Oxidative coupling of dibenzyl disulfide with amines catalyzed by quinoline-bromine complex: access to thioamides.

The reaction of dibenzyl disulfide with various bromine complexes as oxidants and DMSO as solvent can produce thioamides in high yield at 110 °C. Tertiary amines like pyridine and quinoline, which were utilized in this catalyst, are known to generate bromine-addition complexes. The approach is metal- and additive-free, making it a simple and cost-effective way to make a variety of thioamides under favorable circumstances.

Exploring Unusual Effects of the Ring Substituents in the Type II Reaction with TD-DFT and DFT.

The type II photoelimination reactions are important in biological systems. The different roles played by ring substituents are often not obvious from quantum yields for product formation and the rate constant for hydrogen abstraction is quite low (<107  s-1 ), but Hautala (Tetrahedron Lett. 1977, 18, 2499-2502) reported unusual effects of the nitro substituent in aryl ketones. They reported the first examples of such and discuss for another role played by the nitro group. They determined an upper limit of less than 2 × 10-5 to the quantum yield for formation of nitro substituent. They hypothesized the carbonyl localized state may be populated with high quantum efficiency, rapid deactivation occurs to populate the lower lying nitro localized state. We focus on the case where the theoretical studies are of great importance and indispensable, such as resolving the debate on the stepwise and concerted mechanism of hydrogen abstraction. Our proposed new mechanisms for 2-ethoxy-1-phenylethanone are based on the energy, HOMO-LUMO, dipole moments, etc. We provide modifications to experimentally proposed mechanisms or completely new mechanism with Hammett, synchronicity, singlet fission and relative rate equations to explain successfully the previous result. At the end, we show why an unusual effect of the nitro substituent exists in it.

The 2019-2020 Khalili (Iran) Earthquake Sequence-Anthropogenic Seismicity in the Zagros Simply Folded Belt?

We investigate the origin of a long-lived earthquake cluster in the Fars arc of the Zagros Simply Folded Belt that is colocated with the major Shanul natural gas field. The cluster emerged in January 2019 and initially comprised small events of M n ∼ 3-4. It culminated on 9 June 2020 with a pair of M w 5.4 and 5.7 earthquakes, which was followed by >100 aftershocks. We assess the spatiotemporal evolution of the earthquake sequence using multiple event hypocenter relocations, waveform inversions, and Sentinel-1 Interferometric Synthetic Aperture Radar (InSAR) measurements and models. We find that the early part of the sequence is spatially distinct from the 9 June 2020 earthquakes and their aftershocks. Moment tensors, centroid depths, and source parameter uncertainties of 15 of the largest (M n ≥ 4.0) events show that the sequence is dominated by reverse faulting at shallow depths (mostly ≤4 km) within the sedimentary cover. InSAR modeling shows that the M w 5.7 mainshock occurred at depths of 2-8 km with a rupture length and maximum slip of ∼20 km and ∼0.5 m, respectively. Our results suggest that the 2019-2020 Khalili earthquake sequence was likely influenced by operation of the Shanul field, though elevated natural seismicity in the Zagros makes the association difficult to prove. Understanding how to distinguish man-made from natural seismicity is helpful for hazard and risk assessment, notably in the Zagros, which is both seismically active and rich in oil and gas reserves.

Photophysical and Optical Properties of Semiconducting Polymer Nanoparticles Prepared from Hyaluronic Acid and Polysorbate 80.

A nanoprecipitation procedure was utilized to prepare novel diketopyrrolopyrrole-based semiconducting polymer nanoparticles (SPNs) with hyaluronic acid (HA) and polysorbate 80. The nanoprecipitation led to the formation of spherical nanoparticles with average diameters ranging from 100 to 200 nm, and a careful control over the structure of the parent conjugated polymers was performed to probe the influence of π-conjugation on the final photophysical and thermal stability of the resulting SPNs. Upon generation of a series of novel SPNs, the optical and photophysical properties of the new nanomaterials were probed in solution using various techniques including transmission electron microscopy, dynamic light scattering, small-angle neutron scattering, transient absorption, and UV-vis spectroscopy. A careful comparison was performed between the different SPNs to evaluate their excited-state dynamics and photophysical properties, both before and after nanoprecipitation. Interestingly, although soluble in organic solution, the nanoparticles were found to exhibit aggregative behavior, resulting in SPNs that exhibit excited-state behaviors that are very similar to aggregated polymer solutions. Based on these findings, the formation of HA- and polysorbate 80-based nanoparticles does not influence the photophysical properties of the conjugated polymers, thus opening new opportunities for the design of bioimaging agents and nanomaterials for health-related applications.

Anti-inflammatory drugs interacting with Zn (II) metal ion based on thiocyanate and azide ligands: synthesis, spectroscopic studies, DFT calculations and antibacterial assays.

Zinc (II) complexes with non-steroidal anti-inflammatory drugs (NSAIDs) naproxen (nap) and ibuprofen (ibu) were synthesized in the presence of nitrogen donor ligands (thiocyanate or azide). The complexes were characterized by elemental analysis, FT-IR, (1)H NMR and UV-Vis spectroscopes. The binding modes of the ligands in complexes were established by means of molecular modeling of the complexes, and calculation of their IR, NMR and absorption spectra at DFT (TDDFT)/B3LYP level were studied. The experimental and calculated data verified monodentate binding through the carboxylic oxygen atoms of anti-inflammatory drugs in the zinc complexes. The calculated (1)H, FT-IR and UV-Vis data are in better agreement with the experimental results, and confirm the predicted tetrahedral structures for the Zn (II) complexes. In addition to DFT calculations of complexes, natural bond orbital (NBO) was performed at B3LYP/6-31+G(d,p) level of theory. Biological studies showed the antibacterial activity of zinc complexes against Gram-positive and Gram-negative bacterial strains.