Mass Range Of Ions Research Articles

Machine learning for the prediction of stopping powers

The stopping power of a material upon interaction with an energetic ion is the key measure of how far that ion will travel. The implications of accurate particle range calculations are tremendous, affecting every single application in which particle radiation is involved, from nuclear power to medicine. An approach is presented which attempts to overcome current shortcomings in the theoretical understanding of stopping power, as well as the methods used to interpret and exploit measured data. This is a considerable challenge, however the use of a novel machine learning methodology is shown to hold great promise in this endeavour: the ultimate aim being the ability to correctly predict the stopping value for any energy, ion and target combination, having no pre-existing experimental data.A random forest regression algorithm is trained using over 34,000 experimental measurements, representing stopping power values for 522 ion-target combinations across the energy range 10-3 to 102 MeV/amu, and ion and target atomic masses 1 to >240. Evaluation is carried out using several fundamental error metrics, over the whole dataset as well as for individual combinations, to provide the most comprehensive understanding of performance when tested under strict cross-validation criteria. The resulting model is shown to yield predicted stopping power curves corresponding closely to those of the true experimental values, with an ability to generalise across target elements, compounds, mixtures, alloys and polymers, irrespective of phase, and for a wide range of ion masses.

Mass Spectrometry of Glutamic Acid and Glutamine in the Gas Phase

We report on the method and results of a mass-spectrometric investigation of the yield of positive ions formed as a result of the dissociative ionization of glutamic acid and glutamine by electron impact in the gas phase. The measurements were performed at various temperatures using a monopole mass spectrometer of MX-7304A type in a range of ion masses within 10–150 Da. Peculiarities of the formation of molecular fragment ions of glutamic acid and glutamine by electron impact were studied in detail and the dynamics of fragment ion yield was measured at various temperatures of evaporation of the initial substances within 310–430 K.

Reprint Of: Enhanced spatially-resolved trace analysis using combined SIMS–single-stage AMS

Abstract Secondary ion mass spectrometry (SIMS) provides spatially resolved trace analysis of solid materials, but can be complicated by unresolved abundant molecular isobars. By adding a 300-kV single-stage accelerator mass spectrometer (SSAMS) as a detector for a Cameca ims 4f SIMS, one can measure more abundant positive ions from the SIMS while removing molecular isobars, thus improving very low abundance trace element and isotope analysis. This paper describes important features and capabilities of such an integrated system at the Naval Research Laboratory using charge state +1 ions. Transmission loss is compared to molecule destruction as gas flow to the molecule-destruction cell increases. As most measurements tolerate more modest abundance sensitivities than for 14C analysis, a lower gas flow is acceptable, so good transmission of 20–50% for ions of interest can be maintained for a broad range of ion masses. This new instrument has measured isotope ratios for uranium, lead, rare earths, and other elements from particulates and localized regions, with molecule destruction enabling the measurement at low SIMS mass resolving power and thus high transmission, as examples will show. This new and world-unique instrument provides improved capabilities for applications in nuclear and other forensics, geochemistry, cosmochemistry, and the development of optical, electronic, multifunctional, and structural materials.

Enhanced spatially-resolved trace analysis using combined SIMS–single-stage AMS

Abstract Secondary ion mass spectrometry (SIMS) provides spatially resolved trace analysis of solid materials, but can be complicated by unresolved abundant molecular isobars. By adding a 300-kV single-stage accelerator mass spectrometer (SSAMS) as a detector for a Cameca ims 4f SIMS, one can measure more abundant positive ions from the SIMS while removing molecular isobars, thus improving very low abundance trace element and isotope analysis. This paper describes important features and capabilities of such an integrated system at the Naval Research Laboratory using charge state +1 ions. Transmission loss is compared to molecule destruction as gas flow to the molecule-destruction cell increases. As most measurements tolerate more modest abundance sensitivities than for 14C analysis, a lower gas flow is acceptable, so good transmission of 20–50% for ions of interest can be maintained for a broad range of ion masses. This new instrument has measured isotope ratios for uranium, lead, rare earths, and other elements from particulates and localized regions, with molecule destruction enabling the measurement at low SIMS mass resolving power and thus high transmission, as examples will show. This new and world-unique instrument provides improved capabilities for applications in nuclear and other forensics, geochemistry, cosmochemistry, and the development of optical, electronic, multifunctional, and structural materials.

