Mechanism Of Ion Formation Research Articles

In Situ, Real-Time Identification of Biological Tissues by Ultraviolet and Infrared Laser Desorption Ionization Mass Spectrometry

Laser desorption ionization-mass spectrometric (LDI-MS) analysis of vital biological tissues and native, ex vivo tissue specimens is described. It was found that LDI-MS analysis yields tissue specific data using lasers both in the ultraviolet and far-infrared wavelength regimes, while visible and near IR lasers did not produce informative MS data. LDI mass spectra feature predominantly phospholipid-type molecular ions both in positive and negative ion modes, similar to other desorption ionization methods. Spectra were practically identical to rapid evaporative ionization MS (REIMS) spectra of corresponding tissues, indicating a similar ion formation mechanism. LDI-MS analysis of intact tissues was characterized in detail. The effect of laser fluence on the spectral characteristics (intensity and pattern) was investigated in the case of both continuous wave and pulsed lasers at various wavelengths. Since lasers are utilized in various fields of surgery, a surgical laser system was combined with a mass spectrometer in order to develop an intraoperative tissue identification device. A surgical CO(2) laser was found to yield sufficiently high ion current during normal use. The principal component analysis-based real-time data analysis method was developed for the quasi real-time identification of mass spectra. Performance of the system was demonstrated in the case of various malignant tumors of the gastrointestinal tract.

About the plausible contribution of field ionization in the mechanism of the formation of dyes of ions under conditions of laser desorption/ionization from a nanostructurized graphite surface

An approach is proposed for the estimation of the contribution of field ionization (FI) to the mechanism of dye ion formation under the conditions of laser desorption/ionization (LDI) from a nanostructurized graphite surface. As test systems, rough graphite layers with dyes, e.g., imidazophenazine derivatives applied to them were chosen; these ensure FI in a strong electric field. The dyes form three neutral precursors upon reduction and various types of ions in different ionization methods. It was found that the mass distribution within the group of peaks formed by the initial dye molecule and the products of its reduction in the positive ion mode upon LDI from a rough graphite surface is shifted to lower masses by one atomic mass unit in comparison to the distribution recorded for LDI from a smooth metal support. The analysis of plausible pathways of ion formation has shown that such a shift may be due to the superposition of ions formed by the FI mechanism on a graphite substrate with a number of ions formed by protonation in LDI with no dependence on the support type. In the negative ion mode, the registration of LDI dye spectra succeeded only if the graphite substrates used favored negative FI and electron emission enhanced by the field.

Negative ion formation in laser ion mobility increment spectrometer

A new method is proposed and implemented, according to which small concentrations of organic compounds in the atmosphere are measured by combining the ion mobility increment spectrometer and laser ionization. The experimental setup makes use of the pulsed fourth-harmonic radiation of a YAG:Nd3+ laser (λ = 266 nm). At high intensities (q ∼ 107 W/cm2) of laser radiation, ion spectra with reactant peaks are observed, which are identical to the spectra obtained with traditional sources of ionization by corona discharge and β radiation. The ion spectra obtained at low laser radiation intensities (q ∼ 105 W/cm2) are free of background and reactant peaks, which ensures the high selectivity of the analysis. It is concluded that the mechanism of negative ion formation from the molecules of nitro compounds can change depending on the intensity of ionizing laser radiation.

Pulsed-jet discharge matrix isolation and computational study of CX 2Br + (X = H, F)

Pulsed-jet discharge matrix isolation spectroscopy and computational methods were used to characterize the CX 2Br + (X = H, F) ions. Our experiments combined matrix isolation techniques with a pulsed DC discharge nozzle, where a dilute CX 2Br 2:Ar sample was discharged and the products deposited onto a KBr window held at ∼8 K. This study represents the first spectroscopic observation of CH 2Br +, and the first report of the C–Br stretching frequency of CF 2Br +. Our results suggest that the primary mechanism for ion formation is ionization/fragmentation of the precursor by collision with metastable rare gas (Ar) atoms.

