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1.
Molecules ; 29(2)2024 Jan 08.
Artículo en Inglés | MEDLINE | ID: mdl-38257229

RESUMEN

Electrospray ionization (ESI) is among the commonly used atmospheric pressure ionization techniques in mass spectrometry (MS). One of the drawbacks of ESI is the formation of divergent plumes composed of polydisperse microdroplets, which lead to low transmission efficiency. Here, we propose a new method to potentially improve the transmission efficiency of ESI, which does not require additional electrical components and complex interface modification. A dielectric plate-made of ceramic-was used in place of a regular metallic sampling cone. Due to the charge accumulation on the dielectric surface, the dielectric layer around the MS orifice distorts the electric field, focusing the charged electrospray cloud towards the MS inlet. The concept was first verified using charge measurement on the dielectric material surface and computational simulation; then, online experiments were carried out to demonstrate the potential of this method in MS applications. In the online experiment, signal enhancements were observed for dielectric plates with different geometries, distances of the electrospray needle axis from the MS inlet, and various compounds. For example, in the case of acetaminophen (15 µM), the signal enhancement was up to 1.82 times (plate B) using the default distance of the electrospray needle axis from the MS inlet (d = 1.5 mm) and 12.18 times (plate C) using a longer distance (d = 7 mm).

2.
Mass Spectrom Rev ; 41(2): 338-351, 2022 03.
Artículo en Inglés | MEDLINE | ID: mdl-33521990

RESUMEN

The world of Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry has witnessed, especially in the last 30 years significant advances in many fields of science, such as electronics, magnets, new ICR cell designs, developed ICR event sequences, modern external ionization sources, and linear ion beam guides, as well as modern vacuum technology. In this review, a brief account is given focusing especially on the studies performed in Wanczek's group and ICR research laboratory at the University of Bremen. An FT-ICR mass spectrometer has been developed with a high magnetic field superconducting magnet, operating at 4.7 T. At this magnetic field, a trapping time of 13.5 h was obtained with 30% efficiency. For the tetrachloromethane molecular ion, m/z 166, a mass-resolving power m/Δm = 1.5 × 106 was measured at a pressure of 2 × 10-8 Torr. The transition from magnet sweep to frequency sweep and the application of Fourier-transform has greatly enhanced the ICR technology. External ion sources were invented and differential pumping schemes were developed for enabling ultrahigh vacuum condition for ICR detection, while guiding ions at relatively higher pressures, during their flight to the ICR cell. With the external ion source, a time-of-flight ICR tandem instrument is built. A method to measure the ion flight time and to trap the ions in the ICR cell is described. Many ICR cell characteristics such as z-axis ion ejection and coupling of radial and axial ion motions in a superposed homogeneous magnetic and inhomogeneous trapping electric field were extensively studied. Gas-phase ion-molecule reactions of several reactive inorganic compounds with a focus on phosphorous and sulfur as well as silicon chemistry were also studied in great detail. The gas-phase ion chemistry of several trifluoromethyl-reagents such as trifluoromethyltrimethylsilane and tris(trifluoromethyl)phosphine were also investigated in ICR. Dual polarities multisegmented ICR cells were invented and deeply characterized. Sophisticated ICR pulse event programs were developed to enable long-range ion-ion interactions between simultaneously trapped positive and negative ions.


Asunto(s)
Imanes , Superconductividad , Análisis de Fourier , Iones , Espectrometría de Masas/métodos
3.
Sensors (Basel) ; 22(5)2022 Feb 25.
Artículo en Inglés | MEDLINE | ID: mdl-35270963