4D phase-space acceptance of the quadrupole mass filter.

Simulations of the four-dimensional (4D) phase-space acceptance volume of a quadrupole mass filter (QMF) are discussed. The 4D acceptance is considered since the ion trajectories in the X and Y phase planes are dependent via the initial RF phase at ion entry into QMF. The QMF parameters are set up for resolution equal to the ion mass number M. For a wide range of ion masses, the acceptance is characterized by relatively large aperture with about 5% transmission, primarily defined by phase dependent ellipses. Contrary to expectations, the small-aperture central spot with 75% transmission accepts a very small portion, namely less than 1% of the passed through particles.

Multigenerational Broadband Collision-Induced Dissociation of Precursor Ions in a Linear Quadrupole Ion Trap.

A method of fragmenting ions over a wide range of m/z values while balancing energy deposition into the precursor ion and available product ion mass range is demonstrated. In the method, which we refer to as "multigenerational collision-induced dissociation", the radiofrequency (rf) amplitude is first increased to bring the lowest m/z of the precursor ion of interest to just below the boundary of the Mathieu stability diagram (q = 0.908). A supplementary AC signal at a fixed Mathieu q in the range 0.2-0.35 (chosen to balance precursor ion potential well depth with available product ion mass range) is then used for ion excitation as the rf amplitude is scanned downward, thus fragmenting the precursor ion population from high to low m/z. The method is shown to generate high intensities of product ions compared with other broadband CID methods while retaining low mass ions during the fragmentation step, resulting in extensive fragment ion coverage for various components of complex mixtures. Because ions are fragmented from high to low m/z, space charge effects are minimized and multiple discrete generations of product ions are produced, thereby giving rise to "multigenerational" product ion mass spectra. Graphical Abstract ᅟ.

Development of a new RFQ beam cooler and buncher for the CANREB project at TRIUMF

A new radiofrequency quadrupole (RFQ) based ion beam cooler and buncher is under development for the CANadian Rare-isotope facility with Electron Beam ion source (CANREB) project at TRIUMF. The CANREB project requires an RFQ buncher that will efficiently accept continuous beams of rare isotopes from either the Advanced Rare IsotopE Laboratory (ARIEL) or Isotope Separator and ACcelerator (ISAC) target by way of a high resolution magnetic spectrometer, with energies up to 60keV and deliver bunched beams to an electron beam ion source (EBIS) for charge breeding. The energy of the bunched beam delivered to the EBIS will be adjustable to match the requirements of the existing post acceleration infrastructure. The CANREB RFQ incorporates design considerations to facilitate ease of use over a wide range of ion masses, and is intended to accommodate incident beam rates as high as 108pps, delivering beam bunches at 100Hz. An overview of the CANREB RFQ design concept will be presented, informed by results from both ion optical simulations as well as commissioning efforts with other beam cooler and buncher devices. Simulation results indicate that the design is well suited to deliver high quality bunched beams with high efficiency with as many as 106 ions per bunch.

Characterization of Traveling Wave Ion Mobility Separations in Structures for Lossless Ion Manipulations.

We report on the development and characterization of a traveling wave (TW)-based Structures for Lossless Ion Manipulations (TW-SLIM) module for ion mobility separations (IMS). The TW-SLIM module uses parallel arrays of rf electrodes on two closely spaced surfaces for ion confinement, where the rf electrodes are separated by arrays of short electrodes, and using these TWs can be created to drive ion motion. In this initial work, TWs are created by the dynamic application of dc potentials. The capabilities of the TW-SLIM module for efficient ion confinement, lossless ion transport, and ion mobility separations at different rf and TW parameters are reported. The TW-SLIM module is shown to transmit a wide mass range of ions (m/z 200-2500) utilizing a confining rf waveform (∼1 MHz and ∼300 Vp-p) and low TW amplitudes (<20 V). Additionally, the short TW-SLIM module achieved resolutions comparable to existing commercially available low pressure IMS platforms and an ion mobility peak capacity of ∼32 for TW speeds of <210 m/s. TW-SLIM performance was characterized over a wide range of rf and TW parameters and demonstrated robust performance. The combined attributes of the flexible design and low voltage requirements for the TW-SLIM module provide a basis for devices capable of much higher resolution and more complex ion manipulations.

