ЭКСТРАКЦИОННО-ФЛУОРИМЕТРИЧЕСКОЕ ОПРЕДЕЛЕНИЕ КОДЕИНА В МОЧЕ ЧЕЛОВЕКА

For the extraction-fluorimetric determination of nanogram amounts of codeine in human urine the use of the fluorescence of the toluene extract of the codeine ionic associate with eosin was proposed. The formed ionic associate was characterized by the intensive fluorescence with a maximum of 550 nm. It was shown that the fluorescence intensity of the codeine ion associate with eosin in toluene was 10 times higher than the intensity of its luminescence in carbon tetrachloride, and 3 times higher than its intensity in chloroform. The optimal conditions for the formation of the fluorescent ion associate of the positively charged codeine ion with a negatively charged form of eosin were determined. The maximum fluorescence intensity of the ion associate was observed during the toluene extraction from the aqueous solutions with pH of 6 - 8 and the eosin concentration in the range of 1·10-5-1·10-3 mol·L-1. The fluorescence intensity of the extract was maintained at the initial level for 24 hours. The extraction-fluorometric procedure for determining the nanogram amounts of codeine in human urine was developed. The limit of detection of codeine, calculated by 3s-criterion, was equal to 6 ng·ml-1. The calibration curve linearity was maintained in the range of 30 – 320 ng·ml-1. The procedure for the determination of codeine in real expert samples of urine was tested. The relative standard deviation did not exceed 0.08. The obtained results for the extraction-fluorimetric determination of codeine in human urine allowed recommending the developed procedure for its use in the solutions of certain tasks in the practice of the institutions of the corresponding profile.Keywords: Сodeine, determination, human urine, extraction, fluorescence(Russian)DOI: http://dx.doi.org/10.15826/analitika.2017.21.4.006S.I. Metelitsa1, E.V. Kireeva1, V.V. Nemikhin2, S.V. Kachin1, V.N. Losev1, S.A. Sagalakov1 1Siberian Federal University, Svobodnyi pr., 79, Krasnoyarsk, 660041,Russian Federation2Krasnoyarsk Regional Bureau of Forensic Medical Examination, Mira pr., 35, Krasnoyarsk, 660049, Russian FederationДля экстракционно-флуориметрического определения нанограммовых содержаний кодеина в моче человека предложено использование флуоресценции толуольного экстракта ионного ассоциата кодеина с эозином. Образующийся ионный ассоциат характеризуется интенсивной флуоресценцией с максимумом при 550 нм. Показано, что интенсивность флуоресценции ионного ассоциата кодеина с эозином в толуоле в 10 раз выше интенсивности его свечения в четыреххлористом углероде и в 3 раза – в хлороформе. Определены оптимальные условия образования флуоресцирующего ионного ассоциата положительно заряженного иона кодеина с отрицательно заряженной формой эозина. Максимальная интенсивность флуоресценции ионного ассоциата наблюдается при его экстракции толуолом из водных растворов с рН = 6-8 и концентрации эозина в диапазоне 1·10-5-1·10-3 М. Интенсивность флуоресценции экстракта сохраняется в течение 24 часов. Разработана методика экстракционно-флуориметрического определения нанограммовых содержаний кодеина в моче человека. Предел обнаружения кодеина, рассчитанный по 3s-критерию, равен 6 нг/мл. Линейность градуировочной зависимости сохраняется в диапазоне 30 – 320 нг/мл. Методика апробирована при определении содержания кодеина в экспертных образцах мочи человека. Относительное стандартное отклонение при определении более 50 нг/мл кодеина не превышает 0.08. Полученные результаты экстракционно-флуориметрического определения кодеина в моче человека позволяют рекомендовать разработанную методику при решении определенных задач в практике учреждений соответствующего профиля.Ключевые слова: кодеин, определение, моча человека, экстракция, флуориметрияDOI: http://dx.doi.org/10.15826/analitika.2017.21.4.00

Synthesis of Novel Iono- and Photochromic Spiropyrans Derived from 6,7-Dihydroxy-8-Formyl-4-Methyl-2H-Chromene-2-One

Novel photochromic spiropyrans (SPPs) containing 6′-hydroxy group were synthesized and their spectral properties as well as abilities for complexation with metal ions studied. In solutions they exist as equilibrium mixture of spirocyclic (A) and merocyanine (B) isomers. The largest content of merocyanine form was found for the derivative with an electron-donating methyl group in position 5 of hetaryl fragment. The irradiation of SPPs in acetonitrile shifts the equilibrium to the B form. Similar effect causes the addition of metal cations due to formation of colored complexes with merocyanine isomers

