D.M. Chernyshev

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.

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 cm2 V−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 100 s 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”.

Multisectional linear ion trap and novel loading method for optical spectroscopy of electron and nuclear transitions

There is a growing need for the development of atomic and nuclear frequency standards because of the important contribution of methods for precision time and frequency measurements to the development of fundamental science, technology and the economy. It is also conditioned by their potential use in optical clocks and quantum logic applications. It is especially important to develop a universal method that could allow one to use ions of most elements effectively (including ones that are not easily evaporated) proposed for the above-mentioned applications. A linear quadrupole ion trap for the optical spectroscopy of electron and nuclear transitions has been developed and evaluated experimentally. An ion source construction is based on an ultra-high vacuum evaporator in which a metal sample is subjected to an electron beam of energy up to 1 keV, resulting in the appearance of gaseous atoms and ions of various charge state. The linear ion trap consists of five successive quadrupole sections including an entrance quadrupole section, quadrupole mass filter, quadrupole ion guide, ion-trap section and exit quadrupole section. The same radiofrequency but a different direct current voltage feeds the quadrupole sections. The instrument allows the mass- and energy-selected trapping of ions from ion beams of various intensities and their localization in the area of laser irradiation. The preliminary results presented show that the proposed instrument and methods allow one to produce effectively up to triply charged thorium ions as well as to trap ions for future spectroscopic study. The instrument is proposed for future use in optical clocks and quantum logic application development.

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.