Synthesis, Structural Elucidation, And Biochemical Analysis of Immunoactive Glucuronosyl Diacylglycerides of Mycobacteria and Corynebacteria
| Autor: | Paul K. Crellin, Benjamin Cao, Spencer J. Williams, Thusita Rupasinghe, Roisin O'Flaherty, Ross L. Coppel, Malcolm J. McConville, Kirstee L. Martin, Xingqiang Chen, George N. Khairallah, Julie E. Ralton, Richard A. J. O'Hair, Mark B. Richardson, Yoshiki Yamaryo-Botté |
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| Rok vydání: | 2013 |
| Předmět: |
Mannosyltransferase
Glycosylation Stereochemistry Mycobacterium smegmatis Corynebacterium Mannosyltransferases Mass Spectrometry Glycerides Mycobacterium Corynebacterium glutamicum Acylation chemistry.chemical_compound Glycolipid Bacterial Proteins Magnesium biology Chemistry Organic Chemistry biology.organism_classification Biosynthetic Pathways Biochemistry lipids (amino acids peptides and proteins) Glycolipids Stearic Acids |
| Zdroj: | The Journal of Organic Chemistry. 78:2175-2190 |
| ISSN: | 1520-6904 0022-3263 |
| DOI: | 10.1021/jo302508e |
| Popis: | Glucuronosyl diacylglycerides (GlcAGroAc2) are functionally important glycolipids and membrane anchors for cell wall lipoglycans in the Corynebacteria. Here we describe the complete synthesis of distinct acyl-isoforms of GlcAGroAc2 bearing both acylation patterns of (R)-tuberculostearic acid (C19:0) and palmitic acid (C16:0) and their mass spectral characterization. Collision-induced fragmentation mass spectrometry identified characteristic fragment ions that were used to develop "rules" allowing the assignment of the acylation pattern as C19:0 (sn-1), C16:0 (sn-2) in the natural product from Mycobacterium smegmatis, and the structural assignment of related C18:1 (sn-1), C16:0 (sn-2) GlcAGroAc2 glycolipids from M. smegmatis and Corynebacterium glutamicum. A synthetic hydrophobic octyl glucuronoside was used to characterize the GDP-mannose-dependent mannosyltransferase MgtA from C. glutamicum that extends GlcAGroAc2. This enzyme is an Mg(2+)/Mn(2+)-dependent metalloenzyme that undergoes dramatic activation upon reduction with dithiothreitol. |
| Databáze: | OpenAIRE |
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