Fused 1,2,3-dithiazoles: convenient synthesis, structural characterization, and electrochemical properties

A new general protocol for synthesis of fused 1,2,3-dithiazoles by the reaction of cyclic oximes with S2Cl2 and pyridine in acetonitrile has been developed. The target 1,2,3-dithiazoles fused with various carbocycles, such as indene, naphthalenone, cyclohexadienone, cyclopentadiene, and benzoannulene, were selectively obtained in low to high yields. In most cases, the hetero ring-closure was accompanied by chlorination of the carbocyclic moieties. With naphthalenone derivatives, a novel dithiazole rearrangement (15→13) featuring unexpected movement of the dithiazole ring from α- to β-position, with respect to keto group, was discovered. Molecular structure of 4-chloro-5H-naphtho[1,2-d][1,2,3]dithiazol-5-one 13 was confirmed by single-crystal X-ray diffraction. Electrochemical properties of 13 were studied by cyclic voltammetry and a complex behavior was observed, most likely including hydrodechlorination at a low potential

New NIR-emissive tetranuclear Er(III) complexes with 4-hydroxo-2,1,3-benzothiadiazolate and dibenzoylmethanate ligands: synthesis and characterization

New tetranuclear heteroleptic complexes [Er4(dbm)6(O-btd)4(OH)2] (1) and [Er4(dbm)4(O-btd)6(OH)2] (2) (O-btd = 4-hydroxo-2,1,3-benzothiadiazolate and dbm = dibenzoylmethanide) and their solvates with toluene, THF and CH2Cl2 were prepared using two synthetic approaches. The structures of the products were confirmed by single-crystal X-ray diffraction. Magnetic properties of 1 and 2 are in good agreement with X-ray data. The effective magnetic moment (μeff) values at 300 K for 1 and 2 corresponds to a system of 4 non-interacting Er(III) ions in the ground state 4J15/2 with g = 6/5. At ambient temperature and upon excitation with λexc = 450 nm, complexes 1 and 2 exhibit luminescence at ∼1530 nm, i.e. in the near infra-red (NIR) region. The luminescence intensity grows with increasing the number of the (O-btd)−ligands in the complexes. This observation suggests (O-btd)− as a new efficient antenna ligand for the lanthanide-based NIR luminescence

New NIR-emissive tetranuclear Er(III) complexes with 4-hydroxo-2,1,3-benzothiadiazolate and dibenzoylmethanide ligands: Synthesis and characterization

© The Royal Society of Chemistry 2015. New tetranuclear heteroleptic complexes [Er4(dbm)6(O-btd)4(OH)2] (1) and [Er4(dbm)4(O-btd)6(OH)2] (2) (O-btd = 4-hydroxo-2,1,3-benzothiadiazolate and dbm = dibenzoylmethanide) and their solvates with toluene, THF and CH2Cl2 were prepared using two synthetic approaches. The structures of the products were confirmed by single-crystal X-ray diffraction. Magnetic properties of 1 and 2 are in good agreement with X-ray data. The effective magnetic moment (μeff) values at 300 K for 1 and 2 corresponds to a system of 4 non-interacting Er(iii) ions in the ground state 4J15/2 with g = 6/5. At ambient temperature and upon excitation with λexc = 450 nm, complexes 1 and 2 exhibit luminescence at ∼1530 nm, i.e. in the near infra-red (NIR) region. The luminescence intensity grows with increasing the number of the (O-btd)- ligands in the complexes. This observation suggests (O-btd)- as a new efficient antenna ligand for the lanthanide-based NIR luminescence

Бактерицидная эффективность излучения светодиода с длиной волны 272 нм в отношении госпитального штамма Klebsiella pneumoniae

