Redox-induced change in the ligand coordination mode

© 2014 American Chemical Society. The reaction of cobalt(II) pivalate with a spin-labeled Schiff base (HL1) in organic solvents formed trinuclear complex [Co3(Piv)2L1 2L2 2]·Solv (Solv is Me2CO and/or C7H16 and CH3CN) containing both nitroxide L1 and the product of its single-electron reduction, nitrone L2. The formation of [Co3(Piv)2L1 2L2 2] was a consequence of an unusual phenomenon, which we called "redox-induced change in the ligand coordination mode". A reduction of L1 to L2 led to a change in the set of donor atoms and even in the size of the metallocycle. This phenomenon was also found for mononuclear [CrL1 2L2] and [FeL1 2L2]·Me2CO

Дыхательная реабилитация у больных вирусной пневмонией на фоне новой коронавирусной инфекции

Pulmonary rehabilitation in COVID-19 patients with pneumonia is associated with better treatment outcomes. However, existing protocols have never been evaluated in randomized control studies. The aim. To evaluate the effectiveness of newly-developed pulmonary rehabilitation protocol compared to basic Russian COVID-19 guidelines for patients with oxygenation index (OI) between 200 and 400 points without IMV. Methods. Based on literature reviews and own clinical experience, standard rehabilitation protocol was designed and tailored for specific needs of low-OI patients. Two clinical centers participated in the study and included total 73 patients in main group. Control group included 73 retrospective patients based in propensity score; this patients received standard protocol of early pneumonia activation from official COVID-19 guidelines. Ten-days clinical outcomes were assessed based on parameter distribution type. Results. Evidence show significant difference in required time of continuous oxygen support in (5.1 ± 3.3 vs 8.0 ± 4.6 days for main and control group respectively. Main group also had mildly better functional. We’ve observed less mortality in main group, but attribute it not to the program, but for growing experience of health professionals and decreased loads on health system. Malignancy as comorbidity was considered a significant cofactor also. Conclusion. New pulmonary rehabilitation protocol improves clinical outcomes in critical COVID-19 patients by decreasing the demand fox oxygen support.При использовании дыхательной реабилитации при пневмонии, ассоциированной с новой коронавирусной инфекцией (НКИ), отмечено улучшение результатов лечения. Однако типовые протоколы дыхательной реабилитации для тяжелых форм коронавирусной пневмонии по данным рандомизированных исследований до настоящего момента не оценивались. Целью рандомизированного клинического исследования, проведенного в 2 клинических центрах, явилось определение эффективности протокола дыхательной реабилитации у больных с индексом оксигенации < 400 и > 200 при самостоятельном дыхании или кислородной поддержке по сравнению с пациентами, у которых реабилитация не проводилась. Материалы и методы. В исследовании приняли участие пациенты (n = 146) с ДН, отобранные методом ретроспективной псевдорандомизации среди больных, проходивших лечение ранее. Разработан протокол из 5 последовательных упражнений дыхательной гимнастики. Пациентам основной группы (n = 73) к лечению в течение 10 дней добавлена исследуемая реабилитационная программа, затем оценивались результаты. Результаты. Получено достоверное различие продолжительности непрерывной кислородной поддержки между группами (5,1 ± 3,3 дня vs 8,0 ± 4,6 дня). При анализе в подгруппах важной самостоятельной ковариатой исхода оказалось наличие онкологического заболевания. Заключение. При использовании комплекса лечебной физической культуры в остром периоде течения НКИ повышается эффективность лечения за счет раннего снижения потребности в кислородной поддержке, ускоренной нормализации индекса оксигенации, повышения толерантности к физической нагрузке

Class I methanol masers in low-mass star formation regions

Four Class I maser sources were detected at 44, 84, and 95 GHz toward chemically rich outflows in the regions of low-mass star formation NGC 1333I4A, NGC 1333I2A, HH25, and L1157. One more maser was found at 36 GHz toward a similar outflow, NGC 2023. Flux densities of the newly detected masers are no more than 18 Jy, being much lower than those of strong masers in regions of high-mass star formation. The brightness temperatures of the strongest peaks in NGC 1333I4A, HH25, and L1157 at 44 GHz are higher than 2000 K, whereas that of the peak in NGC 1333I2A is only 176 K. However, rotational diagram analysis showed that the latter source is also a maser. The main properties of the newly detected masers are similar to those of Class I methanol masers in regions of massive star formation. The former masers are likely to be an extension of the latter maser population toward low luminosities of both the masers and the corresponding YSOs.Comment: 5 pages, 1 figure, Proc. IAU Symp. 287 "Cosmic Masers: from OH to H0". LSR velocities of the HH25 masers, which are presented in Table 1, are correcte

