Cao, Benjamin and Chen, Xingqiang and Yamaryo-Botte, Yoshiki and Richardson, Mark B and Martin, Kirstee L and Khairallah, George N and Rupasinghe, Thusita W T and O'Flaherty, Roisin and O'Hair, Richard A J and Ralton, Julie E and Crellin, Paul K and Coppel, Ross L and McConville, Malcolm J and Williams, Spencer J
(2013)
Synthesis, Structural Elucidation, And Biochemical Analysis of
Immunoactive Glucuronosyl Diacylglycerides of Mycobacteria and
Corynebacteria.
Journal of Organic Chemistry, 78 (6).
pp. 2175-2190.
ISSN 0022-3263
Abstract
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 Mg2+/Mn2+-dependent metalloenzyme that undergoes dramatic activation upon reduction with dithiothreitol.
| Item Type: |
Article
|
| Keywords: |
Synthesis; Structural Elucidation; Biochemical; Analysis;
Immunoactive; Glucuronosyl; Diacylglycerides; Mycobacteria;
Corynebacteria; |
| Academic Unit: |
Faculty of Science and Engineering > Chemistry |
| Item ID: |
15033 |
| Identification Number: |
https://doi.org/10.1021/jo302508e |
| Depositing User: |
Roisin O'Flaherty
|
| Date Deposited: |
16 Nov 2021 15:31 |
| Journal or Publication Title: |
Journal of Organic Chemistry |
| Publisher: |
American Chemical Society |
| Refereed: |
Yes |
| URI: |
|
| Use Licence: |
This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available
here |
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