Rearrangement and predissociation processes in negative molecular ions of nitrobenzenes

The reactions of resonant electron capture by the molecules of benzene nitroderivatives has been studied in the gas phase. Some fragment negative ions were found to be unstable with respect to electron autodetachment. This circumstance has been used for the determination of their structure. In particular, it has been established that the low measured appearance energy of neutral component of [M-H](-) ion beam is a result of isomerization of nitrobenzenes' molecular ion, leading to the 2-nitrosophenol structure with the subsequent formation of the phenoxide anion in the autodetaching state. The effective yield curves of some types of fragment ions demonstrate fine vibrational structures, testifying the predissociation mechanism of ion formation. For all detected ions, the absolute cross sections of formation have been measured.

Metal dicarbides as intermediate species in thermal ion formation mechanisms

Lanthanide elements (lanthanum to lutetium) and actinide elements (uranium and plutonium) adsorbed onto resin beads and mounted on rhenium filaments were studied as thermal ionization sources. Temperatures at which these ion sources gave maximum intensities were measured for each of these elements. The temperature trends correlate with the dissociation energies of the corresponding metal dicarbide compounds. The metal dicarbide functions as a carrier to take the lanthanide and actinide elements to higher temperatures than would be attainable otherwise. This results in release of the atomic species at a higher temperature where ionization probability is significantly increased.

Fast polymer fingerprinting using flowing afterglow atmospheric pressure glow discharge mass spectrometry

Flowing afterglow atmospheric pressure glow discharge mass spectrometry (FA-APGD-MS) was used to interrogate different polymer species such as biopolymers, synthetic homo- and co-polymers. The main advantages of FA-APGD-MS for polymer samples include speed (<30 s per sample) and analysis at atmospheric pressures. Moreover, there are essentially no restrictions as to the kind of polymer sample that can be analyzed because FA-APGD-MS can deal with liquid and solid (soluble or insoluble) bulk polymers and granulates, irrespective of their conductivity, without requiring any sample preparation prior to analysis. We will discuss the mechanism of ion formation as well as the limitation of the accessible mass range (m/z < 500) in view of what type of information can be gained from the mass spectra obtained. Monomer units and some fragments were detected for homopolymers, e.g.cis-polyisoprene (IR), poly(ethylene glycol) (PEG), poly(ethylene terephthalate) (PET), which allowed identification of the polymer composition. The mass spectra obtained were further processed using principal component analysis (PCA) for a better visualization and assessing of mass-spectral reproducibility. Combination with PCA even allowed differentiation of pectin, amylopectin, and cellulose, chemically very similar polysaccharides whose characteristic differences lie in the nature of the glycosidic linkage. Finally, we were able to detect and identify phthalate plasticizers, bis(2-ethylhexyl) phthalate (BEHP) and dibutyl phthalate (DBP), present in poly(vinyl chloride)-based food wraps.

Competitive processes in the associative ionization ofC−withC+,N+, andO+

Absolute integral cross sections have been measured for associative ionization reactions involving the ${\mathrm{C}}^{\ensuremath{-}}$ and ${\mathrm{C}}^{+}$, ${\mathrm{N}}^{+}$, and ${\mathrm{O}}^{+}$ reactants. These measurements, obtained using a merged-beam setup in the keV range, provide us with useful experimental information on the efficiency and mechanisms of molecular ion formation from ionic reactants. The relative magnitudes of the different cross sections are rationalized by considering the spin multiplicities of initial and final states, and the exothermicities of the detachment and transfer ionization channels. The very different production efficiencies of $\mathrm{C}{\mathrm{O}}^{+}$ ions via the ${\mathrm{O}}^{\ensuremath{-}}+{\mathrm{C}}^{+}$ and ${\mathrm{C}}^{\ensuremath{-}}+{\mathrm{O}}^{+}$ channels are explained by statistical and energetic considerations. The potential energy curves of CO and $\mathrm{C}{\mathrm{O}}^{+}$ have been calculated by quantum ab initio methods in order to characterize the reactive pathways leading to autoionization. Thermal rate coefficients are derived to serve the plasma physics community.

