Development of a PIXE method at high energy with the ARRONAX cyclotron

The high energy PIXE (HEPIXE) method is a multi-elemental non-destructive ion beam analysis technique. It is based on the detection of the X-ray emitted due to the interaction of high energy particle beam with a sample. This technique is fast and allows the analysis of heavy and medium elements in thin (μm), thick (mm) and multilayer samples. At the ARRONAX facility (Nantes, France), the HEPIXE method has been used to determine the composition of natural and synthetic sodalites. Photochromic properties of these samples are supposed to come from the trace elements (concentration in the ppm range) present in the samples. Taking advantage of the 70 MeV proton beam available at our facility, the HEPIXE method has been also used to study multilayer samples. It has been shown that it is possible to determine the composition of each layer, their thicknesses and their depth position by analyzing the recorded X-ray spectra.     

The mechanism of proton exchange: guided ion beam studies of the reactions, H(H2O)n+ (n=1-4)+D2O and D(D2O)n+ (n=1-4)+H2O

Reactions of protonated water clusters, H(H(2)O)(n) (+) (n=1-4) with D(2)O and their "mirror" reactions, D(D(2)O)(n) (+) (n=1-4) with H(2)O, are studied using guided-ion beam mass spectrometry. Absolute reaction cross sections are determined as a function of collision energy from thermal energy to over 10 eV. At low collision energies, we observe reactions in which H(2)O and D(2)O molecules are interchanged and reactions where H-D exchange has occurred. As the collision energy is increased, the H-D exchange products decrease and the water exchange products become dominant. At high collision energies, processes in which one or more water molecules are lost from the reactant ions become important, with simple collision-induced dissociation processes, i.e., those without H-D exchange, being dominant. Threshold energies of endothermic channels are measured and used to determine binding energies of the proton bound complexes, which are consistent with those determined by thermal equilibrium measurements and previous collision-induced dissociation studies. A kinetic scheme that relies only on the ratio of isomerization and dissociation rate constants successfully accounts for the kinetic energy dependence observed in the branching ratios for H-D and water exchange products in all systems. Rice-Ramsperger-Kassel-Marcus theory and ab initio calculations confirm the feasibility and establish the details of this kinetic model.     

Collision-induced dissociation and theoretical studies of Cu+-dimethoxyethane complexes

Collision-induced dissociation of the dimethoxyethane (DXE) complexes with copper ions, Cu⁺(DXE)_n, n = 1 and 2, is studied using kinetic energy dependent guided ion beam mass spectrometry. For Cu⁺(DXE)₂, the only product formed corresponds to endothermic loss of a neutral ligand, while the Cu⁺(DXE) complex dissociates by several competitive channels. The cross-section thresholds for single ligand loss are interpreted to yield 0 and 298 K bond energies for Cu⁺-DXE and (DXE)Cu⁺-DXE after accounting for the effects of multiple ion-molecule collisions, internal energy of the reactant ions, and dissociation lifetimes. We find absolute 0 K bond dissociation energies for these complexes of 2.74 ± 0.08 and 1.87 ± 0.06 eV, respectively. These values are compared with theoretical values obtained using density functional and second order Møller-Plesset perturbation, MP2, theories. We also compare our results with previously studied alkali cation-ether complexes. Although Cu⁺ and all alkali cations have ¹S electronic ground states, the comparison shows different trends for Cu⁺ because of hybridization effects involving the valence d-electrons.     

Collision induced dissociations of radical cations

The collision induced dissociation spectra of ions generated by ionization or fragmentation of various samples reveal at least five non-decomposing structures. In contrast, the kinetic energy release measurements for the loss of carbon monoxide from the metastable ions are in agreement with the occurrence of a common reactive species. Isomerization into an ‘α,β-unsaturated aldehyde-like’ structure prior to fragmentation is proposed to accommodate these collision induced dissociation and mass analysed ion kinetic energy data. Some resuts suggest also that carbon monoxide loss from the phenol molecular ion may not occur via the cyclohexadienone tautomer.     

