Comparison of thermospray and ion spray mass spectrometry in an atmospheric pressure ion source

Ion spray is an approach to liquid chromatography, mass spectrometry which includes features common to the electrospray and ion evaporation interfaces. Thermospray is a liquid chromatographic/mass spectrometric technique which utilizes heat and electrolytes in the mobile phase to generate sample ions. In this paper the operation of these two techniques at atmospheric pressure are compared with respect to the effects of solvent composition and electrolyte ion concentration for the production of ions from compounds that are ionized in solution (safranin orange, acid black 1 and testosterone sulfate) and un-ionized in solution (methyl red, adenosine and diethylstilbestrol). The results indicate that at atmospheric pressure ion spray produces ions by the ion evaporation mechanism while thermospray produces ions by both gas-phase chemical ionization and ion evaporation processes.     

Investigation of the quantitative properties of the quadrupole orthogonal acceleration time-of-flight mass spectrometer with electrospray ionisation using 3,4-methylenedioxymethamphetamine

This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time-of-flight mass spectrometer (Q-TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4-methylenedioxymethamphetamine standards and 3,4-methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4-methylenedioxymethamphetamine and its metabolite 3,4-methylenedioxyamphetamine was prepared in each of these matrices again using 3,4-methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q-TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2-10 000 pg on-column, r(2) = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC-fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q-TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright 1999 John Wiley & Sons, Ltd.     

Crystallization kinetics study on higher homologues of benzylidene aniline compounds: impact of phase variant on nucleation process

A systematic kinetic study leading to the crystallization process from the kinetophases (which occur prior to crystal phase) smectic B, crystal G and smectic F is performed on representative compounds of the homologous series p-phenylbenzylidene-p'-alkylanilines (PBnA) and p-n-alkoxybenzylidene-p'-alkylanilines (nO.m) these compounds are p-phenylbenzylidene-p'-nonylaniline (PB9A), p-phenylbenzylidene-p'-tetradecylaniline (PB14A), p-n-pentadecyloxybenzylidene p'-tetradecylaniline (15O.14) and p-n-octadecyloxybenzylidene-p'-nonylaniline (18O.9). The molecular mechanism and dimensionality in crystal growth from the kineto phases are computed from the Avrami equation, while the characteristic crystalline time (t*) at each crystallization temperature is deduced from the individual plots of log t vs. ΔH. The low magnitudes of the dimensionality parameter n infers the occurrence of diffusion-controlled transformations leading to the formation of plates or needles of finite size possessing impinged edges. The degree of variation in the value of n at each crystallization temperature also reveals the existence of an independent nucleation mechanism for any individual member of the series. The influence of the terminal alkyl chain lengths on the rate of crystallization is determined from a comparative study with the reported analogous compounds.     

Study of three types of essential oil of valeriana officianalis L. S1 by combined gas chromatography-negative ion chemical ionization mass spectrometry

OH^- ions have been shown to produce abundant (M - H)^- ions of most oxygenated mono- and sesquiterpenes. Esters are cleaved by an apparent nucleophilic displacement reaction, with the formation of RCOO^- ions.Three types of essential oil of valerian, having different chemical compositions, were subjected to combined gas chromatography-OH^- negative ion chemical ionization mass spectrometry. Extracted ion current profiles, reconstructed by the data system, of various (M - H H)^- ions and RCOO^- ions, have given a clear insight into the presence of the components of interest. The method is particularly suitable for the identification of esthers, as shoen by the results obtained for acetates and isovalerates.     

Magnetic moments of (νi132)−n isomers in neutron-deficient lead isotopes

The magnetic moments of the 12⁺ isomers in ^{192, 196, 198, 200, 206}Pb and of the $\text{33}\text{2}{}^{\mathrm{+}}$ isomer in ²⁰⁵Pb have been measured using the PAD technique. The results for the g-factors are: g(192) = ?0.173(2), g(196) = ?0.1600(15), g(198) = ?0.1552(15), g(200) = ?0.1512(15), g(206) = ?0.1496(18), and g(205) = ?0.148(5). As all states have a rather pure $\text{(νi}{}_{\mathrm{<mtext>13</mtext><mtext>2</mtext>}}\text{)}{}^{\mathrm{?n}}$ configuration, the values reflect directly the $\text{νi}{}_{\mathrm{<mtext>13</mtext><mtext>2</mtext>}}$ orbital. They show a decrease towards the more neutron-deficient isotopes attributed to the reduced core polarisation as a result of decreasing occupation of the $\text{i}{}_{\mathrm{<mtext>13</mtext><mtext>2</mtext>}}$ neutron shell. The measured systematics are discussed regarding core polarisation, mesonic corrections, and small admixtures of core-excited states to the $\text{i}{}_{\mathrm{<mtext>13</mtext><mtext>2</mtext>}}$ wave function.     

Tetraethylammonium chloride tetrahydrate,a ‘double channel’ host lattice constructed from (H2O)4Cl− tetrahedra linked between vertices

Crystals of (C₂H₅)₄NCl·4H₂O are orthorhombic, space groupCcca, witha=19.104(3),b=23.084(4),c=13.330(3) , andZ=16. The structure features an anionic host lattice constructed from the linkage of (H₂O)₄Cl^– tetrahedra by hydrogen bonds between vertices, generating two open linear channel systems which accommodate the ordered cations. FinalR _F =0.080 for 1516 observed MoK data measured at 22°C. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82035 (12 pages)Dedicated to Professor G. A. Jeffrey     

Chain length effects in the competition between intramolecular hydrogen migrations in the molecular ions of hydrogen migration in the molecular ions of α-benzylamino-ω-benzyloxyalkanes as studied by deuterium labelling

The unimolecular decompositions upon electron impact of the bifunctional compounds ØCH₂-NH? (CH₂)_n-O? CH₂Ø(n=2 to 7)have been studied by deuterium labelling. The molecular ions lose a benzyl radical and/or a benzaldehyde molecule, depending on the length of the aliphatic chain. Both reactions appear to be the result of the transfer of a hydrogen atom to the charge localized amino function in a cyclic transition state. The ring size of this transition state turns out to play a far more important role than the difference in reactivity of the migrating hydrogen atoms.     

Electron-induced neutron knockout from 4He

The differential cross section for electron-induced neutron knockout in the reaction 4He(e,e(')n)(3)He has been measured for the first time with a statistical accuracy of 11%. The experiment was performed in quasielastic kinematics at a momentum transfer of 300 MeV/c and in the missing-momentum range of 25-70 MeV/c. The comparison of the data with theoretical calculations shows an impressive increase of the cross section resulting from final state interaction effects. Specifically, the p-n charge-exchange process dominates the cross section in this kinematical regime.