RESUMEN

The misuse of pesticides poses a tremendous threat to human health. Excessive pesticide residues have been shown to cause many diseases. Many sensor detection methods have been developed, but most of them suffer from problems such as slow detection speed or narrow detection range. So, the development of rapid, direct and sensitive means of detecting trace amounts of pesticide residues is always necessary. A novel online sensor technique was developed for direct analysis of pesticides in complex matrices with no sample pretreatment. The portable sensor ion source consists of an MPT (microwave plasma torch) with desolventizing capability and an APCI (atmosphere pressure chemical ionization), which provides abundant precursor ions and a strong electric field. The performance which improves the ionization efficiency and suppresses the background signal was verified by using pesticide standard solution and pesticide pear juice solution measurements with an Orbitrap mass spectrometer. The limit of detection (LOD) and the limit of quantization (LOQ) of the method were measured by pear juice solutions that were obtained in the ranges of 0.034-0.79 µg/L and 0.14-1 µg/L. Quantitative curves were obtained ranging from 0.5 to 100 µg/L that showed excellent semi-quantitative ability with correlation coefficients of 0.985-0.997. The recoveries (%) of atrazine, imidacloprid, dimethoate, profenofos, chlorpyrifos, and dichlorvos were 96.6%, 112.7%, 88.1%, 85.5%, 89.2%, and 101.9% with the RSDs ranging from 5.89-14.87%, respectively. The results show that the method has excellent sensitivity and quantification capability for rapid and direct detection of trace pesticide.


Asunto(s)
Residuos de Plaguicidas , Plaguicidas , Humanos , Límite de Detección , Espectrometría de Masas/métodos , Residuos de Plaguicidas/análisis , Plaguicidas/análisis
4.
Nucl Instrum Methods Phys Res B ; 530: 1-7, 2022 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-38390228

RESUMEN

The Lawrence Livermore National Laboratory - Center for Accelerator Mass Spectrometry (LLNL/CAMS) 1 MV AMS system was converted from a biomedical AMS instrument to a natural abundance 14C spectrometer. The system is equipped with a gas-accepting hybrid ion source capable of measuring both solid (graphite) and gaseous (CO2) samples. Here we describe a series of experiments intended to establish and optimize 14CO2 measurement capabilities at natural abundance levels. A maximum instantaneous ionization efficiency of 8 % was achieved with 3 % CO2 in helium at a flow rate of approximately 220 µL/min (3.5 µg C/min). For modern materials (e.g., OX I) we measured an average of 240 ± 50 14C counts/µg C, equivalent to a total system efficiency of approximately 3 %. Experimental CO2 samples with F14C values ranging from 0.20 to 1.05 measured as both graphite and directly as CO2 gas produced equivalent values with an average offset of < 2σ.

5.
Shokuhin Eiseigaku Zasshi ; 62(1): 14-19, 2021.
Artículo en Japonés | MEDLINE | ID: mdl-33658459

RESUMEN

We evaluated an analytical method to detect pesticide residues in agricultural products through the use of a self-cleaning ion source GC-MS/MS. The self-cleaning ion source minimizes ion source contamination by ensuring that hydrogen is pumped into the source at a fixed pressure after or during measurement. When we employed our self-cleaning ion source GC-MS/MS technique to analyze pesticides residues in agricultural products, we observed that pollution of the ion source surface was considerably reduced. Good peak sensitivity was obtained for 251 pesticides, and a calibration curve with a coefficient of determination (R2) of 0.990 or higher was obtained for 253 pesticides. In the recovery test with 6 types of agricultural products, the acceptability criteria of recovery (70-120%) and standard deviation of repeatability (RSD<25%) was met in 180-221 pesticides.


Asunto(s)
Residuos de Plaguicidas , Plaguicidas , Cromatografía de Gases , Cromatografía de Gases y Espectrometría de Masas , Residuos de Plaguicidas/análisis , Espectrometría de Masas en Tándem
6.
J Microsc ; 277(1): 42-48, 2020 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-31855279

