Synthesis of New Bitopic Tetra(pyrazolyl)-Ligands with Neopentane and O-Xylene Backbones

Several new bitopic pyrazole-containing ligands were prepared from the corresponding pyrazoles and tetrahalogen or tetratosyloxy derivatives of o-xylene and neopentane in a superbasic medium (KOH-DMSO)

Facile Synthesis of Pyrazole- and Benzotriazole-Containing Selenoethers

Azole-containing selenoethers, 1,5-bis(3,5-dimethylpyrazol-1-yl)-3-selena pentane and 1,3-bis(1,2,3-benzotriazol-1-yl)-2-selena propane were prepared by the reaction of corresponding tosylate or chloride with sodium selenide generated in situ from elemental selenium and sodium formaldehydesulfoxylate (rongalite)

The Eurasian Modern Pollen Database (EMPD), version 2

The Eurasian (née European) Modern Pollen Database (EMPD) was established in 2013 to provide a public database of high-quality modern pollen surface samples to help support studies of past climate, land cover, and land use using fossil pollen. The EMPD is part of, and complementary to, the European Pollen Database (EPD) which contains data on fossil pollen found in Late Quaternary sedimentary archives throughout the Eurasian region. The EPD is in turn part of the rapidly growing Neotoma database, which is now the primary home for global palaeoecological data. This paper describes version 2 of the EMPD in which the number of samples held in the database has been increased by 60 % from 4826 to 8134. Much of the improvement in data coverage has come from northern Asia, and the database has consequently been renamed the Eurasian Modern Pollen Database to reflect this geographical enlargement. The EMPD can be viewed online using a dedicated map-based viewer at https://empd2.github.io and downloaded in a variety of file formats at https://doi.pangaea.de/10.1594/PANGAEA.909130 (Chevalier et al., 2019)Swiss National Science Foundation | Ref. 200021_16959

The Eurasian Modern Pollen Database (EMPD), version 2

The Eurasian (nee European) Modern Pollen Database (EMPD) was established in 2013 to provide a public database of high-quality modern pollen surface samples to help support studies of past climate, land cover, and land use using fossil pollen. The EMPD is part of, and complementary to, the European Pollen Database (EPD) which contains data on fossil pollen found in Late Quaternary sedimentary archives throughout the Eurasian region. The EPD is in turn part of the rapidly growing Neotoma database, which is now the primary home for global palaeoecological data. This paper describes version 2 of the EMPD in which the number of samples held in the database has been increased by 60% from 4826 to 8134. Much of the improvement in data coverage has come from northern Asia, and the database has consequently been renamed the Eurasian Modern Pollen Database to reflect this geographical enlargement. The EMPD can be viewed online using a dedicated map-based viewer at https://empd2.github.io and downloaded in a variety of file formats at https://doi.pangaea.de/10.1594/PANGAEA.909130 (Chevalier et al., 2019).Peer reviewe

Динамика изменения состава и устойчивости нефти Усинского месторождения в результате обработки пласта золеобразующей композицией для интенсификации нефтеотдачи

The paper deals with a sol-forming system for oil recovery enhancement (EOR system) used to increase the rate of heavy oil displacement. The effect of sol-forming EOR system during the heavy oil displacement on the composition and stability of oil sampled from the Usinskoye oil field of Russia is investigated. The composition of a crude oil also plays an important role in changing its stability. The work is aimed to investigate stability of heavy crude oil in regards to asphaltene precipitation. For asphaltene toluene/n-heptane solutions, the aggregation stability of asphaltenes based on сhange in the optical density with time is investigated via spectrophotometry. SARA analysis is used to characterize the compositions of heavy oils. First, the content of asphaltenes precipitated from the oil samples is determined and then the samples of deasphalted crude oil (maltenes) are analyzed by the method of liquid adsorption chromatography for the purpose to study the composition of oil sampled from the wells before and after their treatment with the sol-forming EOR system. It is found out that the treatment of reservoir crude oil with the sol-forming EOR system results in changes in composition of saturated, aromatic hydrocarbons, resins, and asphaltenes (SARA components) and aggregative stability of produced oil. The results obtained showed that the aggregative stability of heavy oil depends not only on the content of SARA components in the dispersion medium but on the presence of metalloporphyrins in the oil. Metalloporphyrins could act as inhibitors of asphaltene precipitation, which is an additional factor responsible for the stabilization of the oil dispersed systemЧтобы улучшить интенсивность вытеснения тяжелой нефти, используют золеобразующую композицию для увеличения нефтеотдачи (EOR). Исследовано влияние золеобразующей композиции в качестве метода увеличения нефтеотдачи (EOR) при вытеснении тяжелой нефти на состав и устойчивость образцов из Усинского нефтяного месторождения России. Важное влияние на устойчивость нефти оказывает ее состав. Целью исследования является изучение устойчивости тяжелой нефти в отношении осаждения асфальтенов. Агрегационная устойчивость асфальтенов была изучена на основе изменения оптической плотности во времени для растворов асфальтенов в толуоле/н-гептане методом спектрофотометрии, для характеристики состава тяжелых нефтей использовали анализ содержания насыщенных ароматических углеводородов, смол и асфальтенов. Состав образцов нефти из скважин до и после обработки золеобразующей композицией, используемой для увеличения нефтеотдачи, изучали методом жидкостно-адсорбционной хроматографии деасфальтизированной нефти (мальтенов). Предварительно было проведено выделение и определение содержания асфальтенов в образцах нефти. Установлено, что обработка пластовой нефти золеобразующей композицией EOR приводит к изменениям состава компонентов (насыщенных ароматических углеводородов, смол и асфальтенов) и агрегационной устойчивости добываемой нефти. Полученные результаты показали, что агрегационная устойчивость тяжелой нефти зависит не только от содержания насыщенных, ароматических углеводородов, смол и асфальтенов в дисперсионной среде. Дополнительным фактором стабилизации нефтяной дисперсной системы является наличие металлопорфиринов в нефти, которые могут действовать как ингибиторы осаждения асфальтено

