Papers by Nikolay Solovyev
Polymers, 2022
Ethylene glycol (EG) is widely used in various economic and industrial fields. The demand for its... more Ethylene glycol (EG) is widely used in various economic and industrial fields. The demand for its efficient separation and recovery from water is constantly growing. To improve the pervaporation characteristics of a poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) membrane in dehydration of ethylene glycol, the modification with graphene oxide (GO) nanoparticles was used. The effects of the introduction of various GO quantities into the PPO matrix on the structure and physicochemical properties were studied by Fourier-transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies, scanning electron (SEM) and atomic force (AFM) microscopies, thermogravimetric analysis (TGA), swelling experiments, and contact angle measurements. Two types of membranes based on PPO and PPO/GO composite were developed: dense membranes and supported membranes on a fluoroplast substrate (MFFC). Transport properties of the developed membranes were evaluated in the pervaporation dehydration of EG...
Biomedical copper speciation in relation to Wilson’s disease using strong anion exchange chromatography coupled to triple quadrupole inductively coupled plasma mass spectrometry
Analytica Chimica Acta, 2019
Biomedical analytical methods often rely on indirect measurements, such as immunoassays, which ca... more Biomedical analytical methods often rely on indirect measurements, such as immunoassays, which can lack effective metrological traceability. In the nephelometric determination of ceruloplasmin (Cp), an important protein whose circulating level is altered in Wilson's disease (WD), the anti-Cp antibody used is not specific for the biologically active holoprotein so the assay can overestimate the concentration of Cp due to the presence of the apoprotein. By providing quantitation using elemental standards, the use of strong anion exchange chromatography (SAX) coupled to triple quadrupole inductively coupled plasma mass spectrometry (ICP-MS-MS) can overcome the drawbacks of methods for the measurement of metalloproteins reliant on immunoassays. In the current study, a SAX-ICP-MS-MS method for Cp quantification was designed and tested in samples of blood serum of WD patients and healthy controls. Using standards based on a copper-EDTA complex for calibration, the method provides relatively simple quantification of Cp with the limit of detection of 0.1 μg L-1 (limit of quantification 0.4 μg L-1). The method was also used to investigate the copper species separated by using a 30 kDa cut-off ultrafiltration device. The so-called "exchangeable" copper fraction is considered as an alternative clinical biomarker of WD. Using the designed speciation approach, it was shown that the ultrafiltration method can overestimate the "exchangeable" copper fraction due to a removal of copper from Cp. This was confirmed by comparing the enzymatic activity of the fractions. Thus, the specificity of the "exchangeable" copper test can be ensured only under strict maintenance of ultrafiltration conditions.
Hormones, 2019
Alzheimer's disease (AD) is the most common neurodegenerative disease associated with cognitive d... more Alzheimer's disease (AD) is the most common neurodegenerative disease associated with cognitive decline, loss of memory, and progressive cerebral atrophy. The trace element selenium (Se) is known to be involved in brain pathology. Selenoprotein P (SELENOP), as the main Se transport protein, is, to a great extent, responsible for maintaining Se homeostasis and the hierarchy of selenoprotein expression in the body. Adequate Se supply through SELENOP is vital for proper brain development and function. Additionally, SELENOP may be implicated in pathological processes in the central nervous system, including those in AD. The current review summarizes recent findings on the possible role of SELENOP in AD, with a focus on probable mechanisms: Se delivery to neurons, antioxidant activity, cytoskeleton assembly, interaction with redox-active metals (e.g., copper and iron), and misfolded proteins (amyloid beta and tau protein). The use of SELENOP as a biomarker of Se status is also briefly discussed. Epidemiological studies on Se supplementation are beyond the scope of the current review.
