ОПРЕДЕЛЕНИЕ МОНОЗАМЕЩЕННЫХ НИТРОФЕНОЛОВ В ВОДЕ МЕТОДОМ ГАЗОВОЙ ХРОМАТОГРАФИИ

Nitrophenols are highly toxic hydrophilic organic compounds. Nitrophenols prevalence in the biosphere is associated with both human industrial activity and with natural processes in the atmosphere and hydrosphere. Nitrophenols determination using gas chromatography requires chemical modification in order to reduce the hydrophilicity and polarity of the analytes. The derivatization must be carried out before the extraction concentration stage, but in most methods of the nitrophenols determination in water this approach is not implemented. The method of determination of mononitrophenols (2-, 3-, and 4-nitrophenols) in water was developed. It involved the nitrophenols bromination directly in the water, bromoderivatives liquid extraction with toluene, silylation by N-tert-Butyldimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA) extract and gas chromatographic determination with the electron-capture detector (GC-ECD). The nitrophenols bromination conditions in aqueous solutions were optimized (pH value, bromination duration, bromide-ions concentration). In order to reduce the oxidizing activity of bromine, the nitrophenols bromination was recommended in the presence of bromide anions. The extraction (degree of extraction) and gas chromatographic (retention indices, ECD relative molar responses) properties and nitrophenols bromoderivatives properties were studied. It was shown that the degree of extraction of brominated nitrophenols in the toluene/water system exceeded 80% and the subsequent silylation of the bromoderivatives significantly improved their chromatographic properties. The analytical range of nitrophenols in water was 0.02-10 µg/dm3 with an error of 10-35%, the detection limits were 0.05-0.07 μg/dm3, the sample volume for analysis was 50 cm3, the analysis duration was 90 min.Key words: mononitrophenols, chemical modification, gas-chromatography, electron-capture detector  DOI: http://dx.doi.org/10.15826/analitika.2020.24.2.006I.V. Gruzdev, B.M. Kondratenok, E.I. Lyu-Lyan-Min Institute of Biology of Komi Scientific Centre of the Ural Branch of the Russian Academy of Sciences (IB FRC Komi SC UB RAS),Kommunisticheskaya st., 28, Syktyvkar, 167982, Russian FederationНитрофенолы – высокотоксичные гидрофильные органические соединения, распространение которых в окружающей среде связано как с промышленной деятельностью человека, так и с протеканием ряда природных процессов в атмосфере и гидросфере. При определении нитрофенолов методом газовой хроматографии требуется снижать их гидрофильность и полярность, для чего применяется химическая модификация с различными реагентами. Дериватизацию нитрофенолов необходимо проводить до стадии их экстракционного концентрирования, но в большинстве методик этот подход не реализуется. Разработан способ определения изомерных нитрофенолов (2-, 3- и 4-нитрофенол) в различных водных объектах, предполагающий получение их бромпроизводных непосредственно в воде, жидкостную экстракцию толуолом, силилирование в экстракте N-трет-бутилдиметилсилил-N-метилтрифторацетамидом (MTBSTFA) и газохроматографическое определение полученных эфирных производных с галогенселективным детектором электронного захвата (ГХ-ДЭЗ). Установлены оптимальные условия проведения бромирования нитрозамещенных фенолов в условиях водного раствора (значение рН, продолжительность бромирования, концентрация бромид-ионов). Для снижения окислительной активности брома и повышения устойчивости в растворе получаемых аналитических форм, бромирование нитрофенолов рекомендуется проводить в присутствии бромид-анионов. Изучены экстракционные (степень извлечения) и газохроматографические (индексы удерживания, относительные мольные отклики ДЭЗ) характеристики нитрофенолов и их бромсодержащих производных. Показано, что степень извлечения бромированных нитрофенолов при выбранных условиях экстракции в системе толуол/вода превышает 80 %, а последующее силилирование бромпроизводных значительно улучшает их хроматографические свойства. Интервал определяемых концентраций нитрофенолов в воде 0.2-10 мкг/дм3, пределы обнаружения 0.05-0.07 мкг/дм3, погрешность определения – 10-35 %, объем пробы – 50 см3, продолжительность анализа – 90 минут.Ключевые слова: нитрофенолы, газовая хроматография, химическая модификация, детектор электронного захватаDOI: http://dx.doi.org/10.15826/analitika.2020.24.2.00

