Ion Source For Mass Spectrometry Research Articles

Determination of drugs and drug-like compounds in different samples with direct analysis in real time mass spectrometry.

Direct analysis in real time (DART), a relatively new ionization source for mass spectrometry, ionizes small-molecule components from different kinds of samples without any sample preparation and chromatographic separation. The current paper reviews the published data available on the determination of drugs and drug-like compounds in different matrices with DART-MS, including identification and quantitation issues. Parameters that affect ionization efficiency and mass spectra composition are also discussed.

Dielectric barrier discharges in analytical chemistry

The present review reflects the importance of dielectric barrier discharges in analytical chemistry. Special about this discharge is-and in contrast to usual discharges with direct current-that the plasma is separated from one or two electrodes by a dielectric barrier. This gives rise to two main features of the dielectric barrier discharges; it can serve as dissociation and excitation device and as ionization mechanism, respectively. The article portrays the various application fields for dielectric barrier discharges in analytical chemistry, for example the use for elemental detection with optical spectrometry or as ionization source for mass spectrometry. Besides the introduction of different kinds of dielectric barrier discharges used for analytical chemistry from the literature, a clear and concise classification of dielectric barrier discharges into capacitively coupled discharges is provided followed by an overview about the characteristics of a dielectric barrier discharge concerning discharge properties and the ignition mechanism.

Desorption Corona Beam Ionization Coupled with a Poly(dimethylsiloxane) Substrate: Broadening the Application of Ambient Ionization for Water Samples

Current direct analysis methods in mass spectrometry (MS) are predominantly focused on desorbing and ionizing samples in the solid phase. Some sampling difficulties are associated with liquid (solution) or gas samples. The present study has expanded direct MS analysis to solution samples by using the desorption corona beam ionization (DCBI) technique in combination with poly(dimethylsiloxane) (PDMS) substrate sampling. Typically, the PDMS substrate is dipped in water for microextraction of pesticide compounds and then is transferred to an MS ion source for desorption and ionization. This approach improves the detection limit for DCBI and allows more organic compounds in complex mixtures to be identified within seconds. The practical application of this device is demonstrated by identifying five pesticides (acephate, isoprocarb, dimethoate, dichlorvos, and dicofol) in water. The obtained detection limits of pesticides are 1 μg/L, the measured dynamic ranges are 3 orders of magnitude, the calculated correlation coefficients are between 0.939 and 0.979 at concentration levels of 5-5000 μg/L, and the repeatabilities defined as a relative standard deviation of five successive injections are in the range of 13-17%. The results indicate that the DCBI technique coupled with PDMS sampling is an excellent method for the analysis of organic pesticides in solution, and it also opens up a new avenue for direct MS studies of solution samples with general importance.

New Ionization Source for Mass Spectrometry

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The emerging role of ICP-MS in proteomic analysis

Quantitative proteomics and absolute determination of proteins are topics of fast growing interest, since only the quantity of proteins or changes in their abundance reflect the status and extent of changes of a given biological system. Quantification of the desired proteins has been carried out by molecule specific MS techniques, but relative quantifications are commonplace so far even resorting to stable isotope labelling techniques such as ICAT and SILAC. In the last decade the idea of using element-selective mass spectrometric detection (e.g. ICP-MS instruments) to achieve absolute quantification has been realised and ICP-MS stands now as a new tool in the field of quantitative proteomics. In this review the emerging role of ICP-MS in protein and proteomic analysis is highlighted. The potential of ICP-MS methods and strategies for screening multiple heteroatoms (e.g. S, P, Se, metals) in proteins and their mixtures and extraordinary capabilities to tackle the problem of absolute protein quantifications, via heteroatom determinations, are discussed and illustrated. New avenues are also open derived from the use of ICP-MS for precise isotope abundance measurements in polyisotopic heteroatoms. The "heteroatom (isotope)-tagged proteomics" concept is focused on the use of naturally present element tags and also extended to any protein by resorting to bioconjugation reactions (i.e. labelling sought proteins and peptides with ICP-MS detectable heteroatoms). A major point of this review is displaying the possibilities of using a "hard" ion source, the ICP, to complement well-established "soft" ion sources for mass spectrometry to tackle present proteomic analysis.

Characterization of Charge Separation in the Array of Micromachined UltraSonic Electrospray (AMUSE) Ion Source for Mass Spectrometry

An initial investigation into the effects of charge separation in the Array of Micromachined UltraSonic Electrospray (AMUSE) ion source is reported to gain understanding of ionization mechanisms and to improve analyte ionization efficiency and operation stability. In RF-only mode, AMUSE ejects, on average, an equal number of slightly positive and slightly negative charged droplets due to random charge fluctuations, providing inefficient analyte ionization. Charge separation at the nozzle orifice is achieved by the application of an external electric field. By bringing the counter electrode close to the nozzle array, strong electric fields can be applied at relatively low DC potentials. It has been demonstrated, through a number of electrode/electrical potential configurations, that increasing charge separation leads to improvement in signal abundance, signal-to-noise ratio, and signal stability.