Relevance. Currently, the use of ultraviolet (UV) radiation for the disinfection of objects and the treatment for infectious diseases is considered as a promising alternative to chemical biocides and antibiotics. Shortwave — UV-C and UV-B -light emitting diodes (LED) are a relatively new type of UV radiation sources and potentially able to meet the requirements of current medical technologies. However, their possibilities for the treatment of wounds and infectious diseases have not been practically researched to date, which determines the relevance of experiments aimed at studying the biocidal and therapeutic properties of shortwavelength UV LEDs.Purpose. OF STUDY To evaluate the bactericidal efficacy of 272 nm LED radiation against hospital strains of Klebsiella pneumoniae bacteria characterized by multidrug resistance.Materials and Methods. The studies were carried out with an experimental sample of the LED apparatus for UV irradiation. In the irradiator of the device, 5 LEDs are installed with a maximum radiation at a wavelength of 272 nm and a total electrical power of 10 watts. The UV radiation dose achieved in one irradiation session (12 seconds) at a distance of 10 cm from the irradiator was 8 mJ/cm2 . In the experiments, a hospital strain of the bacterium Klebsiella pneumoniae, isolated from the patient’s blood, was used. The strain was characterized by multidrug resistance. A daily culture suspension of K. pneumoniae with a concentration of 108 CFU/ml in a volume of 100 µl was transferred into a Petri dish with a diameter of 9 cm with meat-peptone agar and evenly distributed over a surface with a diameter of 8 cm. Petri dishes were irradiated from a distance of 10 cm from the irradiator. The change in the dose of UV irradiation from 4 to 80 mJ/cm2 was carried out by varying the exposure time. Studies were carried out in 4 repetitions at each dose. After irradiation, the experimental and control (without irradiation) Petri dishes were placed in a thermostat at 37ºC for 24 hours, then the grown colonies were counted. A total of 60 experiments were carried out.Results. As a result of the research, it was shown that the LED device based on five 272 nm diodes provides deep and prompt disinfection of the surface from hospital strains of K. pneumoniae bacteria characterized by multidrug resistance. A dose of UV radiation of 8 mJ/cm2 reduces surface contamination with K. pneumoniae bacteria by more than a million times (decontamination efficiency over 99.9999%). At doses less than 10 mJ/cm2 , the efficiency of the 272 nm LED device in terms of inactivation of K. pneumoniae bacteria is 3–4 times higher than the bactericidal efficiency of mercury lamps.Conclusion.The prospects of using UV devices based on LEDs with a maximum radiation at a wavelength of 272 nm in systems for the operational disinfection of massively contaminated surfaces, potentially including wound surfaces, have been shown.Актуальность. В настоящее время применение ультрафиолетового (УФ) излучения для дезинфекции объектов и терапии инфекционных заболеваний рассматривается как перспективная альтернатива химическим биоцидным средствам и антибиотикам. Коротковолновые светоизлучающие диоды в спектральном диапазоне 200–280 нм и 280–315 нм являются сравнительно новым типом источников УФ излучения и потенциально способны удовлетворить требованиям актуальных медицинских технологий. Однако их возможности для лечения ран и инфекционных заболеваний на сегодняшний день практически не исследованы, что определяет актуальность экспериментов, направленных на изучение биоцидных и терапевтических свойств коротковолновых УФ светодиодов.Цель исследования. Оценить бактерицидную эффективность излучения светодиода с длиной волны 272 нм (272 нм светодиод) в отношении госпитальных штаммов бактерий Klebsiella pneumoniae, характеризующихся множественной лекарственной устойчивостью.Материал и методы. Исследования выполнены с использованием экспериментального образца светодиодного аппарата УФ облучения с максимумом излучения при длине волны 272 нм и суммарной электрической мощностью 10 Вт. Доза УФ излучения (энергетическая экспозиция), достигаемая за один сеанс облучения (12 секунд) на расстоянии 10 см от облучателя, составляла 8 мДж/см2 . В экспериментах использовали госпитальный штамм бактерии Klebsiella pneumoniae, выделенный из крови больного. Штамм характеризовался множественной лекарственной устойчивостью. Суспензию суточной культуры K. pneumoniae с концентрацией 108 КОЕ/мл в объеме 100 мкл переносили в чашку Петри диаметром 9 см с мясопептонным агаром и равномерно распределяли по поверхности диаметром 8 см. Чашки Петри облучали с расстояния 10 см от облучателя. Изменение дозы УФ облучения от 4 до 80 мДж/см2 осуществляли варьированием продолжительности облучения. После облучения экспериментальные и контрольные (без облучения) чашки Петри помещали в термостат при 37°С на 24 часа, а затем проводили подсчет выросших колоний. Всего проведено 60 экспериментов.Результаты. В результате исследований показано, что светодиодный аппарат на основе пяти 272 нм светодиодов обеспечивает глубокое и оперативное обеззараживание поверхности от госпитальных штаммов бактерий K. pneumoniae, характеризующихся множественной лекарственной устойчивостью. Доза УФ излучения, равная 8 мДж/см2 , снижает контаминацию поверхности бактериями K. pneumoniae более чем в миллион раз (эффективность обеззараживания более 99,9999%). При дозах менее 10 мДж/см2 эффективность 272 нм светодиодного аппарата в отношении инактивации бактерий K. pneumoniae на 3–4 порядка выше бактерицидной эффективности ртутных ламп.Вывод. Показана перспективность применения ультрафиолетовых аппаратов на основе светодиодов с максимумом излучения на длине волны 272 нм в системах оперативного обеззараживания массивно контаминированных поверхностей, потенциально включая и раневые поверхности