Molecular imaging by Mid-IR laser ablation mass spectrometry

Mid-IR laser ablation at atmospheric pressure (AP) produces a mixture of ions, neutrals, clusters, and particles with a size distribution extending into the nanoparticle range. Using external electric fields the ions can be extracted and sampled by a mass spectrometer. In AP infrared (IR) matrix-assisted laser desorption ionization (MALDI) experiments, the plume was shown to contain an appreciable proportion of ionic components that reflected the composition of the ablated target and enabled mass spectrometric analysis. The detected ion intensities rapidly declined with increasing distance of sampling from the ablated surface to ∼4 mm. This was rationalized in terms of ion recombination and the stopping of the plume expansion by the background gas. In laser ablation electrospray ionization (LAESI) experiments, the ablation plume was intercepted by an electrospray. The neutral particles in the plume were ionized by the charged droplets in the spray and enabled the detection of large molecules (up to 66 kDa). Maximum ion production in LAESI was observed at large (∼15 mm) spray axis to ablated surface distance indicating a radically different ion formation mechanism compared to AP IR-MALDI. The feasibility of molecular imaging by both AP IR-MALDI and LAESI was demonstrated on targets with mock patterns.

Selective Detection of Specific Protein–Ligand Complexes by Electrosonic Spray–Precursor Ion Scan Tandem Mass Spectrometry

A novel mass spectrometric method for the selective detection of specific protein-ligand complexes is presented. The new method is based on electrosonic spray ionization of samples containing protein and ligand molecules, and mass spectrometric detection using the precursor ion scanning function on a triple quadrupole instrument. Mass-selected intact protein-ligand complex ions are subjected to fragmentation by means of collision-induced dissociation in the collision cell of the instrument, while the second mass analyzer is set to the m/z of protonated ligand ions or their alkali metal adducts. The method allows for the detection of only those ions which yield ions characteristic of the ligand molecules upon fragmentation. Since the scan range of first analyzer is set well above the m/z of the ligand ion, and the CID conditions are established to permit fragmentation of only loosely bound, noncovalent complexes, the method is specific to the detection of protein-ligand complexes under described conditions. Behavior of biologically specific and nonspecific complexes was compared under various instrumental settings. Parameters were optimized to obtain maximal selectivity for specific complexes. Specific and nonspecific complexes were found to show markedly different fragmentation characteristics, which can be a basis for selective detection of complexes with biological relevance. Preparation of specific and nonspecific complexes containing identical building blocks was attempted. Complex ions with identical stoichiometry but different origin showed the expected difference in fragmentation characteristics, which gives direct evidence for the different mechanism of specific versus nonspecific complex ion formation.

Role of the support material on laser desorption/ionization mass spectra

We report the results of experimental studies on the effects of sample supports in laser desorption/ionization mass spectrometry (LDI-MS). LDI time-of-flight (TOF) mass spectra obtained for C(60) and insulin samples deposited onto standard stainless steel substrate and/or onto some non-metallic materials (glass, scotch tape, floppy disc foil, Teflon foil, photocopy film), all recorded under identical, typical experimental conditions, have been compared with regard to their intensity and quality. The LDI investigations show that compared with stainless steel, glass and floppy disc foil sample supports boost (2-3.5 times) ion yields for C(60)(+) and C(60)(-) ions, respectively. The stainless steel and scotch tape sample supports are the best for the mass resolution of positive ions and the formation of (C(60))(n)(-) (n <or= 4) cluster ions, respectively. In the case of detection of insulin by matrix-assisted laser desorption/ionization (MALDI) we did not observe significant differences in sensitivity for the support materials tested. A mechanism of ion formation in the desorption plume is suggested.

