Application of mass spectrometry for the analysis of organic tautomeric compounds

Терентьев, П. Б.; Kalandarishvili, A. G.

doi:10.1002/(sici)1098-2787(1996)15:6<339::aid-mas1>3.0.co;2-j

Cited by 31 publications

(23 citation statements)

References 77 publications

(64 reference statements)

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“…8) Information about tautomers avoiding effects of the solvent can be obtained in the gas phase. It is also possible either using computational chemistry (see Chapters 10 and 13) or through, for instance, NMR [47], mass spectrometry [48,49], electron diffraction [50], or double resonance techniques (cf. Chapter 7).…”

Section: Tautomeric Equilibrium: Historical Overview Of An Analyticalmentioning

confidence: 99%

Tautomerism: Introduction, History, and Recent Developments in Experimental and Theoretical Methods

Taylor¹,

Zwan²,

Antonov³

2013

Tautomerism

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Section: Tautomeric Equilibrium: Historical Overview Of An Analyticalmentioning

confidence: 99%

Tautomerism: Introduction, History, and Recent Developments in Experimental and Theoretical Methods

Taylor¹,

Zwan²,

Antonov³

2013

Tautomerism

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“…T he analysis of tautomers-isomeric species that differ only in the positioning of a labile proton [1] -has challenged mass spectrometry (MS) for many decades [2,3]. In rare cases, orthogonal separation of tautomers prior to MS analysis could be afforded by gas chromatography [4], but the vast majority of cases involve MS analysis of convolved mixtures of tautomers.…”

Section: Introductionmentioning

confidence: 99%

“…When only using a trace amount of deuterium oxide (D 2 O) in the throttle gas, differences in the number of hydrogens exchanged were observed for each 4-ABA tautomer. However, when the amount of D 2 O was increased or a more basic HDX reagent was employed (e.g., d 1 -methanol, CH 3 OD), both tautomers exhibited equivalent numbers of exchanged hydrogens, which we initially interpreted as overexposure of HDX reagent to these ions. However, another explanation for this equivalent HDX behavior is that both ions share the same structure as a result of tautomerization during the HDX reaction, converting the N-to the O-protonated form of 4-ABA.…”

Section: Introductionmentioning

confidence: 99%

Studying Gas-Phase Interconversion of Tautomers Using Differential Mobility Spectrometry

Campbell

Yang

Melo

et al. 2016

J. Am. Soc. Mass Spectrom.

125

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Abstract. In this study, we report on the use of differential mobility spectrometry (DMS) as a tool for studying tautomeric species, allowing a more in-depth interrogation of these elusive isomers using ion/molecule reactions and tandem mass spectrometry. As an example, we revisit a case study in which gas-phase hydrogendeuterium exchange (HDX)-a probe of ion structure in mass spectrometry-actually altered analyte ion structure by tautomerization. For the N-and O-protonated tautomers of 4-aminobenzoic acid, when separated using DMS and subjected to subsequent HDX with trace levels of D 2 O, the anticipated difference between the exchange rates of the two tautomers is observed. However, when using higher levels of D 2 O or a more basic reagent, equivalent and almost complete exchange of all labile protons is observed. This second observation is a result of the interconversion of the N-protonated tautomer to the Oprotonated form during HDX. We can monitor this transformation experimentally, with support from detailed molecular dynamics and electronic structure calculations. In fact, calculations suggest the onset of bulk solution phase properties for 4-aminobenzoic acid upon solvation with eight CH 3 OH molecules. These findings also underscore the need for choosing HDX reagents and conditions judiciously when separating interconvertible isomers using DMS.

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“…Although the tautomeric state in solution and in the gas phase may clearly differ from each other our earlier experience shows that NMR measurements in solution are often rather predictive of what will be observed in the mass spectrometric conditions 3, 10, 11, 18. Therefore, we inspected the solution‐state tautomerism of the compounds with 1 H and 13 C NMR spectroscopy for 1a , 1d , 1g , 2 , 3d , 3g , 4d and 4g .…”

Section: Resultsmentioning

confidence: 99%

Electron ionization mass spectra of aryl‐ and benzyl‐substituted 2,3‐dihydroimidazo[1,2‐a]pyrimidine‐5,7(1H,6H)‐diones

Martiskainen

Kivelä

Matosiuk

et al. 2007

Rapid Comm Mass Spectrometry

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The electron ionization mass spectra of the 1-phenyl-, 1-benzyl- and 6-benzyl-1-phenyl-2,3-dihydroimidazo[1,2-a]pyrimidine-5,7(1H,6H)-dione derivatives were recorded at 70 eV to find out the effects of substituents on their fragmentations. Fragmentation pathways were studied using B/E and B(2)/E scans. Some fragmentations involved the loss of C(3)HO(2) or carbon suboxide. The possibility of keto-enol tautomerism was also studied. For comparison selected compounds were studied using (1)H and (13)C NMR spectroscopy to reveal the presence of possible tautomerism. Some ions including [M-OH](+) and [M-HCO](+) and NMR results indicate that the enol form is predominant both in the gas and in the liquid phase.

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Application of mass spectrometry for the analysis of organic tautomeric compounds

Cited by 31 publications

References 77 publications

Tautomerism: Introduction, History, and Recent Developments in Experimental and Theoretical Methods

Tautomerism: Introduction, History, and Recent Developments in Experimental and Theoretical Methods

Studying Gas-Phase Interconversion of Tautomers Using Differential Mobility Spectrometry

Electron ionization mass spectra of aryl‐ and benzyl‐substituted 2,3‐dihydroimidazo[1,2‐a]pyrimidine‐5,7(1H,6H)‐diones

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