Novel approach to constructing laser ionization elemental time-of-flight mass spectrometer.

The main advantages of laser sampling are associated with following features: sample preparations as well as consumables are not needed, low risk of sample contamination, good spatial resolution. In mass spectrometry, high laser irradiance can be used for both ablation and ionization processes. The method is especially profitable in time-of-flight mass spectrometry. A new principle of constructing laser ionization time-of-flight mass spectrometer based on wedge-shaped ion mirrors and the absence of electrostatic ion acceleration before mass analysis is discussed. Among advantages of the analyzer there are ability to provide temporal focusing of ions in a wide energy range (±20%), compactness of the analyzer, and minimization of the requirements for power supplies. The approach is expected to be profitable for standardless elemental analysis of solid samples, which should be possible at laser irradiation power density more than 3 × 109 W/cm2 that ensures complete ionization of all elements in a laser plasma. The analytical signal of each element is formed as the sum of the signals for all charge states and the energy scan of the mass spectra is provided.

A new approach to improving the accuracy of elemental analysis in laser mass spectrometry.

It is shown that the main reason affecting the accuracy and reproducibility of the elemental analysis of solids with a laser source of ions is the difference in the ionization cross sections of different elements in the generation of laser plasma. Computer modeling was carried out for the evaporation of the sample and generation of laser plasma at different values of laser power density. The aim of modelling was to determine the cause of the low accuracy of analysis by direct selection of ions from the plasma. The researches have shown that we cannot get satisfactory accuracy of analysis using analytical signal formed only on the base of single-charged ions. At the same time, in the formation of an analytical signal, as a sum of the intensities of the mass peaks of all charges of each element, the accuracy of the analysis does not depend either on the ionization cross section or on the nonreproducibility of the laser radiation power. It is shown that this approach completely eliminates the "matrix effect."

A computer model of comprehensive modeling of the laser time-of-flight analyzer.

This article offers a new approach to computer modeling of time-of-flight analyzers of mass spectrometers. The main feature of the model is comprehensive tracking of the processes from the laser plasma generation until the final stage, on which the isotopic or elemental composition is determined for the analyzed solid sample. Apart from usual models based on SIMION-8 3D or similar software, this article proposes fundamentally new modeling stages. These stages are (1) generation and spread of laser plasma, (2) formation of the ion packages, (3) ion detection, and (4) formation and processing of the analytical signals. In order to provide consistent modeling of all the stages, special software units were developed. Program control of the analyzer ion optics (electrodes voltages) allows scan of mass spectra by ion energy. Additional complex of the programs provides simulation of mass spectra digitization, summation of digitized mass spectra for a wide range of variable parameters, and consideration of the discriminatory effects. According to the data, the software calculates ion-optical characteristics of the analyzer and the analytical parameters of measurement results.

Rapid identification of triphenylmethane dyes by ion mobility time-of-flight mass spectrometry.

An ion mobility time-of-flight mass spectrometry (IM-TOFMS)-based method has been preliminarily investigated for the identification of triphenylmethane ballpoint pen dyes on paper. The dyes were sampled from one-year-old ballpoint pen ink entries. The entries were written on paper documents stored in the dark in a bookcase. Sample solutions were prepared by extraction of dyes in a vial. Basic violet 2, Methyl violet 6B, Methyl violet 2B and Crystal violet were characterized by IM-TOFMS. Since the ballpoint ink dyes contain ionic compounds, the studied compounds were expected to form stable peaks in the atmospheric pressure drift tube ion mobility spectrometry, and this was experimentally verified. The studied dyes produce [M - Cl]+ ions in electrospray and form stable individual mass-selective reduced mobility peaks. The values of the characteristic reduced mobility are: 1.187 cm2/(V·s) for Basic violet 2 (m/z 330.20), 1.165 cm2/(V·s) for Methyl violet 6B (m/z 344.21), 1.156 cm2/(V·s) for Methyl violet 2B (m/z 358.23), 1.123 cm2/(V·s) for Crystal violet (m/z 372.24). IM-TOFMS is expected to be a promising tool for fast and reliable analysis of dyes in complex matrixes.

Letter: A method for the chromatic aberration correction of a laser time of-flight mass analyzer.

The new ion-optical system of the laser time-of-flight (TOF) mass spectrometer on the basis of two tandem wedge-shape reflectors has been offered and implemented. A new method of correcting chromatic aberration by the ion energy was proposed that used a wire electrode unit with adjustable potentials. This unit allows one to adjust the local TOF of the ions in a narrow energy range ± (1-2)% within the total ion packet with an energy spread of ± 20%. The method reduces the duration of the ion packets by up to 1.5ns, which enables us to obtain the restriction of resolution at a level not worse than R ~ 10500 for a TOF ~35 µs. The aim of the project is to increase the separation of isobaric ions to improve the limit of detection of the laser TOF-MS for the analysis of high-purity samples.

Letter: Compact analyzer for a laser time-of-flight mass spectrometer.

Aspects of a new type of laser time-of-flight mass spectrometer are described in this letter. It is based on a wedge-shaped reflecting mirror and is used as an ion analyzer. The analyzer provides time focusing by both energy and a divergence angle of ions. Time focusing of good quality is acquired in the energy range of ±20% of the average ion energy, which is, at least, two times wider than the energy range of the known ion optical systems for similar applications. The mass resolution of the analyzer is ~600, while overall dimensions are very small (10 × 10 × 5 cm).

Analysis of new synthetic drugs by ion mobility time-of-flight mass spectrometry.

