Multiply Charged Ions Research Articles

Calcium and Potassium Spectra in the EUV

In online data bases, the entries on extreme ultraviolet (EUV) spectra of Ca are much more sparse than those of neighbouring elements such as Ar, K, Sc and Ti. This may be a result of experimental problems with Ca in the laboratory as well as of the limited role of multiply charged Ca ions in solar observations. Beam-foil EUV spectra of Ca and K are presented that provide survey data of a single element each.

Metal ions shape \u03b1-synuclein

α-Synuclein is an intrinsically disordered protein that can self-aggregate and plays a major role in Parkinson’s disease (PD). Elevated levels of certain metal ions are found in protein aggregates in neurons of people suffering from PD, and environmental exposure has also been linked with neurodegeneration. Importantly, cellular interactions with metal ions, particularly Ca2+, have recently been reported as key for α-synuclein’s physiological function at the pre-synapse. Here we study effects of metal ion interaction with α-synuclein at the molecular level, observing changes in the conformational behaviour of monomers, with a possible link to aggregation pathways and toxicity. Using native nano-electrospray ionisation ion mobility-mass spectrometry (nESI-IM-MS), we characterize the heterogeneous interactions of alkali, alkaline earth, transition and other metal ions and their global structural effects on α-synuclein. Different binding stoichiometries found upon titration with metal ions correlate with their specific binding affinity and capacity. Subtle conformational effects seen for singly charged metals differ profoundly from binding of multiply charged ions, often leading to overall compaction of the protein depending on the preferred binding sites. This study illustrates specific effects of metal coordination, and the associated electrostatic charge patterns, on the complex structural space of the intrinsically disordered protein α-synuclein.

Net Electron Capture in Collisions of Multiply Charged Projectiles with Biologically Relevant Molecules

A model for the description of proton collisions from molecules composed of atoms such as hydrogen, carbon, nitrogen, oxygen and phosphorus (H, C, N, O, P) was recently extended to treat collisions with multiply charged ions with a focus on net ionization. Here we complement the work by focusing on net capture. The ion–atom collisions are computed using the two-center basis generator method. The atomic net capture cross sections are then used to assemble two models for ion–molecule collisions: An independent atom model (IAM) based on the Bragg additivity rule (labeled IAM-AR), and also the so-called pixel-counting method (IAM-PCM) which introduces dependence on the orientation of the molecule during impact. The IAM-PCM leads to significantly reduced capture cross sections relative to IAM-AR at low energies, since it takes into account the overlap of effective atomic cross sectional areas. We compare our results with available experimental and other theoretical data focusing on water vapor (H2O), methane (CH4) and uracil (C4H4N2O2). For the water molecule target we also provide results from a classical-trajectory Monte Carlo approach that includes dynamical screening effects on projectile and target. For small molecules dominated by a many-electron atom, such as carbon in methane or oxygen in water, we find a saturation phenomenon for higher projectile charges (q=3) and low energies, where the net capture cross section for the molecule is dominated by the net cross section for the many-electron atom, and the net capture cross section is not proportional to the total number of valence electrons.

Development of a new atmospheric pressure plasmaspray ionization for ambient mass spectrometry.

A new atmospheric pressure ionization method, plasmaspray ionization, termed as PSI, was developed to be an alternative ambient ion source for mass spectrometry. It comprises a plasma jet device and a sample spray part. While the nonthermal plasma jet strikes the surface of stainless steel tube out of the spray capillary, the sprayed sample will be ionized with the assistant of auxiliary gas. Although PSI is a little bit more complex than electrospray ionization (ESI) in instrument, it shows both better linearity and higher sensitivity for organic compounds. For protein samples, it presents wider distributions of multiply charged ions and higher mass resolution without sacrificing any sensitivity. For the mechanism of PSI, the charge build-up process on the tip of capillary should play a key role for the ion formation, and the stimulated pulsed voltage on the flow tube will promote the ion aggregation speed until the charge density is high enough. PSI source contains the features of plasma ionization and ESI and can be considered as a novel combo bridging these techniques. These results reflect that this method of PSI can be applied and further developed as a versatile new ion source for a wild range of organic and biological samples.

Cross-field electron diffusion due to the coupling of drift-driven microinstabilities.

