Show legend Show as text

Structure type: oligomer ; 778 [M+Na]+
Contained glycoepitopes: IEDB_137339,IEDB_142488,IEDB_146664,IEDB_983931,SB_192,SB_5

• Article ID: 6874
  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 β-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, ESI-CID-MS, TOCSY, HMBC, HSQC, ion exchange chromatography, silica gel chromatography
  
   
  
  Paracoccidioides brasiliensis Pb18, Paracoccidioides brasiliensis B339, Aspergillus fumigatus ATCC 9197, Aspergillus fumigatus strain 237
  CSDB ID 40859 (all data & tools)

Show legend Show as text

Structure type: oligomer ; 778 [M+Na]+
Contained glycoepitopes: IEDB_137339,IEDB_142488,IEDB_146664,IEDB_983931,SB_192,SB_5

• Article ID: 6875
  Duarte RS, Polycarpo CR, Wait R, Hartmann R, Bergter EB "Structural characterization of neutral glycosphingolipids from Fusarium species" - Biochimica et Biophysica Acta 1390 (1998) 186-196
  

  Glycosphingolipids were extracted from hyphae of Fusarium solani and from an unnamed Fusarium species, and were purified by silica and Iatrobead column chromatography. Their structures were determined by compositional analysis, nuclear magnetic resonance spectroscopy, gas chromatography/mass spectrometry and by fast atom bombardment mass spectrometry of the native and peracetylated materials, which defined their sugar, long-chain base and fatty acid compositions. The locations of the double bonds in the bases were established by 2D NMR spectroscopy and by novel mass spectrometric approaches, including collisional activation of the protonated and lithium-cationized glycosphingolipids, and of the sphingadienene-derived fragment ion at m/z 276. From these results we propose that the structures of the glycosphingolipids from F. solani and Fusarium sp. are N-2'-hydroxyoctadecanoyl-1-O-β-D-glucopyranosyl-9-methyl-4, 8-sphingadienine and N-2'-hydroxyoctadecenoyl-1-O-β-D-glucopyranosyl-9-methyl-4, 8-sphingadienine, respectively

  NMR spectroscopy, mass spectrometry, glycosphingolipid, Fast Atom Bombardment, Fusarium

  Journal NLM ID: 0217513
  WWW link: http://www.sciencedirect.com/science/article/pii/S0005276097001793
  Publisher: Elsevier
  Correspondence: immgbel@microbio.ufrj.br
  Institutions: Instituto de Microbiologia, Universidade Federal do Rio de Janeiro, 21 944 970-Cidade Universitária, Rio de Janeiro, RJ, Brazil, Centre for Applied Microbiology and Research, Salisbury, SP4 0JG, UK, Institut für Physiologische Chemie, Universität Bonn, Bonn, Germany
  Methods: 1H NMR, FAB-MS, GC-MS, acid hydrolysis, GLC, GC, paper chromatography, methanolysis, HPTLC, COSY, silica gel chromatography
  
   
  
  Fusarium
  CSDB ID 40840 (all data & tools)

Show legend Show as text

Structure type: monomer
Compound class: cerebroside
Contained glycoepitopes: IEDB_137339,IEDB_142488,IEDB_146664,IEDB_983931,SB_192,SB_5

• Article ID: 6921
  Toledo MS, Levery SB, Suzuki E, Straus AH, Takahashi HK "Characterization of cerebrosides from the thermally dimorphic mycopathogen Histoplasma capsulatum: expression of 2-hydroxy fatty N-acyl (E)-Δ3-unsaturation correlates with the yeast-mycelium phase transition" - Glycobiology 11 (2001) 113-124
  

  Cerebroside (monohexosylceramide) components were identified in neutral lipids extracted from both the yeast and mycelial forms of the thermally dimorphic mycopathogen Histoplasma capsulatum. The components were purified from both forms and their structures elucidated by 1- and 2-dimensional nuclear magnetic resonance (NMR) spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and low energy tandem collision-induced dissociation mass spectrometry (ESI-MS/CID-MS). Both components were characterized as β-glucopyranosylceramides (GlcCers) containing (4E,8E)-9-methyl-4,8-sphingadienine as the long-chain base, attached to 18-carbon 2-hydroxy fatty N-acyl components. However, while the fatty acid of the yeast form GlcCer was virtually all N-2′-hydroxyoctadecanoate, the mycelium form GlcCer was characterized by almost exclusive expression of N-2′-hydroxy-(E)-Δ3-octadecenoate. These results suggest that the yeast—mycelium transition is accompanied by up-regulation of an as yet uncharacterized ceramide or cerebroside 2-hydroxy fatty N-acyl (E)-Δ3-desaturase activity. They also constitute further evidence for the existence of two distinct pathways for ceramide biosynthesis in fungi, since glycosylinositol phosphorylceramides (GIPCs), the other major class of fungal glycosphingolipids, are found with ceramides consisting of 4-hydroxysphinganine (phytosphingosine) and longer chain 2-hydroxy fatty acids. In addition to identification of the major glucocerebroside components, minor components (<5%) detectable by molecular weight differences in the ESI-MS profiles were also characterized by tandem ESI-MS/CID-MS analysis. These minor components were identified as variants differing in fatty acyl chain length, or the absence of the sphingoid 9-methyl group or (E)-Δ8-unsaturation, and are hypothesized to be either biosynthetic intermediates or the result of imperfect chemical transformation by the enzymes responsible for these features. Possible implications of these findings with respect to chemotaxonomy, compartmentalization of fungal glycosphingolipid biosynthetic pathways, and regulation of morphological transitions in H.capsulatum and other dimorphic fungi are discussed.