НОВЫЕ ПРЕПАРАТЫ ДЛЯ ЗАЩИТЫ ЖИВОТНЫХ ОТ КРОВОСОСУЩИХ ДВУКРЫЛЫХ НАСЕКОМЫХ

Development of livestock as well as increase of milk and meat production depends considerably on prompt and qualified veterinary measures. One of the reserves of lifestock profitability rise is prevention of infectious diseases including entomosis, and animals' protection from bloodsucking dipterous insects: deer flies, mosquitos, gadflies and biting midges also known as gnats. In Belorussia dairy cows lost up to 15–20 % of milk and in single seasons up to 30–40 % due to bloodsucking dipterous insects attack. The task of present research is the study of insecticide efficacy of drugs: Delcid, Almet, Fenmet, Breeze 25 % applied as aerosols using ultra low-volume spraying when cattle in pastures are massively attacked by gnats. The repellent efficacy of drugs Breeze-Prof, Polevik, Phytolym, Tobol and Alezan spray against gad-flies are studied. While using of ultra low-volume hitch spraying of young cattle herds: 0,05 % solution of Delcid, Almet, Fenmet, Breeze 25 % at the rate of 10 ml per cattle it is found that the protective action coefficient according to average data related to gadflies family Tabanidae within first 30 minutes makes: for Delcid – 92,49 %, Almet – 100, Fenmet – 100, Breeze 25 % – 95,3 %, and within 24 hours: Delcid – 81,7 %, Almet – 71,4, Fenmet – 56,2, Breeze 25 % – 81,8 %.Изучено действие некоторых репеллентов и ин-сектицидов, рекомендуемых против гнуса. Разрабо-таны режимы их применения, проведены широкие производственные испытания и рекомендованы для практического применения наиболее эффективные и безопасные препараты на основе синтетических пире-троидов. Проведенными исследованиями изучена репеллентная эффективность против слепней семейст-ва Tabanidae новых препаратов, которые показали удовлетворительную эффективность

New V-shaped 2,4-di(hetero)arylpyrimidine push-pull systems: Synthesis, solvatochromism and sensitivity towards nitroaromatic compounds

Novel D–π–A–π–D type pyrimidine-based dyes, possessing (hetero)aryl electron-donating groups in 2,4-positions were synthesized, and their photophysical properties were investigated by using absorption and emission spectral analyses. All dyes proved to exhibit a strong emission solvatochromism with quantum yields up to 0.96, depending on their molecular structure and solvent polarity. The compounds have been established to undergo a reversible protonation, directed at nitrogen atoms of the pyrimidine ring, and these phenomena are associated with dramatic color changes. In addition, fluorophores 5a-d show a high sensitive response for nitroaromatic traces in solutions or real-time detection of their vapors in air. These findings indicate that the compounds obtained can be regarded as excellent fluorophores for fluorescent material applications. © 2018 Elsevier LtdRussian Foundation for Basic Research, RFBR: 17-03-00011-AMinistry of Education and Science of the Russian Federation, Minobrnauka: 4.6759.2017/BCThis work (synthetic part and sensory properties) was supported by the Russian Foundation for Basic Research (Research Project No. 17-03-00011-A ). N.I. Makarova, E.V.V. and A.V.M. would like to acknowledge financial support for the absorption and fluorescence studies from the Ministry of Education and Science of the Russian Federation within the framework of the State Assignment for Research (project No. 4.6759.2017/BC ). The authors are grateful to Mr. Grigory A. Kim for carrying out the DFT calculations which were performed by using « Uran » supercomputer of the Institute of mathematic and mechanics of the Ural Brach of the Russian Academy of Sciences. NMR experiments were carried out by using equipment of the Center for Joint Use “Spectroscopy and Analysis of Organic Compounds” at the Postovsky Institute of Organic Synthesis of the Ural Branch of the Russian Academy of Sciences. VNC is grateful to the Ural Branch of the Russian Academy of Sciences (project № 0398-2018-0054 )

Extraction-fluorimetric determination of codeine in human urine

For the extraction-fluorimetric determination of nanogram amounts of codeine in human urine the use of the fluorescence of the toluene extract of the codeine ionic associate with eosin was proposed. The formed ionic associate was characterized by the intensive fluorescence with a maximum of 550 nm. It was shown that the fluorescence intensity of the codeine ion associate with eosin in toluene was 10 times higher than the intensity of its luminescence in carbon tetrachloride, and 3 times higher than its intensity in chloroform. The optimal conditions for the formation of the fluorescent ion associate of the positively charged codeine ion with a negatively charged form of eosin were determined. The maximum fluorescence intensity of the ion associate was observed during the toluene extraction from the aqueous solutions with pH of 6 - 8 and the eosin concentration in the range of 1·10-5-1·10-3 mol·L-1. The fluorescence intensity of the extract was maintained at the initial level for 24 hours. The extraction-fluorometric procedure for determining the nanogram amounts of codeine in human urine was developed. The limit of detection of codeine, calculated by 3s-criterion, was equal to 6 ng·ml-1. The calibration curve linearity was maintained in the range of 30 – 320 ng·ml-1. The procedure for the determination of codeine in real expert samples of urine was tested. The relative standard deviation did not exceed 0.08. The obtained results for the extraction-fluorimetric determination of codeine in human urine allowed recommending the developed procedure for its use in the solutions of certain tasks in the practice of the institutions of the corresponding profile.Для экстракционно-флуориметрического определения нанограммовых содержаний кодеина в моче человека предложено использование флуоресценции толуольного экстракта ионного ассоциата кодеина с эозином. Образующийся ионный ассоциат характеризуется интенсивной флуоресценцией с максимумом при 550 нм. Показано, что интенсивность флуоресценции ионного ассоциата кодеина с эозином в толуоле в 10 раз выше интенсивности его свечения в четыреххлористом углероде и в 3 раза – в хлороформе. Определены оптимальные условия образования флуоресцирующего ионного ассоциата положительно заряженного иона кодеина с отрицательно заряженной формой эозина. Максимальная интенсивность флуоресценции ионного ассоциата наблюдается при его экстракции толуолом из водных растворов с рН = 6-8 и концентрации эозина в диапазоне 1·10-5-1·10-3 М. Интенсивность флуоресценции экстракта сохраняется в течение 24 часов. Разработана методика экстракционно-флуориметрического определения нанограммовых содержаний кодеина в моче человека. Предел обнаружения кодеина, рассчитанный по 3s-критерию, равен 6 нг/мл. Линейность градуировочной зависимости сохраняется в диапазоне 30 – 320 нг/мл. Методика апробирована при определении содержания кодеина в экспертных образцах мочи человека. Относительное стандартное отклонение при определении более 50 нг/мл кодеина не превышает 0.08. Полученные результаты экстракционно-флуориметрического определения кодеина в моче человека позволяют рекомендовать разработанную методику при решении определенных задач в практике учреждений соответствующего профиля

