Lomonosov Moscow State University, Chemistry department
RESEARCH, TEACHING, or OTHER INTERESTS
Analytical Chemistry, Clinical Biochemistry, Surfaces, Coatings and Films
9
Scopus Publications
Scopus Publications
Quantitative analysis of phylloquinone (vitamin K1) and menaquinone (vitamin K2) in serum of Russians by liquid chromatography-tandem mass spectrometry Mikhail Vokuev, Anastasia Frolova, Stepan Makarkin, Daria Prosuntsova, Timur Baygildiev, Lidia Nefedova, Oleg Klychnikov, Igor Rodin Clinical Chemistry and Laboratory Medicine, 2026 Objectives Vitamin K homologues are essential to human health, and their concentrations in biological samples serve as valuable diagnostic biomarkers. This study was aimed to develop a method for determining vitamins K1 (phylloquinone, VK1) and K2 (menaquinone, MK-4) in human serum. The proposed method was validated and applied to the serum of a cohort of 20 Russian individuals. Methods High-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS) was used to analyse the content of VK1 and MK-4 in serum. Atmospheric pressure chemical ionisation (APCI) in negative mode was applied to ionise VK1 and MK-4. Protein precipitation and solid-phase extraction (SPE) on polystyrene-divinylbenzene resin were combined to isolate and preconcentrate the analytes from serum. Results The HPLC-MSMS method was developed and validated for the determination of vitamins VK1 and MK-4 in human serum. The method demonstrated a lower limit of quantification (LLOQ) of 0.05 μg/L, with more than 71 % recoveries and precision within 17 %. To demonstrate the applicability of the method to real samples, serum from 20 healthy adults was analyzed. VK1 was detected in four individuals (0.094–0.96 μg/L), whereas MK-4 concentrations were below 0.22 μg/L in all cases. Conclusions The validated HPLC-MS/MS workflow provides a reliable and sensitive approach for the quantification of VK1 and MK-4 in minimal serum volumes. The method demonstrates robustness, reproducibility, and suitability for large-scale analytical applications. The proposed LC-MS/MS protocol successfully applied to native human serum samples, illustrating its applicability for future clinical and biochemical studies involving vitamin K.
Chiral Stationary Phases with Eremomycin and Its Derivatives for Determining Pharmaceutical Enantiomers in Natural Waters D. S. Prosuntsova, B. S. Burtsev, I. A. Ananieva Journal of Analytical Chemistry, 2026 Abstract A method is developed for the enantioselective determination of pharmaceutical environmental pollutants (beta-blockers, profens) by high-performance liquid chromatography using promising chiral stationary phases based on eremomycin derivatives. The specificity of the studied selectors is revealed: the phase based on eremomycin aglycone is effective for separating more polar pharmaceuticals, including β-blockers, while the phase containing chloreremomycin demonstrated high selectivity for less polar profens. A possibility of the simultaneous separation of the enantiomers of substances in multicomponent mixtures is demonstrated. A method for water sample preparation using solid-phase extraction is developed and tested. An analysis of real natural and wastewater samples confirmed the applicability of the developed approach to identifying chiral pharmaceutical contaminants.
Analysis of the Composition of Some Phenolcarboxylic Acids and Terpenes in the Fruits and Needles of Common Juniper (Juniperus commúnis L.) by Gas and Liquid Chromatography–Mass Spectrometry A. R. Ermakov, N. V. Bobkova, O. V. Nesterova, G. V. Nesterov, A. V. Pirogov, E. S. Chichkanova, I. A. Anan’eva, D. S. Prosuntsova, A. N. Kuz’menko Journal of Analytical Chemistry, 2025 Abstract Common juniper (Juniperus commúnis L.), Cypress family (Cupressaceae), is a promising source of biologically active substances for the treatment and prevention of chronic diseases. Extracts of juniper needles and fruits are analyzed by high-resolution HPLC–MS and thermal desorption (TD) GC–MS. Six hydroxybenzoic acids and four hydroxycinnamic acids were identified on the chromatograms of the extracts recorded in the full scan mode. The content of salicylic, p-hydroxybenzoic, gallic, coumaric, and ferulic acids was estimated at 0.03–17 mg/L. In the TD-GC–MS mode, peaks of substances were recorded in the range of retention times 9–25 min (by retention indices from 900 to 1700). For a more reliable identification, experimental retention indices were calculated and compared with those presented in the literature. It was suggested that the presence of substances such as cosmene, pinocarveol, and 2-pinen-4-one in the chromatograms can serve markers of the presence of juniper berries in the dietary supplement of juniper needles.