Dynamics of nonequilibrium quasiparticles in a double superconducting tunnel junction detector

We study a class of superconductive radiation detectors in which the absorption of energy occurs in a long superconductive strip while the redout stage is provided by superconductive tunnel junctions positioned at the two ends of the strip. Such a device is capable both of imaging and energy resolution. In the established current scheme, well studied from the theoretical and experimental point of view, a fundamental ingredient is considered the presence of traps, or regions adjacent to the junctions made of a superconducting material of lower gap. We reconsider the problem by investigating the dynamics of the radiation induced excess quasiparticles in a simpler device, i.e. one without traps. The nonequilibrium excess quasiparticles can be seen to obey a diffusion equation whose coefficients are discontinuous functions of the position. Based on the analytical solution to this equation, we follow the dynamics of the quasiparticles in the device, predict the signal formation of the detector and discuss the potentiality offered by this configuration.Comment: 16 pages, 5 figures Submitted to Superconducting Science and Technolog

Self-Assembly of Supramolecular Triblock Copolymer Complexes

Four different poly(tert-butoxystyrene)-b-polystyrene-b-poly(4-vinylpyridine) (PtBOS-b-PS-b-P4VP) linear triblock copolymers, with the P4VP weight fraction varying from 0.08 to 0.39, were synthesized via sequential anionic polymerization. The values of the unknown interaction parameters between styrene and tert-butoxystyrene and between tert-butoxystyrene and 4-vinylpyridine were determined from random copolymer blend miscibility studies and found to satisfy 0.031<χS,tBOS<0.034 and 0.39<χ4VP,tBOS<0.43, the latter being slightly larger than the known 0.30<χS,4VP≤0.35 value range. All triblock copolymers synthesized adopted a P4VP/PS core/shell cylindrical self-assembled morphology. From these four triblock copolymers supramolecular complexes were prepared by hydrogen bonding a stoichiometric amount of pentadecylphenol (PDP) to the P4VP blocks. Three of these complexes formed a triple lamellar ordered state with additional short length scale ordering inside the P4VP(PDP) layers. The self-assembled state of the supramolecular complex based on the triblock copolymer with the largest fraction of P4VP consisted of alternating layers of PtBOS and P4VP(PDP) layers with PS cylinders inside the latter layers. The difference in morphology between the triblock copolymers and the supramolecular complexes is due to two effects: (i) a change in effective composition and, (ii) a reduction in interfacial tension between the PS and P4VP containing domains. The small angle X-ray scattering patterns of the supramolecules systems are very temperature sensitive. A striking feature is the disappearance of the first order scattering peak of the triple lamellar state in certain temperature intervals, while the higher order peaks (including the third order) remain. This is argued to be due to the thermal sensitivity of the hydrogen bonding and thus directly related to the very nature of these systems.

ITO-free silicon-integrated perovskite electrochemical cell for light-emission and light-detection

Halide perovskite light-emitting electrochemical cells are a novel type of the perovskite optoelectronic devices that differs from the perovskite light-emitting diodes by a simple monolayered architecture. Here, we develop a perovskite electrochemical cell both for light emission and detection, where the active layer consists of a composite material made of halide perovskite microcrystals, polymer support matrix, and added mobile ions. The perovskite electrochemical cell of CsPbBr3:PEO:LiTFSI composition, emitting light at the wavelength of 523 nm, yields the luminance more than 7000 cd/m2 and electroluminescence efficiency of 1.3×105 lm/W. The device fabricated on a silicon substrate with transparent single-walled carbon nanotube film as a top contact exhibits 40% lower Joule heating compared to the perovskite optoelectronic devices fabricated on conventional ITO/glass substrates. Moreover, the device operates as a photodetector with a sensitivity up to 0.75 A/W, specific detectivity of 8.56×1011 Jones, and linear dynamic range of 48 dB. The technological potential of such a device is proven by demonstration of 24-pixel indicator display as well as by successful device miniaturization by creation of electroluminescent images with the smallest features less than 50 μm

Фармакоэкономическая оценка программы ускоренного выздоровления и кровосбережения при расширенно-комбинированных операциях на органах малого таза

