Formaldehyde in Alcoholic Beverages: Large Chemical Survey Using Purpald Screening Followed by Chromotropic Acid Spectrophotometry with Multivariate Curve Resolution

A strategy for analyzing formaldehyde in beer, wine, spirits, and unrecorded alcohol was developed, and 508 samples from worldwide origin were analyzed. In the first step, samples are qualitatively screened using a simple colorimetric test with the purpald reagent, which is extremely sensitive for formaldehyde (detection limit 0.1 mg/L). 210 samples (41%) gave a positive purpald reaction. In the second step, formaldehyde in positive samples is confirmed by quantitative spectrophotometry of the chromotropic acid-formaldehyde derivative combined with Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS). Calculation of UV-VIS and 13C NMR spectra confirmed the monocationic dibenzoxanthylium structure as the product of the reaction and disproved the widely cited para,para-quinoidal structure. Method validation for the spectrophotometric procedure showed a detection limit of 0.09 mg/L and a precision of 4.2–8.2% CV. In total, 132 samples (26%) contained formaldehyde with an average of 0.27 mg/L (range 0–14.4 mg/L). The highest incidence occurred in tequila (83%), Asian spirits (59%), grape marc (54%), and brandy (50%). Our survey showed that only 9 samples (1.8%) had formaldehyde levels above the WHO IPCS tolerable concentration of 2.6 mg/L

A productive approach to building educational programs in mathematics for csto cadets

For the implementation of educational programs for joint training of cadets mathematics from the member countries of the Collective Security Treaty Organization (CSTO) it is proposed to rely on developed information technologiesРассматриваются вопросы реализации образовательных программ совместного обучения математике курсантов из стран-членов Организации Договора о коллективной безопасности (ОДКБ) с использованием информационных технологи

Independent components in spectroscopic analysis of complex mixtures

We applied two methods of "blind" spectral decomposition (MILCA and SNICA) to quantitative and qualitative analysis of UV absorption spectra of several non-trivial mixture types. Both methods use the concept of statistical independence and aim at the reconstruction of minimally dependent components from a linear mixture. We examined mixtures of major ecotoxicants (aromatic and polyaromatic hydrocarbons), amino acids and complex mixtures of vitamins in a veterinary drug. Both MICLA and SNICA were able to recover concentrations and individual spectra with minimal errors comparable with instrumental noise. In most cases their performance was similar to or better than that of other chemometric methods such as MCR-ALS, SIMPLISMA, RADICAL, JADE and FastICA. These results suggest that the ICA methods used in this study are suitable for real life applications. Data used in this paper along with simple matlab codes to reproduce paper figures can be found at http://www.klab.caltech.edu/~kraskov/MILCA/spectraComment: 22 pages, 4 tables, 6 figure

Spectroscopic studies of compounds containing a P —H bond: 4. Vibrational spectra and conformational multiformity of di- tert-butylphosphorous acid molecules

IR and Raman spectra of liquid di- tert-butylphosphorous acid and its two low-temperature crystalline modifications are studied. It is found that at least three stable conformations of acid molecules can exist in the liquid state. © 1995, Plenum Publishing Corporation. All rights reserved