RESUMEN

Li can find itself a wide range of applications since it is the lightest metal. However, Li detection by microscopy-based techniques is problematic because of the highly susceptible nature during electron beam irradiation. ToF-SIMS is a versatile technique to detect Li but the detection of light materials is also problematic due to the large ion contaminated zone and low sputtering yield. By combining ToF-SIMS with a recently launched Xe ion source FIB-SEM, which has small ion contamination and high sputtering yield features, can produce more realistic data at near surface and below the surface region especially for the detection of lightweight materials such as Li. In this study, Li detection and mapping capabilities of ToF-SIMS attached to the FIB-SEM with Ga and Xe ion sources were discussed for Al incorporated Li7 La3 Zr2 O12 solid electrolyte sample that contains Li and Al rich regions at triple junctions. In spite of smoother milling from Ga source, Xe performs more precisely in Li mapping. Low ion contaminated zone, high sputtering yield and low straggling obtained from Monte Carlo simulations are the main advantages of Xe ion sources. The Li detection efficiency for Xe is higher than Ga source discriminating the LiAlO2 phase placed at the triple junctions of grains and La2 Zr2 O7 regions placed at the outer side of LLZO neighbouring the LiAlO2 phase. LAY DESCRIPTION: Li can find itself a wide range of applications since it is the lightest metal. However, Li detection by microscopy-based techniques is problematic because of the highly susceptible nature during electron beam irradiation. ToF-SIMS is a versatile technique to detect Li but the detection of light materials is also problematic due to the large ion contaminated zone and low sputtering yield. By combining ToF-SIMS with a recently launched Xe ion source FIB-SEM, which has small ion contamination and high sputtering yield features, can produce more realistic data at near surface and below the surface region especially for the detection of lightweight materials such as Li. In this study, Li detection and mapping capabilities of ToF-SIMS attached to the FIB-SEM with Ga and Xe ion sources were discussed for Al incorporated Li7 La3 Zr2 O12 solid electrolyte sample that contains Li and Al rich regions at triple junctions. In spite of smoother milling from Ga source, Xe performs more precisely in Li mapping. Results were also supported from Monte Carlo simulations of ion-atom interactions. The Li detection resolution of xenon is much higher than gallium source discriminating the LiAlO2 phase placed at the triple junctions of grains and La2 Zr2 O7 regions placed at the outer side of LLZO neighbouring the LiAlO2 phase.

7.
Molecules ; 25(14)2020 Jul 16.
Artículo en Inglés | MEDLINE | ID: mdl-32708799

RESUMEN

A closed atmospheric pressure chemical ionization (APCI) ion source as interface between a gas chromatograph (GC) and a triple quadrupole mass spectrometer (QqQ-MS) was developed. The influence of different ion source conditions, such as humidity, make-up gas flow, and the position of the GC column, were investigated and determined as main factors to increase sensitivity and repeatability of the system. For a performance test under real conditions, the new APCI ion source was used for the determination of plant protection products in commercially available coffee beans from Vietnam. The ionization behavior was investigated and the majority of the analytes were detected as [MH]+, [M]+∙, or as characteristic fragment ions, which have been assigned to ion source fragmentation. The developed GC-MS methods are based on tandem MS (MS/MS) and revealed for the plant protection products limits of detection (LOD) between 1 and 250 pg on column and relative standard derivations for all compounds < 16%. The used ultrasonic solid-liquid extraction yielded recovery rates of approximately 60 to 100%. Residues of herbicide methyl esters, organophosphorus compounds, and organonitrogen compounds have been detected in the analyzed coffee beans.


Asunto(s)
Iones/aislamiento & purificación , Compuestos Organofosforados/aislamiento & purificación , Presión Atmosférica , Cromatografía de Gases y Espectrometría de Masas , Humanos , Iones/química , Límite de Detección , Compuestos Organofosforados/química , Vietnam
8.
Molecules ; 25(11)2020 May 28.
Artículo en Inglés | MEDLINE | ID: mdl-32481752

RESUMEN

The emergence of the hydrogen economy requires development in the storage, generation and sensing of hydrogen. The indium selenide ( γ -InSe) van der Waals (vdW) crystal shows promise for technologies in all three of these areas. For these applications to be realised, the fundamental interactions of InSe with hydrogen must be understood. Here, we present a comprehensive experimental and theoretical study on the interaction of γ -InSe with hydrogen. It is shown that hydrogenation of γ -InSe by a Kaufman ion source results in a marked quenching of the room temperature photoluminescence signal and a modification of the vibrational modes of γ -InSe, which are modelled by density functional theory simulations. Our experimental and theoretical studies indicate that hydrogen is incorporated into the crystal preferentially in its atomic form. This behaviour is qualitatively different from that observed in other vdW crystals, such as transition metal dichalcogenides, where molecular hydrogen is intercalated in the vdW gaps of the crystal, leading to the formation of "bubbles" for hydrogen storage.


