Mass spectrometric separation and quantitation of overlapping isotopologues. H2O/HOD/D2O and H2Se/HDSe/D2Se mixtures

Meija, Juris; Mester, Zoltán; D’Ulivo, Alessandro

doi:10.1016/j.jasms.2006.02.008

Cited by 31 publications

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“…In this case, relative abundances of the arsane and monomethylarsane isotopologues were estimated using mathematical deconvolution techniques previously developed for quantitation of hydrides EH 2 (E = O, Se) [15], EH 3 (E = As, Sb, Bi) and EH 4 (E = Ge, Sn) [16] Electron impact mass spectra of the pure arsane isotopologues are given below: …”

Section: Introductionmentioning

confidence: 99%

Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl- and dimethylarsane by aqueous borohydride and (methyl) arsenates

et al. 2011

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Access and use of this website and the material on it are subject to the Terms and Conditions set forth at Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl-and dimethylarsane by aqueous borohydride and (methyl) arsenates D'Ulivo, Alessandro; Meija, Juris; Mester, Zoltán; Pagliano, Enea; Sturgeon, Ralph E.http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/jsp/nparc_cp.jsp?lang=fr L'accès à ce site Web et l'utilisation de son contenu sont assujettis aux conditions présentées dans le site LISEZ CES CONDITIONS ATTENTIVEMENT AVANT D'UTILISER CE SITE WEB. NRC Publications Record / Notice d'Archives des publications de CNRC:http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?action=rtdoc&an=21268282&lang=en http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?action=rtdoc&an=21268282&lang=fr READ THESE TERMS AND CONDITIONS CAREFULLY BEFORE USING THIS WEBSITE.http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/jsp/nparc_cp.jsp?lang=en Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions? Contact the NRC Publications Archive team atPublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://doi.org/10.1007/s00216-011-5503-4Analytical and Bioanalytical Chemistry, 402, 2, pp. 921-933, 2011-10-30 ABSTRACTThe formation of volatile products during the reaction of As(III), As(V), MeAsO(OH) 2 and Me 2 AsO(OH) with aqueous NaBH 4 has been investigated and the formation of arsanes, di-and triarsanes has been detected . The presence of triarsanes is reported here for the first time. Di-and triarsanes are likely formed in condensation cascade reactions, whereas trimethylarsane arises via the transfer of a methyl group. The formation of volatile byproducts is considerably reduced by increasing the acidity of the medium and the concentration of NaBH 4 or by the addition of thiols, such as cysteine. A reaction scheme is proposed which reconciles the evidence reported herein and elsewhere in the literature that is valid for both analytical (trace analysis) and non-analytical reaction conditions.

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Section: Introductionmentioning

confidence: 99%

Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl- and dimethylarsane by aqueous borohydride and (methyl) arsenates

et al. 2011

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“…Statistical Model for the Mass Spectra of As 2 H n D 4-n and As 3 H n D 5-n Statistical reconstruction of partially deuterated hydride has been reported previously for deuterated homologues of diborane [17], methane [18], ethane [19], water, selane [15], arsane, stibane, bismuthane, stannane, and germane [16]. Here, a model proposed by Meija et al [16] was used for this purpose.…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, it is not feasible to synthesize pure partially deuterated isotopologues or separate them by conventional gas chromatography. Nevertheless, the determination of the mole fraction of each isotopologue in a mixture can be achieved mathematically by applying a statistical mass balance model [15,16]. Using this method, it was possible to delineate the mechanism of formation of diarsane and triarsane in the As(III)/[BH 4 ] − system and to discover a strong perturbation to the mechanism of arsane generation due to the presence of Rh(III).…”

Section: Resultsmentioning

confidence: 99%

“…Although the statistical model suffers limitations when applied to small molecules (it fails to predict the mass spectrum of HOD with great accuracy [15]), it has proven to be effective for heavier molecules such as selane [15], arsane, stibane, bismuthane, stannane, and germane [16].…”

Section: Resultsmentioning

confidence: 99%

“…In particular, this work illustrates how complex mass spectra can be deconstructed and interpreted with the aid of simple mathematical models based on molecular symmetry considerations [15,16] so as to infer valuable information about the mechanisms of arsane condensation.…”