BEYOND CLOTHING

BEYOND CLOTHING, a sole proprietorship business formed in February 2020 by Pia Andrade, officially started operations in November 2020 with the mission to provide athletic apparel to Generation Y and Generation Z residing in Region IV-A as they want to help promote healthy lifestyles. BEYOND CLOTHING offered athletic Coolpass fabric shirts priced at Php 400.00 which are available in five sizes and four colors as their flagship product. They diversified into athletic Taslan shorts priced at Php 349.00, which are available in two sizes and two colors. BEYOND CLOTHING entered the athletic apparel market using the market penetration pricing strategy. BEYOND CLOTHING used digital marketing in advertising their products. Both their flagship product and their product diversification, featuring designs made and owned by BEYOND CLOTHING, are comfortable and durable. The strengths of BEYOND CLOTHING that set it apart from its competitors are its products’ durability and features, their meet-up and delivery services, their efficient teamwork, their good supplier relationship and inventory management, and their effective advertising. A total of 120 shirts were produced by the business with a start-up capital of Php 30,000.00 sourced from the owner and the managers. As their break-even was reached, BEYOND CLOTHING allocated Php 3,800.00 for their product diversification. BEYOND CLOTHING will continue its operations after graduating at the end of the academic year

Parental wellbeing after diagnosing a child with biliary atresia:A prospective cohort study

PURPOSE: To determine anxiety, stress, and quality of life (QoL) in parents of children who are diagnosed with biliary atresia (BA). METHODS: Parents of BA patients (0-3 years) completed validated questionnaires at three time points: at first hospitalization (T0); 1-2 months post diagnosis (T1); and 2-3 years post diagnosis (T2). Results are presented in medians (min-max). RESULTS: We included 52 parents (age 31 [24-51 y], 31 females) of 30 BA patients. In fathers, neither anxiety nor stress levels significantly differed from reference values. Mothers reported significantly higher anxiety levels compared to reference values (T0: 48 vs 35, p = 0.001; T1: 43 vs 35, p = 0.03; T2: 37 vs 35, p = 0.04), which significantly decreased over time (-23% between T0 and T2: p = 0.04). Stress in mothers was significantly higher at T1 than at T2 (+35%, p = 0.02), but was not significantly different from reference values at each time point (T0: 17 vs 14, p = 0.07; T1: 18 vs 14, p = 0.09; T2: 13 vs 14, p = 0.52).The overall QoL in mothers and fathers was rather unaffected. CONCLUSIONS: Particularly mothers of infants diagnosed with BA report high anxiety levels up to three years after diagnosis. The overall QoL of parents is rather unaffected after diagnosing BA in their child. LEVEL OF EVIDENCE: Level 2

Health-Related Quality of Life in Biliary Atresia Patients with Native Liver or Transplantation

Introduction We aimed to assess health-related quality of life (HrQoL) in biliary atresia (BA) patients, based on original data and a literature review, and to determine factors associated with their HrQoL. Materials and Methods We reviewed available studies describing HrQoL in BA patients. We assessed HrQoL in Dutch BA patients (6-16 years) using the validated Child Health Questionnaire. We compared HrQoL scores in BA patients with healthy peers and with children who had undergone major surgery in infancy or children with chronic conditions. We determined the relationship between specific patient-related factors and HrQoL. Results Literature data indicated that HrQoL in children with BA is lower than in healthy peers. In Dutch BA patients (n = 38; age 10 ± 3 years), parent-proxy physical HrQoL (48 ± 11) was significantly lower compared with two reference groups of healthy peers (59 ± 4 and 56 ± 6, respectively, each p < 0.001), and lower than in children with attention deficit hyperactivity disorder (60 ± 5), asthma (54 ± 6), attending a cardiology clinic (52 ± n / r), congenital diaphragmatic hernia (53 ± 7) or D-transposition of the great arteries (54 ± 6; all p < 0.05). Psychosocial HrQoL (50 ± 9) was lower than in healthy peers (54 ± 6, p = 0.02, and 53 ± 6, p = 0.07) and children with asthma (54 ± 6, p = 0.02), and largely comparable to children with other chronic conditions. Parent-proxy physical HrQoL was adversely related to adverse medical event in the past year, special education, and motor impairments; psychosocial HrQoL was adversely related to behavioral problems. Conclusion Children with BA are at risk of impaired HrQoL. Special attention is warranted for children with adverse medical events and special education

Long-Term Neurodevelopmental Outcomes in Children with Biliary Atresia

Objective: To assess long-term neurodevelopmental outcomes in school-aged children with biliary atresia. Study design: All Dutch children (6-12 years of age) diagnosed with biliary atresia were invited to participate in this study. We used validated neurodevelopmental tests to assess motor skills and cognition, and questionnaires to assess behavior. Scores were compared with the Dutch norm population, by means of 1-sample tests. Results are given as number and percentage or mean ± SD. Results: We included 46 children, with a median age of 11 years (range, 6-13 years); 36 children had undergone a liver transplantation (78%). Twelve children (26%) received special education (vs 2.4% in the norm population; P <.01). Motor outcomes were significantly affected compared with the norm population (P <.01), with 25% normal (vs 85%), 25% borderline (vs 10%), and 50% low scores (vs 5%). Total IQ was lower in patients with biliary atresia, compared with the norm population (91 ± 18 vs 100 ± 15; P <.01). There were no significant differences in test scores between children with native liver and after liver transplantation. Conclusions: School-aged children with biliary atresia show neurodevelopmental impairments compared with the norm population, especially in motor skills. Our data strongly warrant evaluation of neurodevelopmental intervention programs to assess whether long-term outcomes could be improved