Ion internal energy distributions validate the charge residue model for small molecule ion formation by spray methods

This paper reports a detailed study of the internal energy distribution of ions formed by four electrospray ionization (ESI)-related ionization methods, with particular emphasis on electrosonic spray ionization (ESSI). Substituted benzylpyridinium ions were used as thermometer ions to probe the internal energy distribution. The influence of different instrumental parameters was studied. Cone and skimmer voltages as well as the collision energy were found to strongly affect the ion internal energy distribution, whereas the distance between the emitter and the inlet of the mass spectrometer, the nebulizing gas pressure or the flow rate showed no influence. The internal energy distribution obtained with an ESSI source was compared with those obtained for electrospray (ESI), nanoelectrospray (nanoESI) and sonic spray ionization (SSI) on the same mass spectrometer with the same instrumental parameters. No clear differences were observed. As the charge residue model is the only ion formation mechanism possible for SSI, we conclude that benzylpyridinium ions are formed by the pathway suggested by this model.

Detection of free amino acids in proxies of marine aerosol by photoelectron resonance capture ionization aerosol mass spectrometry

Photoelectron resonance capture ionization aerosol mass spectrometry (PERCI-AMS) has been applied to the analysis of proxies for marine aerosols with and without ozone; proxies used were mixed oleic acid–amino acid particles. The mechanism of ion formation for serine (104 m/z), glutamic acid (146 m/z), and phenylalanine (164 m/z) was dissociative electron attachment. This corresponds to loss of the hydrogen atom only, allowing for straightforward identification of the free amino acids. No ozonolysis products for the free amino acids were observed, even at high concentrations of ozone (500 ppm for 19 s). The direct detection of a novel gas-phase hydrated anion, [serine + H2O–H]–, is described. These preliminary results suggest that PERCI-AMS may provide an effective, simple and direct online method for the detection of organic nitrogen from free amino acids for future field studies of the marine troposphere.

Can electrospray ionization help the characterization of iron gall inks? Investigation on the interactions of gallic acid with iron ions in aqueous solutions

In the present work, an investigation has been conducted by electrospray ionization (ESI) experiments to characterize the structures of iron gall ink complexes in solution. Simple mono and polyphenolic acid molecules added to iron sulfate salts were chosen to model the recipes of ink composition. Theoretical calculations have been used (1) to determine the stability of the ionic complexes generated in the gas phase, (2) to explain which structures are more likely generated in the electrospray ion source, and (3) to determine which mechanisms are likely involved in their formation. Fragmentation pathways of the derived structures have also been investigated and rationalized to facilitate the interpretation of the data obtained under collisionally induced dissociation (CID) conditions.The present study confirms the assumption that ESI experiments with ions that are preformed in solution must be considered carefully. As a matter of fact, the study of ion formation mechanisms in the ion source is necessary to establish relationships between the ion structures in the condensed phase and the gas phase.

Ion Formation Mechanism in Laser Desorption Ionization of Individual Nanoparticles

Covariance mapping is used to study ion formation mechanisms in laser desorption ionization of individual 50 or 220 nm diameter particles having compositions similar to ambient aerosol. Single particle mass spectra are found to vary substantially from particle to particle. This variation is systematic--the energetically preferred ions (e.g., lowest ionization energy, highest electron affinity) are positively correlated with each other and negatively correlated with less preferred ions. For the compositions studied, the average positive ion yield is two to five times greater than the negative ion yield, indicating that free electrons are the main negatively charged species. For many particles, typically 20% to 40% of those analyzed, only positive ions are detected. Smaller particles give fewer negative ions, presumably because the plume is less dense and electron capture is less likely. The results suggest that ion formation occurs by a two stage process. In the first stage, photoionization of laser desorbed neutrals gives cations and free electrons. In the second stage, collisions in the plume cause electron capture and competitive charge transfer. When the particle ablates in a manner giving a dense plume with many collisions, the energetically preferred positive and negative ions are dominant. When the particle ablates in a manner giving a less dense plume with fewer collisions, the less preferred ions are able to survive and the energetically preferred ions constitute a lower fraction of the total ion signal. Systematic particle to particle variations of relative signal intensities can complicate ambient particle classification efforts by spreading a single particle composition over several classes.

