Thermal Ion Source Research Articles

Helium gas cell with RF wire carpets for KEK Isotope Separation System

We have developed radio-frequency (RF) wire carpets and installed them in a cryogenic helium gas cell to increase the extraction yields of target-like fragments (TLFs) produced in multi-nucleon transfer (MNT) reactions at the KEK Isotope Separation System (KISS). KISS is an on-line isotope separator based on a gas cell system, and has been implemented for nuclear spectroscopy of isotopes approaching the N=126 neutron shell closure below lead and neutron-rich actinides. We optimized the design of the RF wire carpet for efficient ion transport of TLFs from the simulations. We then performed experiments both off-line using rubidium ions from an alkali thermal ion-source in the gas cell, and on-line using TLFs produced by a 136Xe beam impinging upon a 198Pt target system, to confirm the performance expected of the design. We confirmed an increase in the extraction yields of more than an order of magnitude when using the cryogenic He gas cell with RF wire carpets as compared to our typical argon gas cell system with laser resonant ionization. The techniques and knowledge acquired in the development of these RF wire carpets will be applied to new RF wire carpets for use in a large-volume helium gas cell which will be installed at an upgraded KISS facility in the near future.

Ionization Efficiency Measurement and Optimization of a Thermal Ion Source for Radioisotope Electromagnetic Separation

An available supply of high-specific-activity radioisotopes was identified by the U.S. Department of Energy as a critical priority in the development and eventual deployment of next-generation medical diagnostic and cancer therapy tools. A radioisotope mass separator, located at the Missouri University Research Reactor Center, was developed to provide radioactive ion beams for the separation and production of high-specific-activity lanthanides used in radiopharmacology. Experiments characterizing the ionization efficiency of a thermal ion source supporting the production of high-specific-activity 153Sm are reported. With the goal of maximizing ion current while maintaining beam stability, experiments with the test ion source expand upon previously reported data from a titanium prototype ion source. Experimental results of various factors affecting ion source performance, such as diameter of the extraction orifice, ionizer geometry, ionizer temperature, and sample evaporation rate, are presented.

Ultrasonic sample introduction combined with flame assisted thermal ionization: Pretreatment-free direct mass spectrometry analysis for fraction collecting tubes of preparative liquid chromatography

Ultrasonic sample introduction combined with flame assisted thermal ionization mass spectrometry (USI-FATI-MS) was developed to monitor the fractions of preparative liquid chromatography. Recently, ultrasound-based sample introduction techniques have achieved great advance in the field of high-throughput analysis. However, it is still a challenge to directly apply these existing techniques to the analysis of macro volume samples (mL level). In this work, ultrasonic sample introduction combined with flame assisted thermal ionization was used for pretreatment-free direct mass spectrometry analysis of micro to macro volume samples (μL-mL level). Utilizing this unique design of ultrasonic sample introduction, liquid sample in the container can be quickly atomized to the gas phase without contact. Then, due to the flame assisted thermal ionization source, desolvation and ionization of the sample droplets will occur immediately. USI-FATI-MS has shown excellent sensitivity, repeatability and great compatibility to solvents and compounds with a wide range of polarity. As a proof of concept, USI-FATI-MS has been applied for rapid monitoring and identification of purified synthetic and natural products in fractions.

Rapid Identification of Illicit Drugs Using Portable Thermal Desorption – Electrospray Ionization (TD-ESI) Ion Trap – Mass Spectrometry (IT-MS) with Two-Step Scanning

With the increasing prevalence of illicit drugs, social security and human health are at serious risk. However, traditional detection techniques require a lengthy pretreatment process to eliminate matrix interference and do not allow rapid, in situ analysis. Ambient ionization is a powerful tool for the rapid determination of illicit drugs in different matrices because it usually eliminates the need for sample pretreatment, and the portable mass spectrometer brings convenience to in situ detection. This study employed a thermal desorption-electrospray ionization (TD-ESI) source combined with a portable mass spectrometer to rapidly characterize illicit drugs in drinks, instant powders, and solid food surfaces. Air was utilized instead of nitrogen as the carrier gas for TD-ESI/MS in order to save space and cost together with rapid on-site analysis. A full-scan waveform combined with a qualitative pre-scan waveform (QPSW) was employed to form a two-step scanning mode to accurately identify the drugs. The results showed that the limits of detection (LODs) for the analytes were 100–200 ppb in drinks, 700–1000 ppb in instant powders, and 1 ng/cm2 on solid food surfaces. The complete TD-ESI/MS analysis time was less than 1 min.

