Combined experimental and computational study of the reactivity of the methanimine radical cation (HCNH˙) and its isomer aminomethylene (HCNH˙) with propene (CHCHCH).

The gas phase reactivity of the radical cation isomers HCNH˙ (methanimine) and HCNH˙ (aminomethylene) with propene (CHCHCH) has been investigated by measuring absolute reactive cross sections and product branching ratios, under single collision conditions, as a function of collision energy (in the range ∼0.07-11.80 eV) using guided ion beam mass spectrometry coupled with VUV photoionization for selective isomer generation.

Selected ice nanoparticle accelerator hypervelocity impact mass spectrometer (SELINA-HIMS): features and impacts of charged particles.

The selected ice nanoparticle accelerator, SELINA, was used to prepare beams of single ice particles with positive or negative charge. Positively charged particles were prepared from deionized water and 0.05-0.

Reactivity of the Ethenium Cation (CH) with Ethyne (CH): A Combined Experimental and Theoretical Study.

The gas-phase reaction between the ethyl cation (CH) and ethyne (CH) is re-investigated by measuring absolute reactive cross sections (CSs) and branching ratios (BRs) as a function of collision energy, in the thermal and hyperthermal energy range, via tandem-guided ion beam mass spectrometry under single collision conditions. Dissociative photoionization of CHBr using tuneable VUV radiation in the range 10.5-14.

Charged Ice Particle Beams with Selected Narrow Mass and Kinetic Energy Distributions.

Small ice particles play an important role in atmospheric and extraterrestrial chemistry. Circumplanetary ice particles that are encountered by space probes at hypervelocities play a critical role in the determination of surface and subsurface properties of their source bodies. Here we present an apparatus for the generation of low-intensity beams of single mass-selected charged ice particles under vacuum.

OLYMPIA-LILBID: A New Laboratory Setup to Calibrate Spaceborne Hypervelocity Ice Grain Detectors Using High-Resolution Mass Spectrometry.

The coupling of an Orbitrap-based mass analyzer to the laser-induced liquid beam ion desorption (LILBID) technique has been investigated, with the aim to reproduce the mass spectra recorded by Cassini's Cosmic Dust Analyzer (CDA) in the vicinity of Saturn's icy moon Enceladus. LILBID setups are usually coupled with time-of-flight (TOF) mass analyzers, with a limited mass resolution (∼800 /Δ). Thanks to the Orbitrap technology, we developed a unique analytical setup that is able to simulate hypervelocity ice grains' impact in the laboratory (at speeds in the range of 15-18 km/s) with an unprecedented high mass resolution of up to 150 000 /Δ (at 19 for a 500 ms signal duration).

State-Selected Reactivity of Carbon Dioxide Cations ( ) With Methane.

The reactivity of with CD has been experimentally investigated for its relevance in the chemistry of plasmas used for the conversion of CO in carbon-neutral fuels. Non-equilibrium plasmas are currently explored for their capability to activate very stable molecules (such as methane and carbon dioxide) and initiate a series of reactions involving highly reactive species (e.g.

Effects of collision energy and vibrational excitation of CH cations on its reactivity with hydrocarbons: But-2-yne CHCCCH as reagent partner.

The methyl carbocation is ubiquitous in gaseous environments, such as planetary ionospheres, cometary comae, and the interstellar medium, as well as combustion systems and plasma setups for technological applications. Here we report on a joint experimental and theoretical study on the mechanism of the reaction CH + CHCCCH (but-2-yne, also known as dimethylacetylene), by combining guided ion beam mass spectrometry experiments with ab initio calculations of the potential energy hypersurface. Such a reaction is relevant in understanding the chemical evolution of Saturn's largest satellite, Titan.

The reaction of CN with acetylene as a possible intermediate step to produce large anions in Titan's ionosphere.

A theoretical and experimental investigation of the reaction CN + CH has been carried out. This reaction is of astrophysical interest since the growth mechanism of large anions that have been detected in Titan's upper atmosphere by the Cassini plasma spectrometer are still largely unknown. The experimental studies have been performed using a tandem quadrupole mass spectrometer which allows identification of the different reaction channels and assessment of their reaction thresholds.

Selected ion flow tube study of the reactions of H O and NO with a series of primary alcohols in the presence of water vapour in support of selected ion flow tube mass spectrometry.

Rationale: Alcohols are often present in foods and other biological media, including exhaled breath, urine and cell culture headspace. For their analysis by selected ion flow tube mass spectrometry (SIFT-MS), the ion chemistry initiated by the reactions of the reagent ions H O and NO with alcohol molecules in the presence of water molecules needs to be understood and quantitatively described.

Methods: The reactions of H O and NO ions have been studied with the primary alcohols, methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol and 1-hexanol, under the conditions used for SIFT-MS analyses (1 Torr He; 0.

Is the Reaction of C3N(-) with C2H2 a Possible Process for Chain Elongation in Titan's Ionosphere?