Fast atom bombardment combined with mass spectrometry for characterization of polycyclic aromatic hydrocarbons

A new approach using fast atom bombardment combined with mass spectrometry to characterize polycyclic aromatic hydrocarbons (PAHs) in the range of 128-252 u molecular weight is described. Sulfolane was employed as a liquid matrix for these π-conjugated hydrocarbons. Bombardment of sulfolane solution of certain PAHs with an atom beam produces both radical cation (M^+.) and protonated molecule [(M + H)⁺], with no evidence of fragmentation. Collisional activation of the fast atom bombardment-desorbed M^+. ions, however, results in several structure-specific fragment ions. Structural differences in a few isomeric hydrocarbons can be detected using the [(M + H)⁺]/[M^+.] abundance ratio and in the pyrene-fluoranthene pair by the B/E linked-field-collision-activated dissociation data. The [(M + H)⁺]/[M^+.] was found to be compound-specific and correlated well with certain properties (resonance energy, proton affinity, and ionizing energy) of PAHs.     

Fragmentation dynamics of ammonia cluster ions after single photon ionisation

A reflecting time of flight mass spectrometer (RETOF) is used to study unimolecular and collision induced fragmentation of ammonia cluster ions. Synchrotron radiation from the BESSY electron storage ring is used in a range of photon energies from 9.08 up to 17.7 eV for single photon ionisation of neutral clusters in a supersonic beam. The threshold photoelectron photoion coincidence technique (TPEPICO) is used to define the energy initially deposited into the cluster ions. Metastable unimolecular decay (µs range) is studied using the RETOF's capacity for energy analysis. Under collision free conditions the by far most prominent metastable process is the evaporation of one neutral NH₃ monomer from protonated clusters (NH₃) _{n ? 2}NH ₄ ⁺ . Abundance of homogeneous vs. protonated cluster ions and of metastable fragments are reported as a function of photon energy and cluster size up ton=10.     

The metastable formation of di-ethylchloronium ions from ethylchloride dimer ions in a seeded molecular beam

Cluster ions of ethylchloride and their dissociation products have been produced in a supersonic expansion of ethylchloride seeded in Ar and energy selected by the threshold photoelectron photoion coincidence (TPEPICO) method. The peak widths of the ion time of flight distribution indicate that all of the clusters are produced by dissociative photoionization of higher order clusters. Thus, trimer ions dissociate to form dimer ions and an ethylchloride monomer. This dimer ion was found to be metastable with respect to the formation of the di-ethylchloronium ion and a chlorine atom. The measured dissociation rate as a function of the dimer ion internal energy was compared to the calculated rates based on the statistical RRKM/QET theory. Good agreement was found when the dimer adiabatic IP was assumed to be 10.2 eV. The Cl loss from the ethylchloride dimer ion is associated with a reverse activation energy of about 0.32 eV.     

Influence of d orbital occupation on the binding of metal ions to adenine

Threshold collision-induced dissociation of M(+)(adenine) with xenon is studied using guided ion beam mass spectrometry. M(+) includes all 10 first-row transition metal ions: Sc(+), Ti(+), V(+), Cr(+), Mn(+), Fe(+), Co(+), Ni(+), Cu(+), and Zn(+). For the systems involving the late metal ions, Cr(+) through Cu(+), the primary product corresponds to endothermic loss of the intact adenine molecule, whereas for Zn(+), this process occurs but to form Zn + adenine(+). For the complexes to the early metal ions, Sc(+), Ti(+), and V(+), intact ligand loss competes with endothermic elimination of purine and of HCN to form MNH(+) and M(+)(C(4)H(4)N(4)), respectively, as the primary ionic products. For Sc(+), loss of ammonia is also a prominent process at low energies. Several minor channels corresponding to formation of M(+)(C(x)H(x)N(x)), x = 1-3, are also observed for these three systems at elevated energies. The energy-dependent collision-induced dissociation cross sections for M(+)(adenine), where M(+) = V(+) through Zn(+), are modeled to yield thresholds that are directly related to 0 and 298 K bond dissociation energies for M(+)-adenine after accounting for the effects of multiple ion-molecule collisions, kinetic and internal energy distributions of the reactants, and dissociation lifetimes. The measured bond energies are compared to those previously studied for simple nitrogen donor ligands, NH(3) and pyrimidine, and to results for alkali metal cations bound to adenine. Trends in these results and theoretical calculations on Cu(+)(adenine) suggest distinct differences in the binding site propensities of adenine to the alkali vs transition metal ions, a consequence of s-dsigma hybridization on the latter.     