ОСОБЕННОСТИ ПРОБОПОДГОТОВКИ ПРИ ОПРЕДЕЛЕНИИ ФЕНОЛА В ВЫСОКОЦВЕТНЫХ ПРИРОДНЫХ ВОДАХ МЕТОДОМ ГАЗОВОЙ ХРОМАТОГРАФИИ

Existing the phenol determination methods in water suggest the use of extraction concentration combined with heating the sample and phenol derivatization in alkaline media. It is shown that humic substances of water samples is destructed by the alkaline solutions or heating. Humic substances destruction produces phenol and distorts the results of quantitative chemical analysis. The interfering effect of humic substances need to be eliminate in beginning of the analytical cycle. A method for removing humus by coagulation on the Al2O3 layer with simultaneous impregnation of the sorbent with copper (II) cations is proposed. The method allows to eliminate the interfering effect of humic substances in the phenol quantification in natural waters. The conditions of humic substances complete removal from the water samples is established, the role of copper (II) cations in this process is shown. Under optimal conditions, the native phenol adsorption on alumina surface does not exceed 3 %. For selective and sensitive gas-chromatographic determination of phenol in the eluate we used preliminary bromination. Phenol bromoderivative (2,4,6-tribromophenol) with a halogen-selective electron-capture detector was detected. A procedure was developed for phenol determination in water of 0.2 to 10 μg/dm3, the relative error of measurement in this range does not exceed 30 %. The water sample volume is 25 cm3, the analysis duration is 30 min.Keywords: phenol, gas chromatography, high-color natural water, chemical modification, humic substances, aluminum oxideDOI: http://dx.doi.org/10.15826/analitika.2019.23.2.004(Russian)I.V. Gruzdev, B.M. Kondratenok, O.M. Zueva, E.I. Lyu-Lyan-Min Institute of Biology of Komi Scientific Centre of the Ural Branch of the Russian Academy of Sciences (IB Komi SC UB RAS), Kommunisticheskaya st., 28, Syktyvkar, 167982, Russian FederationРяд методик определения фенольных соединений в водных средах предполагает использование в аналитическом цикле экстракционного концентрирования в сочетании с нагреванием пробы и проведение реакций дериватизации в щелочных средах. Показано, что такие операции, проводимые в присутствии гумусовых веществ, вызывают их деструкцию с образованием фенола. Предложен способ удаления гумуса путем коагуляции на слое Al2O3 при одновременном импрегнировании сорбента катионами меди (II). Способ позволяет устранить мешающее влияние гумусовых веществ при количественном определении фенола в природных водах. Установлены условия, при которых достигается полное удаление гумусовых веществ из анализируемой пробы воды, показана роль катионов меди в этом процессе. При установленных оптимальных условиях адсорбция нативного фенола на оксиде алюминия не превышает 3 %. С целью повышения чувствительности и селективности определения фенола в получаемом элюате проводится его химическая модификация в 2,4,6-трибромфенол с последующим газохроматографическим анализом с галогенселективным электронозахватным детектором. Диапазон определяемых концентраций фенола в воде от 0.2 до 10 мкг/дм3 с относительной погрешностью не более 30 %. Объем пробы воды, необходимый для анализа, – 25 см3, продолжительность анализа – 30 минут.Ключевые слова: фенол, газовая хроматография, высокоцветные природные воды, химическая модификация, гумусовые вещества, оксид алюминияDOI: http://dx.doi.org/10.15826/analitika.2019.23.2.00

Surveillance of high-risk early postsurgical patients for real-time detection of complications using wireless monitoring (SHEPHERD study):results of a randomized multicenter stepped wedge cluster trial

