Luminescence Properties of ZrO2: Ti Ceramics Irradiated with Electrons and High-Energy Xe Ions.

Samples of ZrO2 ceramics with different concentrations of impurity titanium ions were synthesized by mixing zirconium and titanium oxide powders in different mass ratios. The X-ray diffraction analysis was used to determine the phase composition, lattice parameters, and crystallite size of the ceramics with varying dopant concentrations. Upon irradiation of the samples with 220 MeV Xe ions to a fluence of 1010 ions/cm2, a decrease in the intensity of the pulsed cathodoluminescence band at 2.5 eV was observed. Additionally, ion irradiation resulted in the emergence of a new thermoluminescence peak at 450-650 K attributed to radiation-induced traps of charge carriers. Further analysis revealed that the thermoluminescence curves of samples irradiated with electrons and ions comprise a superposition of several elementary peaks. Notably, a complex non-monotonic dependence of cathodo- and thermoluminescence intensity on titanium concentration was observed, suggesting the influence of concentration quenching and the presence of tunneling transitions.

Observation of the radiation environment and solar energetic particle events in Mars orbit in May 2018- June 2022.

The dosimeter Liulin-MO for measuring the radiation environment onboard the ExoMars Trace Gas Orbiter (TGO) is a module of the Fine Resolution Epithermal Neutron Detector (FREND). Here we present results from measurements of the charged particle fluxes, dose rates and estimation of dose equivalent rates at ExoMars TGO Mars science orbit, provided by Liulin-MO from May 2018 to June 2022. The period of measurements covers the declining and minimum phases of the solar activity in 24th solar cycle and the rising phase of the 25th cycle. Compared are the radiation values of the galactic cosmic rays (GCR) obtained during the different phases of the solar activity. The highest values of the dose rate and flux from GCR are registered from March to August 2020. At the minimum of 24th and transition to 25th solar cycle the dose rate from GCR is 15.9 ± 1.6 µGy h-1, particle flux is 3.3 ± 0.17 cm-2s-1, dose equivalent rate is 72.3 ± 14.4 µSv h-1. Since September 2020 the dose rate and flux of GCR decrease. Particular attention is drawn to the observation of the solar energetic particle (SEP) events in July, September and October 2021, February and March 2022 as well as their effects on the radiation environment on TGO during the corresponding periods. The SEP event during15-19 February 2022 is the most powerful event observed in our data. The SEP dose during this event is 13.8 ± 1.4 mGy (in Si), the SEP dose equivalent is 21.9 ± 4.4 mSv. SEP events recorded in Mars orbit are related to coronal mass ejections (CME) observed by SOHO and STEREO A coronagraphs. Compared are the time profiles of the count rates measured by Liulin-MO, the neutron detectors of FREND and neutron detectors of the High Energy Neutron Detector (HEND) aboard Mars Odyssey during 15-19 February 2022 event. The data obtained is important for the knowledge of the radiation environment around Mars, regarding future manned and robotic flights to the planet. The data for SEP events in Mars orbit during July 2021-March 2022 contribute to the details on the solar activity at a time when Mars is on the opposite side of the Sun from Earth.

Laser-Induced Ion Formation and Electron Emission from a Nanostructured Gold Surface at Laser Fluence below the Threshold for Plasma Formation.

The laser formation of positive and negative ions on a nanostructured metal surface is observed at laser fluence below the plasma formation threshold. The laser radiation energy dependences of the yield of positive and negative Au ions and charged clusters as well as electrons from the laser-induced nanostructures on the surface of gold are obtained at laser fluence below the plasma formation threshold using a pulsed laser with a wavelength of 355 nm and a pulse duration of 0.37 ns. It is shown that the ratio of the signals of positive and negative ions is constant over the entire range of the laser radiation energies, while the ion signal dependence on the laser radiation energy is described by a power function with an exponent of 9. The role of gold nanoparticles with a size of less than 5 nm in the formation of Au ions and charged Au clusters is discussed.

Paramagnetic Defects and Thermoluminescence in Irradiated Nanostructured Monoclinic Zirconium Dioxide.