In this paper, the nonlinear interaction between kinetic instabilities driven by multiple ion beams and magnetized electrons is investigated. Electron diffusion across magnetic field lines is enhanced by the coupling of plasma instabilities. A two-dimensional collisionless particle-in-cell simulation is performed accounting for singly and doubly charged ions in a cross-field configuration. Consistent with prior linear kinetic theory analysis and observations from coherent Thomson scattering experiments, the present simulations identify an ion-ion two-stream instability due to multiply charged ions (flowing in the direction parallel to the applied electric field) which coexists with the electron cyclotron drift instability (propagating perpendicular to the applied electric field and parallel to the E×B drift). Small-scale fluctuations due to the coupling of these naturally driven kinetic modes are found to be a mechanism that can enhance cross-field electron transport and contribute to the broadening of the ion velocity distribution functions.

New mass spectrometry concepts for characterization of synthetic polymers and additives.

New ionization processes have been developed for biological mass spectrometry (MS) in which the matrix lifts the nonvolatile analyte into the gas phase as ions without any additional energy input. We rationalized that additional fundamental knowledge is needed to assess analytical utility for the field of synthetic polymers and additives. Different mass spectrometers (Thermo Orbitrap (Q-)Exactive (Focus); Waters SYNAPT G2(S)) were employed. The formation of multiply charged polymer ions upon exposure of the matrix/analyte(/salt) sample to sub-atmospheric pressure directly from the solid state and surfaces facilitates the use of advanced mass spectrometers for detection of polymeric materials including consumer products (e.g., gum). Astonishingly, using nothing more than a small molecule matrix compound (e.g., 2-methyl-2-nitropropane-1,3-diol or 3-nitrobenzonitrile) and a salt (e.g., mono- or divalent cation(s)), such samples upon exposure to sub-atmospheric pressure transfer nonvolatile polymers and nonvolatile salts into the gas phase as multiply charged ions. These successes contradict the conventional understanding of ionization in MS, because can nonvolatile polymers be lifted in the gas phase as ions not only by as little as a volatile matrix but also by the salt required for ionizing the analyte through noncovalent metal cation adduction(s). Prototype vacuum matrix-assisted ionization (vMAI) and automated sources using a contactless approach are demonstrated for direct analyses of synthetic polymers and plasticizers, minimizing the risk of contamination using direct sample introduction into the mass spectrometer vacuum. Direct ionization methods from surfaces without the need of high voltage, a laser, or even applied heat are demonstrated for characterization of detailed materials using (ultra)high-resolution and accurate mass measurements enabled by the multiply charged ions extending the mass range of high-performance mass spectrometers and use of a split probe sample introduction device. Our vision is that, with further development of fundamentals and dedicated sources, both spatial- and temporal-resolution measurements are within reach if sensitivity is addressed for decreasing sample-size measurements.

Principles of Operation of a Rotating Wall Mass Analyzer for Preparative Mass Spectrometry.

In this contribution, we describe the principles of operation of a rotating wall mass analyzer (RWMA), a mass-dispersive device for preparative mass spectrometry. Ions of different m/z are spatially separated by RWMA and deposited onto ring-shaped areas of distinct radii on a surface. We use a combination of an analytical equation for predicting the radius of the deposition ring and SIMION simulations to understand how to optimize the experimental conditions for the separation of multicomponent mixtures. The results of these simulations are compared with the experimental data. We introduce a universal mass calibration procedure, based on a series of polyacrylamide ions, which is subsequently used to predict the deposition radii of unknown analytes. The calibration is independent of the polarity, kinetic energy, and charge state of the ion as demonstrated by assigning m/z values of different analytes including multiply charged ubiquitin ions. We demonstrate that mass resolution of the RWMA is affected by the width and kinetic energy distribution of the ion beam. The best mass resolution obtained in this study is m/Δm = ∼20. Preparative mass spectrometry using RWMA provides the advantages of simplicity, compactness, and low fabrication cost, which are particularly promising for the development of miniaturized instrumentation. The results presented in this work can be readily adapted to preparative separation of a variety of charged species of interest to the broad scientific community.

Method for the Precise Measurement of Wavelengths for Main Shell Transitions in He- and Li-like Ca Ions

A possible approach to obtain a precise experimental data on the atomic structure of highly charged ions is considered. Since the key point determining measurement accuracy is the presence of reference lines with precisely known wavelengths, it is proposed first to to use hydrogen-like reference lines for precise measurements of the helium-like resonant transition and their dielectronic satellites. Then in turn these lines, which exist in the plasma over a wide temperature range, can be used as the reference in the wavelength measurement for other ions. The problems associated with the creation of the plasma conditions under which the reference and measured lines have comparable intensities are discussed. The irradiation of minerals with laser pulses, which, in terms of their chemical composition, are a set of elements with average 15 < Z < 30 and light Z < 15 nuclear charges, is proposed. Several experimental schemes to measure the wavelengths of the spectral lines of multiply charged calcium ions with an expected error of up to 0.125 mA are considered as an example.