Targeted proteomics for the analysis of cultural heritage: application of broadband collision-induced dissociation mass spectrometry
Analytical and Bioanalytical Chemistry, 2022
A broadband collision-induced dissociation (bbCID) fragmentation mode was proposed for liquid chr... more A broadband collision-induced dissociation (bbCID) fragmentation mode was proposed for liquid chromatography–mass spectrometric targeted analysis of tryptic peptides obtained from proteins in samples of decoration paint coating. In this approach, a mass spectrometric dataset contains the information on the parent and all fragment ions. This maintains a balance between the quantity of simultaneously acquired data and the sensitivity of the method, which is beneficial under coupling with analytical chromatography. In this study, characteristic peptides were selected for casein, ovalbumin, and collagen, which are the most commonly used binder proteins in the artworks. A simplified sample preparation protocol including only protein extraction and trypsinization was tested and successfully implemented. The combination of analytical chromatography with bbCID MS technique is a lower cost alternative to the use of high-end nano-LC–MS approaches in the investigation of cultural heritage objects of regional or local importance, e.g., prior to and/or during restoration works. It was demonstrated that, for the paint coating samples, the required level of sensitivity could be acquired through the data-independent MS/MS strategy. The proposed approach was tested on a sample obtained during the restoration work at the Gromov cottage in the Lopukhin Garden (middle of the XIX century). As a result, the main protein component, collagen, was identified using 6 characteristic peptides, which may indicate the use of gelatin-based glue. For instance, the identification of the peptide GVQGPPoxGPAGPR of the incoming collagen composition α-1 was undertaken by three parameters: m / z of the precursor ion of 553.2910, m / z of the fragment ion y9 of 821.4238, and retention time of 1.9 min. Graphical abstract
Membranes, 2021
Transport characteristics of sodium alginate (SA) membranes cross-linked with CaCl2 and modified ... more Transport characteristics of sodium alginate (SA) membranes cross-linked with CaCl2 and modified with fullerenol and fullerene derivative with L-arginine for pervaporation dehydration were improved applying various approaches, including the selection of a porous substrate for the creation of a thin selective SA-based layer, and the deposition of nano-sized polyelectrolyte (PEL) layers through the use of a layer-by-layer (Lbl) method. The impacts of commercial porous substrates made of polyacrylonitrile (PAN), regenerated cellulose, and aromatic polysulfone amide were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), standard porosimetry method, and water filtration. The effects of PEL combinations (such as poly(sodium 4-styrene sulfonate) (PSS)/SA, PSS/chitosan, PSS/polyacrylic acid, PSS/poly(allylamine hydrochloride)) and the number of PEL bilayers deposited with the Lbl technique on the properties of the SA and SA/fullerene derivative membranes wer...
Spectrochimica Acta Part B: Atomic Spectroscopy, 2020
Recently glow discharge (GD) mass spectrometry, which is conventionally used to analyze solid sam... more Recently glow discharge (GD) mass spectrometry, which is conventionally used to analyze solid samples, was successfully applied for ionization and the subsequent determination of volatile organic compounds (VOCs). In the present study, the possibility of direct determination of VOCs in ambient air using time-of-flight mass spectrometry with microsecond pulsed discharge in a copper hollow cathode was considered for the first time. The discharge cell of the mass spectrometer was modified for the direct analysis of gaseous samples by the introduction of a quartz capillary into the argon input channel. Various classes of compounds (aromatic and aliphatic hydrocarbons and derivatives of carboxylic acids) were studied. Particular attention was paid to the ionization mechanisms of VOCs. New mechanisms of chemical and electron ionization, resulting in the formation of associate ions with cathode material (copper)-CuM + , were demonstrated and implemented. Alternative mechanisms of organic compounds ionization in GD may be related to Penning process and proton transfer reactions. These processes are mainly responsible for the formation of molecular and protonated molecular ions. The relative contribution of all these mechanisms can be adjusted by operating parameters. In general, an extremely low degree of fragmentation of molecular ions or associates was observed. Due to its isotopic structure (only two isotopes 63 Cu and 65 Cu with comparable abundances), the use of copper as cathode material additionally increases the reliability of VOC identification in the form of their CuM + associates. Such association shifts the detected ions to the region of large masses with fewer interferences and noise related to scattered ions.