Direct localisation of molecules in tissue sections of growing antler tips using MALDI imaging.

The astonishing growth rate of deer antlers offers a valuable model for the discovery of novel factors and regulatory systems controlling rapid tissue growth. Numerous molecules have been identified in growing antlers using a variety of techniques. However, little is known about the spatial distribution of these molecules in situ. A technique that has the potential to help in this regard is direct proteomic analysis of tissue sections by matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS). The present study applied this technique to spatially map molecules in antler tissue sections. Two protonated molecular ions were selected: m/z 6679 and m/z 6200 corresponding to VEGF and thymosin beta-10, respectively. Superimposition of the respective ion images on to histologically stained samples showed distinct spatial distribution across the antler tissue sections which were consistent with the previous reports using in situ hybridization. Two other molecular ions specifically m/z 8100 and m/z 11,800 were also selected, corresponding to reported masses of urocortin precursor and thioredoxin, respectively. As the spatial distribution of these proteins is not specifically known, MALDI-IMS was used as a potential technique to obtain information on their distribution on antler tips. The presence of all these molecules in deer antlers were further confirmed using LC-MS/MS data. The present study also demonstrated that MALDI-IMS could be further used to image antler sections with an extended ion mass range of up to m/z 45,000, thus potentially increasing the ability to discover the distribution of a larger set of molecules that may play an important role in antler growth. We have thus demonstrated that MALDI-IMS is a promising technique for generating molecular maps with high spatial resolution which can aid in evaluating the function of novel molecules during antler growth.

Ghost peaks observed after atmospheric pressure matrix-assisted laser desorption/ionization experiments may disclose new ionization mechanism of matrix-assisted hypersonic velocity impact ionization.

Understanding the mechanisms of matrix-assisted laser desorption/ionization (MALDI) promises improvements in the sensitivity and specificity of many established applications in the field of mass spectrometry. This paper reports a serendipitous observation of a significant ion yield in a post-ionization experiment conducted after the sample had been removed from a standard atmospheric pressure (AP)-MALDI source. This post-ionization is interpreted in terms of collisions of microparticles moving with a hypersonic velocity into a solid surface. Calculations show that the thermal energy released during such collisions is close to that absorbed by the top matrix layer in traditional MALDI. The microparticles, containing both the matrix and analytes, could be detached from a film produced inside the inlet capillary during the sample ablation and accelerated by the flow rushing through the capillary. These observations contribute some new perspective to ion formation in both laser and laser-less matrix-assisted ionization. An AP-MALDI ion source hyphenated with a three-stage high-pressure ion funnel system was utilized for peptide mass analysis. After the laser had been turned off and the MALDI sample removed, ions were detected during a gradual reduction of the background pressure in the first funnel. The constant-rate pressure reduction led to the reproducible appearance of different singly and doubly charged peptide peaks in mass spectra taken a few seconds after the end of the MALDI analysis of a dried-droplet spot. The ion yield as well as the mass range of ions observed with a significant delay after a completion of the primary MALDI analysis depended primarily on the background pressure inside the first funnel. The production of ions in this post-ionization step was exclusively observed during the pressure drop. A lower matrix background and significant increase in relative yield of double-protonated ions are reported. The observations were partially consistent with a model of the supersonic jet from the inlet capillary accelerating detached particles to kinetic energies suitable for matrix-assisted hypersonic-velocity impact ionization.

