Selective generation of charge-cependent/independent ion energy distributions from a heated capillary electrospray source

Retarding grid and Fourier transform ion cyclotron resonance (FTICR) mass spectrometry variable trap potential measurements are performed to determine factors that contribute to the kinetic energy distribution of ions formed in an electrospray source that uses a heated capillary for desolvation. The control of ion kinetic energies is achieved by manipulating the skimmer position in the postcapillary expansion and by varying the potential appEed to the skimmer. The selective generation of either charge-dependent or charge-independent ion energy distributions is demonstrated. Charge-dependent energy distributions of electro-sprayed ions are created by sampling ions near the Mach disk of the supersonic expansion and by using a larger diameter skimmer orifice; the FTICR spectra acquired under these conditions exhibit mass-to-charge ratio-dependent mass discrimination determined by the potential used to trap the ions. Charge-independent energies of electrosprayed ions are created by positioning the capillary adjacent to the skimmer to sample thermal ions and by using a smaller skimmer orifice to reduce expansion cooling; under these conditions ion kinetic energy is determined primarily by the skimmer potential and no mass-to-charge ratio-dependence is observed in the selection of optimum FTICR trapping conditions. The ability to select between proteins of different conformation on the basis of kinetic energy differences is demonstrated. For example, a 0.4 V difference in trap potential is observed in the selective trapping of open and closed forms of the +10 charge state of lysozyme. Finally, it is demonstrated that by operating the source under conditions which deliver a beam of ions with charge-independent energies to the cell, it is possible to obtain precursor and product ion signal magnitudes in FTTCR spectra without charge-dependent mass discrimina-tion.     

Mean Gas Cluster Size Determination from Cluster Beam Cross-Section

This paper describes the simple experimental method of size determination of gas clusters in molecular beams formed from supersonic jets. Mean cluster size N is calculated from broadening of the transverse profile of beam intensity at a fixed distance behind the skimmer. The described method allows determining the mean sizes of the clusters of any pure gases. It does not require the building of some special models, or determination of empirical constants. Due to the high intensity of the supersonic beams, the measurements do not require any complex highly sensitive equipment. The effectiveness of the present method is validated by measurements in a cluster beams of test gases (easily condensable CO₂, Ar, and weakly condensable N₂) and the beam of C₂H₄ (ethylene), formed from a supersonic jet behind conical nozzles. The certainty of measured characteristics is confirmed by the results of numerical simulations. By using the described method the mean cluster sizes from 50 to 2000 molecules per cluster were determined. The correctness of the obtained cluster sizes of CO₂ and Ar is proved by comparison with results of other authors, obtained by other experimental methods, and estimations according to the empirical correlations using condensation scaling parameter Г^*.     

Langmuir probe measurements of the ion extraction process in inductively coupled plasma-mass spectrometry. Part 2. Measurements of floating voltage and radiofrequency voltage

A single Langmuir probe is thrust axially through the skimmer into the supersonic jet of a typical interface for inductively coupled plasma-mass spectrometry (ICP-MS). Floating voltage V_f is measured from current-voltage curves at various axial positions and is generally in the range +2 to +7 V in the supersonic jet. A disturbance at the skimmer, when present, induces a sharp increase in V_f in the vicinity of the skimmer tip. Floating voltage generally decreases as the probe is retracted farther behind the skimmer. The measured d.c. voltages are attributed primarily to plasma rectification and to the calorelectric effect between two metal surfaces at different temperatures in a plasma. An r.f. voltage of up to 25 V (peak-to-peak) at the frequency of the plasma generator can also be measured behind the sampler.     

Fundamental aspects of ion extraction in inductively coupled plasma mass spectrometry

The present understanding of the ion extraction process in inductively coupled plasma mass spectrometry (ICP-MS) is reviewed critically. Topics include ion production in the ICP, origins of polyatomic ions, causes of and remedies for the secondary discharge, properties of the supersonic jet and of the beam leaving the skimmer, space charge effects, and matrix interferences. Areas of recent interest are also described from the perspective of the ion extraction process. These recent topics include “cool” plasmas, the three-aperture interface, ion extraction from helium plasmas, and ion sampling considerations unique to magnetic sector, time-of-flight, and ion trap mass spectrometers.     

