Mass Spectrometry as a Crucial Analytical Basis for Omics Sciences

Abstract: This review is devoted to the consideration of mass spectrometric platforms as applied to omics sciences. The most significant attention is paid to omics related to life sciences (genomics, proteomics, meta-bolomics, lipidomics, glycomics, plantomics, etc.). Mass spectrometric approaches to solving the problems of petroleomics, polymeromics, foodomics, humeomics, and exosomics, related to inorganic sciences, are also discussed. The review comparatively presents the advantages of various principles of separation and mass spectral techniques, complementary derivatization, used to obtain large arrays of various structural and quantitative information in the mentioned omics sciences. © 2021, Pleiades Publishing, Ltd

A “soft” ionization mass spectrometric study of organic sulfides as sulfonium salts

Preliminary conversion of nonpolar organic sulfides into sulfonium salts was proposed for their study and analysis by laser desorption/ionization (MALDI and SALDI) and electrospray/ionization (ESI) mass spectrometry. General possibilities of the methodology proposed were demonstrated on examples of dialkyl sulfides, substituted thiacyclanes, dibenzothiophene, and methionine methyl ester. Various alkyl and aralkyl halides, as well as trimethyl- and triethyloxonium salts were tested as alkylating agents. S-alkylation was shown to proceed quantitatively under mild conditions. MALDI and SALDI mass spectra (a matrix-free nanostructurized target was used in SALDI experiments) displayed only ion peaks corresponding to sulfonium cations whose mass numbers were equal to the sum of molecular weights of sulfides and weight increments of the introduced alkyl and aralkyl groups. Trans-alkylation was observed for benzyl-substituted sulfides. Tandem mass spectrometry provided preliminary data on the fragmentation of ESI-generated sulfonium cations and demonstrated differences in the MS/MS spectra of regioisomers. © 2016, Pleiades Publishing, Ltd

A “soft” ionization mass spectrometric study of organic sulfides as sulfonium salts

Preliminary conversion of nonpolar organic sulfides into sulfonium salts was proposed for their study and analysis by laser desorption/ionization (MALDI and SALDI) and electrospray/ionization (ESI) mass spectrometry. General possibilities of the methodology proposed were demonstrated on examples of dialkyl sulfides, substituted thiacyclanes, dibenzothiophene, and methionine methyl ester. Various alkyl and aralkyl halides, as well as trimethyl- and triethyloxonium salts were tested as alkylating agents. S-alkylation was shown to proceed quantitatively under mild conditions. MALDI and SALDI mass spectra (a matrix-free nanostructurized target was used in SALDI experiments) displayed only ion peaks corresponding to sulfonium cations whose mass numbers were equal to the sum of molecular weights of sulfides and weight increments of the introduced alkyl and aralkyl groups. Trans-alkylation was observed for benzyl-substituted sulfides. Tandem mass spectrometry provided preliminary data on the fragmentation of ESI-generated sulfonium cations and demonstrated differences in the MS/MS spectra of regioisomers. © 2016, Pleiades Publishing, Ltd

Mass Spectrometry in Petroleum Chemistry (Petroleomics) (Review)

Abstract: The review discusses the achievements of the last 5 years in the field of using mass spectrometry for the analysis of crude oils and some oil refining products. The presented materials are systematized according to properties of the analyzed compounds and ionization techniques used. The capabilities and disadvantages of existing approaches are discussed. © 2019, Pleiades Publishing, Ltd

Investigation of 1,1′-disubstituted 4,4′-bipyridinium salts by various mass spectrometry techniques

The mass spectrometric behavior of symmetrically disubstituted 4,4′-bipyridinium salts under electron ionization (EI), electrospray ionization (ESI), direct analysis in real time (DART) ionization, and matrix-assisted laser desorption-ionization (MALDI) has been investigated. Electron ionization spectra were recorded using the direct injection of the probe at elevated temperature, when the salts were decomposed with the loss of counter-ions. In the case of ESI, primary ions are radical cations [Cat] +· and cations [Cat-H]+, decomposed further by the loss of N-substituents. More complicated DART spectra revealed the peaks characterizing both bipyridyl group and organic substituents. MALDI spectra were rather simple and contained the peaks for [Cat]+ · ions that are structurally identical to radical cations formed during the reduction of the salts in solution. Among all the methods, DART and MALDI are suitable for the qualitative analysis of such bis-quaternary salts, while ESI is convenient for the quantitative analysis of these analytes. © 2013 Pleiades Publishing, Ltd

Features of the First and Second Order Electrospray Ionization Mass Spectra for Salt-Like Products Derived from Monools and Diols Using Combined Reagents Based on ω-Bromoacyl Chlorides and Nitrogen Bases

Derivatization by composite reagents based on ω-bromoacyl chlorides [ClCO(C2)nBr (n = 1–4)] and pyridine was applied to study aliphatic and alicyclic alcohols and diols by ordinary and tandem electrospray ionization (ESI) mass spectrometry. The applied derivatization involves the simultaneous acylation of hydroxyl groups with an acyl chloride moiety and the quaternization of pyridine with a terminal bromoalkyl group. Under the ESI conditions, quaternary salts produce corresponding mono and diammonium cations, which are detected in the first-order mass spectra. Collision-induced dissociation (CID) of primary cations generated from monool derivatives gives rise to ammonium cations of the corresponding acids HOOC(CH2)n–N+(C5H5). The CID of primary dications affords the same cations which are also eliminated from dications to form mono-charged fragments. © 2017, Pleiades Publishing, Ltd

The use of on‐line H/D exchange for the investigation of alcohols and carbonyl compounds by reaction gas chromatography/mass spectrometry

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