The Structure of New Oligosaccharide Antibiotics, 13-384 Components 1 and 5

Ganguly, Ashit K.; Pramanik, Birendra N.; Sarre, Olga Z.; Liu, Y. T.; Morton, James; Girijavallabhan, Viyyor M.; Chan, Tze‐Ming

doi:10.3987/com-88-s36

Cited by 46 publications

(26 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The structure of the ion at m/z 1670 representing the product for addition of one molecule of water (Scheme 2, B) is consistent with our previous report that SCH 27899 can undergo sequential hydrolysis of ortho ester functionalities [8,11]. The initial hydrolysis occurs at the central ortho ester group (between ring B and D, Scheme 1, A).…”

Section: Resultssupporting

confidence: 88%

See 1 more Smart Citation

Multiple-stage mass spectrometric analysis of complex oligosaccharide antibiotics (everninomicins) in a quadrupole ion trap

Chen¹,

Pramanik²,

Bartner³

et al. 2002

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

Section: Resultssupporting

confidence: 88%

“…The isolation procedures were described previously [2,11,25,26]. The samples were dissolved in HPLCgrade acetonitrile (Fisher Scientific, Fair Lawn, NJ).…”

Section: Methodsmentioning

confidence: 99%

Multiple-stage mass spectrometric analysis of complex oligosaccharide antibiotics (everninomicins) in a quadrupole ion trap

Chen¹,

Pramanik²,

Bartner³

et al. 2002

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

“…M. carbonacea var. africana produces fourteen previously described everninomicin congeners (31)(32)(33)(34). Before genetic manipulation, we assessed which everninomicin congeners are produced by M. carbonacea var.…”

Section: Resultsmentioning

confidence: 99%

Oxidative cyclizations in orthosomycin biosynthesis expand the known chemistry of an oxygenase superfamily

McCulloch

McCranie

Smith

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

Orthosomycins are oligosaccharide antibiotics that include avilamycin, everninomicin, and hygromycin B and are hallmarked by a rigidifying interglycosidic spirocyclic ortho-δ-lactone (orthoester) linkage between at least one pair of carbohydrates. A subset of orthosomycins additionally contain a carbohydrate capped by a methylenedioxy bridge. The orthoester linkage is necessary for antibiotic activity but rarely observed in natural products. Orthoester linkage and methylenedioxy bridge biosynthesis require similar oxidative cyclizations adjacent to a sugar ring. We have identified a conserved group of nonheme iron, α-ketoglutarate-dependent oxygenases likely responsible for this chemistry. High-resolution crystal structures of the EvdO1 and EvdO2 oxygenases of everninomicin biosynthesis, the AviO1 oxygenase of avilamycin biosynthesis, and HygX of hygromycin B biosynthesis show how these enzymes accommodate large substrates, a challenge that requires a variation in metal coordination in HygX. Excitingly, the ternary complex of HygX with cosubstrate α-ketoglutarate and putative product hygromycin B identified an orientation of one glycosidic linkage of hygromycin B consistent with metal-catalyzed hydrogen atom abstraction from substrate. These structural results are complemented by gene disruption of the oxygenases evdO1 and evdMO1 from the everninomicin biosynthetic cluster, which demonstrate that functional oxygenase activity is critical for antibiotic production. Our data therefore support a role for these enzymes in the production of key features of the orthosomycin antibiotics.antibiotic biosynthesis | oxidative cyclization | crystal structure | nonheme iron α-ketoglutarate-dependent oxygenases

show abstract

“…It is well documented in the literature that SCH 27899 can undergo sequential hydrolysis at both ortho ester groups with the initial hydrolysis occurring at the central ortho ester group. 11 The presence of molecular ions as well as hydrolysis product ions has complicated the ESI mass spectra for data interpretation. The most effective way of deriving structural information from fragmentation is to perform tandem mass spectrometric experiments in a multiple-stage fashion.…”

Section: Sch 27899 Sch 27899mentioning

confidence: 99%

“…Although the early structural characterization work on this class of compounds was based on Ganguly-Sarre chemical degradation procedure, [5][6][7] fast-atom bombardment (FAB) mass spectrometry (MS) has become a primary method of characterizing everninomicins [8][9][10][11][12][13][14] . However, there are some limitations to this approach, including the limited tandem mass spectrometry (MS/MS) capability for fragmentation pathway studies on sector-based FAB-MS.…”

Section: Introductionmentioning

confidence: 99%

Negative ion multiple-stage mass spectrometric analysis of complex oligosaccharides (everninomicins) in a quadruple ion trap: implications for charge-remote fragmentation

Ganguly¹,

Chen²,

Pramanik³

et al. 2003

Arkivoc

View full text Add to dashboard Cite

Negative ion electrospray ionization (ESI) tandem mass spectrometry (MS/MS) by a quadrupole ion-trap has been utilized to characterize a class of complex oligosaccharide antibiotics (everninomicins), that includes everninomicin-D, SCH 27899, amino everninomicin (SCH 27900), and SCH 49088 containing a hydroxylamino-ether sugar. The deprotonated molecules are dominant ions in the negative ion ESI mass spectra of these compounds. The multiple-stage mass spectrometric analysis (MS n ) of these deprotonated species indicates that the negative charge resides in the deprotonated dichlorophenoxyl group in the substituted aromatic ester ring (ring 1) and the fragmentation occurs remote to this charge site in generating simple sugar sequence-specific fragment ions. One exception to this process is SCH 49088 in which the side chain of the hydroxylamino-ether sugar dominates fragmentation pathway in a charge-driven mechanism and results in less structural information.

show abstract

The Structure of New Oligosaccharide Antibiotics, 13-384 Components 1 and 5

Cited by 46 publications

References 0 publications

Multiple-stage mass spectrometric analysis of complex oligosaccharide antibiotics (everninomicins) in a quadrupole ion trap

Multiple-stage mass spectrometric analysis of complex oligosaccharide antibiotics (everninomicins) in a quadrupole ion trap

Oxidative cyclizations in orthosomycin biosynthesis expand the known chemistry of an oxygenase superfamily

Negative ion multiple-stage mass spectrometric analysis of complex oligosaccharides (everninomicins) in a quadruple ion trap: implications for charge-remote fragmentation

Contact Info

Product

Resources

About