UV Photodissociation Action Spectroscopy of Haloanilinium Ions in a Linear Quadrupole Ion Trap Mass Spectrometer

UV-vis photodissociation action spectroscopy is becoming increasingly prevalent because of advances in, and commercial availability of, ion trapping technologies and tunable laser sources. This study outlines in detail an instrumental arrangement, combining a commercial ion-trap mass spectrometer and tunable nanosecond pulsed laser source, for performing fully automated photodissociation action spectroscopy on gas-phase ions. The components of the instrumentation are outlined, including the optical and electronic interfacing, in addition to the control software for automating the experiment and performing online analysis of the spectra. To demonstrate the utility of this ensemble, the photodissociation action spectra of 4-chloroanilinium, 4-bromoanilinium, and 4-iodoanilinium cations are presented and discussed. Multiple photoproducts are detected in each case and the photoproduct yields are followed as a function of laser wavelength. It is shown that the wavelength-dependent partitioning of the halide loss, H loss, and NH3 loss channels can be broadly rationalized in terms of the relative carbon-halide bond dissociation energies and processes of energy redistribution. The photodissociation action spectrum of (phenyl)Ag-2 (+) is compared with a literature spectrum as a further benchmark.

Does Addition of NO2 to Carbon-Centered Radicals Yield RONO or RNO2? An Investigation Using Distonic Radical Ions

Nitrogen dioxide is used as a "radical scavenger" to probe the position of carbon-centered radicals within complex radical ions in the gas phase. As with analogous neutral radical reactions, this addition results in formation of an \[M + NO2](+) adduct, but the structural identity of this species remains ambiguous. Specifically, the question remains: do such adducts have a nitro-(RNO2) or nitrosoxy-(RONO) moiety, or are both isomers present in the adduct population? In order to elucidate the products of such reactions, we have prepared and isolated three distonic phenyl radical cations and observed their reactions with nitrogen dioxide in the gas phase by ion-trap mass spectrometry. In each case, stabilized \[M + NO2](+) adduct ions are observed and isolated. The structure of these adducts is probed by collision-induced dissociation and ultraviolet photodissociation action spectroscopy and a comparison made to the analogous spectra of authentic nitro-and nitrosoxy-benzenes. We demonstrate unequivocally that for the phenyl radical cations studied here, all stabilized \[M + NO2](+) adducts are exclusively nitrobenzenes. Electronic structure calculations support these mass spectrometric observations and suggest that, under low-pressure conditions, the nitrosoxy-isomer is unlikely to be isolated from the reaction of an alkyl or aryl radical with NO2. The combined experimental and theoretical results lead to the prediction that stabilization of the nitrosoxy-isomer will only be possible for systems wherein the energy required for dissociation of the RO-NO bond (or other low energy fragmentation channels) rises close to, or above, the energy of the separated reactants.

Characterisation of the ionic products arising from electron photodetachment of simple dicarboxylate dianions

Much of what we currently understand about the structure and energetics of multiply charged anions in the gas phase is derived from the measurement of photoelectron spectra of simple dicarboxylate dianions. Here we have employed a modified linear ion-trap mass spectrometer to undertake complementary investigations of the ionic products resulting from laser-initiated electron photodetachment of two model dianions. Electron photodetachment (ePD) of the \[M-2H](2-) dianions formed from glutaric and adipic acid were found to result in a significant loss of ion signal overall, which is consistent with photoelectron studies that report the emission of slow secondary electrons (Xing et al., 2010 \[201). The ePD mass spectra reveal no signals corresponding to the intact \[M-2H](center dot-) radical anions, but rather \[M-2H-CO2](center dot-) ions are identified as the only abundant ionic products indicating that spontaneous decarboxylation follows ejection of the first electron. Interestingly however, investigations of the structure and energetics of the \[M-2H-CO2](center dot-) photoproducts by ion-molecule reaction and electronic structure calculation indicate that (i) these ions are stable with respect to secondary electron detachment and (ii) most of the ion population retains a distonic radical anion structure where the radical remains localised at the position of the departed carboxylate moiety. These observations lead to the conclusion that the mechanism for loss of ion signal involves unimolecular rearrangement reactions of the nascent \[M-2H](center dot-) carbonyloxyl radical anions that compete favourably with direct decarboxylation. Several possible rearrangement pathways that facilitate electron detachment from the radical anion are identified and are computed to be energetically accessible. Such pathways provide an explanation for prior observations of slow secondary electron features in the photoelectron spectra of the same dicaboxylate dianions. (C) 2013 Elsevier B.V. All rights reserved.