Asunto(s)
Hidrógeno/química , Enlace de Hidrógeno , Indio/química , Microscopía Óptica no Lineal , Teoría Cuántica , Termodinámica
9.
Zhongguo Yi Liao Qi Xie Za Zhi ; 44(1): 92-94, 2020 Jan 08.
Artículo en Zh | MEDLINE | ID: mdl-32343077

RESUMEN

OBJECTIVE: To compare the performance of the GE cyclotron MINItrace system before and after the upgrade. METHODS: The upgrade of the MINItrace system included replacing the silver target with the Nb syetem and adopting the latest RF control and management system and lastest ion source system.The failrue rate and production efficiency were retrospectively analyzed before and after the upgrade. RESULTS: After the upgrade, the cyclotron failure rate decreased by 86.2%, the average capacity increased by 45%. CONCLUSIONS: After the upgrade of MINItrace cyclotron, the failure rate is sharply reduced, and the production efficiency is grately improved.


Asunto(s)
Ciclotrones/normas , Falla de Equipo , Estudios Retrospectivos
10.
Anal Bioanal Chem ; 411(16): 3533-3542, 2019 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-31025182

RESUMEN

Choosing an appropriate ion source is a crucial step in liquid chromatography mass spectrometry (LC/MS) method development. In this paper, we compare four ion sources for LC/MS analysis of 40 pesticides in tomato and garlic matrices. We compare electrospray ionisation (ESI) source, thermally focused/heated electrospray (HESI), atmospheric pressure photoionisation (APPI) source with and without dopant, and multimode source in ESI mode, atmospheric pressure chemical ionisation (APCI) mode, and combined mode using both ESI and APCI, i.e. altogether seven different ionisation modes. The lowest limits of detection (LoDs) were obtained by ESI and HESI. Widest linear ranges were observed with the conventional ESI source without heated nebuliser gas. In comparison to HESI, ESI source was significantly less affected by matrix effect. APPI ranked second (after ESI) by not being influenced by matrix effect; therefore, it would be a good alternative to ESI if low LoDs are not required. Graphical abstract.

11.
Xenobiotica ; 49(6): 655-670, 2019 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-29897827

RESUMEN

To elucidate the metabolism of pazopanib, a metabolomics approach was performed based on ultra-performance liquid chromatography coupled with electrospray ionization quadrupole mass spectrometry. A total of 22 pazopanib metabolites were identified in vitro and in vivo. Among these metabolites, 17 were novel, including several cysteine adducts and aldehyde derivatives. By screening using recombinant CYPs, CYP3A4 and CYP1A2 were found to be the main forms involved in the pazopanib hydroxylation. Formation of a cysteine conjugate (M3), an aldehyde derivative (M15) and two N-oxide metabolites (M18 and M20) from pazopanib could induce the oxidative stress that may be responsible in part for pazopanib-induced hepatotoxicity. Morphological observation of the liver suggested that pazopanib (300 mg/kg) could cause liver injury. The aspartate transaminase and alanine aminotransferase in serum significantly increased after pazopanib (150, 300 mg/kg) treatment; this liver injury could be partially reversed by the broad-spectrum CYP inhibitor 1-aminobenzotriazole (ABT). Metabolomics analysis revealed that pazopanib could significantly change the levels of L-carnitine, proline and lysophosphatidylcholine 18:1 in liver. Additionally, drug metabolism-related gene expression analysis revealed that hepatic Cyp2d22 and Abcb1a (P-gp) mRNAs were significantly lowered by pazopanib treatment. In conclusion, this study provides a global view of pazopanib metabolism and clues to its influence on hepatic function.


Asunto(s)
Antineoplásicos/toxicidad , Hígado/efectos de los fármacos , Pirimidinas/toxicidad , Sulfonamidas/toxicidad , Alanina Transaminasa/sangre , Animales , Antineoplásicos/metabolismo , Aspartato Aminotransferasas/sangre , Biomarcadores/sangre , Cromatografía Líquida de Alta Presión , Sistema Enzimático del Citocromo P-450/genética , Sistema Enzimático del Citocromo P-450/metabolismo , Sistema Enzimático del Citocromo P-450/fisiología , Indazoles , Hígado/metabolismo , Hígado/patología , Masculino , Metabolómica , Ratones , Ratones Endogámicos C57BL , Análisis Multivariante , Estrés Oxidativo/efectos de los fármacos , Pirimidinas/metabolismo , Espectrometría de Masa por Ionización de Electrospray , Sulfonamidas/metabolismo
12.
Sensors (Basel) ; 19(3)2019 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-30717216