  glycosphingolipid, yeast, fungus, glucosylceramide, thermal dimorphis

  Publication DOI: 10.1093/glycob/11.2.113
  Journal NLM ID: 9104124
  Publisher: IRL Press at Oxford University Press
  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: 13C NMR, 1H NMR, gel filtration, ESI-MS, HPTLC, ESI-CID-MS, TOCSY, HMBC, HSQC
  
   
  
  Histoplasma capsulatum 496
  CSDB ID 40479 (all data & tools)

Show legend Show as text

Structure type: monomer
Contained glycoepitopes: IEDB_137339,IEDB_142488,IEDB_146664,IEDB_983931,SB_192,SB_5

• Article ID: 6929
  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-CID-MS
  
   
  
  Sporothrix schenckii 65
  CSDB ID 40496 (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: 6929
  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-CID-MS
  
   
  
  Sporothrix schenckii 65
  CSDB ID 40710 (all data & tools)

Show legend Show as text

Structure type: monomer ; 762 [M+Li]+
Contained glycoepitopes: IEDB_137339,IEDB_142488,IEDB_146664,IEDB_983931,SB_192,SB_5

• Article ID: 6966
  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-CID-MS
  
   
  
  Paracoccidioides brasiliensis Pb18
  CSDB ID 40546 (all data & tools)

Show legend Show as text

Structure type: monomer ; 772.5937 [M+H]+
C₄₃H₈₁NO₁₀
Trivial name: termitomycesphin B
Contained glycoepitopes: IEDB_142488,IEDB_146664,IEDB_983931,SB_192

• Article ID: 6968
  Qi JH, Ojika M, Sakagami Y "Termitomycesphins A-D, novel neuritogenic cerebrosides from the edible Chinese mushroom Termitomyces albuminosus" - Tetrahedron 56 (2000) 5835-5841
  

  Four novel cerebrosides, termitomycesphins A–D, were isolated from the edible Chinese mushroom Termitomyces albuminosus (Berk.) Heim. (‘Jizong’ in Chinese), shown to induce neuronal differentiation in rat PC12 cells. The absolute stereostructures were elucidated by spectroscopic methods and chemical derivatization. These new cerebrosides have a unique C19 hydroxylated sphingosine base with branching around the middle. Termitomycesphins A and C possessing a C16 α-hydroxy fatty acid showed a higher neuritogenic activity than did termitomycesphins B and D possessing a C18 α-hydroxy fatty acid.

  glycolipids, fungi, biologically active compounds

  Publication DOI: 10.1016/S0040-4020(00)00548-2
  Journal NLM ID: 2984170R
  Publisher: Pergamon Press
  Correspondence: ojika@agr.nagoya-u.ac.jp
  Institutions: Graduate School of Bioagricultural Sciences, Nagoya University, Chikusa-ku, Nagoya 464-8601, Japan
  Methods: 13C NMR, 1H NMR, FAB-MS, TLC, HPLC, HR-ESI-MS, DQF-COSY, HMBC, HMQC, bioassay, optical rotation
  
   
  
  Termitomyces albuminosus
  CSDB ID 40812 (all data & tools)

Show legend Show as text

Structure type: monomer ; 794.5753 [M+Na]+
C₄₃H₈₁NO₁₀
Trivial name: termitomycesphin D
Contained glycoepitopes: IEDB_142488,IEDB_146664,IEDB_983931,SB_192

• Article ID: 6968
  Qi JH, Ojika M, Sakagami Y "Termitomycesphins A-D, novel neuritogenic cerebrosides from the edible Chinese mushroom Termitomyces albuminosus" - Tetrahedron 56 (2000) 5835-5841
  