The ESR spectra of nanostructured samples of monoclinic ZrO2 irradiated by electrons with energies of 130 keV, 10 MeV, and by a beam of Xe ions (220 MeV) have been studied. It has been established that irradiation of samples with electrons (10 MeV) and ions leads to the formation of radiation-induced F+ centers in them. Thermal destruction of these centers is observed in the temperature range of 375-550 K for electron-irradiated and 500-700 K for ion-irradiated samples. It is shown that the decrease in the concentration of F+ centers is associated with the emptying of traps responsible for thermoluminescence (TL) peaks in the specified temperature range. In the samples irradiated with an ion beam, previously unidentified paramagnetic centers with g = 1.963 and 1.986 were found, the formation of which is likely to involve Zr3+ ions and oxygen vacancies. Thermal destruction of these centers occurs in the temperature range from 500 to 873 K.

Laser-induced electron transfer desorption/ionization on MoO3 and WO3 surfaces for the determination of dithiocarbamates.

Surface layers of molybdenum oxide MoO3 and tungsten oxide WO3 produced by thermal oxidation of molybdenum and tungsten plates in the air were studied for the first time as a platform for laser-induced electron transfer desorption/ionization. High analytical performance of such layers for the determination of metal complexes with dithiocarbamates, such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, and diethyldithiocarbamate, has been demonstrated. All studied complexes are detected as radical cations, with no fragment ions. The ion yields from MoO3 and WO3 surfaces were found to be more than two orders of magnitude higher than those from nanocrystalline silicon surfaces. A novel method has been developed for the determination of trace amounts of dithiocarbamates based on the complexation of analytes with gold ions, followed by laser-induced electron transfer desorption/ionization. The limits of detection of dithiocarbamates were estimated to be about 1 ng/mL. The proposed method was successfully applied to the rapid screening of tetramethylthiuram disulfide residues in juice.

Ionization of organic molecules with metal ions formed in the laser plasma.

A laser plasma ion source was used to ionize volatile organic compounds in a gas sample. The plasma was generated on a metal target in the intermediate vacuum region of ~0.3 Torr using a pulsed Nd:YAG laser with a wavelength of 1 µm. The resulting ions mass spectra were acquired using orthogonal time-of-flight mass spectrometer (O-TOF MS). When using a copper target, the ions formed are simple complexes (CuM+ ) of copper ions with organic molecules. The possibility of online identification of trace amounts of alkanes in nitrogen and air, with a detection limit of ~10 ppb, was demonstrated. The ionization efficiency of volatile organic compounds through the formation of clusters with metal ions is 10-4 in terms of the quasimolecular complex ions. The rate constants of ion-molecular reactions of copper ions with octane and water molecules in nitrogen and air are estimated.

Silicon surface assisted laser desorption ionization mass spectrometry for quantitative analysis.

The approach to quantitative analysis by silicon Surface Assisted Laser Desorption Ionization Mass Spectrometry (Si-SALDI) is proposed. The approach is based on the new method for forming an active surface layer on a silicon substrate by exposing to laser radiation directly in the ion source of a mass spectrometer. The method can be used repeatedly on the same substrate, providing high reproducibility of its surface ionization properties and high ionization efficiency of organic compounds. Within the proposed approach, the methods of improvement of signal reproducibility are also considered, including continuous monitoring of the silicon surface ionization properties using a Knudsen effusion cell; scanning the surface of a silicon substrate with a laser beam; selecting the optimal value of laser fluence and using a reproducible sample introduction technique. It is demonstrated that this approach can be successfully applied to quantify clinically relevant concentrations of pharmaceutical drugs in extracts of blood.

Improvement of m/z accuracy for linear matrix-assisted laser desorption/ionization time-of-flight mass spectrometer.

RATIONALE: Linear matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) is widely used in analytical and biomedical applications. The use of delayed extraction increases the resolution, but the roughness of the matrix crystals and the misalignment of the target plate in the order of a few micrometers cause a substantial spread in the ion TOF values and a decrease in mass accuracy. METHODS: The method of mass spectra correction based on the correlation of matrix fragment peaks in MALDI mass spectra was used. Experiments were performed using the MALDI-TOF instrument CMI-1600. SIMION 8.1 and MATLAB were used for ion motion simulations. Data analysis was done using the home-built custom-developed software and MATLAB. RESULTS: It was shown that the peak position drift in the MALDI-TOF mass spectra depends linearly on the TOF in a wide mass range. While using the linear correction of the TOF scale, an increase in m/z accuracy of more than 10 times was achieved. The mass accuracy was limited by the resolution of the fast Analog-to-Digital Converter (ADC) used. CONCLUSIONS: It is expected that the proposed method will significantly increase the dynamic range, since it becomes possible to sum up corrected individual mass spectra without a significant loss of resolution. Timescale adjusting can be used for both linear TOF instruments and reflector systems of various configurations.