Conjugates of titanocene with non-steroidal anti-inflammatory drugs: synthesis, unusual NMR characteristics, stability and cytotoxicity Dmitry A. Guk, Karina R. Gibadullina, Anna A. Moiseeva, Yuri K. Grishin, Vitaly A. Roznyatovsky, Daria S. Prosuntsova, Irina A. Ananieva, Erik R. Gandalipov, Alexander A. Shtil, Elena K. Beloglazkina New Journal of Chemistry, 2023 Titanocene conjugates with four different non-steroidal anti-inflammatory drugs (flurbiprofen, naproxen, ibuprofen, and diclofenac; NSAIDs) were obtained and studied for the first time.
Novel Mixed-Mode Adsorbents for HPLC Based on Different Substrates Modified with Eremomycin N. Yu. Chikurova, D. S. Prosuntsova, A. N. Stavrianidi, S. M. Staroverov, I. A. Ananieva, A. D. Smolenkov, A. V. Chernobrovkina Journal of Analytical Chemistry, 2023 Abstract New adsorbents based on silica and polystyrene–divinylbenzene (PS–DVB) for hydrophilic interaction liquid chromatography (HILIC) with eremomycin in functional layers were obtained. The chromatographic properties of the new adsorbents were assessed using the Tanaka test for hydrophilic stationary phases and by studying the retention of substances of various classes in HILIC, chiral, and reversed-phase chromatography modes. It was shown that the use of eremomycin to create functional layers leads to an increase in the hydrophilicity of the adsorbents on different types of substrates and ensures the shielding of their charge. Eleven nitrogenous bases, nucleosides with an efficiency of up to 25 000 tp/m, or seven vitamins with an efficiency of up to 40 000 tp/m can be separated on a modified sorbent based on aminopropyl silica, and three different HPLC modes can be implemented on the sorbent with eremomycin based on PS–DVB.
Sorbent for HPLC based on copolymer of styrene and divinylbenzene with gold nanoparticles stabilized by eremomycin D. S. Prosuntsova, Irina A. Ananieva, Tatiana A. Moskaleva, О. А. Шпигун Sorbtsionnye I Khromatograficheskie Protsessy, 2023 In liquid chromatography, the use of new hybrid materials with nanoparticles as stationary phases offers an alternative to the commonly used silica-based phases. This paper presents a study of polymer nanohybrid sorbent with macrocyclic antibiotic. Eremomycin-stabilized gold-coated polystyrene-divinylbenzene (PS-DVB) particles are synthesized. PS-DVB-Au-eremomycin sorbent is characterized by atomic emission spectroscopy and elemental analysis. The concentration of gold nanoparticles (GNPs) immobilized onto PS-DVB matrix is approximately equal to 3.5∙1014 particles per gram. The immobilization of eremomycin provides bonding density of 20 µmol/g. Sorbent has a mesoporous structure according to the low-temperature nitrogen adsorption results. The functional surface area of the obtained sorbent compared to unmodified PS-DVB increases by 30%, despite the immobilization of large molecules of antibiotic, which is an important benefit of GNPs adsorption. The obtained sorbent is studied as a stationary phase for high performance liquid chromatography (HPLC). A detailed study of the retention mechanisms of profens and β-blockers on PS-DVB-Au-eremomycin is presented. The retention factors are obtained at varied pH, organic solvent content, and ionic strength of the mobile phase. The retention factors of profens at pH 4.0 are low, however, an increase in retention with an increase in acetonitrile content from 20 % to 80% is observed. This behavior could be explained by a growing contribution of hydrophilic interactions into retention. The best separation of the mixture of profens is obtained at 80 vol. % acetonitrile. At pH 9.9, the presence of hydrophobic interactions was indicated by the decrease of retention with an increase of organic content. The best separation of the four profens is achieved at 20 vol. % of acetonitrile. Retention order: indoprofen < ketoprofen < ibuprofen < flurbiprofen, corresponds to the increase in the hydrophobicity of the substances. This indicates to a typical reversed-phase mechanism. At pH 6.2, the retention order of analytes changes, which means a change in the retention mechanism; an increase in the retention times of analytes is also observed. Retention is determined by a mix of ion exchange and classical adsorption mechanisms. The retention of profens decreases with an increase in the concentration of the buffer solution, which also indicates the presence of ionic interactions. Retention of β-blockers increases with an increase in acetonitrile content. This effect seems to match well with an electrostatic repulsion hydrophilic interaction retention mechanism. However, a dependence between hydrophobicity and retention of β-blockers was also found. At pH 9.9, at which β-blockers