[1,2,5]Thiadiazolo[3,4-d]Pyridazine as an Internal Acceptor in the D-A-π-A Organic Sensitizers for Dye-Sensitized Solar Cells

Four new D-A-π-A metal-free organic sensitizers for dye-sensitized solar cells (DSSCs), with [1,2,5]thiadiazolo[3,4-d]pyridazine as internal acceptor, thiophene unit as π-spacer and cyanoacrylate as anchoring electron acceptor, have been synthesized. The donor moiety was introduced into [1,2,5]thiadiazolo[3,4-d]pyridazine by nucleophilic aromatic substitution and Suzuki cross-coupling reactions, allowing design of D-A-π-A sensitizers with the donor attached to the internal heterocyclic acceptor not only by the carbon atom, as it is in a majority of DSSCs, but by the nitrogen atom also. Although low values of power conversion efficiency (PCE) were found, a few important consequences were identified: (i) poor PCE data can be attributed to high electron deficiency of the internal [1,2,5]thiadiazolo[3,4-d]pyridazine acceptor due to lower light harvesting by the dye; (ii) the manner in which the donor was attached to the internal acceptor (by carbon or nitrogen) did not play an essential role in the photovoltaic properties of the dyes; (iii) dyes based on the novel donor 2,3,4,4a,9,9a-hexahydro-1H-1,4-methanocarbazolyl and 9-(p-tolyl)-2,3,4,4a,9,9a-hexahydro-1H- carbazole moieties showed similar photovoltaic properties to dyes based on the well-known 4-(p-tolyl)-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indolyl building block, which opens the door for further optimization potential of new dye families

Two Decades of Satellite Observations of Carbon Monoxide Confirm the Increase in Northern Hemispheric Wildfires

Biomass burning is an important and changing component of global and hemispheric carbon cycles. Boreal forest fires in Russia and Canada are significant sources of the greenhouse gases carbon dioxide (CO2) and methane (CH4). The influence of carbon monoxide (CO) on the greenhouse effect is practically absent; its main absorption bands of 4.6 and 2.3 μm are far away from the climatically important spectral regions. Meanwhile, CO concentrations in fire plumes are closely related to CO2 and CH4 emissions from fires. On the other hand, satellite measurements of CO are much simpler than those of the aforementioned gases. The Atmospheric Infrared Sounder (AIRS) operating in the Thermal IR spectral region has provided a satellite-based CO data set since October 2002. This satellite data allow to estimate CO emissions from biomass burning north of 30° N using a simple two-box mass-balance model. These results correlate closely with independently estimated CO emissions from the GFED4c bottom-up database. In 2021, both estimate record high emissions throughout the preceding two decades, double the annual emissions compared to previous periods. There have been two years with extremely high emissions (2003 and 2021) but for the rest of the data, an upward trend with a rate of 3.6 ± 2.2 Tg CO yr−2 (4.8 ± 2.7% yr−1) was found. A similar rate of CO emissions can be seen in the GFED4c data

4,7-Dichloro[1,2,5]oxadiazolo[3,4-d]pyridazine 1-oxide

Dihalogenated derivatives of [1,2,5]chalcogenadiazolo[3,4-d]pyridazines are of interest as precursors for both photovoltaic materials and biologically active compounds. In this communication, 4,7-dichloro[1,2,5]oxadiazolo[3,4-d]pyridazine 1-oxide was prepared via the reaction of 3,6-dichloro-5-nitropyridazin-4-amine with oxidizing agents; the best yield of the target compound was achieved in the reaction with (diacetoxyiodo)benzene in benzene by heating at reflux for two hours. The structure of the newly synthesized compound was established by means of 13C-NMR and IR spectroscopy, mass-spectrometry and elemental analysis

Severe Wildfires Near Moscow, Russia in 2010: Modeling of Carbon Monoxide Pollution and Comparisons with Observations

The spatial and temporal distributions of the carbon monoxide (CO) concentration were calculated with the Regional Atmospheric Modeling System and Hybrid Particle and Concentration Transport model (RAMS/HYPACT) in the provinces near Moscow during the abnormally hot summer of 2010. The forest, steppe and meadow hot spots were defined by the satellite data MCD14ML (MODIS Terra and Aqua satellite data). The calculations indicated that the surface CO concentrations from the model were two times less than the experimental data obtained from the Moscow State University (MSU) station and Zvenigorod Scientific Station (ZSS). Conversely, the total column CO concentrations obtained from the model were two to three times larger than the experimental values obtained from the Obukhov Institute of Atmospheric Physics (OIAP) and ZSS stations. The vertical transfer of pollutants was overestimated. Tentatively, it could be assumed that an aerosol influence in the model calculations is a reason for the overestimation. The comparisons between the wind speed, temperature and humidity profiles calculated in the model with the data from the standard balloon sounding exhibited good agreement. The CO total column data of the Measurements of Pollution in the Troposphere (MOPITTv5 NIR and TIR/NIR) obtained from the OIAP and ZSS stations appear more realistic than do the MOPITTv4 data. However, the surface MOPITT values of CO concentration for Moscow have the large distinction from the ground measurements. A careful proposal regarding satellite orbit optimization was made, which could improve future spectrometric measurements, such as the MOPITT, Atmospheric Infrared Sounder (AIRS) and Infrared Atmospheric Sounding Interferometer (IASI) measurements

