Skip Navigation

This Article
Right arrow Full Text (PDF)
Right arrow Alert me when this article is cited
Right arrow Alert me if a correction is posted
Services
Right arrow Email this article to a friend
Right arrow Similar articles in this journal
Right arrow Similar articles in PubMed
Right arrow Alert me to new issues of the journal
Right arrow Add to My Personal Archive
Right arrow Download to citation manager
Right arrow Request Permissions
Google Scholar
Right arrow Articles by Taketomi, T.
Right arrow Articles by Sugiyama, E.
Right arrow Search for Related Content
PubMed
Right arrow PubMed Citation
Right arrow Articles by Taketomi, T.
Right arrow Articles by Sugiyama, E.
Social Bookmarking
Add to CiteULike   Add to Connotea   Add to Del.icio.us  
What's this?

J. Biochem, 1990, Vol. 107, No. 5 680-684
© 1990 Japanese Biochemical Society

research-article

New Approach for Characterization of Lysosulfatide by TLC, Fast Atom Bombardment Mass Spectrometry and NMR Spectroscopy

Tamotsu Taketomi, Atsushi Hara, Yukie Kutsukake and Eiko Sugiyama

Department of Lipid Biochemistry, Institute of Cardiovascular Disease, Shinshu University School of Medicine Matsumoto, Nagano 390

Thin layer chromatography of lysosulfatide showed anomalous Rf- values in contrast with such lysosphingolipids as glucopsychosine and galactopsychosine with neutral, acidic, and alkaline developing solvents. This was thought to be due to the presence of oppositely charged sulfate and amino groups in the lysosulfatide. In the negative mode of fast atom bombardment mass spectrometry, the lysosulfatide showed the pseudo molecular ion (M—H){small tilde} peak at m/z 540 and sulfate ion peak at m/z 97, whereas in the positive mode, it showed not only the pseudo molecular ion (M + H)+ peak at m/z 542, but also the major peaks of protonated psychosine at m/z 462 and fragment ions of dehydrated sphingosine at m/z 282 and 264.13C-NMR signals of all carbons of lysosulfatide were determined by using distortionless enhancement by polarization transfer. The difference in chemical shifts of ring carbons of galactose residue between lysosulfatide and galactopsychosine was largest at C-3 (downfield shift), thereby indicating the location of the sulfate group to be at C-3 of galactose. This conclusion is supported by the 1H-NMR spectra of the lysosulfatide and galactopsychosine. Thus, the chemical structure of lysosulfatide was confirmed by fast atom bombardment mass spectrometry and 13C- and 1H-NMR spectroscopy. Furthermore, 13C-NMR signals of C-l to C-5 of the sphingosine moiety showed significantly different chemical shifts between the lysosulfatide and galactopsychosine. These differences suggested that C-l to C-5 of sphingosine might be influenced by intramolecular or inter-molecular interaction between the sulfate group of the galactose residue and the amino group of sphingosine. In particular, the order of the absolute value of difference in chemical shift (| {Delta}{delta} |) being C-l > C-3> C-5 in the sphingosine between lysosulfatide and galactopsychosine suggested that the sulfate group might influence the carbons at C-l, -3, and -5, inducing a zigzag conformation of sphingosine in lysosulfatide. Also, the downfield shift of protons at C-l, -3, and -5 of sphingosine in lysosulfatide relative to sulfatide indicated that the removal of fatty acid from sulfatide might similarly induce a zigzag conformation of sphingosine in lysosulfatide. The interaction between the sulfate and amino groups was also suggested by the 1H-NMR spectra of the lysosulfatide and galactopsychosine, because the former showed no amino proton signal.


Add to CiteULike CiteULike   Add to Connotea Connotea   Add to Del.icio.us Del.icio.us    What's this?


This article has been cited by other articles:


Home page
 J. Biol. Chem.Home page
T. Hikita, K. Tadano-Aritomi, N. Iida-Tanaka, J. K. Anand, I. Ishizuka, and S.-i. Hakomori
A Novel Plasmal Conjugate to Glycerol and Psychosine ("Glyceroplasmalopsychosine"). ISOLATION AND CHARACTERIZATION FROM BOVINE BRAIN WHITE MATTER
J. Biol. Chem., June 15, 2001; 276(25): 23084 - 23091.
[Abstract] [Full Text] [PDF]


Disclaimer: Please note that abstracts for content published before 1996 were created through digital scanning and may therefore not exactly replicate the text of the original print issues. All efforts have been made to ensure accuracy, but the Publisher will not be held responsible for any remaining inaccuracies. If you require any further clarification, please contact our Customer Services Department.