Development of a compact supersonic jet/multiphoton ionization/time-of-flight mass spectrometer for the on-site analysis of dioxin, part I: Evaluation of basic performance.

A new type of compact supersonic jet/resonance-enhanced multiphoton ionization/time-of-flight mass spectrometer is described. The analytical instrument, consisting of a single turbo molecular pump equipped with a rotary pump, was maintained at < 2 x 10(-3) Pa when a 0.3-atm sample was injected into a vacuum at 10-Hz using a 200-micros pulse valve. The diameters of the extraction and ground skimmer electrodes were expanded to 30 mm in order to avoid strong focusing and defocusing of the ion, and the optimum conditions for the system were investigated. The mass spectrometer functioned as expected: (1) no defocusing of the ion beam was observed even when the potential of the einzel lens was adjusted to zero; (2) the direction of the ion beam to an assembly of microchannel plates deviated in the expected manner when the potential of the defection electrode was changed from 0 to 30 V.     

GC–MS with photoionization of cold molecules in supersonic molecular beams—Approaching the softest ionization method

A new type of photoionization ion source was developed for the ionization of cold molecules in supersonic molecular beams (named Cold PI). The system was based on a GC–MS with supersonic molecular beams and its fly‐through EI of cold molecules ion source (Cold EI) plus quadrupole mass analyzer. A continuously operated deuterium VUV photoionization lamp was added and placed above and between the supersonic nozzle and skimmer whereas the Cold EI ion source served only as a portion of the ion transfer ion optics. The supersonic nozzle and skimmer were voltage biased and the VUV light crossed the supersonic expansion about 10 mm from the nozzle. We obtained over three orders of magnitude enhancement in the relative abundance of the molecular ion of squalane in Cold PI versus in photoionization of this compound as a thermal compound. Accordingly, we also proved that standard photoionization is not as soft ionization method as previously perceived for large compounds. We found that Cold PI is as soft as and possibly softer than field ionization; thus, it could be the softest known ionization method. The ionization yield was about 200–300 times weaker than with Cold EI yet our limit of detection was about 200 femtogram in SIM mode for cholesterol and pyrene which is reasonable. Practically, all hydrocarbons gave only molecular ions with rather uniform response whereas alcohols gave some molecular ions plus major fragment ions particularly with a loss of water (similarly to field ionization). We tested Cold PI in the GC–MS analysis of diesel fuels and analyzed the time averaged data for group type information. We also found that we can analyze the diesel fuels by fast under 20‐s flow injection analysis in which the generated averaged mass spectrum of molecular ions only could serve for the characterization of fuels.     

Lithium and potassium isotope separation using radiofrequency spectroscopy

Separation of lithium and potassium isotopes has been achieved using the isotopic differences in the radiofrequency spectrum. The isotope separation was studied in a supersonic molecular beam magnetic resonance spectrometer, and enrichment factors up to 30 obtained.     

Effect of molecular rotation on the atomic alignment dependence in the oriented Ar (3P2) + CF3H reaction

Atomic alignment effect for the CF3* formation in the oriented Ar (3P2, MJ = 2) + CF3H reaction has been investigated at different two CF3H beam conditions: effusive and supersonic beams. The chemiluminescence intensity of CF3* was measured as a function of the magnetic orientation field direction in the collision frame. A significant contribution of rank 4 moment was recognized. The cross-section for each magnetic M'(J) substate in the collision frame, sigma|M'(J)|, was determined to be sigma(|M'(J)|=0):sigma(|M'(J)|=1):sigma(|M'(J)|=2) = 1.00:0.84 +/- 0.02:0.88 +/- 0.02 for the effusive CF3H beam condition. The atomic alignment effect was found to significantly depend on the CF3H beam condition. For the supersonic beam condition, sigma(|M'(J)|=0&1) was changed to be smaller than sigma(|M'(J)|=2).     

Conformational interconversions in supersonic jets: Matrix IR spectroscopy and model calculations

Terminal conformer populations in supersonic molecular beams have been measured by use of matrix IR spectroscopy. the experimental technique is based on trapping of the beam molecules in to a cryogenic matrix. The ratio of conformational isomers is determined by comparing intensity ratios of infrared absorption bands with those found in analogous experiments with thermal effusive molecular beams. supersonic beams of pure 1,2-difluoroethane a considerable depopulation fo the less stable trans conformer is found, the lowest terminal conformational temperature reached being T_c^t8 = 207 (3) K. In seeded argon beams the cooling of the conformational distribution was found to be weaker. In supersonic beams of 1,2-dichloroethane and of methyl nitrite no significant conformational cooling was found. The experimental results are discussed in terms of a kinetic model of conformational interconversion in the flow field of a continuum free jet. The calculation indicate that conformational cooling by supersonic expansion may be expected only for molecules with a low energy barrier to internal rotation.     

