- Synthesis of Gb3 Glycosphingolipids with Labeled Head Groups: Distribution in Phase-Separated Giant Unilamellar Vesicles
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The receptor lipid Gb3 is responsible for the specific internalization of Shiga toxin (STx) into cells. The head group of Gb3 defines the specificity of STx binding, and the backbone with different fatty acids is expected to influence its localization within membranes impacting membrane organization and protein internalization. To investigate this influence, a set of Gb3 glycosphingolipids labeled with a BODIPY fluorophore attached to the head group was synthesized. C24 fatty acids, saturated, unsaturated, α-hydroxylated derivatives, and a combination thereof, were attached to the sphingosine backbone. The synthetic Gb3 glycosphingolipids were reconstituted into coexisting liquid-ordered (lo)/liquid-disordered (ld) giant unilamellar vesicles (GUVs), and STx binding was verified by fluorescence microscopy. Gb3 with the C24:0 fatty acid partitioned mostly in the lo phase, while the unsaturated C24:1 fatty acid distributes more into the ld phase. The α-hydroxylation does not influence its partitioning.
- Sibold, Jeremias,Kettelhoit, Katharina,Vuong, Loan,Liu, Fangyuan,Werz, Daniel B.,Steinem, Claudia
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supporting information
p. 17805 - 17813
(2019/11/13)
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- Syntheses and biological activities of KRN7000 analogues having aromatic residues in the acyl and backbone chains with varying stereochemistry
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KRN7000 is an important ligand identified for CD1d protein of APC, and KRN7000/CD1d complex can stimulate NKT cells to release a broad range of bioactive cytokines. In an effort to understand the structure-activity relationships, we have carried out synth
- Park, Jeong-Ju,Lee, Ji Hyung,Seo, Kyung-Chang,Bricard, Gabriel,Venkataswamy, Manjunatha M.,Porcelli, Steven A.,Chung, Sung-Kee
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supporting information; scheme or table
p. 814 - 818
(2010/06/16)
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- A modular synthesis of alkynyl-phosphocholine headgroups for labeling sphingomyelin and phosphatidylcholine
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(Figure Presented) A general route to phospho- and sphingolipids that incorporate an alkyne in the phosphocholine headgroup is described. The strategy preserves the ammonium functionality of the phosphocholine and can be easily modified to introduce desir
- Sandbhor, Mahendra S.,Key, Jessie A.,Strelkov, Ileana S.,Cairo, Christopher W.
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supporting information; experimental part
p. 8669 - 8674
(2010/02/28)
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- HIGHLY EFFICIENT SYNTHESIS OF ALPHA-O-GALACTOSYL CERAMIDES
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A method for the production of a-O-galactosyl ceramide precursor is demonstrated. The method involves the reaction of galactosyl iodide with a sphingosine derivative or phytosphingosine derivative in the presence of a quaternary ammonium iodide salt to pr
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Page/Page column 13-14
(2008/06/13)
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- Efficient synthesis of α-galactosyl ceramide analogues using glycosyl iodide donors
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(Chemical Equation Presented) The combination of reactive galactosyl iodide donors with electron-rich acceptor lipids provides highly stereoselective and efficient routes to α GalCer analogues. Using per-O-silylated donors, key intermediates can be obtain
- Du, Wenjun,Gervay-Hague, Jacquelyn
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p. 2063 - 2065
(2007/10/03)
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- The total syntheses of D-erythro-sphingosine, N-palmitoylsphingosine (ceramide), and glucosylceramide (cerebroside) via an azidosphingosine analog
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The total synthesis of D-erythro-sphingosine (9) was performed by a chirospecific method starting from D-galactose via an azidosphingosine intermediate to give highly homogeneous ( > 99.9% C18:1) sphingosine base (9) which contained no observable olefin isomerization by product and was demonstrated to be optically pure by a novel method utilizing Mosher's acid. Ceramide (10) was prepared from this sphingosine (9) with highly homogeneous (99.8% C16:0) palmitic acid by two methods. The cerebroside glucosylceramide (23) was the next sphingolipid in this series to be synthesized in a highly homogeneous form. These three sphingolipids are currently being used for biophysical studies of the structures of their hydrated bio-molecular assemblies.