How Spherical Are Gaseous Low Charged Dendrimer Ions: A Molecular Dynamics/Ion Mobility Study?

The globular shape of gaseous ions, resulting from the ionization of large molecules such as polymers and proteins, is a recurring subject that has undergone a renewed interest with the advent of ion mobility spectrometry (IMS), especially in conjunction with theoretical chemistry techniques such as Molecular Dynamics (MD). Globular conformations result from a fine balance between entropy and enthalpy considerations. For multiply charged ions isolated in the gas phase of a mass spectrometer, the Coulombic repulsion between the different charges tends to prevent the ions from adopting a compact, and folded 3D structure. In the present paper, we closely associate data from IMS experiments and MD simulations to unambiguously access the conformations of dendrimer ions in the gas phase with special attention paid to the dendrimer structure, the generation, and the charge state. By doing so, we here combine a set of structural tools able to evaluate the (non)globular shape of ions based on both experimental and theoretical results.

Resolving Isomers of Star-Branched Poly(Ethylene Glycols) by IMS-MS Using Multiply Charged Ions.

Ion mobility spectrometry (IMS) mass spectrometry (MS) centers on the ability to separate gaseous structures by size, charge, shape, and followed by mass-to-charge (m/z). For oligomeric structures, improved separation is hypothesized to be related to the ability to extend structures through repulsive forces between cations electrostatically bonded to the oligomers. Here we show the ability to separate differently branched multiply charged ions of star-branched poly(ethylene glycol) oligomers (up to 2000 Da) regardless of whether formed by electrospray ionization (ESI) charged solution droplets or from charged solid particles produced directly from a surface by matrix-assisted ionization. Detailed structural characterization of isomers of the star-branched compositions was first established using a home-built high-resolution ESI IMS-MS instrument. The doubly charged ions have well-resolved drift times, achieving separation of isomers and also allowing differentiation of star-branched versus linear oligomers. An IMS-MS "snapshot" approach allows visualization of architectural dispersity and (im)purity of samples in a straightforward manner. Analyses capabilities are shown for different cations and ionization methods using commercially available traveling wave IMS-MS instruments. Analyses directly from surfaces using the new ionization processes are, because of the multiply charging, not only associated with the benefits of improved gas-phase separations, relative to that of ions produced by matrix-assisted laser desorption/ionization, but also provide the potential for spatially resolved measurements relative to ESI and other ionization methods.

Extending the Comprehensiveness of Immunopeptidome Analyses Using Isobaric Peptide Labeling.

Defining the repertoire of peptides presented by the major histocompatibility complex class I (MHC I) is a key step toward the identification of relevant antigens for cancer immunotherapy. However, the identification of cancer-specific antigens is a significant analytical challenge in view of their low abundance and low mutational load found in most primary cancer specimens. Here, we describe the application of isobaric peptide labeling with tandem mass tag (TMT) to improve the detection of the MHC I peptides. Isobaric peptide labeling was found to promote the formation of multiply charged ions and to enhance the formation of b-type fragment ions, thus resulting in a 50% improvement of MHC I peptide identification. The gain in sensitivity obtained using TMT labeling enabled the detection of low-abundance MHC I peptides including tumor-specific antigens (TSAs) and minor histocompatibility antigens (MiHAs). We further demonstrate the application of this approach to quantify MiHAs presented by B-cell lymphocytes and determined their expression levels by LC-MS/MS using both synchronous precursor selection (SPS) and high-field asymmetric waveform ion mobility spectrometry (FAIMS).

Generation of Multiply Charged Protein Anions from Multiply Charged Protein Cations via Gas-Phase Ion/Ion Reactions.

We report a novel charge inversion ion/ion reaction that converts multiply charged protein cations to multiply charged protein anions via a single ion/ion collision using highly charged anions derived from nanoelectrospray ionization (nESI) of hyaluronic acids (HAs). This type of charge inversion reaction is demonstrated with cations derived from cytochrome c, apo-myoglobin, and carbonic anhydrase (CA) cations. For example, the reaction has been demonstrated to convert the [CA+22H]22+ carbonic anhydrase cation to a distribution of anions as high in absolute charge as [CA-19H]19-. Ion/ion reactions involving multiply charged ions of opposite polarity have previously been observed to result predominantly in the attachment of the reactant ions. All mechanisms for ion/ion charge inversion involving low energy ions proceed via the formation of a long-lived complex. Factors that underlie the charge inversion of protein cations to high anionic charge states in reaction with HA anions are hypothesized to include: (i) the relatively high charge densities of the HA anions that facilitate the extraction of multiple protons from the protein leading to multiply charged protein anions, (ii) the relatively high sum of absolute charges of the reactants that leads to high initial energies in the ion/ion complex, and (iii) the relatively high charge of the ion/ion complex following the multiple proton transfers that tends to destabilize the complex.