Radical Cations in Electrospray Mass Spectrometry: Formation of Open‐Shell Species, Examination of the Fragmentation Behaviour in ESI‐MSn and Reaction Mechanism Studies by Detection of Transient Radical Cations

AbstractThe ion formation mechanism in electrospray MS is reviewed, with special focus on the electrochemical red/ox reactions responsible for the formation of radical molecular ions. Prerequisites influencing the likelihood of formation and observation of a particular compound as an open‐shell molecular species in ESI‐MS (i.e., the structure and the oxidation potential of the analyte, the solvent and additives) are evaluated. For illustration of the ESI phenomena governing radical cation formation, an ESI‐MS study of tetra(aryl)benzidine compounds is presented. The facile formation of abundant radical molecular cations in ESI‐MS demonstrates imposingly that the basicity of the analyte's nitrogen atoms is strongly overcompensated by the ability to stabilize unpaired electrons. ESI‐MSn spectra of the tetra(aryl)benzidine molecular ions exhibit a characteristic feature in the loss of radicals. This process is the major fragmentation pathway of open‐shell molecular precursor ions in their MS2 spectra, and also that of even‐electron ions in sequential MSn spectra. The collision‐induced dissociation (CID) behaviour suggests a general assumption: easily oxidizable compounds (e.g., hydrocarbon polyenes, polycyclic aromatic hydrocarbons, porphyrins etc.) generating predominantly molecular radical cations in ESI‐MS contradict the even electron rule in ESI‐MSn experiments. The strong ability to stabilize unpaired electrons is preserved in product ions and makes the formation of open‐shell species energetically less demanding. A selection of solution‐phase reaction mechanistic studies in which open‐shell intermediates were detected and structurally characterized by ESI‐MS and ESI‐MS/MS, respectively, is presented. The merits of ESI‐MS and ESI‐MSn for mechanistic studies of chemical reaction are critically discussed.(© Wiley‐VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2007)

Gas-phase ionisation of sputtered rare gas atoms

During bombardment of solid samples with rare gas ions, charge-transfer events can convert reemitted rare gas atoms to positively charged ions. In analytical applications of secondary ion mass spectrometry (SIMS) this mechanism of ion formation is of considerable interest because, owing to their high ionisation potential, the ion fraction of sputtered rare gas atoms is very low. A quadrupole-based SIMS instrument was used to study details of the gas-phase ionisation process, notably the variation of the ion production rate as a function of the distance from the surface. The relevant information was derived from the apparent energy spectra of gas-phase generated (GPG) ions, observed during bombardment of a variety of elemental targets with Ne +, Ar + and Kr + beams at energies between 3 and 12 keV. Owing to the use of a secondary ion extraction field of low strength, gas-phase ionisation events could be separated by distance δ from the surface, with δ up to about 6 mm. The results were compared with a simple model that describes the ion production rate as the product of the gas-atom flow rate and the ionisation probability. The first factor is proportional to the primary ion current and the second proportional to the current density j 0. Therefore, the intensity of GPG ions is not proportional to j 0 2 , as assumed previously. The mean ionisation probabilities of GPG ions (∼10 −5 at a moderate mean current density of ∼2 mA/cm 2) were found to be higher by more than four orders of magnitude compared to ‘ordinary’ SIMS. In part, this favourable result can be attributed to the low energy of rare gas atom ejection (∼0.1 eV). The experimental data suggest that the angular distributions of ejected rare gas atoms are strongly forward peaked. Presumably for this reason the yields of GPG ions observed with an amorphised target like silicon were distinctly higher than with polycrystalline metals. In the latter case, emission from unfavourably oriented microcrystals causes a large fraction of ejected gas atoms to escape from the interaction volume before ionisation can occur. Further enhancement in yield can be expected by the use of focussed primary ion beams with fairly uniform rather than Gaussian-like current density distributions. If the atomic number of the projectile is slightly lower than that of the target atom, as for Ne + impact on Mg, Al and Si or Ar + impact on Ti +, sizable or even high signals, independent of current density, were observed due to energetic multiply scattered ions.