Journal of Biological Chemistry, 2021
Edited by Paul Fraser Alzheimer's disease (AD) is characterized by accumulation of tau and amyloi... more Edited by Paul Fraser Alzheimer's disease (AD) is characterized by accumulation of tau and amyloid-beta in the brain, and recent evidence suggests a correlation between associated protein aggregates and trace elements, such as copper, iron, and zinc. In AD, a distorted brain redox homeostasis and complexation by amyloid-beta and hyperphosphorylated tau may alter the isotopic composition of essential mineral elements. Therefore, high-precision isotopic analysis may reveal changes in the homeostasis of these elements. We used inductively coupled plasma-mass spectrometry (ICP-MS)-based techniques to determine the total Cu, Fe, and Zn contents in the brain, as well as their isotopic compositions in both mouse brain and serum. Results for male transgenic tau (Line 66, L66) and amyloid/ presenilin (5xFAD) mice were compared with those for the corresponding age-and sex-matched wild-type control mice (WT). Our data show that L66 brains showed significantly higher Fe levels than did those from the corresponding WT. Significantly less Cu, but more Zn was found in 5xFAD brains. We observed significantly lighter isotopic compositions of Fe (enrichment in the lighter isotopes) in the brain and serum of L66 mice compared with WT. For 5xFAD mice, Zn exhibited a trend toward a lighter isotopic composition in the brain and a heavier isotopic composition in serum compared with WT. Neither mouse model yielded differences in the isotopic composition of Cu. Our findings indicate significant pathologyspecific alterations of Fe and Zn brain homeostasis in mouse models of AD. The associated changes in isotopic composition may serve as a marker for proteinopathies underlying AD and other types of dementia. This article contains supporting information.
Mass Spectrometry‐Based Techniques for Direct Quantification of High Ionization Energy Elements in Solid Materials—Challenges and Perspectives
Mass Spectrometry Reviews, 2020
The determination of nonmetals, first of all, the most electronegative ones-nitrogen, oxygen, flu... more The determination of nonmetals, first of all, the most electronegative ones-nitrogen, oxygen, fluorine, chlorine, and bromine, poses the highest challenge for element analysis. These elements are characterized by high reactivity, volatility, high ionization energy, and the absence of intensive spectral lines in the optical spectral range. Conventional techniques of their quantification include considerable "wet chemistry" stages so the application of these techniques for the solid sample is highly laborious and prone to uncontrollable uncertainties. Additionally, current development in material science and other areas requires the quantification of the elements at lower levels with good sensitivity. Owing to their robustness and flexibility, mass spectrometry techniques provide vast possibilities for the quantification, spatial and isotopic analysis, including the solutions for direct analysis of solids. The current review focuses on the application of major mass spectrometric techniques for the quantification of N, O, F, Cl, and Br in solid samples. The following techniques are mainly considered: thermal ionization mass spectrometry (TIMS), isotope-ratio MS (IRMS), secondary ion MS (SIMS), inductively coupled plasma MS (ICP-MS), and glow discharge MS (GDMS); as the most accessible and widely applied for the purpose. General ionization issues, advantages, limitations, and novel methodological solutions are discussed.
Molecules, 2020
Hyperthermic intraperitoneal chemoperfusion (HIPEC) is an established form of locoregional chemot... more Hyperthermic intraperitoneal chemoperfusion (HIPEC) is an established form of locoregional chemotherapy of peritoneum tumors. However, its efficacy and safety status remain a controversy, partially, due to scarce data on pharmacokinetics and toxicity profile of drugs under HIPEC. In the current study, 24 female Wistar rats were randomly assigned to receive cisplatin as HIPEC (n = 12, 20 mg/kg) or intravenously (i.v., n = 9, 4 mg/kg). The subgroups of three animals were used for the initial, intermediate, and late phases of the pharmacokinetic assessment. The animals were sacrificed on days 1 and 5. Blood, liver, kidney, and ovaries were evaluated for platinum content. Histological and immunohistochemical evaluation was undertaken in the liver and kidney. A trend for higher blood plasma platinum levels was observed for HIPEC compared to i.v. Significantly lower (p < 0.001) relative platinum binding to the proteins was observed in HIPEC animals compared to the i.v. administration. ...
