Tandem mass spectra of transition‐metal ion adducts of glycosyl dithioacetals; distinction among stereoisomers

Madhusudanan, K. P.; Kumar, Brijesh; Tiwari, Piyush; Madhusudan, Soni Kamlesh; Misra, Anup Kumar

doi:10.1002/rcm.1811

Cited by 6 publications

(7 citation statements)

References 35 publications

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“…Within the past decade, alkali, alkaline earth, and transition metal ions have been extensively used in ESI for many types of compounds. For example, metal ions have been successfully used for stereochemical differentiation by tandem mass spectrometry of some bicyclic diols [2] and glycosyl dithioacetals [3].…”

Section: Introductionmentioning

confidence: 99%

Differentiation of Isomeric HydroxypyridineN-Oxides Using Metal Complexation and Electrospray Ionization Mass Spectrometry

Butler

Máñez

Cabrera

2011

J. Am. Soc. Mass Spectrom.

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Differentiation between two isomers of hydroxypyridine N-oxide according to the metal cation adducts generated by electrospray ionization (ESI) was investigated for different metal cations, namely Mg (II), Al (III), Ca (II), Sc (III), Fe (III), Co (II), Ni (II), Cu (II), Zn (II), Ga (III), besides the diatomic cation VO(IV). Protonated molecules of the isomeric hydroxypyridine N-oxides as well as the singly/doubly charged adducts formed from neutral or deprotonated ligands and a doubly/ triply charged cation were produced in the gas phase using ESI, recording mass spectra with different metal ions for each isomer. While complex formation was successful for 2-hydroxypyridine N-oxide with trivalent ions, in the case of 3-hydroxypyridine N-oxide, only peaks related to the protonated molecule were present. On the other hand, divalent cations formed specific species for each isomer, giving characteristic spectra in every case. Hence, differentiation was possible irrespective of the metal cation utilized. In addition, quantum chemical calculations at the B3LYP/6-31+G(d,p) level of theory were performed in order to gain insight into the different complexation of calcium(II) with the isomers of hydroxypyridine N-oxide. The relative stability in the gas phase of the neutral complexes of calcium made up of two ligands, as well as the singly charged and doubly charged complexes, was investigated. The results of these calculations improved the understanding of the differences observed in the mass spectra obtained for each isomer.

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Section: Introductionmentioning

confidence: 99%

Differentiation of Isomeric HydroxypyridineN-Oxides Using Metal Complexation and Electrospray Ionization Mass Spectrometry

Butler

Máñez

Cabrera

2011

J. Am. Soc. Mass Spectrom.

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“…Some earlier studies also showed that simple metal‐cationized monomeric or dimeric compounds exhibit stereoisomeric distinction when subjected to CID 50–53. For example, Fe 2+ ions have been used to form regioselective and stereoselective transition metal complexes and characteristic product ions by CID for structural elucidation of carbohydrates 50, 51.…”

Section: Methodsmentioning

confidence: 99%

“…Some earlier studies also showed that simple metalcationized monomeric or dimeric compounds exhibit stereoisomeric distinction when subjected to CID. [50][51][52][53] For example, Fe 2þ ions have been used to form regioselective and stereoselective transition metal complexes and characteristic product ions by CID for structural elucidation of carbohydrates. 50,51 Stereoisomeric differentiation of glycosyl dithioacetals, sulfides, sulfoxides and sulfones has also been successful using different transition-metal ion adducts and tandem mass spectrometry.…”

mentioning

confidence: 99%

“…50,51 Stereoisomeric differentiation of glycosyl dithioacetals, sulfides, sulfoxides and sulfones has also been successful using different transition-metal ion adducts and tandem mass spectrometry. 52,53 In the present study, we first investigated the complexation of di-exo-, di-endo-and trans-2,3-disubstituted trinorbornanediols, 2,5-disubstituted trinorbornanediols, and cis-2,3-disubstituted camphanediols with cobalt(II), copper(II), and nickel(II) in the form of chlorides, nitrates, and acetates (Scheme 1). One purpose was to generate metal complexes with two or more diol molecules attached to the metal ion by ESI.…”

mentioning

confidence: 99%

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Diastereochemical differentiation of bicyclic diols using metal complexation and collision‐induced dissociation mass spectrometry