Production and stability of oxygen cluster cations and anions,revisited

Stoichiometric and non-stoichiometric, positive and negative oxygen cluster ions (n up to 70) have been produced in a crossed neutral beam/electron beam ion source. The abundance and stability of the ions formed have been analyzed with a double focussing sector field mass spectrometer in a series of experiments. Positive and negative ion mass spectra observed exhibit distinct abundance anomalies, however, at different cluster sizes. Abundance maxima and minima correlate with correspondingly small and large metastable fractions of (O₂) _n ⁺ and (O₂) _n ^? ions, respectively. (O₂) _n ⁺ ions may also lose up top=(n?1) monomers by collision induced dissociation with monotonously decreasing probability with increasingp. Metastable fractions determined for (O₂) _n ^? ions produced with appr. zero eV electrons are in general larger than those for ions produced with appr. 7 eV electrons. (O₂) _n ^? ions are also observed to decay via autodetachment, with lifetimes increasing with increasing cluster size. Finally, here we were able to prove that an apparent loss of the monomer fragment O (and higher homologues) observed in the metastable time regime is due to ordinary metastable monomer evaporation in the acceleration region. Moreover, we will also present here some new data and interpretation concerning the electron attachment cross section function for O₂ clusters.     

Changes in a surface of polycrystalline aluminum upon bombardment with argon ions

The interaction between argon ions and a natural oxide layer of polycrystalline aluminum is studied via Auger electron (AE) and electron energy loss (EEL) spectroscopy. It is found that bombardment with argon ions whose energy is lower than the Al₂O₃ sputtering threshold results in the accumulation of bombarding ions in interstitial surface voids, thus forming a supersaturated solid solution of target atoms and bombarding ions of argon and nitrogen entrapped by the ion beam from the residual gas of the working chamber of the spectrometer.     

On the determination of HCl+ (A,v′) vibrational populations from HCl+ (A→X) fluorescence spectra: direct comparison between photoionization and penning ionization

Using a beam apparatus, we have measured the HCl⁺ (A,v′→X,v″) fluorescence spectra of HCl⁺ (A,v′) ions formed in HeI (58.4 nm), and NeI (73.6 nm) photoionization and, for the first time, in He (2³ S) Penning ionization under single collision conditions with a wavelength bandwidth around 1 nm. In addition, we have studied Ne (3s ³ P _{2, 0}) Penning ionization of HCl at three different collision energies. The procedure and the problems in extracting HCl⁺ (A,v′) vibrational populations from the data are discussed in some detail. Thedirect comparison of photoionization and Penning ionization data allows definitive conclusions to be drawn on the question whether final state interactions in the Penning reaction change the “nascent” vibrational population (determined by electron spectrometry); for He (2³ S)+HCl, such changes are shown to be absent within the experimental uncertainty (<±10%). For Ne (3s ³ P _{2, 0})+HCl, the HCl⁺ (A,v′=0, 1) populations are also found to be close to those measured by electron spectrometry and essentially independent of collision energy in the range 34–96 meV. From measurements of the fluorescence intensity as a function of HCl density, we have evidence for a fast loss of HCl⁺ (A,v′) ions in collisions with HCl (rate constant around 5·10^?9 cm³s^?1).     

Role of fragmentation processes in the liquid metal ion source production of aggregates

We analyse the role of the fragmentation processes in the liquid metal ion source technique from a theoretical and an experimental point of view. We show that the “double peak” structure of the energy distribution of Sn ₇ ⁺ ions is due to the fact that there are two kinds of ions. On the one hand, ions which are directly emitted from the tip; on the other hand, ions produced by fragmentation at some distance (100–1000 Å) from the tip. We show that the existence of a peak for the second kind of ions strongly depends on the electric field mapping. We also deduce from the energy separation of the two peaks a life-time of the mother particles. The value obtained is compared to an evaluation made with the RRKM theory. The charge and mass of the mother particles are also discussed.     