ХЕМОМЕТРИЧЕСКИЙ И ИК СПЕКТРОСКОПИЧЕСКИЙ АНАЛИЗ КЛЕЙКИХ ЛЕНТ

Chemometric methods for processing spectroscopic data are commonly used methods for a wide variety of chemical tasks that are gaining increasing popularity. In this work we showed the possibility of applying chemometric algorithms for the analysis of adhesive tapes - very complex objects in terms of their identification and classification.Using principal component analysis (PCA) expert classification and identification tasks in relation to fragments of biaxially oriented films of isotactic polypropylene adhesive tapes were solved, allowing the definition of objects from their FT-IR spectra.Regression methods (projection to latent structures (PLS), ridge regression, multiply linear regression (MLR) and principal component regression (PCR)) were used to construct models for determining the angles between the projection axes of the refractive index ellipsoid in the plane of the geometric boundary and polypropylene tape. The best prediction model was obtained using PLS (RMSE = 1.1, R2 = 0.93 for cross validation) indicated that the application of chemometric methods is promising in the adhesive IR spectra tapes analysis, in particularly in expert applications.Keywords: chemometrics, the principal component analysis (PCA), projection on latent structures (PLS), IR spectroscopy, polypropylene films, expertise(Russian)DOI: http://dx.doi.org/10.15826/analitika.2013.17.3.011 A.M. Tsikin, Y.B. Monakhova, S.P. Kurchatkin, S.P. MushtakovaSaratov State University named after N.G. Chernyshevsky, Saratov, Russian FederationПоказана возможность применения алгоритмов хемометрики для анализа клейких лент – весьма сложных объектов с точки зрения возможности их идентификации и классификации. С помощью метода главных компонент (МГК) решены экспертные классификационные и идентификационные задачи в отношении фрагментов пленок двухосно-ориентированного изотактического полипропилена в клейких лентах, позволяя проводить определение марки объектов по их ИК спектрам.Методы многомерной регрессии (проекции на латентные структуры (ПЛС), регрессия на главные компоненты (РГК), множественная линейная регрессия (МЛР) и ридж-регрессия) использованы при построении моделей для определения значений углов между проекцией осей эллипсоида показателей преломления на плоскость и геометрическим краем ленты полипропилена. Наилучшая модель, полученная с помощью метода ПЛС (RMSE = 1.1, R2 = 0.93 в случае полной кросс-валидации) свидетельствует о перспективности применения хемометрических методов в анализе ИК спектров клейких лент, в частности, в экспертных приложениях.Ключевые слова: хемометрика, метод главных компонент (МГК), проекции на латентные структуры (ПЛС), ИК спектроскопия, полипропиленовые пленки, экспертизаDOI: http://dx.doi.org/10.15826/analitika.2013.17.3.011 Литература1. Курчаткин С.П. Оптические методы в экспертном исследовании липких лент на основе полипропилена // Теория и практика судебной экспертизы в криминалистике: сборник материалов международной научно-практической конференции. Харьков: Право, 2002. Вып. 2. С. 377.2. Курчаткин С.П. Инструментальные методы исследования полипропиленовых пленок // Судебная экспертиза. 2010. № 4. С. 94-100.3. Родионова О.Е., Померанцев А.Л. Хемометрика: достижения и перспективы // Успехи химии. 2006. № 75. С.302-321.4. Szymanska-Chargot M., Zdunek A. Use of FT-IR Spectra and PCA to the Bulk Characterization of Cell Wall Residues of Fruits and Vegetables Along a Fraction Process // Food Biophys. 2013. V. 8. P. 29-42. 5. Wang N., Lim L.T. Fourier transform infrared and physicochemical analyses of roasted coffee // J. Agric. Food Chem. 2012. V. 60. Р. 5446-5453. 6. Identification of colitis and cancer in colon biopsies by Fourier Transform Infrared spectroscopy and chemometrics / X. Li et [al.] // Scientific World J. 2012. V. 2012. Р. 936149. 7. Alterations in the infrared spectral signature of avian feathers reflect potential chemical exposure: a pilot study comparing two sites in Pakistan / V. Llabjani et [al.] // Environ Int. 2012. V. 1. Р. 39-46. 8. Bunaciu A.A., Fleschin S., Aboul-Enein H.Y. A new method for a quantitative determination of piroxicam in pharmaceutical formulations using FT-IR spectrometry // Antiinflamm Antiallergy Agents Med Chem. 2012. V. 11. P. 262-266.9. Quality and statistical classification of Brazilian vegetable oils using mid-infrared and Raman spectroscopy / P. Samyn et [al.] // Appl. Spectrosc. 2012. V. 66. P. 552-565.10. Astakhov S.A., Stogbauer H., Kraskov A., Grassberger P. Spectral Mixture Decomposition by Least Dependent Component Analysis [Электронный ресурс]: http://www.arxiv.org/abs/physics/0412029 (дата обращения 27.06.2013).11. Winding W., Stephenson D.A. Self-Modeling mixture analysis of second-derivative near-infrared spectral data using simplisma approach // Anal. Chem. 1992. V. 64. P. 2735-2742.12. Методы декомпозиции спектров различной природы в анализе смесей сложного состава / Ю.Б. Монахова и [др.] // Ж. аналит. химии. 2011. Т. 66, №4. С. 361-372.13. Leger M. N., Wentzell P. D. Dynamic Monte Carlo self-modelling curve resolution method for multicomponent mixtures // Chemometr. Intell. Lab. Syst. 2002. V. 62. P. 171-188.14. Schoonover J. R., Marx R., Zhang S. Multivariate Curve Resolution in the Analysis of Vibrational Spectroscopy Data Files // Appl. Spectrosc. 2003. V. 57. P. 154A-170A.15. Калитеевский Н.М. Волновая оптика. М.: Наука, 1971. 376 с.16. [Электронный ресурс]: http://www.chimiometrie.fr/saisir_webpage.html / Сайт программного комплекса «SAISIR» (дата обращения: 19.02.2013).17. Wold S., Sjöström M., Eriksson L. PLS-regression: a basic tool of chemometrics // Chemometrics and Intelligent Laboratory Systems. 2001. V. 58. Р. 109-130.18. Trygg J., Wold S. Orthogonal Projections to Latent Structures // J. of Chemometrics. 2002. V. 16. Р. 119-128.19. Jolliffe I.T. A note on the Use of Principal Components in Regression // J. of the Royal Statistical Society. 1982. V. 31. Р. 300-303.20. Hawkins D. M. On the Investigation of Alternative Regressions by Principal Component Analysis // J. of the Royal Statistical Society. V. 22. Р. 275-286.21. Tikhonov A.N. О решении некорректно поставленных задач и методе регуляризации [Solution of incorrectly formulated problems and the regularization method] // Doklady Akademii Nauk SSSR. 1963. V. 151. P. 501-504. Translated in Soviet Mathematics. V. 4. P. 1035-1038.22. Tofallis C. Least Squares Percentage Regression ///J. of Modern Applied Statistical Methods. 2009. V. 7. P. 526-534.23. Monakhova Y.B., Kuballa T., Lachenmeier D.W. Nontargeted NMR analysis to rapidly detect hazardous substances in alcoholic beverages // Applied magnetic resonance. 2012. V. 42, № 3. P. 343-352.24. NMR spectroscopy as a screening tool to validate nutrition labeling of milk, lactose-free milk, and milk substitutes based on soy and grains / Y.B. Monakhova et [al.] // Dairy Science and Technology. 2012. V. 92. P. 109-120.25. Monakhova Y.B., Kuballa T., Lachenmeier D.W. Rapid quantification of ethyl carbamate in spirits using NMR spectroscopy and chemometrics // ISRN Analytical Chemistry. 2012. V. 2012. P. 989174.26. 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Subsets of cerebrospinal fluid lymphocytes in acute pediatric respiratory viral infection with meningeal syndrome

