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A novel and efficient iron-catalyzed cycloaddition reaction using readily available 2,3-diaryl-2H-azirines and primary amides is reported. A wide range of trisubstituted oxazoles could be achieved in good yields with good functional group compatibility. In this transformation, two C-N bonds were cleaed and new C-N and C-O bonds were formed.The electronic and magnetic properties of the ligand-decorated Fe6S8 cluster and fused superatomic dimer are investigated using first-principles density functional theory. It is shown that the redox properties of the Fe6S8 cluster can be effectively controlled by altering the nature of the attached ligands. Donor ligands such as phosphines reduce the ionization energy of the Fe6S8 cluster, whereas the acceptor ligands such as CO increase the electron affinity. Such variation in the redox properties of the Fe6S8 cluster is the result of the ligand-induced shift in the cluster's electronic levels, so the occupation number remains mostly unaffected, leading to a marginal change in the spin magnetic moment of the cluster. A combination of two identical Fe6S8 clusters decorated by unbalanced ligands results in a superatomic dimer with a massive dipole moment and a large spin magnetic moment. Donor ligands on one side of the superatomic dimer with acceptor ligands on the other cause significant intercluster charge transfer. The resulting superatomic dimer offers an interesting motif for spintronics-related applications.The efficient optoelectronic properties of photosynthetic proteins were explored in the quest for the fabrication of novel solid biohybrid devices. As most optoelectronic devices function in a dry environment, an attempt was made to fabricate an efficient electronic junction by covalent binding of photosynthetic reaction center proteins to metals, transparent semiconductor polymers, and solid semiconductors that function in a dry environment. The primary stages of photosynthesis take place in nanometric-size protein-chlorophyll complexes. Such is photosystem I (PSI), which generates a photovoltage of 1 V. The isolated PSI generates an absorbed light-energy conversion efficiency of ∼47% (∼23% solar energy) and internal quantum efficiency of ∼100%. The robust cyanobacterial PSI was used in the fabrication of solid-state optoelectronic devices by forming oriented multilayers from genetically engineered cysteine mutants between metal and transparent conducting semiconductor electrodes. Current-voltage measurements of the cells generated diode- and photodiode-like responses in the dark and the light, respectively. The cells were stable for many months in a dry environment. The generation of photocurrent and Voc indicated the formation of good electronic coupling between PSI and the electrodes, which can serve in the fabrication of solid-state biohybrid optoelectronic devices.Twelve undescribed jatrophane diterpenoids, euphpepluones A-L (1-12), together with seven known analogues (13-19), were isolated from the whole plant of Euphorbia peplus, and their structures were elucidated by spectroscopic studies. The absolute configurations of 1 and 4 were assigned by X-ray crystallographic analysis. All isolates were investigated for their inhibitory effects against the ATR-Chk1 pathway using a Western blotting assay. As a result, 1, 2, 5, 8, 10, and 16 were found to suppress the camptothecin (CPT)-induced phosphorylation of Chk1, indicating that these compounds inhibit the activation of the ATR-Chk1 pathway. A preliminary structure-activity relationship (SAR) study of the isolates was conducted. selleck When compound 10 and CPT were combined, apoptosis was induced in A549 cells with PARP cleavage, while there was no apoptotic effect by treatment with CPT or 10 alone. The data obtained indicate that 10 potentiates the chemotherapeutic sensitivity of A549 cells to CPT.Atmospheric iodine chemistry can significantly affect the atmospheric oxidation capacity in certain regions. In such processes, particle-phase organic iodine compounds (OICs) are key reservoir species in their loss processes. However, their presence and formation mechanism remain unclear, especially in continental regions. Using gas chromatography and time-of-flight mass spectrometry coupled with both electron capture negative ionization and electron impact sources, this study systematically identified unknown OICs in 2-year samples of ambient fine particulate matter (PM2.5) collected in Beijing, an inland city. We determined the molecular structure of 37 unknown OICs, among which six species were confirmed by reference standards. The higher concentrations for ∑37OICs (median 280 pg m-3; range 49.0-770 pg m-3) measured in the heating season indicate intensive coal combustion sources of atmospheric iodine. 1-Iodo-2-naphthol and 4-iodoresorcinol are the most abundant species mainly from primary combustion emission and secondary formation, respectively. The detection of 2- and 4-iodoresorcinols, but not of iodine-substituted catechol/hydroquinone or 5-iodoresorcinol, suggests that they are formed via the electrophilic substitution of resorcinol by hypoiodous acid, a product of the reaction of iodine with ozone. This study reports isomeric information on OICs in continental urban PM2.5 and provides valuable evidence on the formation mechanism of OICs in ambient particles.Two-terminal resistive switching devices are commonly plagued with longstanding scientific issues including interdevice variability and sneak current that lead to computational errors and high-power consumption. This necessitates the integration of a separate selector in a one-transistor-one-RRAM (1T-1R) configuration to mitigate crosstalk issue, which compromises circuit footprint. Here, we demonstrate a multi-terminal memtransistor crossbar array with increased parallelism in programming via independent gate control, which allows in situ computation at a dense cell size of 3-4.5 F2 and a minimal sneak current of 0.1 nA. Moreover, a low switching energy of 20 fJ/bit is achieved at a voltage of merely 0.42 V. The architecture is capable of performing multiply-and-accumulate operation, a core computing task for pattern classification. A high MNIST recognition accuracy of 96.87% is simulated owing to the linear synaptic plasticity. Such computing paradigm is deemed revolutionary toward enabling data-centric applications in artificial intelligence and Internet-of-things.
Website: https://www.selleckchem.com/products/ins018-055-ism001-055.html
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