonance spectroscopy (NMR). The following structures were determined: Manalpha1-3Galbeta1-6Galbeta1-6Galbeta1-Cer; Glcalpha1-2Galbeta1-6Galbeta1-6Galbeta1-Cer; and Manalpha1-3Galbeta1-6(Glcalpha1-4)Galbeta1-6Galbeta1-Cer. In the ceramides, the fatty acids were predominantly saturated h24:0-acids and the sphingoids were predominately t18:0- or t18:1-sphingoids. In contrast, the ceramides of Glcbeta1-Cer contained d18:2- and d19:2-sphingoids. These findings indicate the presence of a novel biosynthetic pathway of neogala-series GSLs in fungi.

  glycosphingolipid, Aureobasidin A, Ascomycota, Hirsutella rhossiliensis, neogalatriaosylceramide

  NCBI PubMed ID: 20007186
  Publication DOI: 10.1093/glycob/cwp190
  Journal NLM ID: 9104124
  Publisher: IRL Press at Oxford University Press
  Correspondence: yasu-t@lif.kyoto-u.ac.jp
  Institutions: Graduate School of Biostudies, Kyoto University, Kyoto 606-8502, Japan, Department of Bioscience and Bioinformatics, Ritsumeikan University, Kusatsu, Shiga 525-8577, and Faculty of Liberal Arts and Education, Shiga University, Otsu, Shiga 520-0862, Japan
  Methods: 1H NMR, GC-MS, sugar analysis, TLC, GC, MALDI-TOF MS, enzymatic digestion, mild alkaline hydrolysis, methylation analysis
  
   
  
  Hirsutella rhossiliensis JCM 23109
  CSDB ID 41937 (all data & tools)