Characteristic ion mobility mass spectrometry data, reduced mobility, and limits of detection (signal-to-noise ratio = 3) were determined for six synthetic drugs and cocaine by ion mobility time-of-flight mass spectrometry (IM-TOF-MS) with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). The studied synthetic illicit drugs recently appeared on the recreational drug market as designer drugs and were methylone, 4-MEC (4'-methylethcathinone), 3,4-MDPV (3,4-methylenedioxypyrovalerone), JWH-210 [4-ethylnaphthalen-1-yl-(1-pentylindol-3-yl)methanone], JWH-250 [2-(2-methoxyphenyl)-1-(1-pentyl-1H-indol-3-yl)ethanone], and JWH-203 [1-pentyl-3-(2'-chlorophenylacetyl) indole]. Absolute reduced mobilities in nitrogen were 1.35, 1.28, 1.41, 1.30, 1.18, 0.98, 1.09, and 1.07 cm2V(-1)s(-1), for methylone [M-H]+, methylone [M+H]+, 4-MEC [M-H]+, 4-MEC [M+H]+, 3,4-MDPV [M+H]+, JWH-210 [M+H]+, JWH-250 [M+H]+, and JWH-203 [M+H]+, respectively. Selected illicit drugs are easily identified by IM-TOF-MS during a 100s analysis. Relative Limits of detection ranged from 4 to 400 nM are demonstrated for these compounds. Such relative limits of detection correspond to 14 pg to 2 ng absolute limits of detection. Better detection limits are obtained in APCI mode for all the illicit drugs except cocaine. ESI mode was found to be preferable for the IM-TOF-MS detection of cocaine at trace levels. A single sample analysis is completed in an order of magnitude less time than that for conventional liquid chromatography/mass spectrometry approach. The application allows one to consider IM-TOF-MS as a good candidate for a method to determine quickly the recently surfaced designer drugs marketed on the internet as "bath salts," "spice," and "herbal blends".

Development of an atmospheric pressure ion mobility spectrometer-mass spectrometer with an orthogonal acceleration electrostatic sector TOF mass analyzer.

Recently developed ion mobility mass spectrometer is described. The instrument is based on a drift tube ion mobility spectrometer and an orthogonal acceleration electrostatic sector time-of-flight mass analyzer. Data collection is performed using a specially developed fast ADC-based recorder that allows real-time data integration in an interval between 3 and 100 s. Primary tests were done with positive ion electrospray. The tests have shown obtaining 100 ion mobility resolving power and 2000 mass resolving power. Obtained for 2,6-di-tert-butylpyridine in electrosprayed liquid samples during 100 s analysis and full IMS/MS data collection mode were 4 nM relative limits of detection and a 1 pg absolute limit of detection (S/N=3). Characteristic ion mobility/mass distributions were recorded for selected antibiotics, including amoxicillin, ampicillin, lomefloxacin, and ofloxacin. At studied conditions, lomefloxacin forms only a protonated molecule-producing reduced ion mobility peak at 1.082 cm(2)/(V s). Both amoxicillin and ampicillin produce [M + H](+), [M + CH3OH + H](+), and [M + CH3CN + H](+). Amoxicillin shows two peaks at 0.909 cm(2)/(V s) and 0.905 cm(2)/(V s). Ampicillin shows one peak at 0.945 cm(2)/(V s). Intensity of protonated methanol containing cluster for both ampicillin and amoxicillin has a clear tendency to rise with sample keeping time. Ofloxacin produces two peaks in the ion mobility distribution. A lower ion mobility peak at 1.051 cm(2)/(V s) is shown to be formed by [M + H](+) ions. A higher ion mobility peak appearing for samples kept more than 48 h is shown to be formed by both [M + H](+) ion and a component identified as the [M + 2H + M](+2) cluster. The cluster probably partly dissociates in the interface producing the [M + H](+) ion.

Review: mass spectrometry in Russia.

The present review covers the main research in the area of mass spectrometry from the 1990s which was about the same time as the Russian Federation emerged from the collapse of the Soviet Union (USSR). It consists of two main parts-application of mass spectrometry to chemistry and related fields and creation and development of mass spectrometric technique. Both traditional and comparatively new mass spectrometric methods were used to solve various problems in organic chemistry (reactivity of gas-phase ions, structure elucidation and problems of identification, quantitative and trace analysis, differentiation of stereoisomers, derivatization approaches etc.), biochemistry (proteomics and peptidomics, lipidomics), medical chemistry (mainly the search of biomarkers, pharmacology, doping control), environmental, petrochemistry, polymer chemistry, inorganic and physical chemistry, determination of natural isotope ratio etc. Although a lot of talented mass spectrometrists left Russia and moved abroad after the collapse of the Soviet Union, the vitality of the mass spectral community proved to be rather high, which allowed the continuation of new developments in the field of mass spectrometric instrumentation. They are devoted to improvements in traditional magnetic sector mass spectrometers and the development of new ion source types, to analysis and modification of quadrupole, time-of-flight (ToF) and ion cyclotron resonance (ICR) analyzers. The most important achievements are due to the creation of multi-reflecting ToF mass analyzers. Special attention was paid to the construction of compact mass spectrometers, particularly for space exploration, of combined instruments, such as ion mobility spectrometer/mass spectrometer and accelerating mass spectrometers. The comparatively young Russian Mass Spectrometry Society is working hard to consolidate the mass spectrometrists from Russia and foreign countries, to train young professionals on new appliances and regularly holds conferences on mass spectrometry. For ten years, a special journal Mass-spektrometria has published papers on all disciplines of mass spectrometry.