Detection of Trace Explosives Using a Novel Sample Introduction and Ionization Method.

A novel sample introduction and ionization method for trace explosives detection is proposed and investigated herein, taking into consideration real-world application requirements. A thermal desorption sampling method and dielectric barrier discharge ionization (DBDI) source, with air as the discharge gas, were developed. The counter flow method was adopted firstly into the DBDI source to remove the interference of ozone and other reactive nitrogen oxides. A separated reaction region with an ion guiding electric field was developed for ionization of the sample molecules. Coupled with a homemade miniature digital linear ion trap mass spectrometer, this compact and robust design, with further optimization, has the advantages of soft ionization, a low detection limit, is free of reagent and consumable gas, and is an easy sample introduction. A range of common nitro-based explosives including TNT, 2,4-DNT, NG, RDX, PETN, and HMX has been studied. A linear response in the range of two orders of magnitude with a limit of detection (LOD) of 0.01 ng for TNT has been demonstrated. Application to the detection of real explosives and simulated mixed samples has also been explored. The work paves the path to developing next generation mass spectrometry (MS) based explosive trace detectors (ETDs).

Ion Source—Thermal and Thermomechanical Simulation

The main purpose of this work is to conduct ground development testing of the ion source intended for use the space debris contactless transportation system. In order to substantiate the operating capability of the developed ion source, its thermal and thermomechanical simulation was carried out. The ion source thermal model should verify the ion source operating capability under thermal loading conditions, and demonstrate the conditions for ion source interfacing with the systems of the service spacecraft with the ion source installed as a payload. The mechanical and mathematical simulation for deformation of the ion source ion-extraction system profiled electrodes under thermal loading in conjunction with the prediction of the strained state based on the numerical simulation of the ion source ion-extraction system units, making it possible to ensure the stability of the ion source performance. Good agreement between the thermal and thermo-mechanical ion source simulation results and experimental data has been demonstrated. It is shown that the developed ion source will be functional in outer space and can be used as an element of the space debris contactless transportation system into graveyard orbits.

Feasibility of on/at Line Methods to Determine Boar Taint and Boar Taint Compounds: An Overview.

Simple SummaryDue to welfare issues, the physical castration of male pigs is decreasing, and the entire male pig production is increasing. Fattening entire male pigs requires control due to the possibility of accumulating off odour/flavour called boar taint, which is mainly due to two compounds - skatole and androstenone. If carcasses with boar taint reach the market, it can cause a negative consumer reaction which may have economic consequences for the whole meat chain. Thus, it is necessary to sort out carcasses at the slaughter line. Today, a sensory quality control (human nose method) is used in some slaughter plants for this purpose. Detection by physical or chemical methods is also envisaged. A colorimetric method to determine skatole has been used in Danish abattoirs for decades, but it is foreseen that it will soon be replaced by the laser diode thermal desorption ion source coupled with a mass spectrometry equipment that allows a fully automated classification based on skatole and androstenone levels at speed line, with a delay of less than 40 min. Other potential methods such as the electrochemical biosensors, rapid evaporative ionization mass spectroscopy and Raman spectroscopy, still need further development and validation for an application at abattoir level.Classification of carcasses at the slaughter line allows an optimisation of its processing and differentiated payment to producers. Boar taint is a quality characteristic that is evaluated in some slaughter plants. This odour and flavour is mostly present in entire males and perceived generally by sensitive consumers as unpleasant. In the present work, the methodologies currently used in slaughter plants for boar taint classification (colorimetric method and sensory quality control-human nose) and the methodologies that have the potential to be implemented on/at the slaughter line (mass spectrometry, Raman and biosensors) have been summarized. Their main characteristics are presented and an analysis of strengths, weaknesses, opportunities and threats (SWOT) has been carried out. From this, we can conclude that, apart from human nose, the technology that arises as very promising and available on the market, and that will probably become a substitute for the colorimetric method, is the tandem between the laser diode thermal desorption ion source and the mass spectrometry (LDTD-MS/MS) with automation of the sampling and sample pre-treatment, because it is able to work at the slaughter line, is fast and robust, and measures both androstenone and skatole.

