A simultaneous TG-DTG-DSC-quadrupole mass spectrometric study

Mechanistic aspects of the thermal decomposition of benzyl-triethyl-ammonium tetrafluoroborate (BTEATFB) employing simultaneous TG-DSC coupled with a quadrupole mass spectrometer are considered in this work. The experiments were conducted in an inert atmosphere of helium. The decomposition of BTEATFB proceeds through several competing mechanisms. While nucleophilic substitution reaction occurs through the formation of a tertiary amine and plays an important role in the initial stages of the decomposition, and the probability of Hoffman elimination also exists.     

A mass spectrometric study of the thermal pyrolysis of S4N4

Mass spectrometric techniques have been used to identify the pyrolysis products of S₄N₄ vapors passed over quartz wool at 80 to 400°C. S₄N₄ decomposes to form S₄N₂, S₃N₃, S₂N₂, and SN at temperatures of less than 250°C.     

A mass spectrometric study of some dihydropyranocoumarins

Summary The mass spectra of ten angular and linear dihydropyranocoumarins without substituents and with hydroxy and acyloxy substituents in position 3 of the dimethylchroman ring have been studied. Depending on the presence and nature of these substituents the mass spectra of the compounds considered have different relative intensities of the fragments with m/e 228, 213, 176, 175, 83, and 85, which permits mass spectrometry to be used in this group of compounds for structural-analytical purposes.All-Union Scientific-Research Institute of Medicinal Plants. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 398–401, July–August, 1971.     

A mass spectrometric study of the structure of fetidine

Chemistry of Natural Compounds -     

A mass spectrometric study of substituted furfuryl compounds

The mass spectra of six furfuryl compounds — namely, furfuryl alcohol, 5-furfuryl-furfuryl alcohol, difurfuryl ether, difurylmethane, 2,5-difurfurylfuran, and 4-furfuryl-2-pentenoic acid-γ-lactone — have been studied. Their fragmentation mechanisms are discussed in detail with particular emphasis on the modes that lead to the formation of aromatic fragments. The majority of the fragment ions are formed by elimination of CO and C₂H₂ from even-electron precursor ions and HCO from odd-electron precursor ions. Molecules containing two furan rings linked by a methylene group give mass spectra that exhibit large abundances of aromatic fragment ions.     

A mass spectrometric study of the vaporization of erbium hexafluoroacetylacetonate

The sublimation of erbium tris-hexafluoroacetylacetonate Er(C₅O₂HF₆)₃ was studied by the Knudsen effusion method with the mass spectrometric determination of vapor composition. Groups of ions containing one, two, and three metal atoms were recorded. The enthalpies of sublimation of the monomeric, dimeric, and trimeric forms Δ_S H°(362 K) were found to be 133 ± 4, 135 ± 7, and 139 ± 38 kJ/mol, respectively. The melting point of Er(C₅O₂HF₆)₃ was 390 ± 2 K. No oligomeric forms were observed in vapor superheated above 430 K.     

A pyrolysis mass spectrometry study of polythiophene copolymers

The thermal behaviour of copolymers of thiophene with decanedioic acid bis-(2-thiophen-3-yl-ethyl)ester (DATE) and terephthalic acid bis-(2-thiophen-3-yl-ethyl)ester (TATE) prepared by potentiostatic polymerization was studied via pyrolysis mass spectrometry. It was determined that the electrolytic films correspond to the related homopolymers. The increase in thermal stability of ester linkages, and evolution of characteristic degradation products of TATE and DATE together with thiophene based products above 400 °C confirmed copolymer formation.     

A tandem mass spectrometric study of saccharides at high mass resolution

Nine monosaccharides and four disaccharides were mass analyzed using a quadrupole time-of-flight tandem mass spectrometer combined with an electrospray ionization source. Product ion mass spectra of deprotonated, protonated, and sodiated saccharides were observed and were compared within each group of saccharides. Each of the deprotonated pentoses, hexoses and disaccharides yielded a significantly different product ion mass spectrum with the exception of alpha-lactose and beta-lactose. The disaccharides alpha- and beta-lactose differ only at the glycosidic linkage. Product ion mass spectra of protonated and sodiated alpha- and beta-lactose were indistinguishable also.     