Synthesis and properties of the heterospin (S1 = S2 = 1/2) radical-ion salt bis(mesitylene)molybdenum(I) [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazolidyl

The authors are grateful to the Presidium of the Russian Academy of Sciences (Project 8.14), the Royal Society (RS International Joint Project 2010/R3), the Leverhulme Trust (Project IN-2012-094), the Siberian Branch of the Russian Academy of Sciences (Project 13), the Ministry of Education and Science of the Russian Federation (Project of Joint Laboratories of Siberian Branch of the Russian Academy of Sciences and National Research Universities), and the Russian Foundation for Basic Research (Projects 13-03-00072 and 15-03-03242) for financial support of various parts of this work. N.A.S. thanks the Council for Grants of the President of Russian Federation for postdoctoral scholarship (grant MK-4411.2015.3). B.E.B. is grateful for an EaStCHEM Hirst Academic Fellowship. A.V.Z. thanks the Foundation named after D. I. Mendeleev, Tomsk State University, for support of his work.Low-temperature interaction of [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (1) with MoMes2 (Mes = mesitylene / 1,3,5-trimethylbenzene) in tetrahydrofuran gave the heterospin (S1 = S2 = 1/2) radical-ion salt [MoMes2]+[1]– (2) whose structure was confirmed by single-crystal X-ray diffraction (XRD). The structure revealed alternating layers of the cations and anions with the Mes ligands perpendicular, and the anions tilted by 45°, to the layer plane. At 300 K the effective magnetic moment of 2 is equal to 2.40 μB (theoretically expected 2.45 μB) and monotonically decreases with lowering of the temperature. In the temperature range 2−300 K, the molar magnetic susceptibility of 2 is well-described by the Curie-Weiss law with parameters C and θ equal to 0.78 cm3⋅K⋅mol–1 and −31.2 K, respectively. Overall, the magnetic behavior of 2 is similar to that of [CrTol2]+[1]– and [CrCp*2]+[1]–, i.e. changing the cation [MAr2]+ 3d atom M = Cr (Z = 24) with weak spin-orbit coupling (SOC) to a 4d atom M = Mo (Z = 42) with stronger SOC does not affect macroscopic magnetic properties of the salts. For the XRD structure of salt 2, parameters of the Heisenberg spin-Hamiltonian were calculated using the broken-symmetry DFT and CASSCF approaches, and the complex 3D magnetic structure with both the ferromagnetic (FM) and antiferromagnetic (AF) exchange interactions was revealed with the latter as dominating. Salt 2 is thermally unstable and slowly loses the Mes ligands upon storage at ambient temperature. Under the same reaction conditions, interaction of 1 with MoTol2 (Tol = toluene) proceeded with partial loss of the Tol ligands to afford diamagnetic product.PostprintPostprintPeer reviewe

