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Vol 80, No 8 (2025)
REVIEWS
Application of “smart materials” in sample preparation of biological fluids and environmental objects
Abstract
Sample preparation of natural objects requires the development of highly sensitive and selective methods for extracting and concentrating biologically active substances. So-called smart materials, which are selected to solve specific analytical problems, are promising in this area. The review considers the main types of such materials (ionic liquids, eutectic solvents, nanomaterials, organometallic and covalent framework structures, molecularly imprinted polymers), their specific features and specific examples of application in chemical analysis for 2020-2025. The possibilities of using smart materials in the analysis of biological fluids and natural objects, available microextraction approaches and methods for subsequent determination are considered. The achieved advantages over previously proposed approaches are emphasized.
Journal of Analytical Chemistry. 2025;80(8):759-781
759-781
ORIGINAL ARTICLES
Determination of oxidative damage markers of nucleic acids 8-hydroxyguanosine and 8-hydroxy-2’-deoxyguanosine in urine by high performance liquid chromatography with tandem mass spectrometric detection
Abstract
Products of oxidative damage to nucleic acids are considered as relatively stable biomarkers in the diagnosis of negative consequences of oxidative stress. The content of biomarkers of oxidative degradation of DNA (8-hydroxy-2’-deoxyguanosine, 8-OHdG) and RNA (8-hydroxyguanosine, 8-OHG) in biofluids increases when the body is exposed to toxic compounds, radiation and other negative factors associated with oxidative stress. Due to the non-invasiveness of sampling and higher concentrations of target analytes, urine is considered as a priority matrix for biomonitoring the consequences of oxidative stress. A procedure for the combined determination of 8-OHdG and 8-OHG in urine by HPLC-MS/MS has been developed. A structurally similar exogenous compound 8-(1-hydroxybutan-2-ylamino)-1,3,7-trimethyl-1-purine-2,6(3H,7H) was selected as an internal standard. The measurement range for both analytes was set within 1 to 50 ng/mL. To prepare bioassays for analysis, a solid-phase extraction procedure on a hydrophilic-lipophilic sorbent (HLB) in the target substance retention mode was optimized. When using high-resolution HPLC-MS/MS technology, the error of analysis does not exceed 25 % over the entire measurement range. A total of 130 urine samples of chemical plant workers aged 20 to 70 years without diagnosed systemic diseases were analyzed. The 8-OHdG content in the urine samples was in the range of 1 to 20 ng/mL, and 8-OHG – from 2 to 12 ng/mL. The dependence of concentrations of both biomarkers in urine on the age of the worker was established.
Journal of Analytical Chemistry. 2025;80(8):865-876
865-876
Features of preconcentration and determination of PAHs in soils with high organic matter content by gas chromatography–mass spectrometry
Abstract
Specific features of the preconcentration and determination of polycyclic aromatic hydrocarbons (PAHs) in humus-rich soils by gas chromatography–mass spectrometry (GC–MS) are studied. The QuEChERS technique and dispersive liquid–liquid microextraction (DLLME) were employed to extract PAHs from soils using acetone and binary extractants of various compositions, including acetonitrile–dichloromethane, acetonitrile–acetone, acetone–hexane, acetone–chloroform, acetone–dichloromethane, and ethyl acetate–dichloromethane. Recoveries of low- and medium-molecular-weight PAHs using these solvent mixtures reached approximately 100%, while the acetone–dichloromethane mixture yielded over 90% recovery for high-molecular-weight PAHs. Under optimized GC–MS conditions with QuEChERS extraction, the limits of quantification (LOQ) for fluoranthene, pyrene, chrysene, and triphenylene reached 5 μg/kg, and for the remaining PAHs, 10 μg/kg in humus-rich soils. It was shown that the reliable GC–MS determination of lower concentrations of PAHs requires both the elimination of the matrix effect and the preconcentration of the analytes. The sequential application of QuEChERS and DLLME techniques enabled a decrease in the limits of quantification by GC–MS to 1.8 μg/kg for fluoranthene, pyrene, chrysene, and triphenylene, and to 3.5 μg/kg for the remaining PAHs. The optimized procedure for PAH determination in humus-rich soils was validated using real chernozem samples.
Journal of Analytical Chemistry. 2025;80(8):852-864
852-864
Regularities of retention of alcohols, ketones and sugars on a sulphonic acid cation-exchanger in H+-, Ca2+- and La3+-forms
Abstract
The chromatographic retention of alcohols, ketones, alditols and carbohydrates on a cation exchange column (200 × 4.6 mm I.D., Sevko AA) packed with sulfonated poly(styrene-divinylbenzene) with a crosslinking degree of 10 % and a particle diameter of 7 μm saturated with various counterions (H+, Ca2+ and La3+) is studied in the ligand exchange chromatography variant. The sorbent in the Ca2+ form shows higher retention times and selectivity in the separation of carbohydrates and ethylene glycols. The sorbent in the La3+ form provides strong retention and better selectivity for the separation of alditols. The possibility of using this column for determining carbohydrates in food products (juice, honey) using refractometric detection is shown.
Journal of Analytical Chemistry. 2025;80(8):838-851
838-851
Preconcentration of quinolones on magnetic hypercrosslinked polystyrene before their determination by high-performance liquid chromatography in milk
Abstract
Magnetic hypercrosslinked polystyrene (MHCPS) is proposed for group sorption isolation and preconcentration of quinolones. The conditions for magnetic solid-phase extraction are selected: 25 mL of solution (pH 6), sorbent mass 20 mg, sorption time 20 min. The analytes have been desorbed with 2 mL of methanol. It is shown that the sorbent provides quantitative isolation of all 23 studied compounds not only from aqueous solutions, but also from milk, bypassing the deproteinization stage. The determination is carried out by HPLC-tandem mass spectrometry using matrix calibration. The detection and determination limits of quinolones are 0.012–0.12 and 0.04–0.4 μg/L, respectively, which are below their maximum residue levels in milk.