A Novel Highly Thermostable Multifunctional Beta-Glycosidase from Crenarchaeon Acidilobus saccharovorans

We expressed a putative β-galactosidase Asac_1390 from hyperthermophilic crenarchaeon Acidilobus saccharovorans in Escherichia coli and purified the recombinant enzyme. Asac_1390 is composed of 490 amino acid residues and showed high sequence similarity to family 1 glycoside hydrolases from various thermophilic Crenarchaeota. The maximum activity was observed at pH 6.0 and 93°C. The half-life of the enzyme at 90°C was about 7 hours. Asac_1390 displayed high tolerance to glucose and exhibits hydrolytic activity towards cellobiose and various aryl glucosides. The hydrolytic activity with p-nitrophenyl (pNP) substrates followed the order pNP-β-D-galactopyranoside (328 U mg−1), pNP-β-D-glucopyranoside (246 U mg−1), pNP-β-D-xylopyranoside (72 U mg−1), and pNP-β-D-mannopyranoside (28 U mg−1). Thus the enzyme was actually a multifunctional β-glycosidase. Therefore, the utilization of Asac_1390 may contribute to facilitating the efficient degradation of lignocellulosic biomass and help enhance bioconversion processes

Ethyl 11a,12-Dihydrobenzo[b]benzo[5,6][1,4]oxazino[2,3-e][1,4]oxazine-5a(6H)-carboxylate

The 11a,12-dihydrobenzo[b]benzo[5,6][1,4]oxazino[2,3-e][1,4]oxazine heterocyclic system has been used in the construction of heteropropellanes, which attracted much attention not only on the possible modification of drugs, but also for novel materials with unusual and important physical properties. In this communication, the reaction of ethyl 2-(hydroxyimino)propanoate 1 with disulfur dichloride and o-aminophenol, which gave ethyl 11a,12-dihydrobenzo[b]benzo[5,6][1,4]oxazino[2,3-e][1,4]oxazine-5a(6H)-carboxylate in moderate yield, was described. The structure of the newly synthesized compound was established by means of elemental analysis, high resolution mass-spectrometry, 1H, 13C NMR and IR spectroscopy, mass-spectrometry and X-ray analysis

EVIDENCE OF ATMOSPHERIC RESPONSE TO METHANE EMISSIONS FROM THE EAST SIBERIAN ARCTIC SHELF

Average atmospheric methane concentration (CH4) in the Arctic is generally higher than in other regions of the globe. Due to the lack of observations in the Arctic there is a deficiency of robust information about sources of the methane emissions. Measured concentrations of methane and its isotopic composition in ambient air can be used to discriminate sources of CH4. Here we present the results of measurements of the atmospheric methane concentration and its isotope composition (δ13CCH4) in the East Siberian Arctic Seas during the cruise in the autumn 2016. Local sections where the concentration of methane in the near-water layer of the atmosphere reaches 3.6 ppm are identified. The measurements indicated possibility of formation of high methane peaks in atmospheric surface air above the East Siberian Arctic Shelf (ESAS) where methane release from the bottom sediments has been assumed

Safe Synthesis of 4,7-Dibromo[1,2,5]thiadiazolo[3,4-d]pyridazine and Its SNAr Reactions

A safe and efficient synthesis of 4,7-dibromo[1,2,5]thiadiazolo[3,4-d]pyridazine from the commercial diaminomaleonitrile is reported. Conditions for selective aromatic nucleophilic substitution of one or two bromine atoms by oxygen and nitrogen nucleophiles are found, whereas thiols formed the bis-derivatives only. Buchwald-Hartwig or Ullmann techniques are successful for incorporation of a weak nitrogen base, such as carbazole, into the [1,2,5]thiadiazolo[3,4-d]pyridazine core. The formation of rather stable S…η2-(N=N) bound chains in 4,7-bis(alkylthio)-[1,2,5]thiadiazolo[3,4-d]pyridines makes these compounds promising for the design of liquid crystals