Analytical performance of a venturi-assisted array of micromachined ultrasonic electrosprays coupled to ion trap mass spectrometry for the analysis of peptides and proteins.

The analytical characterization of a novel ion source for mass spectrometry named array of micromachined ultrasonic electrosprays (AMUSE) is presented here. This is a fundamentally different type of ion generation device, consisting of three major components: (1) a piezoelectric transducer that creates ultrasonic waves at one of the resonant frequencies of the sample-filled device, (2) an array of pyramidally shaped nozzles micromachined on a silicon wafer, and (3) a spacer which prevents contact between the array and transducer ensuring the transfer of acoustic energy to the sample. A high-pressure gradient generated at the apexes of the nozzle pyramids forces the periodic ejection of multiple droplet streams from the device. With this device, the processes of droplet formation and droplet charging are separated; hence, the limitations of conventional electrospray-type ion sources, including the need for high charging potentials and the addition of organic solvent to decrease surface tension, can be avoided. In this work, a Venturi device is coupled with AMUSE in order to increase desolvation, droplet focusing, and signal stability. Results show that ionization of model peptides and small tuning molecules is possible with dc charging potentials of 100 Vdc or less. Ionization in rf-only mode (without dc biasing) was also possible. It was observed that, when combined with AMUSE, the Venturi device provides a 10-fold gain in signal-to-noise ratio for 90% aqueous sample solutions. Further reduction in the diameter of the orifices of the micromachined arrays led to an additional signal gain of at least 3 orders of magnitude, a 2-10-fold gain in the signal-to-noise ratio and an improvement in signal stability from 47% to 8.5% RSD. The effectiveness of this device for the soft ionization of model proteins in aqueous media, such as cytochrome c, was also examined, yielding spectra with an average charge state of 8.8 when analyzed with a 100 Vdc charging potential. Ionization of model proteins was also possible in rf-only mode.

Laser Ablation Electrospray Ionization for Atmospheric Pressure, in Vivo, and Imaging Mass Spectrometry

Mass spectrometric analysis of biomolecules under ambient conditions promises to enable the in vivo investigation of diverse biochemical changes in organisms with high specificity. Here we report on a novel combination of infrared laser ablation with electrospray ionization (LAESI) as an ambient ion source for mass spectrometry. As a result of the interactions between the ablation plume and the spray, LAESI accomplishes electrospray-like ionization. Without any sample preparation or pretreatment, this technique was capable of detecting a variety of molecular classes and size ranges (up to 66 kDa) with a detection limit of 8 and 25 fmol for verapamil and reserpine, respectively, and quantitation capabilities with a four-decade dynamic range. We demonstrated the utility of LAESI in a broad variety of applications ranging from plant biology to clinical analysis. Proteins, lipids, and metabolites were identified, and antihistamine excretion was followed via the direct analysis of bodily fluids (urine, blood, and serum). We also performed in vivo spatial profiling (on leaf, stem, and root) of metabolites in a French marigold (Tagetes patula) seedling.

Microplasma-based atomic emission detectors for gas chromatography

This paper is an update on the development of microplasmas as detectors for gas chromatography. Direct current (dc), alternating current (ac), and radio frequency (rf) microplasmas developed in recent years will be described with their significant analytical results, which mostly concern the detection of halogens and sulfur. New results will be added which employ a microhollow cathode discharge (MHCD) as excitation source. Emphasis will be given to this microplasma which has already been implemented as an element-selective detector for emission spectrometry and as ionization source for mass spectrometry. The possibility to use it as a multielement-selective detector for gas chromatography will be presented. A discussion of the published detection limits of all these microplasmas is given.

Microchip Sonic Spray Ionization

The first microchip version of sonic spray ionization (SSI) as an atmospheric pressure ionization source for mass spectrometry (MS) is presented. The microchip used for SSI has recently been developed in our laboratory, and it has been used before as an atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) source. Now the ionization is achieved simply by applying high (sonic) speed nebulizer gas, without heat, corona discharge, or high voltage. The microchip SSI was applied to the analysis of tetra-N-butylammonium, verapamil, testosterone, angiotensin I, and ibuprofen. The limits of detection were in the range of 15 nM to 4 microM. The technique was found to be highly dependent on the position of the chip toward the mass spectrometer inlet, and on the gas and the sample solution flow rates. The microchip SSI provided dynamic linearity following a pattern similar to that used with electrospray, good quantitative repeatability (RSD=16%), and long-term signal stability.