  Four novel cerebrosides, termitomycesphins A–D, were isolated from the edible Chinese mushroom Termitomyces albuminosus (Berk.) Heim. (‘Jizong’ in Chinese), shown to induce neuronal differentiation in rat PC12 cells. The absolute stereostructures were elucidated by spectroscopic methods and chemical derivatization. These new cerebrosides have a unique C19 hydroxylated sphingosine base with branching around the middle. Termitomycesphins A and C possessing a C16 α-hydroxy fatty acid showed a higher neuritogenic activity than did termitomycesphins B and D possessing a C18 α-hydroxy fatty acid.

  glycolipids, fungi, biologically active compounds

  Publication DOI: 10.1016/S0040-4020(00)00548-2
  Journal NLM ID: 2984170R
  Publisher: Pergamon Press
  Correspondence: ojika@agr.nagoya-u.ac.jp
  Institutions: Graduate School of Bioagricultural Sciences, Nagoya University, Chikusa-ku, Nagoya 464-8601, Japan
  Methods: 13C NMR, 1H NMR, FAB-MS, TLC, HPLC, HR-ESI-MS, DQF-COSY, HMBC, HMQC, bioassay, optical rotation
  
   
  
  Termitomyces albuminosus
  CSDB ID 40814 (all data & tools)

Show legend Show as text

Structure type: monomer
Trivial name: glucosylceramide
Compound class: glycolipid
Contained glycoepitopes: IEDB_137339,IEDB_142488,IEDB_146664,IEDB_983931,SB_192,SB_5

• Article ID: 7002
  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 β-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-β-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 41270 (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: 7002
  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 β-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-β-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 ; 754 [M-H]-
C₄₃H₈₁NO₉
Compound class: glycosphingolipid
Contained glycoepitopes: IEDB_137339,IEDB_142488,IEDB_146664,IEDB_983931,SB_192,SB_5

• Article ID: 7011
  Gao JM, Zhu WM, Zhang SQ, Zhang X, Zhang AL, Chen H, Sun YY, Tang M "Sphingolipids from the edible fungus Tuber indicum" - European Journal of Lipid Science and Technology 106(12) (2004) 815-821
  

  Two sphingolipids, 1-O-β-D-glucopyranosyl-(2S,3R,4E,8E)-2-[(2R)-2-hydroxyhexadecanoylamino]-9-methyl-4,8-octadecadiene-1,3-diol (1) and 1-O-β-D-glucopyranosyl-(2S,3R,4E,8E)-2-[(2R)-2-hydroxyoctadecanoylamino]-9-methyl-4,8-octadecadiene- 1,3-diol (2), have been isolated from the fruiting bodies of the ascomycete fungus Tuber indicum Cooke et Massee. Their structures were established on the basis of spectroscopic and chemical methods. Sphingolipids are reported from the truffle for the first time.

  glycolipid, sphingolipid, cerebroside, truffle, Tuber indicum, ascomycete fungus

  Publication DOI: 10.1002/ejlt.200401052
  Journal NLM ID: 100961908
  Publisher: Weinheim, Germany: Wiley-VCH
  Correspondence: jinminggao@sohu.com
  Institutions: College of Life Sciences, Northwest Sci.-Tech. University of Agriculture and Forestry, Yangling 712100, Shaanxi, P. R. China, R&D Centre of Biorational Pesticides, Northwest Sci.-Tech. University of Agriculture and Forestry, Yangling 712100, Shaanxi, P. R. China, Key Laboratory of Marine Drugs, Ministry of Education, China, Marine Drug and Food Institute, Ocean University of China, Qingdao 266003, P. R. China, Shaanxi Microbiology Institute, Xi’an 710043, Shaanxi, P. R. China
  Methods: 13C NMR, 1H NMR, IR, FAB-MS, GC-MS, sugar analysis, TLC, ESI-MS, methanolysis, extraction, acetylation
  
   
  
  Tuber indicum
  CSDB ID 41290 (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: 7012
  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-β-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-β-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)

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Structure type: monomer ; 778 [M+Na]+
C₄₃H₈₁NO₉
Trivial name: cerebroside D
Compound class: glycosphingolipid
Contained glycoepitopes: IEDB_137339,IEDB_142488,IEDB_146664,IEDB_983931,SB_192,SB_5

• Article ID: 7012
  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-β-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-β-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 41293 (all data & tools)

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Structure type: monomer
Trivial name: glucosylceramide
Compound class: glycosphingolipid
Contained glycoepitopes: IEDB_137339,IEDB_142488,IEDB_146664,IEDB_983931,SB_192,SB_5

• Article ID: 7020
  da Silva AFC, Rodrigues ML, Farias SE, Almeida IC, Pinto MR, Barreto-Bergter E "Glucosylceramides in Colletotrichum gloeosporioides are involved in the differentiation of conidia into mycelial cells" - FEBS Letters 561(1-3) (2004) 137-143
  