Wire Desorption Combined with Electrospray Ionization Mass Spectrometry: Direct Analysis of Small Organic and Large Biological Compounds.

A novel atmospheric pressure ionization mass spectrometry based on wire desorption and electrospray ionization (WD-ESI) for direct analysis was developed to characterize chemical compounds with different polarities and thermal stabilities at atmospheric pressure. This technique is a variant of the thermal desorption electrospray ion source developed by Shiea et al. One large improvement is that the heating speed (>500 °C/s) of the thermal desorption in this work is extremely fast, using a self-heating metal wire, with which sample solution can splash from the surface to form small droplets and thus the analytes can be protected from thermal decomposition. With this feature, we have successfully achieved soft ionization of highly polar organic and biological compounds such as aflatoxin, small peptides, and even large proteins from complex matrices. The simple structure and self-cleaning capability of the WD-ESI source make it ideal for on-site screening in various applications such as food safety and biodrug testing, especially when coupled with a transportable mass spectrometer.

Design of a compact magnets system for a hybrid 2.45 GHz microwave 7Li[formula omitted] ion source

A hybrid ion source with a combination of a 2.45 GHz microwave source and a thermal surface ionization source was designed to generate 7Li3+ ion beam. A minimum-B type magnetic field configuration that consists of axial mirror field and hexapole field was designed. During the design process of the magnets system, the magnetic field configuration, the mechanical structure of the source body and the water cooling system have been carefully calculated and verified. An electrostatic Particle in Cell (PIC) code was developed to simulate the motion of electrons in the designed magnetic field to verify the reasonability of the design.

A configurable ion source for validating spaceflight-based thermal plasma measurement systems.

Thermal ion instruments are valuable for analyzing Earth's upper atmosphere. Prelaunch vacuum chamber testing of such instruments with a thermal ion source is often used to validate the performance of such instruments in a relevant environment, which is a prerequisite for a NASA flight. In this paper, we describe a new ion source that can be used for such tests, compare its performance with simulation results, and present an example of the utility for the source for validating the performance of an instrument.

Thermionic sodium ion source versus corona discharge in detection of alkaloids using ion mobility spectrometry

IMS spectra obtained by using a thermal ionization sodium ion (SI) source and a corona discharge (CD) source were compared in terms of resolution, selectivity and sensitivity. The reactant ion peak (RIP) for the SI source is a single narrow peak which appears in a shorter drift time compared to the main RIP of the CD ion source, (H2O)nH3O+. Comparison of the IMS spectra of selected alkaloids obtained with both the CD and the SI sources shows that the latter exhibits simpler pattern, including a narrow single peak for each compound, well separated from other samples peak. Furthermore, the product ion peaks (PIP) in the SI source appeared at higher drift times leading to higher peak-to-peak resolution. However, the sodium ion source is less sensitive to the selected alkaloids compared to the CD ion source.

Laser diode thermal desorption atmospheric pressure chemical ionization tandem mass spectrometry applied for the ultra-fast quantitative analysis of BKM120 in human plasma.