Current urgency of studying the intrathecal cellular immune response to infections of central nervous system is determined by limited knowledge on existing data about mechanisms of the brain immune protection in normal and diseased state. Implication of multi-colour flow cytometry in clinical laboratory diagnostics allowed to perform detailed studies of biological liquors, including cerebrospinal fluid (CSF). Currently, however, there are only scarce data on the lymphocyte subpopulations in CSF. Appropriate reference values remain a challenging issue. A study of CSF lymphocyte pool in absence of definite results at previous examination may be a potential way to resolve this problem. These clinical conditions include acute respiratory viral infections (ARVI), presenting with pseudomeningitidis (meningism) syndrome. The aim of this work was to characterize the subsets of lymphocytes from CSF of the children with ARVI with the meningism symptoms in order to get basic (control) values for diagnostics of inflammatory brain diseases. We have studied subpopulation composition of the CSF lymphocytes form in 27 children with ARVI complicated by the meningism (pseudomeningitidis) by means of flow cytometry using FACSCalibur analyzer with BD MultiTEST IMK Kit reagents. The data evaluation was performed with FlowJo software. We have studied relative contents of the main subsets, i.e., total Т cells (CD3+); Т helpers (CD3+CD4+Th); cytotoxic T cells (CD3+CD8+CTL); natural killers (СD3-CD16+CD56+NK); В cells (CD3-CD19+), and minor lymphocyte subpopulations: double-positive (DP) (CD3+CD4+CD8+); double-negative (DN) (CD3+CD4-CD8-) T cells; NKT (СD3+CD16+CD56+); CD3+CD8bright, CD3+CD8dim, CD3-CD8+NK. Statistical evaluation was carried out with standard GraphPad Prism 5 software. Among the main lymphocyte populations in CSF, T cell were predominant (96.2%), as well as their subpopulations, i.e., CD4Th (53.4%), and CD8+CTL (28.2%), with low amounts of NK (2.2%) and B cells (0.7%). The mean relative content of minor subpopulations (DN or DP T cells, and NKT cells) was, respectively, 5.3, 4.0, and 9%. Age dependence was revealed for the contents of major and minor lymphocyte subsets. With advancing age of the children, the relative numbers of CD3+ and CD4+Тh cells in CSF increase, as well as CD4/CD8 ratio, associated with decreased share of NK cells, like as DN and CD3+CD8dimТ cells. The results obtained are reflect some features of lymphocyte pool in CSF of the children without inflammatory process in CNS. Thus, they may be referred as control values (inflammation-free brain disorders) when studying immune pathogenesis of neuroinfections and other inflammatory diseases of CNS in the children from different age groups