  Glucosylceramides (GlcCer) were extracted from the plant pathogen Colletotrichum gloeosporioides and purified by several chromatographic steps. By using electrospray ionization mass spectrometry and nuclear magnetic resonance, GlcCer from C. gloeosporioides were identified as N-2'-hydroxyoctadecanoyl-1-β-D-glucopyranosyl-9-methyl-4,8-sphingadienine and N-2'-hydroxyoctadecenoyl-1-β-D-glucopyranosyl-9-methyl-4,8-sphingadienine. Monoclonal antibodies against these structures were produced and used as tools for the evaluation of the role of GlcCer in the morphological transition of C. gloeosporioides. In the presence of antibodies to GlcCer, the differentiation of conidia into mycelia was blocked. Since GlcCer is present in several plant pathogens, the inhibitory activity of external ligands recognizing these structures mail be applicable in other models of fungal infections.

  glucosylceramide, monoclonal antibody to GlcCe, Colletotrichum gloeosporioides

  Publication DOI: 10.1016/S0014-5793(04)00156-5
  Journal NLM ID: 0155157
  Publisher: Elsevier
  Correspondence: eliana.bergter@micro.ufrj.br
  Institutions: Instituto de Microbiologia Professor Paulo de Góes, Universidade Federal do Rio de Janeiro, Centro de Ciências da Saúde, Bloco I, Cidade Universitária, Rio de Janeiro 21941-590, Brazil, Departamento de Fisiologia, Instituto de Ciências Básicas da Saúde, Universidade Federal do Rio Grande do Sul, Porto Alegre, Brazil, Departamento de Parasitologia, Universidade de São Paulo, São Paulo, Brazil
  Methods: 1H NMR, GC-MS, sugar analysis, TLC, ELISA, ESI-MS, acid hydrolysis, ESI-MS/MS, biological assays, serological methods, extraction, HPTLC, immunofluorescence analyses
  
   
  
  Colletotrichum gloeosporioides
  CSDB ID 41322 (all data & tools)

Show legend Show as text

Structure type: monomer
Compound class: glycosphingolipid
Contained glycoepitopes: IEDB_137339,IEDB_142488,IEDB_144998,IEDB_146664,IEDB_983931,SB_192,SB_5

• Article ID: 7065
  Takahashi HK, Toledo MS, Suzuki E, Tagliari L, Straus AH "Current relevance of fungal and trypanosomatid glycolipids and sphingolipids: studies defining structures conspicuously absent in mammals" - Anais Da Academia Brasileira De Ciências 81(3) (2009) 477-488
  

  Recently, glycosphingolipids have been attracting attention due to their role on biological systems as second messengers or modulators of signal transduction, affecting several events, which range from apoptosis to regulation of the cell cycle. In pathogenic fungi, glycolipids are expressed in two classes: neutral monohexosylceramides (glucosyl-or galactosylceramide) and acidic glycosylinositol phosphorylceramides (the latter class carries longer glycan chains). It is worth to mention that monohexosylceramides exhibit significant structural differences in their lipid moieties compared to their mammalian counterparts, whereas the glycosylinositol phosphorylceramides exhibit remarkable structural differences in their carbohydrate moieties in comparison to mammal glycosphingolipids counterpart. We observed that glycosylinositol phosphorylceramides are capable of promoting immune response in infected humans. In addition, inhibiting fungal glycosphingolipid biosynthetic pathways leads to an inhibition of colony formation, spore germination, cell cycle, dimorphism and hyphal growth. Other pathogens, such as trypanosomatids, also present unique glycolipids, which may have an important role for the parasite development and/or disease establishment. Regarding host-pathogen interaction, cell membrane rafts, which are enriched in sphingolipids and sterols, participate in parasite/fungal infection. In this review, it is discussed the different biological roles of (glyco) (sphingo)lipids of pathogenic/opportunistic fungi and trypanosomatids.

  glycosphingolipids, leishmania, glycosylinositol phosphorylceramides, inositol phosphorylceramide, membrane rafts, pathogenic fungi

  NCBI PubMed ID: 19722017
  Publication DOI: 10.1590/S0001-37652009000300012
  Journal NLM ID: 7503280
  Publisher: Academia Brasileira De Ciencias
  Correspondence: Anita H. Straus
  Institutions: Setor de Imunoquímica de Glicoconjugados, Departamento de Bioquímica Ed. J.L. Prado, São Paulo, Brasil, Departamento de Microbiologia, Imunologia e Parasitologia, São Paulo, Brasil
  
   
  
  Paracoccidioides brasiliensis, Histoplasma capsulatum, Aspergillus fumigatus, Sporothrix schenckii, Aspergillus nidulans, Candida, Cryptococcus
  CSDB ID 41731 (all data & tools)