Generation and reactions of substituted phenide anions in an electrospray triple quadrupole mass spectrometer

Substituted benzoic acid anions undergo decarboxylation in the medium-pressure region of an electrospray ion source yielding in most cases the correspondingly substituted phenide anions in high yield. The location of the anionic center is specified by the position of the carboxylic group. The only exceptions are compounds with substituents containing acidic hydrogen atoms, like OH and NH(2) groups. For such compounds, either an intra- or an intermolecular (mediated by the molecules of methanol or water) proton transfer from the more acidic position to the benzene ring is observed. The generated anions can be selected using the first quadrupole for studying their ion-molecule chemistry in the second quadrupole of a triple quadrupole mass spectrometer. Their reactions with CO(2), O(2), CH(3)COCH(3) and CCl(4) may serve as typical examples. The general applicability of this method for the generation of phenide anions has been confirmed on three different mass spectrometers. Experiments performed using carboxylic acids other then benzoic acid and its derivatives show that this method is not limited to phenide anions and can be used for the generation of a much wider range of carbanions in the gas phase.     

Planar Chromatography of Heterocyclic Thiols with Detection by Use of the Iodine-Azide Reaction

JPC – Journal of Planar Chromatography – Modern TLC - Reaction between iodine and the azide ion induced by heterocyclic thiols has been used for detection in TLC and HPTLC. The...     

Divergent coordination mode of magnesium and zinc alkyls supported by the bifunctional pyrrolylaldiminato ligand

The first magnesium and zinc alkyls derived from N-(iso-propyl)-pyrrolylaldimine have been synthesised and structurally characterised: both tBuM(N,N')-type compounds exist as three-coordinate monomers in benzene solution, but in the solid state the magnesium complex is a centrosymmetric dimer with Mg2(mu-N)2 bridges, whereas the zinc complex is a Zn...pi bonded dimer with a pi-coordinated pyrrole unit.     

Similarities and differences in the electron ionization-induced fragmentation of structurally related N-alkoxymethyl lactams and sultams

Unimolecular fragmentation patterns of the molecular ions of selected lactams and sultams bearing alkoxymethyl group at the nitrogen atom were studied. The main common fragmentation reaction observed for all compounds studied in this work is the elimination of an aldehyde molecule. This reaction is considered to proceed via two different mechanisms. For lactams, hydrogen rearrangement within an alkoxymethyl group is observed, which leads to the appropriate N-methyl derivatives. For sultams, transfer of the methyl group to the nitrogen and oxygen atoms, proceeding through an ion-neutral complex, dominates. Another important fragmentation channel characteristic exclusively for lactams is the loss of an alkyl radical. This process takes place within the N-alkoxymethyl moiety, yielding the appropriate protonated ion of N-formyllactams. This process is accompanied by relatively high kinetic energy release.     

Square wave adsorptive stripping voltammetric determination of famotidine in urine

Electrochemical studies of famotidine were carried out using voltammetric techniques: cyclic voltammetry, linear sweep and square wave adsorptive stripping voltammetry. The dependence of the current on pH, buffer concentration, nature of the buffer, and scan rate was investigated. The best results for the determination of famotidine were obtained in MOPS buffer solution at pH 6.7. This electroanalytical procedure enabled to determine famotidine in the concentration range 1 × 10⁻⁹–4 × 10⁻⁸ mol L⁻¹ by linear sweep adsorptive stripping voltammetry (LS AdSV) and 5 × 10⁻¹⁰–6 × 10⁻⁸ mol L⁻¹ by square wave adsorptive stripping voltammetry (SW AdSV). Repeatability, precision and accuracy of the developed methods were checked. The detection and quantification limits were found to be 1.8 × 10⁻¹⁰ and 6.2 × 10⁻¹⁰ mol L⁻¹ for LS AdSV and 4.9 × 10⁻¹¹ and 1.6 × 10⁻¹⁰ mol L⁻¹ for SW AdSV, respectively. The method was applied for the determination of famotidine in urine.     

Composition of the black crusts from the Saint Denis Basilica, France, as revealed by gas chromatography-mass spectrometry

The organic fraction of black crusts from Saint Denis Basilica, France, is composed of a complex mixture of aliphatic and aromatic compounds. These compounds were studied by two different analytical approaches: tetramethyl ammonium hydroxide (TMAH) thermochemolysis in combination with gas chromatography-mass spectrometry (GC-MS), and solvent extraction, fractionation by silica column, and identification of the fraction components by GC-MS. The first approach, feasible at the microscale level, is able to supply fairly general information on a wide range of compounds. Using the second approach, we were able to separate the complex mixture of compounds into four fractions, enabling a better identification of the extractable compounds. These compounds belong to different classes: aliphatic hydrocarbons (nalkanes, n-alkenes), aliphatic and aromatic carboxylic acids (n-fatty acids, alpha,omega-dicarboxylic acids, and benzenecarboxylic acids), polycyclic aromatic hydrocarbons (PAH), and molecular biomarkers (isoprenoid hydrocarbons, diterpenoids, and triterpenoids). With each approach, similar classes of compounds were identified, although TMAH thermochemolysis failed to identify compounds present at low concentrations in black crusts. The two proposed methodological approaches are complementary, particularly in the study of polar fractions.     

Simultaneous difference equations on a restricted domain

Aequationes mathematicae - Given a set $$T\subset (0, +\infty )$$ , a function $$c:T\rightarrow \mathbb R$$ and a real number p we study continuous solutions $$\varphi $$ of the simultaneous...     

Solvability of a nonlinear fifth‐order difference equation

Some formulas for well‐defined solutions to four very special cases of a nonlinear fifth‐order difference equation have been presented recently in this journal, where some of them were proved by the method of induction, some are only quoted, and no any theory behind the formulas was given. Here, we show in an elegant constructive way how the general solution to the difference equation can be obtained, from which the special cases very easily follow, which is also demonstrated here. We also give some comments on the local stability results on the special cases of the nonlinear fifth‐order difference equation previously publish in this journal.     

Fractional electrical model for modified bismuth oxide

Modified bismuth oxide (Bi₂O₃) is of great importance to fuel cells and oxide varistors. The electrical parameters of Bi₂O₃ vary with its modifying components as well as with its aging temperature. This paper presents an analysis of impedance test results carried out to find an equivalent electric model and the relationship between the model's elements to various additives used to modify Bi₂O₃ and to changes in aging temperature. The proposed model was tested via computer simulation and the model parameters correlated to individual modifiers.