Collisionally-Induced Dissociation of Substituted Pyrimidine Antiviral Agents: Mechanisms of Ion Formation Using Gas Phase Hydrogen/Deuterium Exchange and Electrospray Ionization Tandem Mass Spectrometry

ESI and CID mass spectra were obtained for four pyrimidine nucleoside antiviral agents and the corresponding compounds in which the labile hydrogens were replaced by deuterium using gas-phase exchange. The number of labile hydrogens, x, was determined from a comparison of ESI spectra obtained with N(2) and with ND(3) as the nebulizer gas. CID mass spectra were obtained for [M + H](+) and [M - H](-) ions and the exchanged analogs, [M(D(x)) + D](+) and [M(D(x)) - D](-), produced by ESI using a SCIEX API-III(plus) mass spectrometer. Protonated pyrimidine antiviral agents dissociate through rearrangement decompositions of base-protonated [M + H](+) ions by cleavage of the glycosidic bonds to give the protonated bases with a sugar moiety as the neutral fragment. Cleavage of the glycosidic bonds with charge retention on the sugar moiety eliminates the base moiety as a neutral molecule and produces characteristic sugar ions. CID of protonated pyrimidine bases, [B + H](+), occurs through three major pathways: (1) elimination of NH(3) (ND(3)), (2) loss of H(2)O (D(2)O), and (3) elimination of HNCO (DNCO). Protonated trifluoromethyl uracil, however, dissociates primarily through elimination of HF followed by the loss of HNCO. CID mass spectra of [M - H](-) ions of all four antiviral agents show NCO(-) as the principal decomposition product. A small amount of deprotonated base is also observed, but no sugar ions. Elimination of HNCO, HN(3), HF, CO, and formation of iodide ion are minor dissociation pathways from [M - H](-) ions.

Influence of the chemisorption state on the charge distribution of low energy Si scattered from I adatoms

The ion fractions of 5 keV Si + ions singly scattered from iodine adatoms adsorbed on Al(1 0 0), Si(1 1 1) and pre-oxidized Si(1 1 1) were measured with time-of-flight spectroscopy. A considerable ion yield was observed, which did not change significantly with exit angle or I coverage. The mechanism of ion formation is assigned to valence electron resonant charge transfer (RCT) assisted by promotion of the Si ionization level. The yields are smaller than those of Si scattered from Cs adatoms, however, which suggests that electron tunneling from the occupied chemisorption states of the I adatom provides an additional neutralization channel.

Resolution of infrared matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry using glycerol; enhancement with a disperse laser beam

Some experimental factors affecting the resolution in glycerol infrared matrix-assisted laser desorption/ionization (IR-MALDI) time-of-flight (TOF) mass spectrometry were investigated. Loading the sample inside a cavity covered with a grid was found to improve the resolving power as reported previously, although not to the extent attainable in UV-MALDI using the same instrument. The resolving power improved as the laser spot area at the sample position got larger, becoming almost comparable with that in UV-MALDI when the spot area was a little larger than the cavity size. Reduced concentration of the ablated materials in the acceleration region with the use of the grid and large irradiation area may be responsible for the enhanced resolution. In addition, the threshold laser fluences measured in this work were lower than those reported in the literature and tended to decrease more rapidly as the irradiation area increased than predicted previously. The implication of similar threshold fluences for matrix and analyte ions is discussed in relation to the analyte ion formation mechanism.