A Copper-Nitroxide Adduct Exhibiting Separate Single Crystal-to-Single Crystal Polymerization-Depolymerization and Spin Crossover Transitions

© 2016 American Chemical Society.A complex cascade of solid-state processes initiated by variation of temperature was found for the heterospin complex [Cu(hfac)2LMe/Et] formed in the reaction of copper(II) hexafluoroacetylacetonate [Cu(hfac)2] with stable nitronyl nitroxide 2-(1-methyl-3-ethyl-1H-pyrazol-4-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (LMe/Et). The cooling of the compound below 260 K initiated a solid-state chemical reaction, which led to a depolymerization of chains and formation of a pair heterospin complex [Cu(hfac)2LMe/Et2][[Cu(hfac)2]3LMe/Et2]. Further decrease in temperature below 144 K led to a spin transition accompanied by a drastic decrease in the effective magnetic moment from 2.52 to 2.24 μB. When the compound was heated, the order of effects was reversed: at first, the magnetic moment abruptly increased, and then the molecular fragments of the pair cluster united into polymer chains. Two hysteresis loops correspond to this cascade of temperature-induced structural transformations on the experimental dependence μeff(T): one at high (T ' = 283 K and T " = 260 K) and the other at low (T= 161 K, T = 144 K) temperature. The spin transitions were also recorded for the [[Cu(hfac)2]3LBu/Et2] and [[Cu(hfac)2]5LBu/Et4] molecular complexes, which are models of the trinuclear fragment of the {[Cu(hfac)2]3LMe/Et2} pair cluster

Современные концепции молекулярного патогенеза рака щитовидной железы

Thyroid cancer remains the most common malignancy of the endocrine system worldwide. The indicators of its morbidity and mortality rates have been increasing rapidly over the last decades. Most cases of differentiated thyroid cancer (follicular and papillary histotypes) are clinically manifested by nodular goiter frequently combined with uncertain results of cytological diagnosis (categories III and IV according to the Bethesda (Bethesda System for Reporting Thyroid Cytopathology) classification). All of that makes it difficult to choose a proper tactic for patient treatment. It is known that the development, progression, invasion, and metastasis of cancer cells are regulated by a variety of molecular mechanisms. This review describes several molecular aspects of thyroid nodules oncogenesis, as well as its most promising diagnostic tumor markers. Following molecular pathways are described in particular: gene mutations, protein tumor markers, and epigenetic effects of micro-RNA, histones, as well as DNA methylation. The study of the pathogenesis of this disease has a prognostic value and contributes to the search for effective therapeutic and diagnostic methods and their improvement. That is why we also reviewed modern test panels aimed at preoperative differential diagnosis of thyroid nodules. Summarizing the results of world research on this topic allows us not only to expand the understanding of the fundamental processes of oncogenesis, but also to outline promising areas for future experimental research projects. All of that together will contribute to developing new prognostic, diagnostic and therapeutic technologies, and as a result, will improve the quality of medical care for patients with thyroid cancer.Рак щитовидной железы – распространенное злокачественное новообразование эндокринной системы. В последние десятилетия показатели заболеваемости и смертности вследствие этой патологии стремительно увеличиваются. Большинство случаев дифференцированного рака щитовидной железы (фолликулярного и папиллярного гистотипов) клинически проявляются как узловой зоб. Неопределенность результатов цитологической диагностики (категории III и IV по классификации Bethesda (Bethesda System for Reporting Thyroid Cytopathology)) обусловливает сложности в выборе тактики ведения пациентов. Известно, что развитие, прогрессирование, инвазия и метастазирование раковых клеток регулируются множеством молекулярных механизмов. В данной статье описываются некоторые молекулярные аспекты онкогенеза узловых образований щитовидной железы, а также наиболее перспективные диагностические онкомаркеры. В частности, рассматривается роль генных мутаций, белковых маркеров, эпигенетических воздействий микроРНК, гистонов и метилирования ДНК в патогенезе рака щитовидной железы. Изучение патогенеза этого заболевания имеет прогностическую ценность и способствует поиску эффективных лечебно-диагностических методов и их совершенствованию. Поэтому в исследовании были рассмотрены применяемые в настоящий момент тест-панели, направленные на дооперационную дифференциальную диагностику узловых образований щитовидной железы. Анализ и обобщение результатов исследований по данной теме позволят не только расширить понимание фундаментальных процессов онкогенеза, но и наметить перспективные направления планирования экспериментальных научных работ для разработки новых прогностических, диагностических и терапевтических технологий с целью повышения качества медицинской помощи пациентам с раком щитовидной железы