Journal of Analytical Chemistry. 2025;80(8):827-837
827-837
Gas chromatographic determination of ethanol in soft drinks using vapor-phase drop microextraction
Abstract
A simple express procedure for gas chromatographic determination of ethanol in soft drinks is proposed (kvass, grape juice, non-alcoholic beer), based on headspace microextraction of the analyte into a drop (1 μL) of distilled water located above the surface of the analyzed liquid on the tip of the needle of a standard microsyringe for gas chromatography. The detection limit of ethanol is (3–6) × 10–5 vol. %, the parallel determination time, including headspace extraction, does not exceed 5 min. Propanol-2, which is not detected in beverages, is used as an internal standard. The correctness of the procedure is confirmed by the added–found method, the relative standard deviation does not exceed 7 % at an ethanol concentration in the sample of 10–2 vol. %
Journal of Analytical Chemistry. 2025;80(8):809-816
809-816
Microextraction separation and determination of inorganic arsenic forms by inductively coupled plasma mass spectrometry in natural waters
Abstract
The results of microextraction separation and ICP-MS determination of inorganic arsenic forms in natural waters are presented. The necessity of separate determination of analytes is substantiated, since arsenites are tens of times more toxic than arsenates. Separation was carried out by the method of selective liquid-liquid microextraction of As(III) complex compounds with sodium diethyldithiocarbamate into the organic phase. Conditions of extraction of As(III) compounds with the highest degree of recovery of ~95% were established. Complex compounds of As(III) with sodium diethyldithiocarbamate were extracted into the organic phase with carbon tetrachlormethane and methanol as an extractant and dispersant, respectively. The matrix effect of elements on the extraction of analytes from water was eliminated by double microextraction of analytes. The content of total inorganic arsenic and As(V) compounds was established based on the results of ICP-MS analysis of the samples of the original water and the aqueous extract after separation of the material forms of inorganic arsenic. The concentration of As(III) in water was calculated by the difference between the total arsenic content and the content of As(V) compounds. The limits of determination of As(III) and As(V) in waters were the same and amounted to 0.010 μg/L in the linearity range of 0.05–100 μg/L, R2 = 0.9998. The added-found method established the correctness of the determination of inorganic arsenic forms in water. The analysis procedure was tested on model waters and real samples of drinking and natural waters.
Journal of Analytical Chemistry. 2025;80(8):798-808
798-808
IONIC LIQUIDS AS PROMISING FUNCTIONAL MATERIALS FOR MICROEXTRACTION OF STEROID HORMONES
Abstract
Prospects for the use of imidazolium ionic liquids (IL) as extractants of sex steroid hormones (estrogens and androgens) in microextraction methods (dispersive liquid-liquid microextraction, DLLME, and magnetic solid-phase microextraction, mSPME) are identified. The key parameters of DLLME using C6MImNTf2 IL, affecting the extraction efficiency, are optimized using the design of experiment method. High degrees of recovery (88–99 %) are achieved. An approach of dynamic IL immobilization on the surface of magnetic nanoparticles (MNPs) for steroid extraction under mSPME conditions is proposed. Two types of MNP pre-coating are studied: hydrophilic based on silica and hydrophobic with oleic acid. The capabilities of C8MImBF4 IL as a MNP surface modifier for efficient steroid extraction are revealed. Optimum conditions provided high degrees of recovery (83–97 %), with the exception of estriol (60 %). The detection limits are 0.26–1.29 ng/mL. Limitations of the method related to partial removal of IL from the surface of NPs are revealed, which reduces the reproducibility of the results for estriol.
Journal of Analytical Chemistry. 2025;80(8):782-797
782-797
Multi-element analysis of tellurium dioxide with preliminary separation of the sample matrix by reactive distillation
Abstract
A method for separating the sample matrix of tellurium dioxide TeO2 is proposed, based on reactive distillation in a flow reactor, in the form of tellurium tetrachloride at 240°C; the chlorinating agent is gaseous chlorine. The behavior of 59 impurities was studied, it was found that As, Au, B, Bi, Cu, Ga, In, Mo, Nb, Pb, Re, Ru, Sb, Se, Sn, Ta, Ti, V, W and Zn are lost completely or partially; Ag, Al, Ba, Be, Ca, Cd, Ce, Co, Cr, Dy, Er, Eu, Gd, Ir, Hf, Ho, K, La, Li, Lu, Mg, Mn, Na, Nd, Ni, P, Pd, Pr, Pt, Rb, Rh, Sc, Sm, Sr, Tb, Tm, Y, Yb and Zr are retained in the concentrate by more than 75 %. The impurity content in the concentrates was determined by inductively coupled plasma atomic emission spectrometry. The accuracy was confirmed by the added-found method and comparison with the results of analysis without concentration. The limits of detection are in the range from 2 × 10–8 to 8 × 10–6 wt. %, the intralaboratory precision does not exceed 31 %.
Journal of Analytical Chemistry. 2025;80(8):817-826
817-826
EVENTS
Юбилей Руслана Хажсетовича Хамизова
Journal of Analytical Chemistry. 2025;80(8):877-878
877-878
Jubilee of Andrey Yuryevich Bogomolov
Journal of Analytical Chemistry. 2025;80(8):879-880
879-880