Photodissociation of TEMPO-modified peptides: New approaches to radical-directed dissociation of biomolecules

Radical-directed dissociation of gas phase ions is emerging as a powerful and complementary alternative to traditional tandem mass spectrometric techniques for biomolecular structural analysis. Previous studies have identified that coupling of 2-[(2,2,6,6-tetramethylpiperidin-1-oxyl)methyl] benzoic acid (TEMPO-Bz) to the N-terminus of a peptide introduces a labile oxygen-carbon bond that can be selectively activated upon collisional activation to produce a radical ion. Here we demonstrate that structurally-defined peptide radical ions can also be generated upon UV laser photodissociation of the same TEMPO-Bz derivatives in a linear ion-trap mass spectrometer. When subjected to further mass spectrometric analyses, the radical ions formed by a single laser pulse undergo identical dissociations as those formed by collisional activation of the same precursor ion, and can thus be used to derive molecular structure. Mapping the initial radical formation process as a function of photon energy by photodissociation action spectroscopy reveals that photoproduct formation is selective but occurs only in modest yield across the wavelength range (300-220 nm), with the photoproduct yield maximised between 235 and 225 nm. Based on the analysis of a set of model compounds, structural modifications to the TEMPO-Bz derivative are suggested to optimise radical photoproduct yield. Future development of such probes offers the advantage of increased sensitivity and selectivity for radical-directed dissociation. © 2014 the Owner Societies.

Ozone-induced dissociation of conjugated lipids reveals significant reaction rate enhancements and characteristic odd-electron product ions

Ozone-induced dissociation (OzID) is an alternative ion activation method that relies on the gas phase ion-molecule reaction between a mass-selected target ion and ozone in an ion trap mass spectrometer. Herein, we evaluated the performance of OzID for both the structural elucidation and selective detection of conjugated carbon-carbon double bond motifs within lipids. The relative reactivity trends for \[M + X](+) ions (where X = Li, Na, K) formed via electrospray ionization (ESI) of conjugated versus nonconjugated fatty acid methyl esters (FAMEs) were examined using two different OzID-enabled linear ion-trap mass spectrometers. Compared with nonconjugated analogues, FAMEs derived from conjugated linoleic acids were found to react up to 200 times faster and to yield characteristic radical cations. The significantly enhanced reactivity of conjugated isomers means that OzID product ions can be observed without invoking a reaction delay in the experimental sequence (i.e., trapping of ions in the presence of ozone is not required). This possibility has been exploited to undertake neutral-loss scans on a triple quadrupole mass spectrometer targeting characteristic OzID transitions. Such analyses reveal the presence of conjugated double bonds in lipids extracted from selected foodstuffs. Finally, by benchmarking of the absolute ozone concentration inside the ion trap, second order rate constants for the gas phase reactions between unsaturated organic ions and ozone were obtained. These results demonstrate a significant influence of the adducting metal on reaction rate constants in the fashion Li > Na > K.

Formation and Fragmentation of Unsaturated Fatty Acid M-2H+Na (-) Ions: Stabilized Carbanions for Charge-Directed Fragmentation

Fatty acids are long-chain carboxylic acids that readily produce \[M - H](-) ions upon negative ion electrospray ionization (ESI) and cationic complexes with alkali, alkaline earth, and transition metals in positive ion ESI. In contrast, only one anionic monomeric fatty acid-metal ion complex has been reported in the literature, namely \[M - 2H + (FeCl)-Cl-II](-). In this manuscript, we present two methods to form anionic unsaturated fatty acid-sodium ion complexes (i.e., \[M - 2H + Na](-)). We find that these ions may be generated efficiently by two distinct methods: (1) negative ion ESI of a methanolic solution containing the fatty acid and sodium fluoride forming an \[M - H + NaF](-) ion. Subsequent collision-induced dissociation (CID) results in the desired \[M - 2H + Na](-) ion via the neutral loss of HF. (2) Direct formation of the \[M - 2H + Na](-) ion by negative ion ESI of a methanolic solution containing the fatty acid and sodium hydroxide or bicarbonate. In addition to deprotonation of the carboxylic acid moiety, formation of \[M - 2H + Na](-) ions requires the removal of a proton from the fatty acid acyl chain. We propose that this deprotonation occurs at the bis-allylic position(s) of polyunsaturated fatty acids resulting in the formation of a resonance-stabilized carbanion. This proposal is supported by ab initio calculations, which reveal that removal of a proton from the bis-allylic position, followed by neutral loss of HX (where X = F- and -OH), is the lowest energy dissociation pathway.