Charge Transfer and Metastable Ion Dissociation of Multiply Charged Molecular Cations Observed by Using Reflectron Time-of-Flight Mass Spectrometry.

The front cover artwork is provided by the group of Prof. Tomoyuki Yatsuhashi (Osaka City University) as well as Dr. Akimasa Fujihara (Osaka Prefecture University). The image shows that the potential energy of a product ion formed by metastable ion dissociation can be larger than that of a multiply charged precursor ion. Read the full text of the Article at 10.1002/cphc.202000021.

Measurement of the momentum accommodation coefficient for the interactions between electric thruster plume and a solid surface

When the plume of electric thrusters, which is the plasma flow, collides with a surface of spacecraft, a force is exerted on the surface, causing the spacecraft to be flipped or deorbited. The force is generated by the plasma–surface interactions, which can be described using the momentum accommodation coefficient (MAC). As far as we know, only the MAC where the plasma flow is assumed as the combination of singly charged ions, electrons, and neutral gases has been studied. However, the plasma flow of electric thrusters contains not only singly charged ions but also multiply charged ions. In addition, the plasma–surface interactions are usually accompanied by the charged-exchange (CEX), sputtering, and plasma sheath, all of which influence the momentum transfer. Therefore, in this study, the MAC in plasma–surface interactions is developed by quantifying the effect of the multiply charged ions, CEX, sputtering, and plasma sheath. The formulas of the normal momentum accommodation coefficient (NMAC) and tangential momentum accommodation coefficient are derived, respectively, and then, a measurement method of the MAC is proposed with the derived formulas. Moreover, a NMAC was measured when the plasma flow, which was jetted by an ion thruster with an acceleration voltage of 1000 V, impacted an immersed surface vertically, and the measured NMAC is approximated as 1.0. The effect degree and mechanism of the aforementioned factors on the MAC were discussed. Finally, the force exerted on the immersed surface was simulated using the measured NMAC, and the results are in good agreement with the experimental results.

Coefficient of Relative Sensitivity in Mass Spectrometers with Inductively Coupled Plasma

The process of formation of ions upon plasma bunch expansion in mass spectrometers with Inductively coupled plasma (ICP-MS) is considered theoretically and experimentally. Under the assumption that the density and temperature of electron and ion gases in inductively coupled plasma are the same, the relative sensitivity coefficients are calculated for more than 20 elements in the plasma temperature region of 5–25 eV. It is shown that, after the completion of the recombination of multiply charged ions, a thermodynamically nonequilibrium plasma is formed, in which the residual degree of ionization and the charge distribution of ions depend on the ratio of the recombination length and the minimum size of the plasma bunch, lrec/R0. The experimentally determined ratio $${{n_{x}^{{ + 2}}} \mathord{\left/ {\vphantom {{n_{x}^{{ + 2}}} {n_{x}^{ + }}}} \right. \kern-0em} {n_{x}^{ + }}}$$ corresponds to the initial plasma composition.

Total cross sections in five methods for two-electron capture by alpha particles from helium: CDW-4B, BDW-4B, BCIS-4B, CDW-EIS-4B and CB1-4B

This work is on quantum-mechanical four-body distorted wave theories for double electron capture in collisions between fast heavy multiply charged ions and heliumlike atomic systems. The five widely used distorted wave methods of the first- and second-order in the perturbation series expansions are compared with the available experimental data on alpha –He collisions. These are the four-body boundary-corrected first Born (CB1-4B), the boundary-corrected continuum intermediate state (BCIS-4B), the Born distorted wave (BDW-4B), the continuum distorted wave (CDW-4B) and the continuum distorted wave-eikonal initial state (CDW-EIS-4B) methods.We address the complete breakdown of the CDW-EIS-4B method at all impact energies within its expected validity domain (100–10000 keV). Further, the relative performance is evaluated of the second-order theories with and without the eikonalization of the two-electron Coulomb wavefunctions for double continuum intermediate states. Finally, at all the considered intermediate and high energies, the practical aspects of the studied five methods are investigated by protracted evaluations of the convergence rates of total cross sections as a function of the number of quadrature points per axis in numerical computations of multi-dimensional (3D-5D) integrals.