Section: Introductionmentioning

confidence: 99%

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The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BH_nD_4-n]⁻ and the Effect of Trace Amounts of Rh(Iii) Ions

D’Ulivo

Mester

Sturgeon

et al. 2012

J. Am. Soc. Mass Spectrom.

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Recent studies of the formation of arsane in the borohydride/arsenate reaction demonstrate the occurrence of condensation cascades whereby small quantities of di-and triarsanes are formed. In this study, the isotopic composition of these di-and triarsanes was examined using deuterium labelled borohydrides. A statistical model was employed to construct the mass spectra of all diarsane and triarsane isotopologues (As 2 H n D 4-n and As 3 H n D 5-n ) from the mass spectra of isotopically pure compounds (As 2 H 4 , As 2 D 4 , As 3 H 5 , and As 3 D 5 ). Subsequent deconvolution of the experimental mixed spectra shows that incorporation of hydrogen closely follows the binomial distribution, in accord with arsane formation. The H/D distribution in arsane, diarsane, and triarsane isotopologues is binomial in the absence of any interference. However, this is significantly altered by the presence of some transition metals; presented here, for the first time, are the effects of Rh(III). The presence of Rh(III) in the As(III)/ [BD 4 ] − system entails the incorporation of hydrogen into the arsanes arising from the solvent, altering the expected binomial H/D distribution.

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Simultaneous Sensing of H₂O, D₂O and HOD through Peroxo Vibrations

Pal

Chattopadhyay

2023

ChemPhysChem

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Detection of HOD simultaneously in the presence of a mixture of H 2 O and D 2 O is still an experimental challenge. Till date, there is no literature report of simultaneous detection of H 2 O, D 2 O and HOD based on vibrational spectra. Herein we report simultaneous quantitative detection of H 2 O, D 2 O and HOD in the same reaction mixture with the help of bridged polynuclear peroxo complex in absence and presence of Au nanoparticles on the basis of a peroxide vibrational mode in resonance Raman and surface enhanced resonance Raman spectrum. We synthesize bridged polynuclear peroxo complex in different solvent mixture of H 2 O and D 2 O. Due to the formation of different nature of hydrogen bonding between peroxide and solvent molecules (H 2 O, D 2 O and HOD), vibrational frequency of peroxo bond is significantly affected. Mixtures of different H 2 O and D 2 O concentrations produce different HOD concentrations and that lead to different intensities of peaks positioned at 897, 823 and 867 cm À 1 indicating H 2 O, D 2 O and HOD, respectively. The lowest detection limits (LODs) were 0.028 mole fraction of D 2 O in H 2 O and 0.046 mole faction of H 2 O in D 2 O. In addition, for the first time the results revealed that the cis-peroxide forms two hydrogen bonds with solvent molecules.

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Mass spectrometric separation and quantitation of overlapping isotopologues. H₂O/HOD/D₂O and H₂Se/HDSe/D₂Se mixtures

Cited by 31 publications

References 31 publications

Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl- and dimethylarsane by aqueous borohydride and (methyl) arsenates

Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl- and dimethylarsane by aqueous borohydride and (methyl) arsenates

The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BH_nD_4-n]⁻ and the Effect of Trace Amounts of Rh(Iii) Ions

Simultaneous Sensing of H₂O, D₂O and HOD through Peroxo Vibrations

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Mass spectrometric separation and quantitation of overlapping isotopologues. H2O/HOD/D2O and H2Se/HDSe/D2Se mixtures

Cited by 31 publications

References 31 publications

Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl- and dimethylarsane by aqueous borohydride and (methyl) arsenates

Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl- and dimethylarsane by aqueous borohydride and (methyl) arsenates

The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BHnD4-n]− and the Effect of Trace Amounts of Rh(Iii) Ions

Simultaneous Sensing of H2O, D2O and HOD through Peroxo Vibrations

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Mass spectrometric separation and quantitation of overlapping isotopologues. H₂O/HOD/D₂O and H₂Se/HDSe/D₂Se mixtures

The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BH_nD_4-n]⁻ and the Effect of Trace Amounts of Rh(Iii) Ions

Simultaneous Sensing of H₂O, D₂O and HOD through Peroxo Vibrations