Optical measurements of ion density in the second vacuum stage of an inductively coupled plasma mass spectrometer

A portion of the ion beam in the second stage of an inductively coupled plasma mass spectrometer was mapped using laser induced fluorescence (LIF). With LIF relative density measurements are made in real time with minimal interference to the ion beam. We report axial measurements of Ba and Sc ion density from 22 to 45 mm behind the tip of the skimmer cone. Additionally, maps of radial ion density with and without Pb and Mg matrices are given for the same two analyte species. The results reveal that earlier ion deposition experiments dramatically underestimated the extent of the radial spread of the ion beam and the influence of matrix on the ion beam.     

Effect of electrospray ionization conditions on low-energy tandem mass spectra of peptides

The effect of electrospray ionization (ESI) conditions on low-energy tandem mass spectra of peptides in the relative molecular mass range 400–1200 was examined. For singly charged peptide ions the source skimmer potential (which determines the degree of acceleration of the ions through the intermediate pressure region in the source) can strongly influence the extent of fragmentation observed in tandem mass spectra, especially at low collision energies. For each peptide there is an optimum skimmer potential which represents a balance between generating ions with sufficient internal energy for subsequent tandem mass spectrometric experiments and inducing the onset of other processes such as source fragmentation. The fragmentation which can be achieved in tandem mass spectra with high skimmer potentials differs from ESI source fragmentation for the same peptides. We have found that fragmentation in ESI mass spectra depends both on skimmer potential and on solvent pH, presumably because the latter determines the proportion of doubly charged species generated from a given peptide. Low-energy tandem mass spectra of peptides following ESI are equally as sensitive to peptide structure and the type of adduct studied (e.g. [M + H]⁺ vs. [M + NH₄]⁺) as tandem mass spectra obtained following older ionization methods such as fast atom bombardment.     

Merged-beams for slow molecular collision experiments

Molecular collisions can be studied at very low relative kinetic energies, in the milliKelvin range, by merging codirectional beams with much higher translational energies, extending even to the kiloKelvin range, provided that the beam speeds can be closely matched. This technique provides far more intensity and wider chemical scope than methods that require slowing both collision partners. Previously, at far higher energies, merged beams have been widely used with ions and/or neutrals formed by charge transfer. Here, we assess for neutral, thermal molecular beams the range and resolution of collision energy that now appears attainable, determined chiefly by velocity spreads within the merged beams. Our treatment deals both with velocity distributions familiar for molecular beams formed by effusion or supersonic expansion, and an unorthodox variant produced by a rotating supersonic source capable of scanning the lab beam velocity over a wide range.     

How does the molecular velocity distribution affect kinetics measurements by time‐resolved mass spectrometry?

The equations governing the time fidelity in molecular‐beam mass sampling are derived for supersonic‐beam sampling, where the velocity distribution is well‐fitted by a displaced Maxwell–Boltzmann distribution. Supersonic sampling is shown to offer much higher fidelity than the corresponding effusive‐beam sampling, and rules of thumb are derived for the validity of kinetic measurements for supersonic‐beam sampling. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 565–570, 2007     

The vacuum-UV spectra of supersonic jets of ArKrXe mixtures excited by an electron beam

The vacuum-UV spectra of supersonic jets of ArKrXe mixtures excited by an electronic beam were investigated. At small concentrations of Kr and Xe admixtures to the Ar jet, intensive continuous spectra of Kr and Xe were observed. Continuous spectra with intensity maxima at 1350 Å and 1540 Å were also recorded and interpreted as the spectra of the heteroatomic molecules ArKr and KrXe.     

