Computer-based system for correlating molecular structures with mass spectral data Methods for generating molecular substructures and for incorporating fragmentation rules

Siegel, Marshall M.; Бауман, Н. А.; Carter, Guy T.

doi:10.1016/s0003-2670(00)81785-7

Cited by 7 publications

(3 citation statements)

References 4 publications

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“…Initial manual calculations with the mass spectral data demonstrated a strong correlation between the major fragment ions and cleavages about the N‐termini of proline and pipecolic acid residues, previously shown to be a very labile and sensitive cleavage site for proline residues 16. More detailed fragmentation calculations utilized Excel spread‐sheets to calculate connected amino acid residues using the revised amphomycin structure, mimicking the calculations reported earlier for connected superatoms with one, two and three bond cleavages 17, 18…”

Section: Methodsmentioning

confidence: 86%

Structure characterization of lipocyclopeptide antibiotics, aspartocins A, B & C, by ESI‐MSMS and ESI‐nozzle‐skimmer‐MSMS

Siegel¹,

Kong²,

Feng³

et al. 2009

J. Mass Spectrom.

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Three lipocyclopeptide antibiotics, aspartocins A (1), B (2), and C (3), were obtained from the aspartocin complex by HPLC separation methodology. Their structures were elucidated using previously published chemical degradation results coupled with spectroscopic studies including ESI-MS, ESI-Nozzle Skimmer-MSMS and NMR. All three aspartocin compounds share the same cyclic decapeptide core of cyclo [Dab2 (Asp1-FA)-Pip3-MeAsp4-Asp5-Gly6-Asp7-Gly8-Dab9-Val10-Pro11]. They differ only in the fatty acid side chain moiety (FA) corresponding to (Z)-13-methyltetradec-3-ene-carbonyl, (+,Z)-12-methyltetradec-3-ene-carbonyl and (Z)-12-methyltridec-3-ene-carbonyl for aspartocins A (1), B (2), and C (3), respectively. All of the sequence ions were observed by ESI-MSMS of the doubly charged parent ions. However, a number of the sequence ions observed were of low abundance. To fully sequence the lipocyclopeptide antibiotic structures, these low abundance sequence ions together with complementary sequence ions were confirmed by ESI-Nozzle-Skimmer-MSMS of the singly charged linear peptide parent fragment ions H-Asp5-Gly6-Asp7-Gly8-Dab9-Val10-Pro11-Dab2(1+)-Asp1-FA. Cyclization of the aspartocins was demonstrated to occur via the beta-amino group of Dab2 from ions of moderate intensity in the ESI-MSMS spectra. As the fatty acid moieties do not undergo internal fragmentations under the experimental ESI mass spectral conditions used, the 14 Da mass difference between the fatty acid moieties of aspartocins A (1) and B (2) versus aspartocin C (3) was used as an internal mass tag to differentiate fragment ions containing fatty acid moieties and those not containing the fatty acid moieties. The most numerous and abundant fragment ions observed in the tandem mass spectra are due to the cleavage of the tertiary nitrogen amide of the pipecolic acid residue-3 (16 fragment ions) and the proline residue-11 (7 fragment ions). In addition, the neutral loss of ethanimine from alpha,beta-diaminobutyric acid residue 9 was observed for the parent molecular ion and for 7 fragment ions.

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Section: Methodsmentioning

confidence: 86%

Structure characterization of lipocyclopeptide antibiotics, aspartocins A, B & C, by ESI‐MSMS and ESI‐nozzle‐skimmer‐MSMS

Siegel¹,

Kong²,

Feng³

et al. 2009

J. Mass Spectrom.

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“…These ions corresponded to known condensed-phase degradation products of cephalosporins and penicillins (6, 7) and were also observed in condensed-phase accelerated stability studies (8,9). Likewise, in our TSP/MS studies of oligomycins, all the 0003-2700/87/0359-0989$01.50/0 © 1987 American Chemical Society observed ions were interpreted as arising from retro-aldol reactions and lactone ester hydrolysis and elimination reactions which were often accompanied by dehydration reactions (10). These thermally induced reactions appeared to occur principally in the condensed phase.…”

Section: Acknowledgmentmentioning

confidence: 60%

Thermospray mass spectrometer interface used as a flow reactor for in situ thermal degradation studies: applications to .beta.-lactam antibiotics

Siegel¹,

Isensee²,

Beck³

1987

Anal. Chem.

