A method has been developed for the determination of tetrodotoxin in water, blood plasma, and drugs at a level of 0.05—1.0 µg/mL. The method is based on the hydrolytic decomposition of tetrodotoxin by a sodium hydroxide solution, extraction of 2-amino-6-hydroxymethyl-8-hydroxyquinazoline using liquid–liquid extraction, preparation of its derivative by reaction with N,O-bis(trimethylsilyl)trifluroacetamide, and the determination of the derivative by gas–liquid chromatography with a mass-spectrometric detector.

Разработана методика определения 2-эндо-(6-хлорпиридин-3-ил)-7-азабицикло-[2.2.1]гептана (эпибатидин) и 2-эндо-(6-хлорпиридин-3-ил)-7-азабицикло[2.2.1]гептан-7-ола (биомаркер эпибатидина) в плазме крови на уровне 1 ? 10-5 1 ? 10-3 мг/мл. Методика основана на извлечении компонентов из плазмы крови жидкостно-жидкостной экстракцией и газохроматографическом определении с использованием термоионного или масс-спектрального детекторов. С целью снижения предела обнаружения эпибатидина и его биомаркера при использовании масс-спектрометрического детектора в методику включена стадия дериватизации с помощью N,O-бис(триметилсилил)трифторацетамида или 2,3,4,5,6-пентафторбензилбромида.

A method has been developed for the determination of 2-endo(6′-chloropyridin-3′-yl)-7-azabicyclo[2.2.1]heptane (epibatidine) and 2-endo(6′-chloropyridin-3′-yl)-7-azabicyclo[2.2.1]heptane-7-ol (epibatidine biomarker) in blood plasma at a level of 1 × 10−5–1 × 10−3 mg/mL. The method is based on the extraction of components from blood plasma by liquid-liquid extraction followed by gas-chromatographic determination using thermionic or mass spectrometric detectors. To reduce the limit of detection for epibatidine and its biomarker in using the mass-spectrometric detector, a derivatization stage using N,O-bis(trimethylsilyl)trifluoroacetamide or 2,3,4,5,6-pentafluorobenzyl bromide has been included into the procedure.

New achiral separating bifunctional reagents, dichlorides of methylphosphonic and O-ethyl-thiophophoric acids, have been used for the quantitative determination of the enantiomeric composition of α-amino acids (alanine, valine, proline), secondary alcohols (2-octanol, 2-pentanol, 1-methoxy-2-propanol) and α-phenylethylamine. The determination of the enantiomeric composition of optically active α-amino acids, secondary alcohols, and amines is based on the transformation of compounds into symmetric diastereometers using organophosphorous achiral bifunctional reagents followed by the determination of the derivatives by gas chromatography with a mass spectral detector.

The effect of the saturability of noncovalent interactions on the character of opioid activity of opioid receptor ligands belonging to different structural classes was investigated. A three-dimensional model for an opiate pharmacophore was used to show that the involvement of pharmacophore elements, which are responsible for the agonist ligand binding to opioid receptors, in intramolecular interactions gives rise to antagonistic properties.

Разработана методика раздельного определения микроколичеств иприта (2,2-дихлордиэтилсульфида) и -люизита (2-хлорвинилдихлорарсина) в битумных массах, образующихся в процессе битумирования ипритно-люизитных реакционных масс на объектах уничтожения химического оружия в диапазоне концентраций (2–20) ? 10-4 %.

Разработана методика определения тиодигликоля, 1,1-сульфонил-бис[2-(метилсульфонил)-этна], 1-метилсульфонил-2-[2-(метилтио)этилсульфонил]этана (биомаркеры иприта), метилфосфоновой кислоты, О-этилметилфосфоновой кислоты, О-изопропилметилфосфоновой кислоты, О-пинаколилметилфосфоновой кислоты (биомаркеры фосфорорганических отравляющих веществ) в моче. Методика включает извлечение компонентов жидкостной экстракцией, получение производных, разделение газожидкостной хроматографией и детектирование пламенно-фотометрическим и масс-спектрометрическим детекторами. Методика применена для анализа образцов искусственной мочи методом “введено-найдено”.

A procedure is developed for the separate determination of microquantities of iprite (2,2′-dichlorodiethylsulfide) and α-lewisite (2-chlorovinyldichloroarsine) in bituminous masses formed in the bitumenation of iprite-lewisite crude mixtures in objects of the destruction of chemical weapons. The concentration range is (2–20) × 10−4%.

A procedure has been developed for the determination of thioglycol, 1,1′-sulfonyl-bis[2-(methylsulfonyl)-ethane], 1-methylsulfonyl-2-[2-(methylthio)ethylsulfonyl]ethane (biomarkers of mustard agent) and methylphosphonic acid, O-ethylmethylphosphonic acid, O-isopropylmethylphosphonic acid, and O-pinacolyl methylphosphonic acid (biomarkers of organophosphoric toxic agents) in urine. The procedure includes the recovery of components by liquid extraction, derivatization, separation by gas-liquid chromatography, and detection by flame-photometric and mass spectral detectors. The procedure has been applied to the analysis of samples of artificial urine by the standard addition method.