Background: Vital signs measurements on the ward are performed intermittently. This could lead to failure to rapidly detect patients with deteriorating vital signs and worsens long-term outcome. The aim of this study was to test the hypothesis that continuous wireless monitoring of vital signs on the postsurgical ward improves patient outcome. Methods: In this prospective, multicenter, stepped-wedge cluster randomized study, patients in the control group received standard monitoring. The intervention group received continuous wireless monitoring of heart rate, respiratory rate and temperature on top of standard care. Automated alerts indicating vital signs deviation from baseline were sent to ward nurses, triggering the calculation of a full early warning score followed. The primary outcome was the occurrence of new disability three months after surgery. Results: The study was terminated early (at 57% inclusion) due to COVID-19 restrictions. Therefore, only descriptive statistics are presented. A total of 747 patients were enrolled in this study and eligible for statistical analyses, 517 patients in the control group and 230 patients in the intervention group, the latter only from one hospital. New disability at three months after surgery occurred in 43.7% in the control group and in 39.1% in the intervention group (absolute difference 4.6%). Conclusion: This is the largest randomized controlled trial investigating continuous wireless monitoring in postoperative patients. While patients in the intervention group seemed to experience less (new) disability than patients in the control group, results remain inconclusive with regard to postoperative patient outcome due to premature study termination. Clinical trial registration: ClinicalTrials.gov, ID: NCT02957825.</p

Determination of mononitrophenols in water by gaschromatography

Нитрофенолы – высокотоксичные гидрофильные органические соединения, распространение которых в окружающей среде связано как с промышленной деятельностью человека, так и с протеканием ряда природных процессов в атмосфере и гидросфере. При определении нитрофенолов методом газовой хроматографии требуется снижать их гидрофильность и полярность, для чего применяется химическая модификация с различными реагентами. Дериватизацию нитрофенолов необходимо проводить до стадии их экстракционного концентрирования, но в большинстве методик этот подход не реализуется. Разработан способ определения изомерных нитрофенолов (2-, 3- и 4-нитрофенол) в различных водных объектах, предполагающий получение их бромпроизводных непосредственно в воде, жидкостную экстракцию толуолом, силилирование в экстракте N-трет-бутилдиметилсилил-N-метилтрифторацетамидом (MTBSTFA) и газохроматографическое определение полученных эфирных производных с галогенселективным детектором электронного захвата (ГХ-ДЭЗ). Установлены оптимальные условия проведения бромирования нитрозамещенных фенолов в условиях водного раствора (значение рН, продолжительность бромирования, концентрация бромид-ионов). Для снижения окислительной активности брома и повышения устойчивости в растворе получаемых аналитических форм, бромирование нитрофенолов рекомендуется проводить в присутствии бромид-анионов. Изучены экстракционные (степень извлечения) и газохроматографические (индексы удерживания, относительные мольные отклики ДЭЗ) характеристики нитрофенолов и их бромсодержащих производных. Показано, что степень извлечения бромированных нитрофенолов при выбранных условиях экстракции в системе толуол/вода превышает 80 %, а последующее силилирование бромпроизводных значительно улучшает их хроматографические свойства. Интервал определяемых концентраций нитрофенолов в воде 0.2-10 мкг/дм3, пределы обнаружения 0.05-0.07 мкг/дм3, погрешность определения – 10-35 %, объем пробы – 50 см3, продолжительность анализа – 90 минут.Nitrophenols are highly toxic hydrophilic organic compounds. Nitrophenols prevalence in the biosphere is associated with both human industrial activity and with natural processes in the atmosphere and hydrosphere. Nitrophenols determination using gas chromatography requires chemical modification in order to reduce the hydrophilicity and polarity of the analytes. The derivatization must be carried out before the extraction concentration stage, but in most methods of the nitrophenols determination in water this approach is not implemented. The method of determination of mononitrophenols (2-, 3-, and 4-nitrophenols) in water was developed. It involved the nitrophenols bromination directly in the water, bromoderivatives liquid extraction with toluene, silylation by N-tert-Butyldimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA) extract and gas chromatographic determination with the electron-capture detector (GC-ECD). The nitrophenols bromination conditions in aqueous solutions were optimized (pH value, bromination duration, bromide-ions concentration). In order to reduce the oxidizing activity of bromine, the nitrophenols bromination was recommended in the presence of bromide anions. The extraction (degree of extraction) and gas chromatographic (retention indices, ECD relative molar responses) properties and nitrophenols bromoderivatives properties were studied. It was shown that the degree of extraction of brominated nitrophenols in the toluene/water system exceeded 80% and the subsequent silylation of the bromoderivatives significantly improved their chromatographic properties. The analytical range of nitrophenols in water was 0.02-10 µg/dm3 with an error of 10-35%, the detection limits were 0.05-0.07 μg/dm3, the sample volume for analysis was 50 cm3, the analysis duration was 90 min.Исследование выполнено на оборудовании ЦКП «Хроматография» Института биологии Коми НЦ УрО РАН и при финансовой поддержке РФФИ в рамках научного проекта № 18-05-60195 (№ ЦИТиС АААА-А18-118062090029-0).Current study was carried out using the equipment of the “Chromatography” center of collective usage at the Institute of Biology of Komi Scientific Centre of the Ural Branch of the RAS, and with the financial support of the Russian Foundation for Fundamental Research (project No. 18-05-60195)