Background: The newly diagnosed pelvic cancer appears to be locally advanced in every third patient, which requires a comprehensive approach to treatment and often extensive combined surgical interventions. Long duration of operations, blood loss, complications of the tumor process during or after previous treatment often lead to the development of complications, slow rehabilitation and increasing cost of treatment. The use of fast track protocol (FTP) and blood-saving technologies can reduce the impact of these adverse factors.Aim: The evaluation of the pharmaco-economic efficiency of fast track protocol and blood-saving technologies in patients after extended combined operations for pelvic tumors.Materials and methods: The study included 111 patients with pelvic tumors who underwent an extensive combined surgery for rectal or gynecological tumors. Among them, 52 patients were underwent the same fast track protocol with a focus on the use of blood-saving technologies (2020–2021), the management of patients in the control group was more conservative (n = 59, 2018–2019). After analyzing the factors affecting the treatment outcomes, 2 groups of 16 patients comparable in basic clinical indications were formed by selection of pairs patients using quasi-randomization to assess the direct costs of treatment.Results: The cost of treatment in the FTS group and the control group was 157744 ± 32728,72 and 273429 ± 217931,5 (P &lt; 0,05) rubles,  respectively. The lower blood loss (206 ± 70 ml vs 430 ± 208, р = 0,3) allowed for a statistically significant difference in the frequency of transfusion of blood components (2 vs 12, p &lt; 0,0009), despite the higher cost of supplies in the FTS group (132913 vs 57347 rubles). Also, the resuscitation bed-day (1,75 ± 1,3 vs 3,5 ± 2, р = 0,5) and the postoperative bed-day (16,8 ± 8; 8–32; vs 27 ± 18, р = 0,6) were lower in the FTS group.Conclusion: According to our data using the fast track protocol and blood-saving technologies in a group of patients with locally extensive pelvic organs tumors has helped to reduce the cost of treatment and improve the efficiency of the hospital.Актуальность: У каждого третьего пациента с диагностированными впервые опухолями органов малого таза процесс носит местнораспространенный характер, что требует комплексного подхода к лечению и проведения расширенных оперативных вмешательств. Высокая продолжительность операций, кровопотеря, осложнения опухолевого процесса или предшествующего лечения часто приводят к развитию осложнений, замедляют реабилитацию, повышают стоимость лечения. Применение программ ускоренного выздоровления (ПУВ) и кровосберегающих технологий позволяет снизить влияние этих неблагоприятных факторов.Цель исследования: оценка фармако-экономической  эффективности применения программы ускоренного выздоровления и кровосбережения при расширенно-комбинированных операциях по поводу опухолей малого таза.Материалы и методы: В исследование было включено 111 пациентов, которым была выполнена расширенно — комбинированная операция по поводу опухолей прямой кишки или женской репродуктивной сферы. В группе исследования(n = 52, 2020–2021 гг.) использовалась стандартизированная ПУВ с включением кровосберегающих технологий, в группеконтроля (n = 59, 2018–2019 гг.) ведение пациентов было более консервативным. С целью устранить влияние гетерогенности показателей пациентов и выполненных вмешательств на стоимость лечения использован метод псевдорандомизации (propensity score matching): после оценки ковариат исхода «общие затраты на госпитальный этап лечения» путем подбора пар были сформированы сопоставимые по основным клиническим показателям группы по 16 пациентов. В этих группах проведен сравнительный анализ стоимости лечения в целом и его различных компонентов.Результаты: Средняя стоимость лечения составила 161,2 ± 32,7 тыс. рублей в группе исследования против 273,4 ± 217,9 тыс. рублей в группе контроля, соответственно (р = 0,048). Применение  современных электролигирующих устройств, а также отказ от рутинного применения обструктивных резекций прямой кишки привели к увеличению стоимости расходных материалов в группе исследования, однако более низкий объем кровопотери (медиана 200 ± 70 мл против 500 ± 209, р = 0,3) позволил добиться статистически значимого различия по частоте переливания компонентов крови (4 против 12, р = 0,014), сокращения реанимационного (1,75 ± 1,3 против 3,5 ± 2, р = 0,5) и послеоперационного койко-дня (10 ± 8 против 14 ± 15, р = 0,6).Заключение: Применение ПУВ и кровосберегающих технологий при выполнении расширенно-комбинированных вмешательств на органах малого таза способствует снижению затрат на лечение и уменьшению длительности послеоперационного койко-дня, повышая эффективность работы стационара

Redox-induced change in the ligand coordination mode

© 2014 American Chemical Society. The reaction of cobalt(II) pivalate with a spin-labeled Schiff base (HL1) in organic solvents formed trinuclear complex [Co3(Piv)2L1 2L2 2]·Solv (Solv is Me2CO and/or C7H16 and CH3CN) containing both nitroxide L1 and the product of its single-electron reduction, nitrone L2. The formation of [Co3(Piv)2L1 2L2 2] was a consequence of an unusual phenomenon, which we called "redox-induced change in the ligand coordination mode". A reduction of L1 to L2 led to a change in the set of donor atoms and even in the size of the metallocycle. This phenomenon was also found for mononuclear [CrL1 2L2] and [FeL1 2L2]·Me2CO