RESUMEN

It is difficult to generate and maintain the vacuum level in vacuum MEMS (Micro-Electro-Mechanical Systems) devices. Currently, there is still no single method or device capable of generating and maintaining the desired vacuum level in a vacuum device for a long time. This paper proposed a new wide-pressure-range miniature ion source, which can be applied to a vacuum micropump. The miniature ion source consists only of silicon electrodes and a glass substrate. Its operating pressure range covers seven orders of magnitude, starting from atmospheric pressure, a promising solution to the difficulty. Based on the principle of gas discharge, the ion source features a simple two-electrode structure with a two-stage electrode spacing, operating under DC voltage excitation. The first-stage electrode spacing of the ion source is small enough to ensure that it starts working at atmospheric pressure down to a certain reduced pressure when it automatically switches to discharge at the larger second-stage electrode spacing and operates from that pressure down to a high vacuum. Two configurations of the ion source have been tested: without-magnet, operating from atmospheric pressure down to 1 mbar; and with-magnet, operating from atmospheric pressure to 10-4 mbar, which covers seven orders of magnitude of pressure. The ion source can be applied not only to a MEMS ion pump to meet demands of a variety of vacuum MEMS devices, but can also be applied to other devices, such as vacuum microgauges and mass spectrometers.

13.
Nucl Instrum Methods Phys Res B ; 438: 166-171, 2019 Jan 01.
Artículo en Inglés | MEDLINE | ID: mdl-30686849

RESUMEN

We report on the first several years of operation of our recently installed 250 kV SSAMS at LLNL, purchased to replace our 1-MV AMS system for the measurement of 14C from labeled biochemical samples. We have modified the ion source region to improve ion output. Additionally, the SSAMS required significant software modifications to the data acquisition system in order to accurately measure 14C at the high-count rates typically encountered with labeled biochemical samples. We found that the data can be corrected assuming a nonparalyzable dead time response with a single event dead time of 6 µs. Since operation began, we have measured over 13,000 graphitic unknowns and over 1900 standards with an overall precision of 1.0%. We have optimized our system for the analysis of CO2 gas samples. We compared aliquots of identical samples measured as solid graphite and as liquid drops. Excellent agreement was found between the two, although the average precision of the graphite targets was an order of magnitude better than the liquid drop analysis due to the much larger number of 14C atoms available for measurement.

14.
Mass Spectrom Rev ; 36(1): 86-109, 2017 01.
Artículo en Inglés | MEDLINE | ID: mdl-27859457

RESUMEN

The intention of this tutorial is to introduce into the basic concepts of time-of-flight mass spectrometry, beginning with the most simple single-stage ion source with linear field-free drift region and continuing with two-stage ion sources combined with field-free drift regions and ion reflectors-the so-called reflectrons. Basic formulas are presented and discussed with the focus on understanding the physical relations of geometric and electric parameters, initial distribution of ionic parameters, ion flight times, and ion flight time incertitude. This tutorial is aimed to help the applicant to identify sources of flight time broadening which limit good mass resolution and sources of ion losses which limit sensitivity; it is aimed to stimulate creativity for new experimental approaches by discussing a choice of instrumental options and to encourage those who toy with the idea to build an own time-of-flight mass spectrometer. Large parts of mathematics are shifted into a separate chapter in order not to overburden the text with too many mathematical deviations. Rather, thumb-rule formulas are supplied for first estimations of geometry and potentials when designing a home-built instrument, planning experiments, or searching for sources of flight time broadening. © 2016 Wiley Periodicals, Inc. Mass Spec Rev 36:86-109, 2017.

15.
Chromatographia ; 81(6): 901-910, 2018.
Artículo en Inglés | MEDLINE | ID: mdl-29887620

RESUMEN

Baby food has never been the object of biogenic amine profiling. The aim of this study was to develop a highly sensitive method for analysis of biogenic amines in ready-to-eat baby foods. The principle of the developed method involves high-performance liquid chromatography coupled to single-quadrupole mass spectrometry (HPLC-APCI-MS) of dansyl derivatives, presented also in comparison with common diode array and fluorescence detection systems. The confirmation of correct identification of derivatives was performed by in-source fragmentation of the product ion at 170 m/z, performed only in one MS analyzer. The method was used to identify the amine profile and quantify the putrescine, cadaverine, histamine, tyramine, spermidine, and spermine content in 68 ready-to-eat baby foods. The limits of detection and quantification were in the range of 0.07-1.67 and 0.2-5.0 ng mL- 1. The method enabled quantification of amines at ng/g level in almost all analyzed samples, without any preconcentration step. Amine recoveries of 86.0-105.2% were obtained with RSD ≤ 9.7%. The developed method could be used for quantification of the most frequently occurring BAs in foods including vegetables, fish, meat, or fruit at previously undetectable concentration levels, making the method multimatrix applicable and highly-sensitive.