Low‐energy collision‐induced dissociation (low‐energy CID), collision‐induced dissociation (CID), and higher energy collision dissociation (HCD) mass spectrometry for structural elucidation of saccharides and clarification of their dissolution mechanism in DMAc/LiCl

The dissolution mechanism of oligosaccharides in N,N‐dimethylacetamide/lithium chloride (DMAc/LiCl), a solvent used for cellulose dissolution, and the capabilities of low‐energy collision‐induced dissociation (low‐energy CID), collision‐induced dissociation (CID), and higher energy collision dissociation (HCD) for structural analysis of carbohydrates were investigated. Comparing the spectra obtained using 3 techniques shows that, generally, when working with monolithiated sugars, CID spectra provide more structurally informative fragments, and glycosidic bond cleavage is the main pathway. However, when working with dilithiated sugars, HCD spectra can be more informative providing predominately cross‐ring cleavage fragments. This is because HCD is a nonresonant activation technique, and it allows a higher amount of energy to be deposited in a short time, giving access to more endothermic decomposition pathways as well as consecutive fragmentations. The difference in preferred dissociation pathways of monolithiated and dilithiated sugars indicates that the presence of the second lithium strongly influences the relative rate constants for cross‐ring cleavages vs glycosidic bond cleavages, and disfavors the latter. Regarding the dissolution mechanism of sugars in DMAc/LiCl, CID and HCD experiments on dilithiated and trilithiated sugars reveal that intensities of product ions containing 2 Li⁺ or 3 Li⁺, respectively, are higher than those bearing only 1 Li⁺. In addition, comparing the fragmentation spectra (both HCD and CID) of LiCl‐adducted lithiated sugar and NaCl‐adducted sodiated sugar shows that while, in the latter case, loss of NaCl is dominant, in the former case, loss of HCl occurs preferentially. The compiled evidence implies that there is a strong and direct interaction between lithium and the saccharide during the dissolution process in the DMAc/LiCl solvent system.     

Radiative electron capture: a tool for structure studies of heavy few-electron ions

Radiative Electron Capture (REC) in collisions of hydrogenic germanium ions with hydrogen is measured for projectile energies between 4 and 12 MeV/u. Extrapolating the resulting centroid energies of the K-REC radiation to zero collision velocity theK-binding energy in helium-like germanium-ions is determined. The value compares well with the theoretical prediction. REC in atomic collisions is advertised as a spectroscopic tool for structure investigations of very heavy few-electron projectiles.     

Energy Dependence of HCD on Peptide Fragmentation: Stepped Collisional Energy Finds the Sweet Spot

An understanding of the process of peptide fragmentation and what parameters are best to obtain the most useful information is important. This is especially true for large-scale proteomics where data collection and data analysis are most often automated, and manual interpretation of spectra is rare because of the vast amounts of data generated. We show herein that collisional cell peptide fragmentation, in this case higher collisional dissociation (HCD) in the Q Exactive, is significantly affected by the normalized energy applied. Both peptide sequence and energy applied determine what ion fragments are observed. However, by applying a stepped normalized collisional energy scheme and combining ions from low, medium, and high collision energies, we are able to increase the diversity of fragmentation ions generated. Application of stepped collision energy to HEK293T lysate demonstrated a minimal effect on peptide and protein identification in a large-scale proteomics dataset, but improved phospho site localization through increased sequence coverage. Stepped HCD is also beneficial for tandem mass tagged (TMT) experiments, increasing intensity of TMT reporters used for quantitation without adversely effecting peptide identification.

The 3D quadrupole ion trap mass spectrometer as a complete chemical laboratory for fundamental gas-phase studies of metal mediated chemistry

Electrospray ionization provides a "treasure trove" of metal containing ions whose fundamental reactivity can be studied via collision induced dissociation and ion-molecule reactions using the multistage mass spectrometry capabilities of the quadrupole ion trap mass spectrometer. Examples of metal mediated chemistry relevant to catalysis, C-C bond coupling, bioinorganic and supramolecular chemistry are highlighted.     