The reaction of C3N(-) with acetylene was studied using three different experimental setups, a triple quadrupole mass spectrometer (Trento), a tandem quadrupole mass spectrometer (Prague), and the "CERISES" guided ion beam apparatus at Orsay. The process is of astrophysical interest because it can function as a chain elongation mechanism to produce larger anions that have been detected in Titan's ionosphere by the Cassini Plasma Spectrometer. Three major products of primary processes, C2H(-), CN(-), and C5N(-), have been identified, whereby the production of the cyanide anion is probably partly due to collisional induced dissociation.

A Pilot Study of Ion - Molecule Reactions at Temperatures Relevant to the Atmosphere of Titan.

Reliable theoretical models of the chemical kinetics of the ionosphere of Saturn's moon, Titan, is highly dependent on the precision of the rates of the reactions of ambient ions with hydrocarbon molecules at relevant temperatures. A Variable Temperature Selected Ions Flow Tube technique, which has been developed primarily to study these reactions at temperatures within the range of 200-330 K, is briefly described. The flow tube temperature regulation system and the thermalisation of ions are also discussed.

Selective Generation of the Radical Cation Isomers [CH3CN](•+) and [CH2CNH](•+) via VUV Photoionization of Different Neutral Precursors and Their Reactivity with C2H4.

Experimental and theoretical studies have been carried out to demonstrate the selective generation of two different C2H3N(+) isomers, namely, the acetonitrile [CH3CN](•+) and the ketenimine [CH2CNH](•+) radical cations. Photoionization and dissociative photoionization experiments from different neutral precursors (acetonitrile and butanenitrile) have been performed using vacuum ultraviolet (VUV) synchrotron radiation in the 10-15 eV energy range, delivered by the DESIRS beamline at the SOLEIL storage ring. For butanenitrile (CH3CH2CH2CN) an experimental ionization threshold of 11.

Reactions of State-Selected Atomic Oxygen Ions O(+)((4)S, (2)D, (2)P) with Methane.

An experimental study has been carried out on the reactions of state selected O(+)((4)S, (2)D, (2)P) ions with methane with the aims of characterizing the effects of both the parent ion internal energy and collision energy on the reaction dynamics and determining the fate of oxygen species in complex media, in particular the Titan ionosphere. Absolute cross sections and product velocity distributions have been determined for the reactions of (16)O(+) or (18)O(+) ions with CH4 or CD4 from thermal to 5 eV collision energies by using the guided ion beam (GIB) technique. Dissociative photoionization of O2 with vacuum ultraviolet (VUV) synchrotron radiation delivered by the DESIRS beamline at the SOLEIL storage ring and the threshold photoion photoelectron coincidence (TPEPICO) technique are used for the preparation of purely state-selected O(+)((4)S, (2)D, (2)P) ions.

The unimolecular chemistry of protonated and deprotonated 2,2-dinitroethene-1,1-diamine (FOX-7) studied by tandem mass spectrometry and computational chemistry.

2,2-Dinitroethene-1,1-diamine (FOX-7) was studied by means of electrospray ionization (ESI) and chemical ionization (CI) mass spectrometry in both positive and negative ion mode. Detailed mechanisms of unimolecular fragmentations of protonated and deprotonated FOX-7 were investigated using high- and low- energy collision-induced dissociation (CID) mass spectrometry, neutral fragment reionization mass spectrometry and quantum chemistry calculations. In deprotonated FOX-7, elimination of the carbodiimide molecule was identified as the energetically most favored fragmentation channel, closely resembling the base hydrolysis of FOX-7.

Repeat protocol renal biopsy in ANCA-associated renal vasculitis.

Background: Histopathological lesions in renal biopsy (RB) at presentation of ANCA-associated vasculitis (AAV) have been described in depth but repeat protocolized renal biopsies are seldomly performed in AAV. In this study, we present a group of AAV patients with repeat protocolized biopsies, and we evaluate their clinical significance.

Methods: A total of 17 consecutive patients diagnosed between 1991 and 1995 with AAV and renal involvement confirmed by biopsy at presentation in a single center underwent a protocol planned rebiopsy in remission after a median of 13 months (range 11-28) from diagnosis.

Reactions of doubly ionized benzene with nitrogen and water: a nitrogen-mediated entry into superacid chemistry.

Even in the highly diluted gas phase, rather than electron transfer the benzene dication C(6)H(6)(2+) undergoes association with dinitrogen to form a transient C(6)H(6)N(2)(2+) dication which is best described as a ring-protonated phenyl diazonium ion. Isotopic labeling studies, photoionization experiments using synchrotron radiation, and quantum chemical computations fully support the formation of protonated diazonium, which is in turn a prototype species of superacidic chemistry in solution. Additionally, reactions of C(6)H(6)(2+) with background water involve the transient formation of diprotonated phenol and, among other things, afford a long-lived C(6)H(6)OH(2)(2+) dication, which is attributed to the hydration product of Hogeveen's elusive pyramidal structure of C(6)H(6)(2+), as the global minimum of doubly ionized benzene.