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“…Mass spectrometry has seen several expert systems developed for the purpose of fault identification (036) and for the interpretation of spectral peaks (037,038). Kleywegt and van't Klooster discuss the chemical applications of PROLOG for the interpretation of mass spectral peaks in their article (039).…”

Section: Artificial Intelligencementioning

confidence: 99%

Chemometrics

Brown¹,

Barker²,

Larivee³

et al. 1988

Anal. Chem.

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02) Gouveia, M. A.; Seabra e Barros, J.; Tavares, M. J.; Freitas, M. C. J (G4) Routh, M. W. Spectroscopy 1987, 2, 45-52. (G5) Ottaway, J. M.; Littlejohn, D.; Marshall, J. Fortschr. Atomspektrom. (G6) Matuslewlcz, H. Chem. Inz. Chem. 1986, 76, 75-90. (G7) Willoughby, E. J. Commun. Sol Scl. Plant Anal. 1986. 77, 667-677. (G8) Sanz-Medel, A.; Rodriguez Roza, R.; Gonzalez Alonso, R.; Nova1 Valli-(G9) Kratochvil, B.; Motkosky, N.; Duke, M. J. M.: Ng., D. Can. J . Chem.the detailed discussion of computers is somewhat beyond the scone of the review as defined above. a decision was made not Steven D. Brown received his 0.5. degree in chemistry in 1972 and an M.S. in phyaC EaUnwgsnlC ChBmisbY in 1975. both from Pwtland-State Univer&, He obtained the m.D. degree in anawical chemistry from the University 01 Washlngton in 1978 working under the direction 01 Bruce KOwaiSkl. In 1978, he was appointed to the chemistry facuity at the University of California. where he held B joint appointment at the Lawrence m e l e y National Laboratory. He moved to 4 1 i Washington Slate Univer&in 1981. where he war Associate Prolesscr, prior to Ialning the chemistry faculty et the Unlverrny of Delaware In 1986. He is cunentiv AI SOCI --. --ate Professor 01 Chemistry and Operations Research. He I S also Associate Editor Of The Journal Of ChemomsWcs and serves on !he editorial boards of AnaWica Chimica Acta and Anaiyiicai Lstfers . His research interests encompass many aspects of the application Of Computers to chemical problems, including the areas Of real-time analysis, shoat ~rocesGinri. oo!imiratlan. mockling. and process control Todd 0. Barker obtained hi8 B S degree in Chemistry from the University of South Dakota in 1981 Afler working for the South Dakota Geoloaical Survev. he returned to the unker& 01 so&~Dakota. earning an M.A. in analytical chemistry in 1984. He began W.D. studies at Washington state universitv in 1984 and moved to the UniversW of &!aware in 1986 His re-, r L k search ihlere5ts include the development of Kalman finer* for reawme analysis and control and modeling 01 kinetics in flow in]ection anahsls. R a d J. LarlrN earned a B.A. deoree in chemistry from R i d e Island Coiiege in 1978. He began FhD. studies at Washington State Univerrltv ami moved to the LJniV-~~~~~ . ~. . ... ersity 01 Delaware in 1986. His research interests concern development of factor analysis methods fw investigBtion of metal speciation. S1.plrm L. Modre obtained a 0.5. degree in chembtry and computer Science from the University 01 Wisconsin-La Crasse in 1984. That year he moved to Washington State University. where he began Ph.D. studies in Chemistry. He moved lo Oehwars in 1986. where he Is now a graduate research assistant His research interests lie In dlgltal Riierlng. fuzzy matching. and rodeling. Hadan R. Wllk graduated trom Norm Carol!na State University wkh a 0.5. in chemical enginewing in 1984. After beginning his h.0. studies at Washlnglon State University. he moved I O the University Of Delaware h 19%. l i s research Werests lie in th...

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Computer-based system for correlating molecular structures with mass spectral data Methods for generating molecular substructures and for incorporating fragmentation rules

Cited by 7 publications

References 4 publications

Structure characterization of lipocyclopeptide antibiotics, aspartocins A, B & C, by ESI‐MSMS and ESI‐nozzle‐skimmer‐MSMS

Structure characterization of lipocyclopeptide antibiotics, aspartocins A, B & C, by ESI‐MSMS and ESI‐nozzle‐skimmer‐MSMS

Thermospray mass spectrometer interface used as a flow reactor for in situ thermal degradation studies: applications to .beta.-lactam antibiotics

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