A sensitive and ultra-fast method utilizing the laser diode thermal desorption ion source using atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS) was developed for the quantitative analysis of BKM120, an investigational anticancer drug in human plasma. Samples originating from protein precipitation (PP) followed by salting-out assisted liquid-liquid extraction (SALLE) were spotted onto the LazWell™ plate prior to their thermal desorption and detection by tandem mass spectrometry in positive mode. The validated method described in this paper presents a high absolute extraction recovery (>90%) for BKM120 and its internal standard (ISTD) [D8]BKM120, with precision and accuracy meeting the acceptance criteria. Standard curves were linear over the range of 5.00 to 2000ngmL(-1) with a coefficient of determination (R (2)) >0.995. The method specificity was demonstrated in six different batches of human plasma. Intra- and inter-run precision as well as accuracy within ±20% at the lower limit of quantification (LLOQ) and ±15% (other levels) were achieved during a three-run validation for quality control (QC) samples. The post-preparative stability on the LazWell™ plate at room temperature was 72h and a 200-fold dilution of spiked samples was demonstrated. The method was applied successfully to three clinical studies (n = 847) and cross-checked with the validated LC-ESI-MS/MS reference method. The sample analysis run time was 10s as compared to 4.5min for the current validated LC-ESI-MS/MS method. The resultant data were in agreement with the results obtained using the validated reference LC-ESI-MS/MS assay and the same pharmacokinetic (PK) parameters were calculated for both analytical assays. This work demonstrates that LDTD-APCI-MS/MS is a reliable method for the ultra-fast quantitative analysis of BKM120 which can be used to speed-up and support its bioanalysis in the frame of the clinical trials.

Thermal dissociation atmospheric chemical ionization ion trap mass spectrometry with a miniature source for selective trace detection of dimethoate in fruit juices

A miniature thermal dissociation atmospheric chemical ionization (TDCI) source, coupled with LTQ-MS, has been developed for rapid trace detection of pesticide residues such as dimethoate in highly viscous fruit juice samples. Instead of toxic organic solvents and the high electric field used in the conventional ionizations, an ionic liquid, a "green solvent", was employed to directly generate reagent ions in the TDCI process, followed by the proton or charge transfer with the analytes prior to the LTQ instrument for mass analysis. Trace amounts of dimethoate in fresh orange juices have been quantitatively detected, without any sample pretreatment or aid of high-pressure gas. A low limit of detection (LOD = 8.76 × 10(-11) g mL(-1)), acceptable relative standard deviation (RSD = 3.1-10.0%), and reasonable recoveries (91.2-102.8%) were achieved with this method for direct detection of dimethoate in highly viscous orange juice samples. The average analysis time for each single sample was less than 30 seconds. These experimental results showed that the miniature TDCI developed here is a powerful tool for the fast trace detection of pesticide residues in complex viscous fruit juices, with the advantage of high sensitivity, high speed, and high-throughput, ease of operation, and so on. Because of no chemical contamination and high voltage damage to the analytes and the environment, the technique has promising applications for online quality monitoring in the area of food safety.

Study of small chlorine‐doped potassium clusters by thermal ionization mass spectrometry

The theoretical calculations have predicted that nonmetal-doped potassium clusters can be used in the synthesis of a new class of charge-transfer salts which can be considered as potential building blocks for the assembly of novel nanostructured material. In this work, K(n)Cl (n = 2-6) and K(n)Cl(n-1) (n = 3 and 4) clusters were produced by vaporization of a solid potassium chloride salt in a thermal ionization mass spectrometry. The ionization energies (IEs) were measured, and found to be 3.64 ± 0.20 eV for K(2)Cl, 3.67 ± 0.20 eV for K(3)Cl, 3.62 ± 0.20 eV for K(4)Cl, 3.57 ± 0.20 eV for K(5)Cl, 3.69 ± 0.20 eV for K(6)Cl, 3.71 ± 0.20 eV for K(3)Cl(2) and 3.72 ± 0.20 eV for K(4)Cl(3). The K(n)Cl(+) (n = 3-6) clusters were detected for the first time in a cluster beam generated by the thermal ionization source of modified design. Also, this work is the first to report experimentally obtained values of IEs for K(n)Cl(+) (n = 3-6) and K(n)Cl(n-1) (+) (n = 3 and 4) clusters. The ionization energies for K(n)Cl(+) and K(n)Cl(n-1) (+) clusters are much lower than the 4.34 eV of the potassium atom; hence, these clusters should be classified as 'superalkali' species.