Depth profiling by pulsed glow discharge time-of-flight mass spectrometry with a combined hollow cathode cell
Journal of Analytical Atomic Spectrometry, 2020
A combined hollow cathode microsecond direct current pulsed glow discharge time-of-flight mass sp... more A combined hollow cathode microsecond direct current pulsed glow discharge time-of-flight mass spectrometry system has proved its efficiency for quantification; however, it has not been properly tested for the purpose of depth analysis.
Solid State Sciences, 2018
The formation of an oscillating system during the sputtering of sapphire single crystal with puls... more The formation of an oscillating system during the sputtering of sapphire single crystal with pulsed glow discharge, Solid State Sciences (2018),
Russian Chemical Reviews, 2018
Early detection of lung cancer usually markedly increases the efficiency of therapy. However, the... more Early detection of lung cancer usually markedly increases the efficiency of therapy. However, the currently employed diagnostic approaches are not sufficiently effective, resulting in late detection of the disease and high patient mortality. Therefore, development of a high-throughput and reliable diagnostic method is a priority task requiring fast solution. Analysis of exhaled air for a number of organic compounds recognized as lung cancer biomarkers seems to be a promising approach for early diagnosis of the disease. This issue attracts growing interest, as indicated by increasing number of publications on this topic. This review surveys contemporary analytical techniques for analysis of exhaled air, including various spectroscopic and mass spectral methods and also gas sensor-based methods. The key benefits and shortcomings of the techniques, sample injection and pre-concentration methods, and the potential applicability of the methods for lung cancer detection are discussed. The...
Journal of Trace Elements in Medicine and Biology, 2019
Highlights Selenium (Se) and iodine (I) may be implicated in diabetes pathology via different mec... more Highlights Selenium (Se) and iodine (I) may be implicated in diabetes pathology via different mechanisms. Antioxidant Se-enzymes, thyroid hormones/deiodinases are primary interplay points. 2 Leptin signaling and immunity are additional points of interest between Se and I. Epidemiological and experimental data are still inconclusive. The studies should be more focused on chemical speciation of I and, especially, Se.
Analytical and Bioanalytical Chemistry, 2019
Cu isotope fractionation was investigated in the human neuroblastoma SH-SY5Y cell line, in a prol... more Cu isotope fractionation was investigated in the human neuroblastoma SH-SY5Y cell line, in a proliferating/tumor phase (undifferentiated cells), and in a differentiated state (neuron-like cells), induced using retinoic acid (RA). The SH-SY5Y cell line displays genetic aberrations due to its cancerous origin, but differentiation drives the cell line towards phenotypes suitable for the research of neurological diseases (e.g., Alzheimer's disease or Parkinson's disease). Cellular Cu distribution was first explored by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) imaging and, subsequently, Cu isotopic analysis was performed at cellular and sub-cellular levels via multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). The SH-SY5Y cells showed a redistribution of intracellular Cu upon RA differentiation. Both undifferentiated and differentiated cells became systematically enriched in the light 63 Cu isotope with increasing intracellular Cu content. Differentiated neuron-like SH-SY5Y cells showed a heavier Cu isotopic composition (+ 0.3‰) than did the undifferentiated proliferating cells when exposed to Cu for 24 h. However, after a longer exposure time (72 h), no difference was observed between both cellular phenotypes. Mitochondrial fractions were enriched in the light 63 Cu isotope, compared to whole cells, for both undifferentiated and differentiated cells (no significant difference). The Cu isotopic composition of the remaining cell lysates was heavier than that of the whole cells and + 0.2‰ heavier in the differentiated cells than in the undifferentiated cells. These results indicate that neuronal differentiation affects the Cu isotope fractionation accompanying Cu uptake in the cells, but this effect does not seem to be associated with the mitochondrial Cu pathway. Cu isotope fractionation can be an interesting tool for studying Cu metabolism at a (sub)-cellular level in functional neurons.