A procedure was developed for determining traces of O -isopropyl methylphosphonofluoridate (sarin) in soils at a level of 2 × 10 −4 mg/kg. The procedure is based on solvent extraction with a hexane-benzene mixture, the preconcentration of the extract to a small volume, the synthesis of dialkyl esters using secondary alcohol aluminates, and gas-chromatographic separation on an HP-1 column with a flame ionization detector. The determination error does not exceed 29%; the time of analysis is 1 h.

Разработана методика определения микроколичеств O-изопропилового эфира фторангидрида метилфосфоновой кислоты (зарина) в почвах на уровне 2 ? 10-4 мг/кг, основанная на извлечении жидкостной экстракцией смесью растворителей гексан–бензол, концентрировании экстракта, до небольшого объема, получении диалкиловых эфиров с помощью алюминатов вторичных спиртов, разделении методом газовой хроматографии с пламенно-фотометрическим детектором на колонке НР-1. Погрешность определения не превышает 29%, продолжительность анализа составляет 1 ч.

Разработана методика газохроматографического определения S-[2-(N,N-диэтиламино)этил]метилтиофосфоновой кислоты (монотиола) в воде на уровне 5 ? 10-5. Методика основана на извлечении монотиола из воды жидкостно-жидостной экстракцией, обработкой экстракта изопропанолом в присутствии AgNO3 и диазометаном для получения О-изопропил-О-метилметилфосфоната и хроматографировании полученного производного с использованием пламенно-фотометрического детектора. Относительная погрешность определения монотиола в воде не превышает 35%, продолжительность анализа составляет 60 мин.

A procedure is proposed for the gas-chromatographic determination of S-[2-(N,N)-diethylamino) ethyl]methylphosphonothioic acid (monothiol) in water at a level of 5 × 10−5%. The procedure is based on the extraction of monothiol from water by liquid-liquid extraction, treatment of the extract with isopropanol in the presence of AgNO3 and with diazomethane to obtain O-isopropyl-O-methyl methylphosphonate, and the chromatographic detection of the derivative obtained with a flame-photometric detector. The relative error of determining monothiol in water does not exceed 35%; the time of analysis is 60 min.

A procedure was proposed for the gas-chromatographic determination of trace O-isobutyl-S-2-(N,N-diethylamino)ethyl ester of methylthiophosphonic acid (mixed ester, ME) in burning products formed after the detoxication of elements in building constructions, personal protection equipment, waste degassing solutions, and other production wastes (slime) at a level of (1.0–10.0) × 10−8 mg/g. The procedure is based on the extraction of ME from an analyzed material with a mixture of aqueous solutions of monoethanolamine and NaOH, its back extraction to hexane, the evaporation of the hexane layer (with the addition of HCl) to dryness, the transformation of ME into methyl ester of O-isobutylmethylphosphonic acid with the use of methanol in the presence of AgNO3, and the chromatography of the derivative on an open tubular column with the chemically modified HP-INN OWax stationary phase with the use of a flame-photometric detector.

A procedure was developed for the gas-chromatographic determination of sarin and soman in the atmospheric air of work zones and inhabited areas at a level of the maximum permissible concentration 2 × 10−5 and 1 × 10−5 mg/m3 and the tentative safe exposure level 2 × 10−7 and 1 × 10−7 mg/m3, respectively. The procedure is based on the recovery of sarin and soman from analyzed air using an absorbing solution, the extraction of sarin and soman from this solution with ethyl acetate and hexane, respectively, the evaporation of the corresponding extracts to a residual volume of 0.1 cm3, and their subsequent chromatography with flame-photometric and thermoionic detectors. The relative error in the determination of sarin and soman is 20 and 18 rel %, respectively, in the air of work zones and 27 and 23 rel %, respectively, in the air of inhabited areas.

A technique for determining the enantiomeric composition of 2-octanol and α-phenylethylamine with the use of gas chromatography on optically inactive stationary phases is proposed. The technique is based on the formation of symmetrical diastereomeric derivatives upon the interaction of enantiomers with bifunctional achiral reagents: dimethyldichlorosilane, bromochloromethane, and dibromoethane. The reagents were chosen from the viewpoint of the synthesis of diastereomers with a minimum distance between the chiral centers. This minimum distance is responsible for a difference in the energies of interaction of the derivatives with the stationary liquid phase, which is sufficient for the separation of these derivatives.

A method was proposed for the separate gas-chromatographic determination of β-chlorovinylarsonous dichloroanhydride (lewisite) and anhydride (lewisite oxide) in samples of soil and construction materials. Because of the absence of regulations for the maximum permissible concentration (MPC) of lewisite and lewisite oxide in construction materials (concrete, bricks, facing tile, etc.), the MPC level of lewisite in soil (0.1 mg/kg) was taken as the maximum permissible concentration in the development of the method for their determination in the above samples. The method is based on the solid-liquid extraction converting lewisite and lewisite oxide into components that can be separated at the stage of blowing-out the extractant in an inert gas flow and their subsequent conversion into acetylene with a 30% aqueous solution of sodium hydroxide and the chromatography of the vapor phase with flame-ionization detection. The error in the determination is no larger than ±20 rel %. The time of analysis is within 1.5 h.