Gas chromatography and mass spectrometry of the trimethylsilyl derivatives of inorganic anions

Butts, William C.; Rainey, W.T.

doi:10.1021/ac60299a004

Cited by 93 publications

(13 citation statements)

References 13 publications

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“…Phosphoric acid could be identified via the molecular ion of the tris(trimethylsilyl)ester ( 18 OP( 18 Osi (CH 3 ) 3 ) 3 ) at m/z (M + ) = 322 and its fragment originating from the loss of a methyl group at m/z (M + −15) = 307 29 . Phosphonic acid was detected via the molecular ion of the derivatized phosphorous acid tautomer in the form of its tris(trimethylsilyl)ester (P( 18 OSi(CH 3 ) 3 ) 3 ) at m/z (M + ) = 304 and its fragment of the methyl group loss at m/z (M + −15) = 304 30 . Finally, phosphinic acid could be sampled via its hypophosphorous acid tautomer as its bis(trimethylsilyl)ester (HP( 18 OSi(CH 3 ) 3 ) 2 ) at m/z (M + ) = 214 and also by its fragment of the methyl group elimination at m/z (M + −15) = 199.…”

Section: Resultsmentioning

confidence: 99%

An interstellar synthesis of phosphorus oxoacids

et al. 2018

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Phosphorus signifies an essential element in molecular biology, yet given the limited solubility of phosphates on early Earth, alternative sources like meteoritic phosphides have been proposed to incorporate phosphorus into biomolecules under prebiotic terrestrial conditions. Here, we report on a previously overlooked source of prebiotic phosphorus from interstellar phosphine (PH3) that produces key phosphorus oxoacids—phosphoric acid (H3PO4), phosphonic acid (H3PO3), and pyrophosphoric acid (H4P2O7)—in interstellar analog ices exposed to ionizing radiation at temperatures as low as 5 K. Since the processed material of molecular clouds eventually enters circumstellar disks and is partially incorporated into planetesimals like proto Earth, an understanding of the facile synthesis of oxoacids is essential to untangle the origin of water-soluble prebiotic phosphorus compounds and how they might have been incorporated into organisms not only on Earth, but potentially in our universe as well.

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Section: Resultsmentioning

confidence: 99%

An interstellar synthesis of phosphorus oxoacids

et al. 2018

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“…In the database, some dialkyl phosphites are presented with structures ( I* ). At the same time, phosphorous acid H 3 PO 3 forms not bis ‐, but tris ‐trimethylsilyl ester, which suggests the presence of three so‐called active hydrogen atoms in the molecule, i.e., not (HO) 2 PHO, but P(OH) 3 . To distinguish the possible dialkyl phosphonates ( I ) and isomeric dialkyl phosphites ( I* ) with a hydroxyl group ≡ active hydrogen atom in a molecule, the reaction mixture of isopropyl alcohol with PCl 3 was treated with excess of N ‐trimethylsilylimidazole as one of the most active silylating reagents .…”

Section: Resultsmentioning

confidence: 99%

Comparative gas chromatographic/mass spectrometric characterization of di‐ and trialkyl phosphites

Зенкевич

Nosova

2019

Rapid Comm Mass Spectrometry

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Rationale: Homologous series of alkyl esters of phosphorus-containing acids, namely, dialkyl phosphonates (synonym: dialkyl phosphites) and trialkyl phosphites, were characterized by electron ionization (EI) mass spectra and gas chromatographic retention indices (GC RI) on semi-standard non-polar stationary phases. It is confirmed that GC/MS characterization of any sets of homologues should not be restricted to independent registration of these analytical parameters. Their joint processing in the form of so-called homologous increments of GC RIs means, firstly, a novel way of evaluating the chromatographic polarity of analytes and, secondly, a new algorithm for the prediction of their molecular weights if no peaks of molecular ions are registered in the mass spectra. Methods:A standard GC/MS technique, including determination of GC RIs on semi-standard nonpolar stationary phases in temperature-programmed regime and electron ionization (EI) mass spectra was used.Results: A total of 31 dialkyl phosphonate homologues and 37 trialkyl phosphite homologues were characterized by EI mass spectra and GC RIs for the first time.Joint processing of these analytical parameters allows the calculation of so-called homologous increments of GC RIs, which are useful parameters for evaluating the chromatographic polarity of analytes and predicting their molecular weights.Conclusions: GC/MS characterization of any sets of homologues should not be restricted to independent registration of the mass spectra and chromatographic retention parameters. Their joint processing in the form of so-called homologous increments of GC retention indices means, firstly, a novel way of evaluating the chromatographic polarity of analytes and, secondly, a new algorithm for predicting their molecular weights.

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“…Methods used include TLC-AAS [44,143], paper chromatography-AAS [ 1441, paper electrophoresis-AAS [ 1451, ion exchange column chromatography-AAS for the separation and detection of arsenic(III), arsenic(V), MMAA, DMAA [146,147], GC with flame ionization detection (FID) and GC-MS of methylthioglycolate derivatives of MMAA and DMAA [148]. GC-MIP and GC alkali flame ionization for the estimation of the ethylene glycol derivative of MMAA [149], GC-FID and flame spectrometric detection of the trimethyl-silyl [150] and GC-electron capture detection of the diethyldithiocarbamate complex of MMAA and DMAA [150]; solvent extraction followed by detection by AAS [ 15 1,1521, and polarography/voltammetry to discriminate arsenic(II1) and arsenic(V) [ 153,1543. These methods, however, are not likely to possess significant advantages over hydride generation-GC, HPLC-AAS and HPLC-ICP.…”

Section: Other Methodsmentioning

confidence: 99%