Efficiency of collisionally-activated dissociation and 193-nm photodissociation of peptide ions in fourier transform mass spectrometry

For tandem mass spectrometry, the Fourier transform instrument exhibits advantages for the use of collisionally-activated dissociation (CAD). The CAD energy deposited in larger ions can be greatly increased by extending the collision time to as much as 120 s, and the efficiency of trapping and measuring CAD product ions is many times greater than that found for triple-quadrupole or magnetic sector instruments, although the increased pressure from the collision gas is an offsetting disadvantage. A novel system that uses the same laser for photodesorption of ions and their subsequent photodissociation can produce complete dissociation of larger oligopeptide ions and unusually abundant fragment ions. In comparison to CAD, much more internal energy can be deposited in the primary ions using 193-nm photons, sufficient to dissociate peptide ions of m/z > 2000. Mass spectra closely resembling ion photodissociation spectra can also be obtained by' neutral photodissociation (193-nm laser irradiation of the sample) followed by ion photodesorption.     

The Effect of O6+ and Si7+ ion beam irradiations on poly(lactide-co-glycolide) (50: 50) copolymer

Sterilization by ion beam radiations unfortunately also has a significant effect on the degradation of many polymers. The aim of present study is to examine the effect of heavy ion beam irradiation on poly(lactide-co-glycolide) (PLGA) (50: 50). The radiation effect is manifested through its degradation behavior and changes in the morphological, optical and structural properties. PLGA films are prepared by solvent casting method and subsequently irradiated with swift heavy ions O⁶⁺ and Si⁷⁺ ion with fluence in the range of 5 × 10¹⁰?1 × 10¹² ions/cm². The dominant effect on PLGA films is chain scission as evidenced by change in surface modification. Changes in optical and structural properties were analyzed by UV-Vis, XRD and FTIR spectrometric techniques. XRD technique is not responsive to degradation occurring in samples. Surface modifications caused by ion irradiations have been observed with SEM.     

Formation of [M − nH + mNa](m−n)+ and [M − nH + mK](m−n)+ ions in electrospray mass spectrometry of peptides and proteins

The [M - nH + mNa](m-n)+ and [M - nH + mK](m-n)+ ions are common in the electrospray mass spectra of proteins and peptides. The feasibility of forming these ions in the gas phase via collision activation and/or ion-molecule reaction is investigated. Sodium and potassium affinities of the N-methylacetamide anion, the acetate anion, and the 1-propanamide anion have been calculated using density functional theory at the B3LYP/6-311+ +G(d,p) level of theory. These anions were chosen as models for the functional groups on a protein or peptide. These affinity values are then used to calculate reaction enthalpies of alkali hydroxides, chlorides, and hydrates with N-methylacetamide, acetic acid, the acetate anion, and 1-propanamine, model reactions that may lead to formation of the [M - nH + mNa](m-n) and [M - nH + mK](m-n)+ ions. It is found that a number of these reactions are exothermic or slightly endothermic (deltaH(o) < + 20 kcal/mol) and are accessible after collision activation in the lens region. The potential energy hypersurfaces of model reactions between NaOH and formamide as well as NaCl and formamide show relatively flat surfaces devoid of significant barriers.     

Thermodynamic characteristics of acid–base equilibria of glycyl-glycyl-glycine in water–ethanol solutions at 298 K

The enthalpies of the acid dissociation of glycyl-glycyl-glycine zwitterions and triglycinium ions are determined calorimetrically in water–ethanol solvents containing 0.0, 0.10, 0.30, and 0.50 molar fractions of ethanol at ionic strengths of 0.1 (maintained by sodium perchlorate) and Т = 298.15 K. It is found that increasing the ethanol content in the solvent enhances the endothermic effect of triglycinium ion dissociation and reduces the endothermic effect of glycyl-glycyl-glycine dissociation. The results are discussed in terms of the solvation thermodynamics.