New insight in beryllium toxicity excluding exposure to beryllium-containing dust: accumulation patterns, target organs, and elimination
Archives of Toxicology, 2019
There is much contradiction between different experimental studies on beryllium (Be) toxicity. Th... more There is much contradiction between different experimental studies on beryllium (Be) toxicity. The majority of studies focus on occupational pathologies, caused by the exposure to Be dust. However, Be pollution may affect wide population groups through other exposure routes. The discrepancies between experimental studies may be attributed to the lack of adequate Be toxicity model since conventional administration routes are hampered by high acidity and low solubility of Be compounds. This study was aimed to develop a novel way to implement Be toxicity avoiding side effects, related to high acidity or low solubility of Be salts. Intraperitoneal injection of Be–glycine composition (containing BeSO4, glycine, purified water, pH adjusted to 5.5 with NaOH) was tested in the dose range 238–7622 µmol Be kg−1 (body weight, b/w) in full-grown Wistar male rats. The model provided reliable uptake of Be from the peritoneum into general circulation for at least 48 h. LD50 was found to be 687 µmol Be kg−1 (b/w). The established LD50 value differed from previous data on gastrointestinal, intramuscular or intravenous administration of Be compounds. The liver was found to act as a primary elimination route for Be and related to the highest Be content in the animal. However, it had no signs of morphological damage, which was observed only in the testes (deterioration of germinal epithelium). At the same time, the lungs, stated as a primary target tissue for Be in the models of chronic beryllium disease, did not show strong Be accumulation nor morphological changes. Survived animals showed behavioral changes, including increased motor activity and aggressive reactions in some cases, and complete spasticity in other. The obtained data show the applicability of the established modeling protocol and testified for the independence of chronic beryllium disease on Be2+ ion toxicity per se.
Analytical Letters, 2018
A method has been developed for the determination of 24 elements (As,
Vacuum, 2018
Direct quantification of oxygen in dielectric materials using non-destructive or nearly non-destr... more Direct quantification of oxygen in dielectric materials using non-destructive or nearly non-destructive techniques still remains a nontrivial task. Simultaneous assessment of oxygen with other elements in a single analytical procedure is even more challenging. In the current study, a method of direct determination of oxygen and other matrix elements in solid samples, based on time-of-flight mass spectrometry with pulsed glow discharge in combined hollow cathode (CHC) is designed and tested. The possibility to effectively ionise oxygen owing to the electron impact mechanism under short repelling pulse delays has been shown. Stable sputtering and ionisation of dielectric samples were obtained via sample coating with thin conducting layer of silver. The parameters of oxygen quantification were optimised: duration and voltage of the discharge pulse, cell pressure, repelling pulse delay and material of the auxiliary cathode. The calibrations of oxygen, phosphorus and potassium are presented. The intensity of 16 O + was shown to be highly dependent on discharge cell pressure. The limits of detection were 0.001, 0.001, and 0.002 mass% for oxygen, phosphorus and potassium respectively. The designed approach enables direct, fast and accurate quantitative and in depth analysis of oxygen-containing samples.
Spectrochimica Acta Part B: Atomic Spectroscopy, 2018
Pulsed glow discharge enables direct mass spectrometric measurement of fluorine in crystal materi... more Pulsed glow discharge enables direct mass spectrometric measurement of fluorine in crystal materialsfluorine quantification and depth profiling in fluorine doped potassium titanyl phosphate
Neon plasma for effective ionisation of oxygen and fluorine in pulsed glow discharge – high ionisation energy elements quantification in potassium titanyl phosphate single crystals
Journal of Analytical Atomic Spectrometry, 2019
Neon glow discharge was tested for the direct analysis of solid dielectric materials by pulsed gl... more Neon glow discharge was tested for the direct analysis of solid dielectric materials by pulsed glow discharge time-of-flight mass spectrometry with an emphasis on the elements with high ionisation energy....
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Papers by Nikolay Solovyev