Charge Transfer and Metastable Ion Dissociation of Multiply Charged Molecular Cations Observed by Using Reflectron Time-of-Flight Mass Spectrometry.

A multiply charged molecule expands the range of a mass window and is utilized as a precursor to provide rich sequence coverage; however, reflectron time-of-flight mass spectrometer has not been well applied to the product ion analysis of multiply charged precursor ions. Here, we demonstrate that the range of the mass-to-charge ratio of measurable product ions is limited in the cases of multiply charged precursor ions. We choose C6 F6 as a model molecule to investigate the reactions of multiply charged molecular cations formed in intense femtosecond laser fields. Measurements of the time-of-flight spectrum of C6 F6 by changing the potential applied to the reflectron, combined with simulation of the ion trajectory, can identify the species detected behind the reflectron as the neutral species and/or ions formed by the collisional charge transfer. Moreover, the metastable ion dissociations of doubly and triply charged C6 F6 are identified. The detection of product ions in this manner can diminish interference by the precursor ion. Moreover, it does not need precursor ion separation before product ion analysis. These advantages would expand the capability of mass spectrometry to obtain information about metastable ion dissociation of multiply charged species.

Ionization and acceleration of multiply charged gold ions in solid film irradiated by high intensity laser

In this paper, we present the mechanisms of ionization of a thin gold film irradiated by a high-intensity, short-pulse laser in the range of I=1020−22 W/cm2 and the associated acceleration of multiply charged gold ions. A numerical one-dimensional simulation using an extended particle-in-cell code, which includes atomic and collisional relaxation processes, indicates that two types of acceleration, hole-boring radiation pressure acceleration (RPA) and target normal sheath acceleration (TNSA), contribute to the generation of highly charged ions with kinetic energies on the order of 10 MeV/u. In each acceleration, a longitudinal electrostatic field excited by different mechanisms dominantly ionizes atoms to higher charge states and accelerates them to the vacuum region from the rear surface, which is opposite the front surface irradiated by the laser field. The field ionization process dominantly ionizes high energy ions to the high charge state, while a large number of ions with energy &amp;lt;1 MeV/u are ionized by an electron impact ionization process. In TNSA, a multiply charged ion generated at the rear surface is accelerated to the maximum energy although the ion with the highest charge state is generated at the front surface in RPA. However, the existence of contamination, such as water vapor, suppresses the ion energy of TNSA to less than that of RPA since the sheath field readily accelerates the protons and oxygen prior to the acceleration of the gold ions. Our derived theoretical scaling describes the maximum ion energy for each charge state in the cases with and without contamination using the relationship between the longitudinal electrostatic field profile near the rear surface and the classical tunnel field ionization model.

A 2.45 GHz microwave ion source for carbon positive-ion mass spectrometry

Carbon positive-ion mass spectrometry (C-PIMS) is a two stage mass spectrometer by producing high charge state carbon ions (C2+/C3+) directly in the ion source to eliminate molecular interferences and by converting the beam (C2+/C3+) to C− ions in a charge exchange cell to eliminate 14N interference. It has been proven that C-PIMS is an effective method for the detection of radiocarbon at low levels. This article will focus on the multiply charged carbon ion generation. Based on the fact that a C-PIMS system is usually equipped with high frequency electron cyclotron resonance (ECR) ion sources. It is significant to investigate if the simple and low-cost 2.45 GHz ECR ion source is an optional choice for the C-PIMS. At Peking University (PKU), a 2.45 GHz microwave ion source with minimum-B magnetic field configuration is designed for the production of intense C2+ beam. Preliminary experiments have proved that the 2.45 GHz microwave ion source can produce up to 40 μA@40 keV C2+ beam. In addition, it was found that argon could increase the decomposition efficiency of CO2, which can eliminate CO2+ ions of the extracted beam.

Influence of extraction grid on ion beam characteristics.

This work is a part of the development of a laser ion source (LIS) for multiply charged ion injectors. This experiment is devoted to the investigation of the effect of a metal grid on the extracted ion characteristics. The energy spectra of the ions in the plasma expanding into a drift tube with and without a grid have been compared. Plasmas of two different target materials, carbon and tungsten, were generated by the CO2 laser pulses with the focal power density on the target of about 1011 W/cm2. The time-of-flight method with an electrostatic energy analyzer installed just behind the grid is used to measure the charge states and energy distributions of ions. A significant effect of the grid on the ion energy distributions has been observed. This effect depends strongly on the ion mass and should be taken into account when designing a LIS, especially in the case of heavy ions.