- Duclos Jr., Richard I
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p. 111 - 138
(2007/10/03)
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- Synthesis of 5a-Carba-&β-D-glycosylceramide Analogs Linked by Imino, Ether and Sulfide Bridges
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Carbocyclic analogs of glycoceramides, (2S,3R,4E)-1-(5a-carba-β-D-glycopyranosyl)-2-(hexadecanoylamino)-4-octadecen-3-ols E-3 - E-6, linked by imino, ether and sulfide bridges, were synthesized by coupling of aziridines, as the sphingosine precursors, wit
- Tsunoda, Hidetoshi,Ogawa, Seiichiro
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p. 267 - 278
(2007/10/02)
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- TOTAL SYNTHESIS OF THE MOLLU-SERIES GLYCOSYL CERAMIDES α-D-Manp-(1->3)-β-D-Manp-(1->4)-β-D-Glcp-(1->1)-Cer AND α-D-Manp-(1->3)-2)>-β-D-Manp-(1->4)-β-D-Glcp-(1->1)-Cer
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The mollu-series glycosphingolipids, O-α-D-mannopyranosyl-(1->3)-O-β-D-mannopyranosyl-(1->4)-O-β-D-glucopyranosyl-(1->1)-2-N-tetracosanoyl-(4E)-sphingenine and O-α-D-mannopyranosyl-(1->3)-O-2)>-O-β-D-mannopyranosyl-(1->4)-O-β-D-glucopyranosyl-(1->1)-2-N-tetracosanoyl-(4E)-sphingenine, were synthesized for the first time by using 2,3,4-tri-O-acetyl-D-xylopyranosyl trichloroacetimidate, methyl 2,3,4,6-tetra-O-acetyl-1-thio-α-D-mannopyranoside, benzyl O-(4,6-di-O-benzyl-β-D-mannopyranosyl)-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside 9, and (2S,3R,4E)-2-azido-3-O-(tert-butyldiphenylsilyl)-4-octadecene-1,3-diol 6 as the key intermediates.The hexa-O-benzyl disaccharide 9 was prepared by coupling two monosaccharide synthons, namely, 2,3-di-O-allyl-4,6-di-O-benzyl-α-D-mannopyranosyl bromide and benzyl 2,3,6-tri-O-benzyl-β-D-glucopyranoside.It was demonstrated that azide 6 was highly efficient as a synthon for the ceramide part in the coupling with both glycotriaosyl and glycotetraosyl donors, particularly in the presence of trimethylsilyl triflate.
- Mori, Masato,Ito, Yukishige,Ogawa, Tomoya
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p. 199 - 224
(2007/10/02)
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- Synthesis of Sphingosines, 4. - Synthesis of erythro-Sphingosines via Their Azido Derivatives
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The 2,4-O-protected D-threoses 3a and 3b were obtained from D-galactose and D-xylose, respectively, in two-step procedures.Wittig reaction in the presence of an excess of lithium bromide afforded the trans-enetriols 4aA, 4aB, and 4bA.Triflate activation of the unprotected 2-hydroxy group, azide group introduction, and cleavage of the O-protective groups yielded the azidosphingosines 6A,B which provide after azide group reduction the D-erythro-sphingosines 7A,B.For the glycosphingolipid synthesis through azidosphingosine glycosylation, compound 6A was transformed by 1-O tritylation, 3-O protection, and subsequent 1-O detritylation into the 3-O-protected azidosphingosines 11α-11γ.
- Zimmermann, Peter,Schmidt, Richard R.
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p. 663 - 668
(2007/10/02)
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