The oxidation of natural flavonoid quercetin.

This study explains the controversies in the literature concerning the number of electrons involved in the oxidation of quercetin. This stems from inappropriate handling samples, which require strict anaerobic conditions. The redox potential of quercetin strongly depends on the pH and on the presence of dissociation forms in solution.

On the stability of the bioactive flavonoids quercetin and luteolin under oxygen-free conditions.

The natural flavonoid compounds quercetin (3,3',4',5,7-pentahydroxyflavone) and luteolin (3',4',5,7-tetrahydroxyflavone) are important bioactive compounds with antioxidative, anti-allergic, and anti-inflammatory properties. However, both are unstable when exposed to atmospheric oxygen, which causes degradation and complicates their analytical determinations. The oxidative change of these flavonoids was observed and followed by UV-visible spectrophotometry, both in aqueous and ethanolic solutions.

Double ionization of cycloheptatriene and the reactions of the resulting C7H(n)2+ dications (n = 6, 8) with xenon.

The formation and fragmentation of the molecular dication C(7)H(8)(2+) from cycloheptatriene (CHT) and the bimolecular reactivities of C(7)H(8)(2+) and C(7)H(6)(2+) are studied using multipole-based tandem mass spectrometers with either electron ionization or photoionization using synchrotron radiation. From the photoionization studies, an apparent double-ionization energy of CHT of (22.67 ± 0.

[Gastrointestinal stromal tumors].

Gastrointestinal stromal tumours (GISTs) are the most common group of mesenchymal tumours affecting the gastrointestinal tract. Despite this, GISTs are relatively rare, since all mesenchymal tumours constitute just 1 percent of all primary GI cancers. Most often, GISTs affect the stomach and proximal small intestine but can be found in any section of the alimentary tract, including, occasionally, the omentum, mesentery and peritoneum.

Selected ion flow tube study of ion-molecule reactions of N(+)(3P) and Kr+ with C3 hydrocarbons propane, propene, and propyne.

Reactions of (14)N(+)((3)P), (15)N(+)((3)P), and Kr(+) with propane, propene, and propyne were studied using the selected ion flow tube, SIFT, technique. Thermal rate constants in all N(+)/C(3) systems were k = (2 ± 0.4) × 10(-9) cm(3) molecule(-1) s(-1), close to the collisional rate constants.

Formation of organoxenon dications in the reactions of xenon with dications derived from toluene.

The bimolecular reactivity of xenon with C(7)H(n)(2+) dications (n=6-8), generated by double ionization of toluene using both electrons and synchrotron radiation, is studied by means of a triple-quadrupole mass spectrometer. Under these experimental conditions, the formation of the organoxenon dications C(7)H(6)Xe(2+) and C(7)H(7)Xe(2+) is observed to occur by termolecular collisional stabilization. Detailed experimental and theoretical studies show that the formation of C(7)H(6)Xe(2+)+H(2) from doubly ionized toluene (C(7)H(8)(2+)) and xenon occurs as a slightly endothermic, direct substitution of dihydrogen by the rare gas with an expansion to a seven-membered ring structure as the crucial step.

Comparative study of mono- and dinuclear complexes of late 3d-metal chlorides with N,N-dimethylformamide in the gas phase.

Mono- and binuclear complexes of N,N-dimethylformamide (DMF) with chlorides of the divalent, late 3d metals M = Co, Ni, Cu, and Zn are investigated by means of electrospray ionization (ESI). Specifically, ESI leads to monocations of the type [(DMF)(n)MCl](+) and [(DMF)(n)M(2)Cl(3)](+), of which the species with n = 2 and 3 were selected for in-depth studies. The latter include collision-induced dissociation experiments, gas-phase infrared spectroscopy, and calculations using density functional theory.

Reduction from copper(II) to copper(I) upon collisional activation of (pyridine)(2) CuCl(+).

Electrospray ionization of dilute aqueous solutions of copper(II) chloride-containing traces of pyridine (py) as well as ammonia permits the generation of the gaseous ions (py)(2) Cu(+) and (py)(2) CuCl(+) , of which the latter is a formal copper(II) compound, whereas the former contains copper(I). Collision-induced dissociation of the mass-selected ions in an ion-trap mass spectrometer (IT-MS) leads to a loss of pyridine from (py)(2) Cu(+) , whereas an expulsion of atomic chlorine largely prevails for (py)(2) CuCl(+) . Theoretical studies using density functional theory predict a bond dissociation energy (BDE) of BDE[(py)(2) Cu(+) -Cl] = 125 kJ mol(-1) , whereas the pyridine ligand is bound significantly stronger, i.

Crossed-beam scattering studies of electron-transfer processes between the dication CO2(2+) and neutral CO2: electronic states of reactants and products involved.

Crossed-beam scattering experiments were carried out at collision energies of 4.51 and 2.71 eV to elucidate the electronic states involved in the nondissociative and dissociative electron-transfer reactions observed following CO(2)(2+)/CO(2) collisions.