Characterization and application of isotope-substituted (13C15)-deoxynivalenol (DON) as an internal standard for the determination of DON

The powerful combination of liquid chromatography and mass spectrometry (MS) is often limited by matrix effects during ionization in the MS ion source. The use of fully isotope-substituted (13C15)-deoxynivalenol ((13C15)-DON) as an internal standard (IS) corrects matrix effects and improves the accuracy of analytical methods using mass spectrometry for the quantitative determination of the Fusarium mycotoxin deoxynivalenol (DON). The IS was characterized with respect to its chromatographic purity by liquid chromatography-ultraviolet light and its isotope distribution by time-of-flight mass spectrometry. Its low-energy collision-induced dissociation behaviour was compared with DON. Moreover, this work describes the successful application of (13C15)-DON as IS for the determination of DON in maize using high-performance liquid chromatography (HPLC) electrospray (ESI) with tandem mass spectrometry. The results demonstrate that the IS can successfully correct for fluctuations during extraction and clean-up of the sample as well as the ionization of DON in the MS ion source. Random variations in ionization affect the IS in the same way as the analyte. Recoveries for DON in maize of 76% ± 1.9% (external calibration) or 101% ± 2.4% (internal calibration) were reached, respectively, after sample clean-up.

On-line monitoring of pine needles combustion emissions in the presence of fire retardant using a “thermogravimetry (TG)-bridge/mass spectrometry method”

In this work a new method called TG-bridge/mass spectrometry is presented, for the on-line monitoring of the pine needles combustion emissions in a common lab furnace. The TG-bridge (thermogravimetry-bridge) system has been developed in-house as a TG–MS (thermogravimetry–mass spectrometry) interface, for TG–MS analysis. In this work, TG-bridge was used for directly sampling of the combustion emissions from the inside of the furnace and transferring them into the mass spectrometer (MS), without disturbing the sub-pressure conditions inside the MS ion source. The effect of Fire-Trol 931 (a long-term fire retardant) on the emissions, produced during the combustion of pine needles, is tested in the lab for future application in the field. It was shown that in treated samples, increased evolution of ammonia and aromatic compounds took place, compared to untreated samples. Maximum concentrations of specific compounds, such as benzene and toluene, evolved during the combustion experiments in the furnace, were determined.

Acaricidal activity against Panonychus citri of a ginkgolic acid from the external seed coat of Ginkgo biloba

An acaricidal substance extracted from the external seed coat of Ginkgo biloba L. was identified by UV (ultraviolet), IR (infrared), EI-MS (electron impact ion source mass spectrometry), (1)H NMR (nuclear magnetic resonance) and (13)C NMR as 6-[(Z)-10-heptadecenyl]-2-hydroxybenzoic acid (compound 1). Laboratory bioassay on citrus red mite, Panonychus citri (Mcg), showed that compound 1 possessed the following properties. (i) Powerful contact toxicity with an LC(50) of 5.2 mg litre(-1) after 24 h that was similar to that of pyridaben (LC(50) = 3.4 mg litre(-1)) and significantly superior to that of omethoate (LC(50) = 122 mg litre(-1)). Furthermore, its LC(90) was 13.4 mg litre(-1) after 24 h, which is significantly superior to both pyridaben (LC(90) = 69.6 mg litre(-1)) and omethoate (LC(90) = 453 mg litre(-1)). (ii) Quick-acting acaricidal activity. At identical concentrations, compound 1 was much faster-acting than pyridaben or omethoate. (iii) Compound 1 had strong corrosive action on the cuticle of P. citri but no phytotoxicity to plants.

State-of-the-art of the hyphenation of capillary electrochromatography with mass spectrometry.

The high separation efficiency and loading capacity of capillary electrochromatography (CEC) make it an attractive separation mode for coupling with mass spectrometry (MS), which has the ability to unambiguously identify analytes with high selectivity and sensitivity. We present an overview of recent advances on both instrumentation and separation columns employed in CEC-MS systems. In particular, the main characteristics of the stationary phases, as well as the configurations of the column outlet that are related with the coupling arrangements of the MS ionization sources, are reported. At present, packed columns and conventional electrospray ionization (ESI) sources are mainly employed in CEC-MS. Nevertheless, the use of monolithic capillary columns and nanoelectrospray sources has the potential for wide acceptance in the next future. Moreover, the main features of several mass analyzers including ion trap, quadrupole, time-of-flight, magnetic sector, and Fourier transform-ion cyclotron resonance are examined. Finally, current applications of this technology, mainly in the pharmaceutical field and proteomics, are reviewed.