Ozone-induced dissociation : Elucidation of double bond position within mass-selected lipid ions

Ions formed from lipids during electrospray ionization of crude lipid extracts have been mass-selected within a quadrupole linear ion trap mass spectrometer and allowed to react with ozone vapor. Gas-phase ion-molecule reactions between unsaturated lipid ions and ozone are found to yield two primary product ions for each carbon-carbon double bond within the molecule. The mass-to-charge ratios of these chemically induced fragments are diagnostic of the position of unsaturation within the precursor ion. This novel analytical technique, dubbed ozone-induced dissociation (OzID), can be applied both in series and in parallel with conventional collision-induced dissociation (CID) to provide near-complete structural assignment of unknown lipids within complex mixtures without prior fractionation or derivatization. In this study, OzID is applied to a suite of complex lipid extracts from sources including human lens, bovine kidney, and commercial olive oil, thus demonstrating the technique to be applicable to a broad range of lipid classes including both neutral and acidic glycerophospholipids, sphingomyelins, and triacylglycerols. Gas-phase ozonolysis reactions are also observed with different types of precursor ions including \[M + H](+), \[M + Li](+), \[M + Na](+), and \[M H](-): in each case yielding fragmentation data that allow double bond position to be unambiguously assigned. Within the human lens lipid extract, three sphingomyelin regioisomers, namely SM(d18:0/15Z-24:1), SM(d18:0/17Z-24:1), and SM(d18:0/19Z-24:1), and a novel phosphatidylethanolamine alkyl ether, GPEtn(11Z-18:1e/9Z18:1), are identified using a combination of CID and OzID. These discoveries demonstrate that lipid identification based on CID alone belies the natural structural diversity in lipid biochemistry and illustrate the potential of OzID as a complementary approach within automated, high-throughput lipid analysis protocols.

Unusual cross-ring S(N)2 reactions of M-H (-) ions of methoxyacetanilides

Deprotonated o, m-, and p-methoxyacetanilide show pronounced peaks in their collision-induced tandem mass spectra (MS/MS) produced by losses of the elements of C2H6. It is proposed that this reaction is a 'cross-ring' internal S(N)2 reaction involving an incipient methyl anion. For example, p-CH3O-C6H4-N--CO-CH3--> [(p.CH3O-C6H4-N=C=O)CH3-]--> O---C6H4-N=C=O+C2H6.

Production and isolation of ligated metal(IV)-oxo ions by tandem mass spectrometry

High valent metal(IV)-oxo species, \[M(=O)(Melm)(n)(OAc)](+) (M = Mn-Ni, MeIm = 1-methylimidazole, n = 1-2), which are relevant to biology and oxidative catalysis, were produced and isolated in gas-phase reactions of the metal(II) precursor ions \[M(MeIm)(n)(OAc)](+) (M = Mn-Zn, n = 1-3) with ozone. The precursor ions \[M(MeIm)(OAc)](+) and \[M(MeIm)(2)(OAc)](+) were generated via collision-induced dissociation of the corresponding \[M(MeIm)(3)(OAc)](+) ion. The dependence of ozone reactivity on metal and coordination number is discussed. Copyright (C) 2010 John Wiley & Sons, Ltd.

Unusual cross-ring SN2 reactions of [MH]− ions of methoxyacetanilides

Deprotonated o, m-, and p-methoxyacetanilide show pronounced peaks in their collision-induced tandem mass spectra (MS/MS) produced by losses of the elements of C2H6. It is proposed that this reaction is a 'cross-ring' internal S(N)2 reaction involving an incipient methyl anion. For example, p-CH3O-C6H4-N--CO-CH3--> [(p.CH3O-C6H4-N=C=O)CH3-]--> O---C6H4-N=C=O+C2H6.