Supramolecular clusters between carbohydrates and concave pyridines. Detection in the gas phase by resonance-enhanced multi-photon ionization reflectron time-of-flight mass spectrometer

For the first time the formation of supramolecular clusters between concave pyridines and different carbohydrates could be observed in the gas phase. The different clusters have been investigated by means of laser desorption into a supersonic beam followed by resonant multi photon excitation yielding mass spectra with high intensity of the different cluster. These preliminary results open a way for the investigations of the hydrogen bonds in these compounds.     

Influence of sample matrix components on the selection of calibration strategies in electrothermal vaporization inductively coupled plasma mass spectrometry

Quantification of both digested and slurry samples were studied using ultrasonic slurry electrothermal vaporization inductively coupled plasma mass spectrometry (USS-ETV-ICP-MS). The results of external calibration using aqueous standards, method of additions, and In as an internal standard were compared. The elements studied include: Mn, Ni and Cu and the materials analyzed include: NIST SRM 1548 total diet and SRM 1549 milk powder. Palladium was used as a physical carrier and oxygen ashing was used to remove the organic part of the slurry matrix. Different degrees of matrix suppression effects were observed when different skimmer cones were employed. Aging of the skimmer cone and consequent loss of its original circular symmetry and decrease in orifice size resulted in differences in sampling of the ion beam and changes in the degree of matrix effects were observed as the skimmer cone was rotated. The presence of matrix suppression effects is evidenced by strong suppressions in the Ar₂, C and analyte signals. When matrix suppression effects were present, the method of external calibration provided low recoveries (average accuracy 73 ± 12%), therefore it was necessary to use the method of additions to compensate for these problems, providing an average accuracy of 108 ± 13%. When matrix effects were absent, the external calibration method resulted in an average accuracy of 101 ± 16%.     

Spatially resolved measurements of ion density behind the skimmer of an inductively coupled plasma mass spectrometer

Ions are extracted from the inductively coupled plasma through a conventional sampler and skimmer and then deposited on an array of graphite targets at the exit of a set of electrostatic ion lenses. The Sc⁺ signal is enhanced by choosing appropriate potentials on the ion lenses. The Sc⁺ signal is suppressed by the presence of concomitant Cs ions at high concentrations. Comparisons of grounded ion lenses and two different ion lens potential settings are made. The signal is enhanced more extensively by the ion lenses when there are no concentrated concomitant ions. This study indicates that matrix effects in inductively coupled plasma mass spectrometry could possibly be alleviated by choosing ion lens potentials such that the ions enter the ion optics with a relatively broad beam cross section, the beam then being focused to a smaller size. A photon stop inside the ion lens stack reduces ion transmission and changes the shape of the beam profile from conical to bimodal.     

Laser-induced NMR shift of a paramagnetic system

Perturbation theory on optical ac Stark effect is applied to study the NMR spectroscopy in paramagnetic systems. Application of the circularly or linearly polarized optical field would lead to shifts in the NMR lines, which is proportional to the laser intensity and the induced polarizability tensors by hyperfine interaction. The induced shift for 193Ir NMR spectrum of [IrBrg]2- is expected to be of the order of 1-10 Hz as resonance is approached with light intensity 10 W·cm-2. For the supersonic molecular beam samples 193IrC, the laser-induced NMR shift is estimated to be as large as 1-10 MHz near resonance.     

Cluster chemical ionization and deuterium exchange mass spectrometry in supersonic molecular Beams

A cluster-based chemical ionization method has been developed that produces protonated molecular ions from molecules introduced through a supersonic molecular beam interface. Mixed clusters of the analyte and a clustering agent (water or methanol) are produced in the expansion region of the beam, and are subsequently ionized by “fly through” electron impact (EI) ionization, which results in a mass spectrum that is a combination of protonated molecular ion peaks together with the conventional EI fragmentation pattern. The technique is presented and discussed as a tool complementary to electron impact ionization in supersonic molecular beams. Surface-induced dissociation on a rhenium oxide surface is also applied to simplify the mass spectra of clusters and reveal the analyte spectrum. The high gas flow rates involved with the supersonic molecular beam interface that enable the easy introduction of the clustering agents also have been used to introduce deuterating agents. An easy-to-use, fast, and routine on-line deuterium exchange method was developed to exchange active hydrogens (NH, OH). This method, combined with electron impact ionization, is demonstrated and discussed in terms of the unique information available through the EI fragmentation patterns, its ability to help in isomer identification, and possible applications with fast gas chromatography-mass spectrometry in supersonic molecular beams.