The level of free circulating mitochondrial DNA in blood as predictor of death in case of acute coronary syndrome.

BACKGROUND: The efficacy of treating acute myocardial ischemic damages depends, to a large extent, on the development of technologies for predicting their course and outcome. The aim of this paper was to explore whether it would be possible to consider the content of free circulating mitochondrial DNA as a danger-associated molecular pattern for assessing the probability of death from myocardial infarction. METHODS: We have analyzed the clinical outcomes based on discharge summaries and autopsy reports obtained in the course of the PROTOCOL observational trial. This study was approved by the Irkutsk Scientific Center of Surgery and Traumatology ethics committee (protocol No. 3, 10.08.2015). To examine whether the assessment of the level of free circulating mtDNA in acute coronary syndrome can help predicting clinical outcomes, all patients were divided into two groups: group 1, involving those who survived during 30 days after hospitalization, and group 2, involving those who died during this time. A quantitative analysis of the free circulating mtDNA was conducted using the PCR method in situ. RESULTS: The analysis showed that in patients who survived the level of freely circulating mtDNA (36.0 copies/ml) was 164 times lower than in those who died (5900 copies/ml, p = 0.049). It should be mentioned that according to the logistic regression analysis, the probability of death of patients with the increased level of blood plasma mtDNA (more than 4000 copies/ml) is 50%. CONCLUSIONS: Thus, the PROTOCOL observational trial proved that the increase in the content of free circulating mtDNA in blood is a predictor of lethal outcome in patients with acute coronary syndrome. Trial registration The observational studies (those in which the assignment of the medical intervention is not at the discretion of the investigator) do not require registration.

Determination of rhenium and osmium complexes by surface-assisted laser desorption/ionization coupled to Orbitrap mass analyzer.

A surface-assisted laser desorption/ionization (SALDI) source is coupled to the Orbitrap mass analyzer; the instrumental approach is tested for the analysis of rhenium (Re) and osmium (Os) complexes with 8-mercaptoquinoline. Silicon (Si) material obtained by laser treatment of monocrystalline Si is used as SALDI substrate. All studied complexes are detected as radical cations, with no protonated molecules. The comparison of SALDI, matrix-assisted laser desorption/ionization (MALDI), and direct laser desorption/ionization (LDI) on metal plates in the same instrumental setup demonstrated that the detection of the studied complexes using SALDI provides the highest sensitivity. The ability to analyze samples rapidly, high purity of spectra, and good analytical parameters make SALDI coupled to the Orbitrap mass analyzer a potentially powerful tool for the detection of Re and Os complexes and related organic, UV-absorbing compounds.

Surface-assisted laser desorption/ionization mass spectrometry with a rotating ball interface.

A rotating ball interface for surface-assisted laser desorption/ionization (SALDI) mass spectrometry was designed and tested. One side of the ball was exposed to atmospheric pressure and the other to the vacuum in a time-of-flight mass spectrometer. Analytes (arginine, atenolol, reserpine, tofisopam, and chloropyramine) were applied using electrospray to a silicon substrate on the atmospheric side, the ball was rotated 180°, and the analyte was desorbed on the vacuum side using a pulsed, 200 Hz, 355 nm laser. In order to increase the desorption area, the laser focus was scanned over the substrate in a raster pattern repeated once every second. The design allows for rapid sample throughout with a sample turn-around time as short as 5 s. Newly produced porous silicon substrates initially yielded very low ion signals, and they required several hundred laser shots to attain maximum sensitivity. In contrast, amorphous silicon did not require such 'activation'. Quantitative analysis showed a sample-to-sample reproducibility of about 10%. The sensitivities with model analytes were in the 1000 to 10,000 ions/fmole range and detection limits in the low fg range.