16.
Sensors (Basel) ; 17(1)2017 Jan 04.
Artículo en Inglés | MEDLINE | ID: mdl-28054980

RESUMEN

The injection and ionization of volatile organic compounds (VOA) by an integrated chip is experimentally analyzed in this paper. The integrated chip consists of a needle-to-cylinder electrode mounting on the Polymethyl Methacrylate (PMMA) substrate. The needle-to-cylinder electrode is designed and fabricated by Lithographie, Galvanoformung and Abformung (LIGA) technology. In this paper, the needle is connected to a negative power supply of -5 kV and used as the cathode; the cylinder electrodes are composed of two arrays of cylinders and serve as the anode. The ionic wind is produced based on corona and glow discharges of needle-to-cylinder electrodes. The experimental setup is designed to observe the properties of the needle-to-cylinder discharge and prove its functions as an ion source and air pump. In summary, the main results are as follows: (1) the ionic wind velocity produced by the chip is about 0.79 m/s at an applied voltage of -3300 V; (2) acetic acid and ammonia water can be injected through the chip, which is proved by pH test paper; and (3) the current measured by a Faraday cup is about 10 pA for acetic acid and ammonia with an applied voltage of -3185 V. The integrated chip is promising for portable analytical instruments, such as ion mobility spectrometry (IMS), field asymmetric ion mobility spectrometry (FAIMS), and mass spectrometry (MS).

17.
Sci Total Environ ; 935: 173401, 2024 Jul 20.
Artículo en Inglés | MEDLINE | ID: mdl-38782269

RESUMEN

Knowing the sources of precipitation chemical composition is essential to understand the biogeochemical cycle and control air pollution. Despite this issue has been directly investigated with precipitation ion contents, the effects of water vapor transport have not been fully considered. Taking the Loess Plateau of China (LPC) as an example study area, this study established nine precipitation monitoring sites considering the variability in topography and rainfall amounts, and collected 435 precipitation samples during 2020-2022 to measure the chemical composition. The correlation analysis, positive matrix factorization model and backward trajectory model were combined to analyze the characteristics, sources and vapor transport effects of precipitation chemical composition. Seasonally, except for NH4+, the concentration of other ions in the dry season was significantly higher than that in the rainy season. Spatially, the concentrations of Ca2+, Na+, K+, SO42- and NO3- peaked in the Mu Us Sandy Land and industrial areas, while the high level of NH4+ was concentrated in the agricultural areas. The source apportionment found that the primary source of precipitation ions was crust (33 %), followed by coal combustion/vehicle (30 %), aged sea salt (21 %) and agriculture (16 %). The trajectory analysis showed that water vapor paths significantly varied with the seasons, but were primarily dominated by the northwestern air mass with proportions of >40 %. The dust aerosols transported by the northwestern air mass were the main contributor to crust-source precipitation ions. The eastern and southeastern air masses transported anthropogenic pollutants to the LPC, and the southeastern air mass also carried sea-salt precipitation ions. This study provides a framework to incorporate hydrochemical method with vapor source identification method for precipitation chemical source identification, and the results can be a theoretical basis for the treatment of atmospheric environmental problems.

18.
Appl Radiat Isot ; 211: 111382, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-38843622

RESUMEN

Beryllium-7 (7Be) was created by proton irradiation of natural (natB) and enriched (10B) boron targets. The targets were dissolved in nitric acid, and the 7Be was separated from the bulk boron target material by cation-exchange chromatography. An average recovery of (99.4 ± 3.7)% was obtained for 6 separations. The purified 7Be sample was placed into a batch-mode ion source to create a 7Be beam that was delivered at an average rate of 5 × 105 pps to end users at the National Superconducting Cyclotron Laboratory.