are adsorbed as neutral molecules, this dependence is most pronounced. This indicates the presence of hydrophobic interactions. When pH is lowered to 6.2, the retention order of β-blockers changes, which indicates the competition of different mechanisms of interaction between the sorbate and the sorbent. For β-blockers with an increase in the concentration of the buffer solution the retention increases and the selectivity also increases. The obtained results confirm early observations that electrostatic interactions play a significant role in the retention mechanism. The higher ionic strength of the eluent results in the suppression of such interactions and may influence separation selectivity. The enantioselective properties of the sorbent have been demonstrated. The best separation of profene enantiomers is observed when the content of acetonitrile in eluent is 90-95% and at a neutral pH. Enantiomers of β-blockers separate under conditions of neutral pH and the predominance of the water component in eluent. To expand the scope of the chiral sorbent, the separation of enantiomers of benzoxycarbonyl- (CBZ), benzoyl-, tert-butoxy- (BOX) derivatives of amino acids on an experimental sorbent were also studied. Separation of the enantiomers of some CBZ and benzoyl derivatives has been obtained. The column with PS-DVB-Au-eremomycin was used to analyze a drug "Ketonal" by HPLC, the content of two enantiomers of ketoprofen in its composition was confirmed. A mixed-mode retention mechanism with a combination of electrostatic, hydrophobic, and hydrophilic interactions is realized on the synthesized nanohybrid stationary phase. The hydrophobic interactions dominated the retention of the profens at alkaline pH. Electrostatic and hydrophilic retention appears to play a role, under acidic and neutral conditions, in the retention of profens on the stationary phase. The gradual increase in the retention of β-blockers with the addition of acetonitrile into the mobile phase indicates HILIC behavior. Hydrophobic interactions are not entirely dominant on the investigated stationary phase, but they also play an essential role in retention. It has been shown that the retention factors of profens and β-blockers correlated with the polarity. The obtained sorbent showed enantioselectivity to various groups of organic substances, which demonstrates its potential as a chiral stationary phase.
MICROSPHERICAL POLYSTYRENE-DIVINYLBENZENE PARTICLES HYBRIDIZED WITH EREMOMYCIN STABILIZED GOLD NANOPARTICLES AS A STATIONARY PHASE FOR CHIRAL LIQUID CHROMATOGRAPHY D. S. Prosuntsova, I. A. Ananieva, P. N. Nesterenko, O. A. Shpigun Industrial Laboratory Materials Diagnostics, 2022 A novel enantioselective adsorbent was obtained by hybridization of microspherical polystyrene-divinylbenzene (PS-DVB) macroporous particles with eremomycin-stabilized gold nanoparticles (GNPs). Macrocyclic antibiotic eremomycin was used as a stabilization agent to obtain GNPs which were then characterized by transmission electron microscope. The average diameter of obtained nanoparticles is about 16.6 nm. Eremomycin-stabilized nanoparticles were successfully embedded into the porous polymer structure with a resulting chiral selector content of 37.5 pmol/g. The obtained PS-DVB composite containing GNPs with immobilized eremomycin was studied by scanning electron microscopy and diffuse reflectance spectroscopy. The values of the specific surface area (500 m2/g) and porosity of the adsorbent (0.39 cm3/g) are measured using nitrogen adsorption at low temperatures. The obtained composite material was used as a chiral stationary phase of liquid chromatography. A good separation enantio-selectivity to amino acids, their derivatives and beta-blockers under RPC (reversed-phase) and HILIC (Hidrophilic Interaction Liquid Chromatography) mode is demonstrated. The results obtained revealed that the prepared Eremo@GNP@PS-DVB composite is promising for use as a stationary phase in HPLC.
Synthesis and study of a sorbent for HPLC based on a copolymer of styrene and divinylbenzene modified with gold nanoparticles Daria S. Prosuntsova, Irina A. Ananieva, Andrey U. Ploduhin, Elena K. Beloglazkina, Oleg A. Shpigun Sorbtsionnye I Khromatograficheskie Protsessy, 2019 Получен новый сорбент для ВЭЖХ на основе сополимера стирол-дивинилбензола, модифицированного наночастицами золота, стабилизированными липоевой кислотой с привитым лизином, и изучены его физико-химические и хроматографические свойства. Исследовано удерживание профенов и β-блокаторов на полученном сорбенте в зависимости от состава подвижной фазы. Установлено, что для профенов преобладает обращенно-фазовый механизм удерживания, в то время как для β-блокаторов комплексный