Facile Synthesis of Pyrazole-and Benzotriazole-Containing Selenoethers

Azole-containing selenoethers, 1,5-bis(3,5-dimethylpyrazol-1-yl)-3-selena pentane and 1,3-bis(1,2,3-benzotriazol-1-yl)-2-selena propane were prepared by the reaction of corresponding tosylate or chloride with sodium selenide generated in situ from elemental selenium and sodium formaldehydesulfoxylate (rongalite)

Synthesis and oxidation of some azole-containing thioethers

Pyrazole and benzotriazole-containing thioethers, namely 1,5-bis(3,5-dimethylpyrazol-1-yl)-3-thiapentane, 1,8-bis(3,5-dimethylpyrazol-1-yl)-3,6-dithiaoctane and 1,3-bis(1,2,3-benzotriazol-1-yl)-2-thiapropane were prepared and fully characterized. Oxidation of the pyrazole-containing thioether by hydrogen peroxide proceeds selectively to provide a sulfoxide or sulfone, depending on the amount of oxidant used. Oxidation of the benzotriazole derivative by hydrogen peroxide is not selective, and sulfoxide and sulfone form concurrently. Selenium dioxide-catalyzed oxidation of benzotriazole thioether by H2O2, however, proceeds selectively and yields sulfoxide only

The Crystal Structure of Nα-p-tosyl-lysyl Chloromethylketone-Bound Oligopeptidase B from Serratia Proteamaculans Revealed a New Type of Inhibitor Binding

A covalent serine protease inhibitor—Na-p-Tosyl-Lysyl Chloromethylketone (TCK) is a modified lysine residue tosylated at the N-terminus and chloromethylated at the C-terminus, one molecule of which is capable of forming two covalent bonds with both Ser and His catalytic residues, was co-crystallized with modified oligopeptidase B (OpB) from Serratia proteomaculans (PSPmod). The kinetics study, which preceded crystallization, shows that the stoichiometry of TCK-dependent inhibition of PSPmod was 1:2 (protein:inhibitor). The crystal structure of the PSPmod-TCK complex, solved at a resolution of 2.3 Å, confirmed a new type of inhibitor binding. Two TCK molecules were bound to one enzyme molecule: one with the catalytic Ser, the other with the catalytic His. Due to this mode of binding, the intermediate state of PSPmod and the disturbed conformation of the catalytic triad were preserved in the PSPmod-TCK complex. Nevertheless, the analysis of the amino acid surroundings of the inhibitor molecule bound to the catalytic Ser and its comparison with that of antipain-bound OpB from Trypanosoma brucei provided an insight in the structure of the PSPmod substrate-binding pocket. Supposedly, the new type of binding is typical for the interaction of chloromethylketone derivatives with two-domain OpBs. In the open conformational state that these enzymes are assumed in solution, the disordered configuration of the catalytic triad prevents simultaneous interaction of one inhibitor molecule with two catalytic residues

Stable isotopes of organic carbon, palynology, and petrography of a thick low-rank Miocene coal within the Mile Basin, Yunnan Province, China: implications for palaeoclimate and sedimentary conditions

Coal contains detailed long-term records of contemporaneous environment, climate, and subsequent diagenetic processes. Stable isotopes of carbon, petrological, palynological, and mineralogical analyses were carried out on a 28 m thick low-rank Miocene coal seam from the Mile Basin, Yunnan Province, China for the purpose of deciphering the palaeoclimate and sedimentary conditions during peat deposition. The coal is characterized by both pale and dark lithotypes. Palynological analyses show that both lithotypes are dominated by angiosperms, which is interpreted to indicate a moderately warm climate. The absence of Fagus and Taxodiaceae pollen suggests that there may have been dry periods during peat accumulation; in general, both Fagus and Taxodiaceae require a constant wet environment in order to proliferate. Organic petrography, δ13C, and gypsum concentrations corroborate that there were alternating drier and wetter periods within the palaeomire during peat accumulation. The fine-scale variability in the δ13C signature appears to be controlled by plant type. Angiosperm/gymnosperm ratios and Vegetation Index are directly correlated with δ13C isotopic values. Plant type, however, seems to be proximally controlled by water level. Angiosperms were more dominant during times of lower water table or less moist conditions, interpreted to correspond to less negative values of δ13C. The correlation of greater concentrations of gypsum with less negative δ13C values also supports drier conditions. However, in addition to the fine-scale variability, four larger scale cycles are defined based on less negative δ13C values. A less negative δ13C isotopic signature demarcates the top of each of these cycles, which represent spikes of lower water table and/or drier conditions. In addition, a general correlation of the δ13C variations in the studied coal seam with atmospheric CO2 suggests that the atmosphere also had a significant influence on peat formation in the Mile Basin. Although the Mile Basin palaeomire accumulated over a long time, an integrated approach to its analysis has demonstrated considerable variation in palaeoclimate. Changes in wetness/dryness had a direct effect on the ecological composition of the palaeomire. These floral changes would not have only been restricted to the palaeomire but most likely had a regional influence. Thus, detailed analysis of coals can yield useful, insightful and practical knowledge on past regional palaeoenvironmental conditions, which can then be placed within a global context.</p