19.
Artículo en Inglés | MEDLINE | ID: mdl-38513431

RESUMEN

Fat-soluble vitamin D is an essential bioactive compound important for human health. Insufficient vitamin D levels can result not only in bone disease but also in other disorders, such as cancer, metabolic disorders, and diseases related to poor immune function. The current methods commonly used for vitamin D analysis are often applied to determine the levels of the most abundant metabolite in plasma, i.e., 25-OH-D2/D3. These methods do not consider the presence of other hydroxylated and esterified metabolites, including isomers and epimers, which are typically found in low concentrations. In this study, we developed a fast and selective ultra-high performance supercritical fluid chromatography (UHPSFC) method using a 150 mm long 1-amino anthracene (1-AA) column and a mobile phase consisting of carbon dioxide and methanol/isopropanol (1/1, v/v) mixed with 8 % water. After thorough optimization of column temperature and back pressure, the separation of four vitamin D3 esters, vitamin D3 and D2, and eight mono- and di-hydroxylated metabolites, including three groups of isomers, was achieved in 10 min. Two ion sources, atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization optimized within this study, were compared in tandem mass spectrometry (MS/MS) detection. No significant sensitivity differences were observed. Subsequently, the same 1-AA column chemistry was examined in ultra-high performance liquid chromatography (UHPLC) as the stationary phase that could hypothetically bring different selectivity in the separation of vitamin D and its metabolites. However, this hypothesis was rejected, and C18 was used as a stationary phase in the final optimized UHPLC-MS/MS method. Despite detailed optimization, the final 15 min UHPLC method was not able to separate di-hydroxylated isomers of vitamin D3, while it enabled better resolution of esterified forms compared to UHPSFC. Optimized methods provided similar repeatability of retention times and peak areas, with RSD < 2 % and 10 %, respectively. The lowest limits of quantification were in the range of 1.2 - 4.9 ng/mL for UHPSFC-APCI-MS/MS, while for UHPLC-APCI-MS/MS, they were typically in the range of 2.6 - 9.6 ng/mL. Based on the obtained results, the UHPSFC-APCI-MS/MS method was the most promising approach for fast, selective, and sensitive analysis that could be applied in the analysis of biological samples with emphasis on the separation of both hydroxylated and esterified metabolites, including isomeric forms.


Asunto(s)
Cromatografía con Fluido Supercrítico , Vitamina D , Humanos , Espectrometría de Masas en Tándem/métodos , Cromatografía Líquida de Alta Presión/métodos , Cromatografía con Fluido Supercrítico/métodos , Vitaminas , Colecalciferol
20.
Eur J Mass Spectrom (Chichester) ; 30(2): 103-115, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38489825

RESUMEN

Atmospheric pressure field desorption (APFD) mass spectrometry (MS) has recently been introduced as a new variant of field desorption (FD) mass spectrometry. The development aimed at providing the basic characteristics of FD-MS in combination with instruments equipped with an atmospheric pressure (AP) interface. Hitherto, APFD has been demonstrated to yield both positive and negative even electron ions of highly polar or ionic compounds as well as to enable the generation of positive molecular ions, M+•, of polycyclic aromatic compounds. The prototype setup for APFD was based on a nano-electrospray ionization (nanoESI) source slightly modified to allow for emitter positioning in front of the AP interface of a Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer. The entrance electrode of the interface was set to negative or positive high voltage with respect to the emitter at ground potential, thereby permitting the formation of positive or negative ions, respectively. This work describes a custom-built device for quicker and more reproducible sample loading on and positioning of field emitters at the entrance electrode of the atmospheric pressure interface of a mass spectrometer. In addition, the device provides means for observation of the emitter during operation and for resistive emitter heating as employed in traditional FD-MS. Emitter heating both speeds up the desorption of the analytes and allows for the desorption/ionization of analytes of higher molecular weight than without emitter heating. In some cases, the signal-to-noise ratio of APFD mass spectra is improved due to higher ion currents effected by compressing the entire process into shorter periods of spectral acquisition. The new setup enables robust and reliable operation in APFD-MS. Moreover, it has been designed as to allow for use on a range of instruments as it can either be used on an FT-ICR mass spectrometer or in combination with a trapped ion mobility-quadrupole-time-of-flight (TIMS-Q-TOF) instrument.

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