A Copper-Nitroxide Adduct Exhibiting Separate Single Crystal-to-Single Crystal Polymerization-Depolymerization and Spin Crossover Transitions

© 2016 American Chemical Society.A complex cascade of solid-state processes initiated by variation of temperature was found for the heterospin complex [Cu(hfac)2LMe/Et] formed in the reaction of copper(II) hexafluoroacetylacetonate [Cu(hfac)2] with stable nitronyl nitroxide 2-(1-methyl-3-ethyl-1H-pyrazol-4-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (LMe/Et). The cooling of the compound below 260 K initiated a solid-state chemical reaction, which led to a depolymerization of chains and formation of a pair heterospin complex [Cu(hfac)2LMe/Et2][[Cu(hfac)2]3LMe/Et2]. Further decrease in temperature below 144 K led to a spin transition accompanied by a drastic decrease in the effective magnetic moment from 2.52 to 2.24 μB. When the compound was heated, the order of effects was reversed: at first, the magnetic moment abruptly increased, and then the molecular fragments of the pair cluster united into polymer chains. Two hysteresis loops correspond to this cascade of temperature-induced structural transformations on the experimental dependence μeff(T): one at high (T ' = 283 K and T " = 260 K) and the other at low (T= 161 K, T = 144 K) temperature. The spin transitions were also recorded for the [[Cu(hfac)2]3LBu/Et2] and [[Cu(hfac)2]5LBu/Et4] molecular complexes, which are models of the trinuclear fragment of the {[Cu(hfac)2]3LMe/Et2} pair cluster

A Copper-Nitroxide Adduct Exhibiting Separate Single Crystal-to-Single Crystal Polymerization-Depolymerization and Spin Crossover Transitions

© 2016 American Chemical Society.A complex cascade of solid-state processes initiated by variation of temperature was found for the heterospin complex [Cu(hfac)2LMe/Et] formed in the reaction of copper(II) hexafluoroacetylacetonate [Cu(hfac)2] with stable nitronyl nitroxide 2-(1-methyl-3-ethyl-1H-pyrazol-4-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (LMe/Et). The cooling of the compound below 260 K initiated a solid-state chemical reaction, which led to a depolymerization of chains and formation of a pair heterospin complex [Cu(hfac)2LMe/Et2][[Cu(hfac)2]3LMe/Et2]. Further decrease in temperature below 144 K led to a spin transition accompanied by a drastic decrease in the effective magnetic moment from 2.52 to 2.24 μB. When the compound was heated, the order of effects was reversed: at first, the magnetic moment abruptly increased, and then the molecular fragments of the pair cluster united into polymer chains. Two hysteresis loops correspond to this cascade of temperature-induced structural transformations on the experimental dependence μeff(T): one at high (T ' = 283 K and T " = 260 K) and the other at low (T= 161 K, T = 144 K) temperature. The spin transitions were also recorded for the [[Cu(hfac)2]3LBu/Et2] and [[Cu(hfac)2]5LBu/Et4] molecular complexes, which are models of the trinuclear fragment of the {[Cu(hfac)2]3LMe/Et2} pair cluster

A Copper-Nitroxide Adduct Exhibiting Separate Single Crystal-to-Single Crystal Polymerization-Depolymerization and Spin Crossover Transitions

© 2016 American Chemical Society.A complex cascade of solid-state processes initiated by variation of temperature was found for the heterospin complex [Cu(hfac)2LMe/Et] formed in the reaction of copper(II) hexafluoroacetylacetonate [Cu(hfac)2] with stable nitronyl nitroxide 2-(1-methyl-3-ethyl-1H-pyrazol-4-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (LMe/Et). The cooling of the compound below 260 K initiated a solid-state chemical reaction, which led to a depolymerization of chains and formation of a pair heterospin complex [Cu(hfac)2LMe/Et2][[Cu(hfac)2]3LMe/Et2]. Further decrease in temperature below 144 K led to a spin transition accompanied by a drastic decrease in the effective magnetic moment from 2.52 to 2.24 μB. When the compound was heated, the order of effects was reversed: at first, the magnetic moment abruptly increased, and then the molecular fragments of the pair cluster united into polymer chains. Two hysteresis loops correspond to this cascade of temperature-induced structural transformations on the experimental dependence μeff(T): one at high (T ' = 283 K and T " = 260 K) and the other at low (T= 161 K, T = 144 K) temperature. The spin transitions were also recorded for the [[Cu(hfac)2]3LBu/Et2] and [[Cu(hfac)2]5LBu/Et4] molecular complexes, which are models of the trinuclear fragment of the {[Cu(hfac)2]3LMe/Et2} pair cluster