In situ direct sampling mass spectrometric study on formation of polycyclic aromatic hydrocarbons in toluene pyrolysis

The gas-phase reaction products of toluene pyrolysis with and without acetylene addition produced in a flow tube reactor at pressures of 8.15-15.11 Torr and temperatures of 1136-1507 K with constant residence time (0.56 s) have been detected in an in situ direct sampling mass spectrometric study by using a vacuum ultraviolet single-photon ionization time-of-flight mass spectrometry technique. Those products range from methyl radical to large polycyclic aromatic hydrocarbons (PAHs) of mass 522 amu (C(42)H(18)) including smaller species, radicals, polyynes, and PAHs, together with ethynyl, methyl, and phenyl PAHs. On the basis of observed mass spectra, the chemical kinetic mechanisms of the formation of products are discussed. Especially, acetylene is mixed with toluene to understand the effect of the hydrogen abstraction and acetylene addition (HACA) mechanism on the formation pathways of products in toluene pyrolysis. The most prominent outputs of this work are the direct detection of large PAHs and new reaction pathways for the formation of PAHs with the major role of cyclopenta-fused radicals. The basis of this new reaction route is the appearance of different sequences of mass spectra that well explain the major role of aromatic radicals mainly cyclopenta fused radicals of PAHs resulting from their corresponding methyl PAHs, with active participation of c-C(5)H(5), C(6)H(5), C(6)H(5)CH(2) ,and C(9)H(7) in the formation of large PAHs. The role of the HACA only seemed important for the formation of stable condensed PAHs from unstable primary PAHs with zigzag structure (having triple fusing sites) in one step by ring growth with two carbon atoms.     

A vacuum ultraviolet photoionization mass spectrometric study of acetone

The photoionization and dissociative photoionization of acetone have been studied at the photon energy range of 8-20 eV. Photoionization efficiency spectra for ions CH3COCH3+, CH3+, C2H3+, C3H3+, C3H5+, CH(2-)CO+, CH3CO+, C3H4O+, and CH3COCH2+ have been measured. In addition, the energetics of the dissociative photoionization has been examined by ab initio Gaussian-3 (G3) calculations. The computational results are useful in establishing the dissociation channels near the ionization thresholds. With the help of G3 results, the dissociation channels for the formation of the fragment ions CH3CO+, CH2CO+, CH3+, C3H3+, and CH3COCH2+ have been established. The G3 results are in fair to excellent agreement with the experimental data.     

A mass spectrometric study of metal binding to osteocalcin

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry was used to investigate Ca(2+), Mg(2+), and La(3+) binding to bovine bone osteocalcin (OCN). OCN was shown to bind 3 mol Ca(2+) per mol protein. There was also evidence for the presence of four additional metal binding sites. Ca(2+) increased the formation of the OCN dimer. Mg(2+) bound to OCN to the same extent as Ca(2+) but did not induce the dimerization of OCN. La(3+) bound to a lesser extent than either Ca(2+) or Mg(2+) to OCN and, like Mg(2+), did not influence dimerization. Each Gla residue of OCN participates in Ca(2+) binding, whereas Mg(2+) binding may occur preferentially at sites other than Gla residues. This implies that the different natures of Ca(2+)- and Mg(2+)-containing OCN complexes influence the tendency of OCN to form a dimer.     

A mass spectrometric study of some triterpenes of the dammarane series

Summary 1. The mass spectra of tetracyclic triterpenes of the dammarane series with substituents at C-3, 6, and 12 and with side chains of various structures have been studied.2. The main direction of fragmentation is the formation of ions as the result of the decomposition of the side chain and of ring C, the second type of fragmentation being controlled by the structure of the side chain.Institute of Biologically Active Substances of the Far-Eastern Scientific Center of the Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 286–294, May–June, 1971.     

雌酮和雌二醇类似物的质谱研究

本文报道九种雌酮和雌二醇类似物的质谱,并解释了碎片离子的生成途径。讨论了取代基对裂解方式的影响。这种裂解规律的研究有助于这类新化合物的质谱鉴定.