Energy resolution measurement and application of the F series ORTEC SSB detector in TOF-ERDA spectrometry

In the Elastic Recoil Detection Analysis (ERDA) and Heavy Ion Rutherford Backscattering Spectrometry (HIRBS), silicon surface barrier (SSB) detectors as well as other types of Si charged particle detectors are conventionally used for measuring ion energy due to their simplicity and ease of use. Energy resolution of such detectors is a limiting factor for both, mass and depth resolution in the experiment. In the present work we have studied performance of the commercially available F series ORTEC SSB detector designed in particular for heavy ion spectroscopy (BF-023-300-60). Detector energy and mass resolution were measured for a wide range of ion masses (7Li, 16O, 28Si, 35Cl and 81Br) and energies (2–20MeV). Obtained results were compared with the already published data for a standard A series ORTEC SSB detector (BA-017-100-100) and gas ionization chambers. Possible application of the F series SSB detector in time-of-flight ERDA (TOF-ERDA) spectrometer was discussed.

Tailoring properties of carbon-nanotube-based foams by ion bombardment

Particle irradiation is an effective method for manipulating properties of individual carbon nanotubes (CNTs). This potential, however, remains unexplored for macroscopic assemblies of cross-linked CNTs. Here, we study structural and electrical properties of ultralow-density cross-linked CNT-based nanofoams exposed to ion irradiation at room temperature over a wide range of ion masses and fluences. For all irradiation conditions studied, the electrical resistance of nanofoams initially increases with a rate that scales with the number of ballistically generated displacements. This process is attributed to the buildup of defects in graphitic nanoligaments. Irradiation with Ne and heavier ions leads to a decrease in the electrical resistance at large fluences, which is attributed to radiation-induced foam densification. In addition, heavy-ion bombardment causes amorphization of CNTs and smoothing of ligament surfaces. These results demonstrate that ion bombardment can be used for tailoring density, ligament morphology, and electrical properties of CNT-based foams.

Tandem Ion Trap Design with Enhanced Mass Analysis Capabilities for Large Populations of Ions

A new arrangement consisting of two separate radio frequency (rf) quadrupole ion traps is used to analyze large populations of ions over a wide mass-to-charge (m/z) range. The setup consists of an "accumulation" trap that is maintained at a higher pressure than the second high-performance "analyzer" trap. The two traps are scanned simultaneously, with a mass difference between that determines the residence time and mass range of ions in the analytical trap. Initially, all ions are trapped in the accumulation trap and then mass-selectively ejected into the analyzer trap. As ions arrive in the analyzer trap, they cool through collisions with the buffer gas and then are mass selectively ejected toward the detector. This concurrent linked mass scanning reduces the total number of ions present in the analyzer trap during mass analysis, thereby reducing space charge effects and leading to improved resolution and mass accuracy of analytical spectra.

Deciphering sulfoglycolipids of Mycobacterium tuberculosis

For 4 decades, in vivo and in vitro studies have suggested that sulfoglycolipids (SGLs) play a role in the virulence or pathogenesis of the tubercle bacilli. However, the SGL structure and biosynthesis pathway remain only partially elucidated. Using the modern tools of structural analysis, including MALDI-time-of-flight MS, MS/MS, and two-dimensional NMR, we reevaluated the structure of the different SGL acyl (di-, tri-, and tetra-acylated) forms of the reference strain Mycobacterium tuberculosis H37Rv, as well as those produced by the mmpL8 knockout strains previously described to intracellularly accumulate di-acylated SGL. We report here the identification of new acyl forms: di-acylated SGL esterified by simple fatty acids only, as well as mono-acylated SGL bearing a hydroxyphthioceranoic acid, which were characterized in the wild-type strain. In a clinical strain, a complete family of mono-acylated SGLs was characterized in high abundance for the first time. For the mmpL8 mutant, SGLs were found to be esterified i) by an oxophthioceranoic acid, never observed so far, and ii) at nonconventional positions in the case of the unexpected tri-acylated forms. Our results further confirm the requirement of MmpL8 for the complete assembly of the tetra-acylated forms of SGL and also provide, by the discovery of new intermediates, insights in terms of the possible SGL biosynthetic pathways.