Blackbody infrared radiative dissociation at low temperature: hydration of X 2+(H 2O) n, for X = Mg, Ca

A new apparatus for making blackbody infrared radiative dissociation (BIRD) measurements at below ambient temperature is described, and its use for measuring threshold dissociation energies of weakly bound clusters is demonstrated. Hydration energies are determined for alkaline-earth metal water clusters, X 2+(H 2O) n , X=Mg, Ca and n=8–10. For n=8 and 9, the energies obtained from BIRD measurements are in excellent agreement with values reported previously, but for n=10, the energies are slightly lower than those determined previously using the high-pressure ion source mass spectrometry (HPMS) equilibrium method.

Microplasma jet mass spectrometry of halogenated organic compounds

The microhollow cathode discharge is investigated as a promising miniaturized ionization source for mass spectrometry. The plasma operated at atmospheric pressure generates power densities of about 1 MW cm−3 at a small input power of 1 W. It has the advantage of focused sample introduction in the plasma core, exhibits good analytical reproducibility and a long lifetime. The microhollow cathode discharge-mass spectrometry delivers detection limits in the pg s−1 range (corresponding to a few ppbv/v) for halogenated molecules in gaseous or volatile samples.

An overview of some recent developments in ionization methods for mass spectrometry.

An overview of some recent advances in ionization sources for mass spectrometry is presented. Limitations were set so that the overview covers ionization techniques relevant to organic and biological analysis that have appeared in the literature since the year 2000. No effort is made to be comprehensive. Rather, a broad sweep overview of author-subjective highlights among a wide variety of sources is presented. These ionization sources include electron ionization, chemical ionization, various atmospheric plasma ionization sources, laser desorption sources, sonic spray and electrospray ionization sources.

Formation of polyatomic ions from the skimmer cone in the inductively coupled plasma mass spectrometry

The inductively-coupled plasma ion source for mass spectrometry is very sensitive for multielement analysis with detection limits down to sub part per trillion (ppt). Polyatomic ions which could be formed in the mass spectra may interfere in the analysis of some elements. Experimental conditions have great influences on the formation of polyatomic ions. The present work demonstrates that the skimmer materials (Au, Ag, Ni, Cu and Al) are participating in the formation of polyatomic ions. Heats of formation of polyatomic species formed from the skimmer materials such as: AuX, AgX, NiX, CuX and AlX, where X=Ar, O, N and H, are calculated by Gaussian program (G94W).

The Matrix Effect of Biological Concomitant Element on the Signal Intensity of Ge, As, And Se in Inductively Coupled Plasma/Mass Spectrometry

Research Institute for Basic Sciences and Department of Chemistry, Kyunghee University, Seoul 130-701, KoreaReceived April 4, 2002The non-spectroscopic interference effects that occurred in inductively coupled plasma/mass spectrometrywere studied for Ge, As and Se in human urine and serum. Many biological samples contain Na, K, Cl andorganic compounds, which may cause the enhancement and depression on the analyte signal. The effect of 1%concomitant elements such as N, Cl, S, P, C, Na, and K on a 100 µg/L germanium, arsenic and selenium signalhas been investigated by ICP/MS. The interference effects were not in the same direction. It appeared thatconcomitant elements such as Cl, S, and C induce an enhancement effect, whereas N and P did not show anysignificant effect. And, Na and K caused a depression. We have found a link between the abundance of analytesand the ionization potential of concomitant elements (eV), except carbon and nitrogen. Key Words : Matrix effect, Serum, Urine, ICP/MSIntroductionInductively coupled plasma (ICP) as an ionization sourcefor mass spectrometry (MS) has gained general acceptanceas a method to analyze the inorganic elements. The advant-ages of ICP/MS are well known: low limits of detection andsimultaneous multi-element determination with the possibi-lity of measuring isotopic abundance. The main limitationsare the observation of isobaric interferences, mostly due tothe formation of molecular compounds, in particular, oxidesand non-spectroscopic interferences (matrix effect).

A cylindrical capacitor ionization source: droplet generation and controlled charge reduction for mass spectrometry.

A cylindrical capacitor ionization source was used in conjunction with corona discharge charge reduction for generation of singly charged ions for mass spectrometric analysis. The source consists of a fused-silica capillary threaded with a platinum wire and placed inside a stainless steel tube. Application of an electric potential to the wire results in the production of a linear stream of charged droplets when an aqueous solution is pumped through the capillary. Subsequent solvent evaporation yields ions, providing a continuous ion source for mass spectrometry. Passage of the ions through a corona discharge charge reduction chamber permits reduction of the charge state to predominantly singly charged species, facilitating analysis of DNA and protein mixtures. The change from production of multiply charged ions to production of singly charged ions is extremely simple, requiring only modulation of the voltage applied to the corona discharge electrode. A simple technique for construction of the ionization source is reported.