Production and ionization energies of KnF (n = 2–6) clusters by thermal ionization mass spectrometry

The very small clusters of the type K(n)F are of particular importance since their first ionization energies (IEs) are lower than those of the alkali metal atoms. Theoretical calculation has demonstrated that this kind of cluster represents a potential 'building block' for cluster-assembly materials with unique structural, electronic, optical, magnetic, and thermodynamic properties. To date, however, there have been no experimental results on the IEs of K(n)F (n >2) clusters. K(n)F (n = 2-6) clusters were produced by the evaporation of a solid potassium fluoride salt using a modified thermal ionization source of modified design, and mass selected by a magnetic sector mass spectrometer where their IEs were determined. Clusters K(n)F (n = 3-6) were detected for the first time. The order of the ion intensities was K(2)F(+)> > K(4)F(+)> > K(3)F(+)K(6)F(+)> K(5)F(+). The determined IEs were 3.99 ± 0.20 eV for K(2)F, 4.16 ± 0.20 eV for K(3)F, 4.27 ± 0.20 eV for K(4)F, 4.22 ± 0.20 eV for K(5)F, and 4.31 ± 0.20 eV for K(6)F. The IEs of K(n)F increase slightly with the increase in potassium atom number from 2 to 6. We also observed that the presence of a fluorine atom leads to increasing ionization energy of bare metal potassium clusters. The modified thermal ionization source provides an efficient way of obtaining the fluorine-doped potassium clusters. These results also present experimental proof that K(n)F (n = 2-6) clusters belong to the group of 'superalkali' species.

Formation of positive cluster ions LinBr (n = 2–7) and ionization energies studied by thermal ionization mass spectrometry

Clusters of the type Li(n)X (X = halides) can be considered as potential building blocks of cluster-assembly materials. In this work, Li(n)Br (n = 2-7) clusters were obtained by a thermal ionization source of modified design and selected by a magnetic sector mass spectrometer. Positive ions of the Li(n)Br (n = 4-7) cluster were detected for the first time. The order of ion intensities was Li(2)Br(+) > Li(4)Br(+) > Li(5)Br(+) > Li(6)Br(+) > Li(3)Br(+). The ionization energies (IEs) were measured and found to be 3.95 ± 0.20 eV for Li(2)Br, 3.92 ± 0.20 eV for Li(3)Br, 3.93 ± 0.20 eV for Li(4)Br, 4.08 ± 0.20 eV for Li(5)Br, 4.14 ± 0.20 eV for Li(6)Br and 4.19 ± 0.20 eV for Li(7)Br. All of these clusters have a much lower ionization potential than that of the lithium atom, so they belong to the superalkali class. The IEs of Li(n)Br (n = 2-4) are slightly lower than those in the corresponding small Li(n) or Li(n)H clusters, whereas the IEs of Li(n)Br are very similar to those of Li(n) or Li(n)H for n = 5 and 6. The thermal ionization source of modified design is an important means for simultaneously obtaining and measuring the IEs of Li(n)Br (n = 2-7) clusters (because their ions are hermodynamically stable with respect to the loss of lithium atoms in the gas phase) and increasingly contributes toward the development of clusters for practical applications.

Formation and ionization energies of small chlorine‐doped lithium clusters by thermal ionization mass spectrometry

Theoretical calculations have shown that the first ionization energy of clusters of the type Li(n) Cl (n ≥2), with more than eight valent electrons, is lower than that of alkali metal atoms; hence they are named superalkali. Superalkali clusters can mimic the chemical behavior of alkali metals and may be used as building blocks of new cluster-assembled materials. There is currently no reliable experimental proof of this kind of clusters and such proof is required. The Li(n) Cl (n = 2-6) clusters were produced by a thermal ionization source of modified design, and mass selected by a magnetic-sector mass spectrometer. The modification pertains to the replacement of the side filaments by a cylinder in the triple-filament thermal ionization source. The sample, which is LiCl salt, was pressed into a ring and placed on the inner wall of the cylinder. It was observed that the ions of clusters with an even number of lithium atoms (Li(2) Cl(+) , Li(4) Cl(+) , Li(6) Cl(+) ) are more stable than the odd-numbered ones (Li(5) Cl(+) , Li(3) Cl(+) ). The ionization energies were determined to be 3.98 ± 0.25 eV for Li(2) Cl, 4.10 ± 0.25 eV for Li(3) Cl, 3.90 ± 0.25 eV for Li(4) Cl, 4.01 ± 0.25 eV for Li(5) Cl, and 4.09 ± 0.25 eV for Li(6) Cl. The presence of a halogen atom reduces the ionization energy of the metal clusters. The thermal ionization source of modified design presents a suitable simple way to obtaining and measuring the ionization energies of very small lithium monochloride clusters. Clusters Li(n) Cl, n = 4 to 6, were detected for the first time.