CD1d-Expressing Breast Cancer Cells Modulate NKT Cell-Mediated Antitumor Immunity in a Murine Model of Breast Cancer Metastasis

Tumor tolerance and immune suppression remain formidable obstacles to the efficacy of immunotherapies that harness the immune system to eradicate breast cancer. A novel syngeneic mouse model of breast cancer metastasis was developed in our lab to investigate mechanisms of immune regulation of breast cancer. Comparative analysis of low-metastatic vs. highly metastatic tumor cells isolated from these mice revealed several important genetic alterations related to immune control of cancer, including a significant downregulation of cd1d1 in the highly metastatic tumor cells. The cd1d1 gene in mice encodes the MHC class I-like molecule CD1d, which presents glycolipid antigens to a specialized subset of T cells known as natural killer T (NKT) cells. We hypothesize that breast cancer cells, through downregulation of CD1d and subsequent evasion of NKT-mediated antitumor immunity, gain increased potential for metastatic tumor progression.In this study, we demonstrate in a mouse model of breast cancer metastasis that tumor downregulation of CD1d inhibits iNKT-mediated antitumor immunity and promotes metastatic breast cancer progression in a CD1d-dependent manner in vitro and in vivo. Using NKT-deficient transgenic mouse models, we demonstrate important differences between type I and type II NKT cells in their ability to regulate antitumor immunity of CD1d-expressing breast tumors.The results of this study emphasize the importance of determining the CD1d expression status of the tumor when tailoring NKT-based immunotherapies for the prevention and treatment of metastatic breast cancer

Prospects for Creation of Cardioprotective and Antiarrhythmic Drugs Based on Opioid Receptor Agonists

It has now been demonstrated that the μ, δ(1), δ(2), and κ(1) opioid receptor (OR) agonists represent the most promising group of opioids for the creation of drugs enhancing cardiac tolerance to the detrimental effects of ischemia/reperfusion (I/R). Opioids are able to prevent necrosis and apoptosis of cardiomyocytes during I/R and improve cardiac contractility in the reperfusion period. The OR agonists exert an infarct‐reducing effect with prophylactic administration and prevent reperfusion‐induced cardiomyocyte death when ischemic injury of heart has already occurred; that is, opioids can mimic preconditioning and postconditioning phenomena. Furthermore, opioids are also effective in preventing ischemia‐induced arrhythmias

ЛЮМИНЕСЦЕНТНОЕ ОПРЕДЕЛЕНИЕ МЕДИ, СЕРЕБРА, ЗОЛОТА И ПЛАТИНЫ С ИСПОЛЬЗОВАНИЕМ 2-МЕРКАПТО-5-БЕНЗИМИДАЗОЛСУЛЬФОКИСЛОТЫ, В ТОМ ЧИСЛЕ ЗАКРЕПЛЕННОЙ НА ПОВЕРХНОСТИ КРЕМНЕЗЕМА

Текст статьи не публикуется в открытом доступе в соответствии с политикой журнала.2-Mercapto-5-benzimidazolesulfonic acid (MBI), also noncovalently bound to a silica surface, is proposed as a reagent for the low-temperature luminescence determination of Cu(I), Ag(I), Au(I), and Pt(II). Luminescence excitation and luminescence spectra of metal complexes with MBI in solutions and on the adsorbent surface represent broad unstructured bands in the regions 250–400 and 450–700 nm, respectively. The developed procedures for the luminescence and sorption–luminescence determination of Cu, Ag, Au, and Pt with limits of detection at a level of 0.001–0.01 μg on 0.1 g of adsorbent are tested in the determination of metals in natural and industrial samples