Value of determining the cerebrospinal fluid protein markers of amyloidosis and neurodegeneration in the diagnosis of vascular and neurodegenerative cognitive impairments

The article presents data on different forms of moderate cognitive impairments (MCI) and the specific features of their transformation to dementia. Cerebrospinal fluid (CSF) was investigated in 60 patients with the amnestic and neurodynamic types of MCI, in 15 patients with vascular dementia (VD), 50 patients with Alzheimer’s disease (AD), and 23 patients with mixed vascular and neurodegenerative dementia (MVND). The specific features of β-amyloid and τ-protein concentrations were established in the preclinical stages of dementia, which reflects the main components of the pathogenesis of neurodegeneration. In the amnestic form of MCI and AD, there was drastically decreased Aβ-42 and increased τ-protein levels in SCF. As cognitive impairments progressed, there was a rise in the concentration of τ-protein; its level correlated with the severity of dementia. In MND, the level of Aβ-42 was significantly reduced while the concentration of τ-protein was much increased; moreover, to a greater extent than in AD and VD. Cerebrovascular damage and neurodegeneration were related to each other and mutually worsened clinical and pathogenic effects

Опыт применения генозаместительной терапии препаратом Золгенсма® (онасемноген абепарвовек) в реальной клинической практике в России

Objective: to analyze the safety and evaluate the effectiveness of therapy with onasemnogene abeparvovec in patients with spinal muscular atrophy in real clinical practice based on the experience of using the drug in the neuromuscular center of Research Clinical Pediatric Institute of Pirogov Russian National Research Medical University.Materials and methods. Patients with spinal muscular atrophy received therapy with onasemnogene abeparvovec based on the prescription of the drug according to vital indications by a council of physicians of Federal institutions (the availability of the drug was carried out within the framework of the MAP Program (global program of managed access MAP to AVXS-101 for eligible patients in countries, where it is not approved by regulatory authorities (NCT03955679), through funding from the charitable foundations, as well as through funding from the state fund “Circle of Kindness”. The drug tolerance was assessed and the analysis of side effects after drug administration was based on the criteria for adverse events (General criteria Adverse Event Terminology (CTCAE) v. 5.0) Patient motor function was assessed prior to treatment initiation and every 3–6 months after therapy using the Philadelphia Pediatric Hospital’s CHOP INTEND scale, total motor development based on Hammersmith Hospital Neurological Assessment Scale in Young Children, Part 2 (HINE-2), and the acquisition of new motor skills.Results. 41 children aged 5 to 47 months (weighing no more than 21 kg) received therapy with onasemnogene abeparvovec in the period from April 2020 to December 2021. Adverse events (hyperthermia, decreased appetite, nausea, vomiting) were registered in all patients with different degree of severity. Elevated levels of transaminases greater than 2 times the upper limit of the normal range were observed in 32 patients (78 %), thrombocytopenia in 9 patients (22 %). 15 patients (36 %) required a dose adjustment of corticosteroids.17 patients underwent assessment of motor scales after 6 months, 10 children were assessed after a year. The average improvement on the HINE-2 scale was 3.3 / 4.4 points, respectively. The average improvement on the CHOP INTEND Scale was 7.1 / 9.4 points after 6 / 12 months of therapy.Conclusion. The efficacy and safety of onasemnogene abeparvovec have been demonstrated in real clinical practice in the treatment of spinal muscular atrophy for children in different age groups with a body weight of no more than 21 kg.Цель исследования – проанализировать безопасность и оценить эффективность терапии препаратом Золгенсма® (онасемноген абепарвовек) у пациентов со спинальной мышечной атрофией в реальной клинической практике на основании опыта применения препарата в нервно-мышечном центре ОСП «Научно-исследовательский клинический институт педиатрии им. акад. Ю. Е. Вельтищева» ФГБОУ ВО РНИМУ им. Н. И. Пирогова.Материалы и методы. Пациенты со спинальной мышечной атрофией получали терапию препаратом онасемноген абепарвовек на основании назначения препарата по жизненным показаниям консилиумом врачей федеральных учреждений (доступность к препарату осуществлялась в рамках Программы MAP (глобальная программа управляемого доступа MAP к препарату AVXS-101 для пациентов, соответствующих критериям, в странах, где он не был одобрен регулирующими органами (NCT03955679)), за счет финансирования благотворительных фондов, а также за счет финансирования государственным фондом «Круг добра». Проведены оценка переносимости препарата и анализ побочных эффектов после введения препарата на основании критериев нежелательных явлений (Общие критерии терминологии для нежелательных явлений (CTCAE) v. 5.0). Оценивались моторная функция пациентов до начала терапии и каждые 3–6 мес после терапии с помощью шкалы детской больницы Филадельфии для диагностики двигательных функций у новорожденных (CHOP INTEND), общее двигательное развитие по шкале оценки неврологического статуса больницы Хаммерсмит у детей раннего возраста, часть 2 (HINE-2), а также приобретение новых двигательных навыков.Результаты. Терапию препаратом онасемноген абепарвовек получил 41 ребенок в возрасте от 5 до 47 мес (с массой тела не более 21 кг) в период с апреля 2020 г. по декабрь 2021 г. Нежелательные явления (гипертермия, снижение аппетита, тошнота, рвота) зарегистрированы у всех пациентов с разной степенью выраженности. Повышение уровня трансаминаз более чем в 2 раза от верхней границы нормы было отмечено у 32 (78 %) пациентов, тромбоцитопения – у 9 (22 %); 15 (36 %) пациентам потребовалась коррекция дозы кортикостероидов.Семнадцати пациентам проведена оценка по двигательным шкалам через 6 мес, 10 детям – спустя год. Среднее улучшение по шкале HINE-2 составило 3,3 / 4,4 балла соответственно. Среднее улучшение по шкале CHOP INTEND составило 7,1 / 9,4 балла через 6 / 12 мес терапии.Заключение. Продемонстрированы эффективность и безопасность применения препарата онасемноген абепарвовек в условиях реальной клинической практики при терапии спинальной мышечной атрофии для детей в разных возрастных группах с массой тела не более 21 кг