Implantation-induced damage in Ge: strain and disorder profiles during defect accumulation and recovery

We present an experimental study of structural lattice damage in Ge induced by ion implantation. From the strain and disorder profiles, calculated from x-ray diffraction and ion channelling experiments we have investigated the defect accumulation as a function of ion fluence, mass, energy and current density as well as the damage recovery and recrystallization of the implanted region upon annealing. The damage accumulation process can be divided into three different regimes, based on the ion fluence. In the lowest fluence regime, the strain and the defect fraction are linearly proportional to the ion fluence, and the number of defects in the implanted layer is directly related to the deposited energy that is converted into the creation of vacancies. In the second regime, the damage accumulation process is more efficient, due to the increased defect density in the implanted layer. The third fluence regime starts at the critical fluence for amorphization, and this value has been determined for a wide range of ion masses and energies. The recovery study of the implantation-induced damage has revealed two distinct annealing steps. Rapid thermal annealing at temperatures as low as 100 °C results in the removal of isolated defects, which are present in the low-fluence implanted samples, as well as in the tail of the implantation profile of heavily damaged samples. Annealing at 350 °C results in the recrystallization of amorphous Ge at the amorphous–crystalline interface at a rate of 14 ± 3 nm min−1. Although Ge amorphizes at much lower fluences than Si, the influence of the studied implantation parameters on the damage accumulation process is comparable for both group IV semiconductors. This extended experimental overview of implantation-induced structural damage partly fills the large knowledge gap on implantation-related issues in Ge, and provides relevant and complementary information for defect studies in Ge and, in general, for any study using implanted Ge.

Data‐dependent electron transfer dissociation of large peptides and medium size proteins in a QTOF instrument on a liquid chromatography timescale

Liquid chromatography (LC) electron transfer dissociation (ETD) tandem mass spectrometry (MS/MS) of protein digests is demonstrated in a hybrid quadrupole-hexapole orthogonal time-of-flight (OTOF) mass spectrometer. Analyte ions are selected in a mass-analyzing quadrupole, accumulated in the hexapole linear ETD reaction cell and mutually stored with ETD reagent anions. Product ions are collected in an ion cooler and then analyzed by an OTOF mass analyzer. The hexapole structure of the ETD reaction cell allows for a broad fragment ion mass range distribution and a high ion storage capacity. Analytically useful ETD OTOF-MS/MS spectra could be obtained at a rate of faster than 2 Hz. When used in conjunction with LC this high speed allows for several MS and MS/MS spectra to be obtained across each LC peak. An MS scan is used to select the precursor ions. With a 1 m flight tube and single reflection, resolutions of about 10 k and a mass accuracy of 5 ppm were achieved. When analyzing a 100 fmol solution of a tryptic digest of bovine serum albumin (BSA) by LC/ETD MS/MS, 27 unique peptides were identified with a summed Mascot score of 1316 using the Swiss Prot database. In addition, we explored the capability for analyzing small proteins with the present hybrid instrument. ETD MS/MS of intact ubiquitin ([M+12H](12+)) leads to the identification of the protein with a Mascot score of 264.

Characterization of Molecular Mass Ranges of Two Coal Tar Distillate Fractions (Creosote and Anthracene Oils) and Aromatic Standards by LD-MS, GC-MS, Probe-MS and Size-exclusion Chromatography

Laser-desorption mass spectrometry (LD-MS) method development was undertaken to improve estimates of mass ranges for complex hydrocarbon mixtures. A creosote oil, an anthracene oil, and a mixture of known polynuclear aromatic hydrocarbon (PAH) compounds were examined. The data on the mixture of the four PAHs made it possible to define LD-MS conditions necessary to generate artifacts such as cluster ions by the combination of high laser power and high-mass accelerator voltage. The formation of cluster ions was possible without overloading the detector system. These multimer ions overlapped with higher-mass ion signals from the sample. However, careful balancing of sample concentration, laser power, total ion current, and delayed ion extraction appears to show high-mass materials without generating high-mass multimer (artifact) ions. It is possible to suppress the formation of cluster ions by keeping low target concentrations and, consequently, low gas phase concentrations formed by the laser pulse. The principal method used in this work was the fractionation of samples by planar chromatography followed by successive LD-MS analysis of the separated fractions directly from the chromatographic plates. This method separated the more abundant small molecules from the less abundant large molecules to permit the generation of their mass spectra independently, as well as reducing the concentration of sample by spreading over the PC-plate. The technique demonstrably suppressed multimer formation and greatly improved the reproducibility of the spectra. Results showed the presence of molecule ions in the ranges m/z 1000−2000 for the anthracene oil sample and m/z 600−1500 for the creosote oil sample, tailing off to m/z ∼5,000. The creosote oil contained significantly less of this high-mass material than the anthracene oil sample, and in both cases, high-mass material was only present in low quantities. Ion mass range estimates were in close agreement with molecular mass ranges from size exclusion chromatography, and findings were consistent with changes observed in the UV-fluorescence spectra. The method outlined in the paper appears directly applicable to the characterization of heavier coal and petroleum derived fractions.