Chemistry for Sustainable Development 18 (2010) 207219 207 Russian Nanoscience: Bibliometric Analysis Relying on the STN International Database

Abstract Russian investigations in the area of n anoscience and n anotechnology were studied by means of bibliometric methods using the databases of Science Citation Index, Chemical Abstracts and Inspec of the intern ation al research network Scientific and Technical Internation al

Matrix isolation and computational study of the photochemistry of 1,3,2,4-Benzodithiadiazine

Photolysis of 1,3,2,4-benzodithiadiazine (1) at ambient temperature yields stable 1,2,3-benzodithiazolyl radicals. In order to reveal the mechanism of this unusual transformation, the photochemistry of 1 was studied in argon matrices using IR and UV-vis spectroscopy. A series of intermediates, including four- and five-membered heterocyclic and o-quinoid acyclic species, were characterized spectroscopically with the help of quantum chemical calculations. With selective irradiation, these intermediates can be mutually interconverted as well as converted back to the starting compound

Donor-acceptor coordination of anions by chalcogen atoms of 1,2,5-chalcogenadiazoles

Synthetic, structural, and thermodynamic aspects of the recently discovered new reaction, donor-acceptor coordination of anions (A–) by chalcogen atoms (E) of 1,2,5-chalcogenadiazoles, are considered. According to the quantum chemical calculations, the charge transfer from A– to the heterocycle via the mechanism of negative hyperconjugation (i.e., from the MO of the lone pair of A– to the virtual σ* orbital of the E—N bond of chalcogenadiazole) depends on the nature of E and A–, being 0.42—0.52 and 0.30—0.44 e in terms of the Mulliken and NBO methods, respectively. According to the X-ray diffraction data, the E—A– coordinate bond is always longer than the sum of the covalent radii but shorter than the sum of the van der Waals radii of the atoms forming the bond. The E—A– bond energy varies in a wide range, from ~25 kcal mol–1 comparable to the energy of weak covalent bonds (e.g., internal N—N bond in organic azides) to ~86 kcal mol–1 comparable to the C—C bond energy in organic compounds. The quantum chemical estimations of the thermodynamics of the donor-acceptor coordination of the anions by the chalcogen atoms of 1,2,5-chalcogenadiazoles indicate that for E = Te and Se this reaction may be of general character also covering E = S in some cases

Donor-acceptor coordination of anions by chalcogen atoms of 1,2,5-chalcogenadiazoles

Synthetic, structural, and thermodynamic aspects of the recently discovered new reaction, donor-acceptor coordination of anions (A–) by chalcogen atoms (E) of 1,2,5-chalcogenadiazoles, are considered. According to the quantum chemical calculations, the charge transfer from A– to the heterocycle via the mechanism of negative hyperconjugation (i.e., from the MO of the lone pair of A– to the virtual σ* orbital of the E—N bond of chalcogenadiazole) depends on the nature of E and A–, being 0.42—0.52 and 0.30—0.44 e in terms of the Mulliken and NBO methods, respectively. According to the X-ray diffraction data, the E—A– coordinate bond is always longer than the sum of the covalent radii but shorter than the sum of the van der Waals radii of the atoms forming the bond. The E—A– bond energy varies in a wide range, from ~25 kcal mol–1 comparable to the energy of weak covalent bonds (e.g., internal N—N bond in organic azides) to ~86 kcal mol–1 comparable to the C—C bond energy in organic compounds. The quantum chemical estimations of the thermodynamics of the donor-acceptor coordination of the anions by the chalcogen atoms of 1,2,5-chalcogenadiazoles indicate that for E = Te and Se this reaction may be of general character also covering E = S in some cases