Bisphenol A degradation enhanced by air bubbles via advanced oxidation using in situ generated ferrous ions from nano zero-valent iron/palygorskite composite materials

Novel nano zero-valent iron/palygorskite composite materials prepared by evaporative and centrifuge methods are tested for the degradation of bisphenol A in an aqueous medium. A systematic study is presented which showed that nano zero-valent iron material has little effect on bisphenol A degradation. When hydrogen peroxide was added to initiate the reaction, some percentage of bisphenol A removal (∼20%) was achieved; however, with the aid of air bubbles, the percentage removal can be significantly increased to ∼99%. Compared with pristine nano zero-valent iron and commercial iron powder, nano zero-valent iron/palygorskite composite materials have much higher reactivity towards bisphenol A and these materials are superior as they have little impact on the solution pH. However, for pristine nano zero-valent iron, it is difficult to maintain the reaction system at a favourable low pH which is a key factor in maintaining high bisphenol A removal. All materials were characterized by X-ray diffraction, scanning electron microscopy, elemental analysis, transmission electron microscopy and X-ray photoelectron spectroscopy. The optimum conditions were obtained based on a series of batch experiments. This study has extended the application of nano zero-valent iron/palygorskite composites as effective materials for the removal of phenolic compounds from the environment.

Formation of neutral molecules of potential stellar interest by neutralisation of negative ions in a mass spectrometer - The application of experiment and molecular modelling in concert

This paper is a modified version of a lecture which describes the synthesis, structure and reactivity of some neutral molecules of stellar significance. The neutrals are formed in the collision cell of a mass spectrometer following vertical Franck-Condon one electron oxidation of anions of known bond connectivity. Neutrals are characterised by conversion to positive ions and by extensive theoretical studies at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory. Four systems are considered in detail, viz (i) the formation of linear C-4 and its conversion to the rhombus C-4, (ii) linear C-5 and the atom scrambling of this system when energised, (iii) the stable cumulene oxide CCCCCO, and (iv) the elusive species O2C-CO. This paper is not intended to be a review of interstellar chemistry: examples are selected from our own work in this area. (C) 2002 Elsevier Science Inc. All rights reserved.

Effects of ions and atomic hydrogen in plasma-assisted growth of single-walled carbon nanotubes

The growth of single-walled carbon nanotubes (SWCNTs) in plasma-enhanced chemical vapor deposition (PECVD) is studied using a surface diffusion model. It is shown that at low substrate temperatures (≤1000 K), the atomic hydrogen and ion fluxes from the plasma can strongly affect nanotube growth. The ion-induced hydrocarbon dissociation can be the main process that supplies carbon atoms for SWCNT growth and is responsible for the frequently reported higher (compared to thermal chemical vapor deposition) nanotube growth rates in plasma-based processes. On the other hand, excessive deposition of plasma ions and atomic hydrogen can reduce the diffusion length of the carbon-bearing species and their residence time on the nanotube lateral surfaces. This reduction can adversely affect the nanotube growth rates. The results here are in good agreement with the available experimental data and can be used for optimizing SWCNT growth in PECVD.

Ion-acoustic waves in a complex plasma with negative ions

A wave propagation in a complex dusty plasma with negative ions was considered. The relevant processes such as ionization, electron attachment, diffusion, positive-negative ion recombination, plasma particle collisions, as well as elastic Coulomb and inelastic dust-charging collisions were taken self-consistently. It was found that the equilibrium of the plasma as well as the propagation of ion waves were modified to various degrees by these effects.

Charging and trapping of macroparticles in near-electrode regions of fluorocarbon plasmas with negative ions

Charging and trapping of macroparticles in the near-electrode region of fluorocarbon etching plasmas with negative ions is considered. The equilibrium charge and forces on particles are computed as a function of the local position in the plasma presheath and sheath. The ionic composition of the plasma corresponds to the etching experiments in 2.45 GHz surface-wave sustained and 13.56 MHz inductively coupled C4F8+Ar plasmas. It is shown that despite negligible negative ion currents collected by the particles, the negative fluorine ions affect the charging and trapping of particulates through modification of the sheath/presheath structure.