Major and minor lymphocytes subpopulations in peripheral blood and cerebrospinal fluid of children with meningitis

Introduction. The analysis of current publications indicates at our insufficient understanding of subpopulation composition of lymphocytes in peripheral blood and cerebrospinal fluid (CSF) during pediatric neuroinfectious diseases. It has been found that the main lymphocyte populations are divided into many small (minor) subpopulations.The purpose of this research was to assess percentage of major and minor blood and CSF lymphocyte subsets in children with aseptic viral meningitis (AM) or bacterial purulent meningitis (BM).Materials and methods. Phenotyping of blood and CSF lymphocytes of children aged from 4 months to 17 years diagnosed with AM (n = 86) and BM (n = 39) was carried out by using flow cytometry. As a comparison group, we analyzed peripheral blood and CSF samples collected from children with acute respiratory viral infections (ARVIs) associated with syndrome of meningism (n = 27). There was evaluated percentage of the major cell subpopulations (CD3+ T-lymphocytes, T-helpers — CD3+CD4+ Th, cytotoxic T-lymphocytes — CD3+CD8+ CTL, natural killer cells — CD3-CD16+CD56+ NK, B-cells — CD3-CD19+), as well as minor lymphocyte subsets (double positive (DP) (CD3+CD4+CD8+), double negative (DN) (CD3+CD4-CD8-) T-cells, NKT (CD3+CD16+CD56+), CD3-CD8+ NK, CD3+CD8dim and CD3+CD8 8bright).Results. It was found that the acute period of BM and AM vs. the comparison group (ARVI) was characterized by significant differences in the blood and CSF composition of major and minor lymphocyte subsets. In particular, blood T-cells, Th, CTL, NK, NKT, DN, CD3-CD8+ NK, CD3+CD8bright and CD3+CD8dim dominated in parallel with significantly lowered B-cell frequency in AM vs. BM. In the CSF of children with AM, T-cells and Th prevailed, whereas count of B-cells and CD3-CD8+ NK was lower compared to those in BM. In addition, further differences were revealed in CSF and blood cell subset composition depending on nosological entity, while maintaining differences in some major and minor lymphocyte subpopulations lacked in the comparison group. Calculating the CSF/blood ratio for the major and minor lymphocyte subsets uncovered the prevalence for the majority of cell subpopulations (the coefficients ranged from 1.2 to 16.4) in the CSF of the comparison group (ARVI), except B-cells, NK and CD3-CD8+ NK (coefficients ranged from 0.07 to 0.31). AM and BM were featured with various changes in the CSF/blood ratio found for most of the studied subpopulations in the acute period as well as the recovery phase highlighted with characteristic traits for each nosological form.Conclusion. The data obtained indicate about finding specific features in the activation of systemic and intrathecal immune response during viral and bacterial meningitis in children, which may be used as an additional differential diagnostic criterion