Electron transfer dissociation in the hexapole collision cell of a hybrid quadrupole‐hexapole Fourier transform ion cyclotron resonance mass spectrometer

Electron transfer dissociation (ETD) of proteins is demonstrated in a hybrid quadrupole-hexapole Fourier transform ion cyclotron resonance mass spectrometer (Qh-FTICRMS). Analyte ions are selected in the mass analyzing quadrupole, accumulated in the hexapole linear ion trap, reacted with fluoranthene reagent anions, and then analyzed via an FTICR mass analyzer. The hexapole trap allows for a broad fragment ion mass range and a high ion storage capacity. Using a 3 T FTICRMS, resolutions of 60 000 were achieved with mass accuracies averaging below 1.4 ppm. The high resolution, high mass accuracy ETD spectra provided by FTICR obviates the need for proton transfer reaction (PTR) charge state reduction of ETD product ions when analyzing proteins or large peptides. This is demonstrated with the ETD of ubiquitin and apomyoglobin yielding sequence coverages of 37 and 20%, respectively. We believe this represents the first reported successful combination of ETD and a FTICRMS.

Low energy ion assisted atomic assembly of metallic superlattices

Metallic superlattices with planar, unalloyed (unmixed) interfacial structures are difficult to fabricate by all conventional vapor deposition methods. Molecular dynamics simulations have been used to explore the ways in which inert gas ions can be used to control the atomic assembly of a model Cu/Co metallic super lattice system. High energy, high atomic weight ions are shown to smooth rough interfaces but introduce undesirable intermixing at interfaces. Light ions with very low energies fail to flatten the rough surfaces that are naturally created during deposition at ambient temperature where surface atom mobility is kinetically constrained. The optimum energies for achieving the lowest combination of interfacial roughness and interlayer mixing have been found for each inert gas ion species and the key mechanisms of surface structure reorganization activated by ion impacts have been identified over the range of ion masses and energies studied. Optimum ion energies that maximize the interface structural perfection have been identified.

Compilation of a MALDI-TOF mass spectral database for the rapid screening and characterisation of bacteria implicated in human infectious diseases

A database of MALDI-TOF mass spectrometry (MS) profiles has been developed with the aim of establishing a high throughput system for the characterisation of microbes. Several parameters likely to affect the reproducibility of the mass spectrum of a taxon were exhaustively studied. These included such criteria as sample preparation, growth phase, culture conditions, sample storage, mass range of ions, reproducibility between instruments and the methodology prior to database entry. Replicates of 12 spectra per sample were analysed using a 96-well target plate containing central wells for peptide standards to correct against mass drift during analysis. The quality of the data was assessed statistically prior to database addition using root mean squared values of <3.0 as the criterion for rejection. Cluster analysis using a nearest neighbour algorithm also enabled subsets of data to be compared. This was achieved using the bespoke MicrobeLynx™ software. Columbia blood agar was used to standardise all procedures for the database, since it permitted the culture of most human pathogens and also produced spectra with a broad range of mass ions. In some instances, alternative media such as CLED were used in specific studies with greater success. Following standardisation of the procedure, a database was developed comprising ca. 3500 spectra with multiple strain entries for most species. The results to date show unequivocally that as the number of strains per species increased, so too did the success of species matching. The technique demonstrated unique mass spectral profiles for each genus/species, with the variation in mass ions among strains/species being dependent on the intra-specific diversity. The success of identification against the database for wild-type strains ranged between 33 and 100%; the lower percentage results being generally associated with poor representation of some species within the database. These findings provide a new dimension for the rapid and high throughput characterisation of human pathogens with potentially broad applications across the field of microbiology.