Sequential bond energies and barrier heights for the water loss and charge separation dissociation pathways of Cd2+(H2O)n, n = 3–11

The bond dissociation energies for losing one water from Cd(2+)(H(2)O)(n) complexes, n = 3-11, are measured using threshold collision-induced dissociation in a guided ion beam tandem mass spectrometer coupled with a thermal electrospray ionization source. Kinetic energy dependent cross sections are obtained for n = 4-11 complexes and analyzed to yield 0 K threshold measurements for loss of one, two, and three water ligands after accounting for multiple collisions, kinetic shifts, and energy distributions. The threshold measurements are converted from 0 to 298 K values to give the hydration enthalpies and free energies for sequentially losing one water from each complex. Theoretical geometry optimizations and single point energy calculations are performed on reactant and product complexes using several levels of theory and basis sets to obtain thermochemistry for comparison to experiment. The charge separation process, Cd(2+)(H(2)O)(n) → CdOH(+)(H(2)O)(m) + H(+)(H(2)O)(n-m-1), is also observed for n = 4 and 5 and the competition between this process and water loss is analyzed. Rate-limiting transition states for the charge separation process at n = 3-6 are calculated and compared to experimental threshold measurements resulting in the conclusion that the critical size for this dissociation pathway of hydrated cadmium is n(crit) = 4.

Development of Thermal Dissociation Atmospheric Chemical Ionization Source for Rapid Mass Spectrometry Analysis of Ambient Samples

A thermal dissociation atmospheric chemical ionization (TDCI) source was developed for the rapid chemical ionization of ambient analytes in complex matrices. The performance of TDCI has been experimentally explored by coupling the TDCI source to a commercial LTQ XL mass spectrometer, and the dissociation of chemical reagents, for example ionic liquids, has been systematically investigated using multiple stage mass spectrometer. The primary ions, generated through the thermal dissociation process of the ionic liquids, were accelerated by the bias voltage applied to the repelling electrode of the TDCI source, then reacted with the analytes present in the matrices of the raw samples to produce analyte ions. The analyte ions were finally guided into the LTQ instrument for mass analysis. The construction of the TDCI source was detailed in the text. The effects of the experimental parameters such as the temperature, the distance, and the angles formed between the electrodes were experimentally studied using the signals of characteristic fragments of the ionic liquid. Under the optimal experimental conditions, TDCI was able to directly ionize a wide variety of compounds, including the poplar (e.g., amino acids, doping compounds) and nonpolar chemicals (e.g., naphthalene), for sensitive detection using LTQ-MS, without any sample pretreatment. The average time for a single sample analysis was less than 30 s, the relative standard deviation of the method was in the range of 5.89%–11.1%, and the limit of detection (LOD) for naphthalene was estimated to be 2.9 × 10−7 g L−1.

Structural and Mechanical Properties of CrNxCoatings Deposited by Medium-Frequency Magnetron Sputtering with and without Ion Source Assistance

CrNxcoatings were deposited on Si (100) and WC-Co substrates by a home-made medium-frequency magnetron sputtering system with and without thermal filament ion source assistance. The structure and composition of the coatings were characterized by X-ray diffraction, atomic force microscopy, scanning electron microscopy, and transmission electron microscopy. The mechanical and tribological properties were assessed by microhardness and pin-on-disc testing. The ion source-assisted system showed a deposition rate of 3.88 μm/h, much higher than the value 2.2 μm/h without ion source assistance. The CrNxcoatings prepared with ion source assistance exhibited an increase in microhardness (up to 16.3 GPa) and adecrease in friction coefficient (down to 0.48) at the optimized cathode source-to-substrate distance.