Pakarinen

Vainiotalo

2009

Rapid Comm Mass Spectrometry

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Metal complex formation was investigated for di-exo-, di-endo- and trans-2,3- and 2,5-disubstituted trinorbornanediols, and di-exo- and di-endo- 2,3-disubstituted camphanediols using different divalent transition metals (Co(2+), Ni(2+), Cu(2+)) and electrospray ionization quadrupole ion trap mass spectrometry. Many metal-coordinated complex ions were formed for cobalt and nickel: [2M+Met](2+), [3M+Met](2+), [M-H+Met](+), [2M-H+Met](+), [M+MetX](+), [2M+MetX](+) and [3M-H+Co](+), where M is the diol, Met is the metal used and X is the counter ion (acetate, chloride, nitrate). Copper showed the weakest formation of metal complexes with di-exo-2,3-disubstituted trinorbornanediol yielding only the minor singly charged ions [M-H+Cu](+), [2M-H+Cu](+) and [2M+CuX](+). No clear differences were noted for cobalt complex formation, especially for cis-2,3-disubstituted isomers. However, 2,5-disubstituted trinorbornanediols showed moderate diastereomeric differentiation because of the unidentate nature of the sterically more hindered exo-isomer. trans-Isomers gave rise to abundant [3M-H+Co](+) ion products, which may be considered a characteristic ion for bicyclo[221]heptane trans-2,3- and trans-2,5-diols. To differentiate cis-2,3-isomers, the collision-induced dissociation (CID) products for [3M+Co](2+), [M+CoOAc](+), [2M-H+Co](+) and [2M+CoOAc](+) cobalt complexes were investigated. The results of the CID of the monomeric and dimeric metal adduct complexes [M+CoOAc](+) and [2M-H+Co](+) were stereochemically controlled and could be used for stereochemical differentiation of the compounds investigated. In addition, the structures and relative energies of some complex ions were studied using hybrid density functional theory calculations.

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“…There are a number of reviews and reports on the mass spectra of sulfur‐containing organic compounds 11–15. However, there are only a few reports on the mass spectra of S‐containing carbohydrates 16–19…”

Section: Introductionmentioning

confidence: 99%

Tandem mass spectra of divalent metal ion adducts of glycosyl sulfides, sulfoxides and sulfones; distinction among stereoisomers

et al. 2006

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The tandem mass spectra of the divalent metal ion (Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Ni2+, Co2+ and Zn2+) adducts of acetylated 1,2-trans-glycosyl sulfides, sulfoxides and sulfones were examined using low energy collision-induced dissociation on a Quattro II quadrupole tandem mass spectrometer. Abundant doubly charged ions, such as [3M + Met]2+ and [2M + Met]2+, were observed with alkaline earth metal chlorides. The other ions observed were [M + MetCl]+, [M + MetOAc]+, [M + MetO2SPh]+ and [2M + MetCl]+. The deprotonated metal adducts [M + Met-H]+ were seen only in the sulfones. The divalent metal ion adducts showed characteristic fragmentation pathways for the glycosyl sulfides, sulfoxides and sulfones, depending on the site of metal attachment. The doubly charged metal ion adducts dissociate to two singly charged ions, [M + MetOAc]+ and [M - OAc]+, in the sulfides and sulfoxides. In the sulfones, the adducts dissociate to [M + MetO2SPh]+ and [M - O2SPh]+. In contrast to the alkaline earth metals, which attach to the acetoxy functions, the transition metals attach to the sulfide and sulfoxide functions. The metal chloride adducts display characteristic fragmentation for the sulfides, sulfoxides and sulfones. The glucosyl, mannosyl and galactosyl sulfides, sulfoxides and sulfones could be differentiated on the basis of the stereochemically controlled MS/MS fragmentations of the metal chloride adducts.

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Tandem mass spectra of transition‐metal ion adducts of glycosyl dithioacetals; distinction among stereoisomers

Cited by 6 publications

References 35 publications

Differentiation of Isomeric HydroxypyridineN-Oxides Using Metal Complexation and Electrospray Ionization Mass Spectrometry

Differentiation of Isomeric HydroxypyridineN-Oxides Using Metal Complexation and Electrospray Ionization Mass Spectrometry

Diastereochemical differentiation of bicyclic diols using metal complexation and collision‐induced dissociation mass spectrometry

Tandem mass spectra of divalent metal ion adducts of glycosyl sulfides, sulfoxides and sulfones; distinction among stereoisomers

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