Silver nanoclusters doped in zeolite to decontaminate water resources from the quinalphos pesticide

Ag (I) nanoclusters doped in mordenite zeolite were prepared and spectroscopically analyzed. Strong luminescence emission that is dependent on the excitation wavelength was observed. These variations in the emission modes are due to the site selective luminescence where various luminophores might be excited upon selecting the proper excitation wavelength. The selected material was found to have strong affinity to remove the quinalphos pesticide, which is widely used for the protection of several vegetable and fruit crops, from water bodies. HPLC and GC–MS techniques were used to follow the kinetic data and to identify the photodecomposition products, respectively. The photodecomposition of quinalphos in the presence of the silver doped mordenite catalyst gives different products compared to the irradiation of quinalphos without catalyst. The presence of the Ag-mordenite catalyst not only adsorbs the quinalphos from the solution but it also reduces its toxic effect as tested on the fruit fly (Drosophila melanogaster).     

Development and initial application of a hybridization-independent, DNA-encoded reaction discovery system compatible with organic solvents

We have developed and applied an approach to reaction discovery that takes advantage of DNA encoding, DNA-programmed assembly of substrate pairs, in vitro selection, and PCR amplification, yet does not require reaction conditions that support DNA hybridization. This system allows the simultaneous evaluation of >200 potential bond-forming combinations of substrates in a single experiment and can be applied in a range of solvent and temperature conditions. In an initial application, we applied this system to explore Au(III)-mediated chemistry and uncovered a simple, mild method for the selective Markovnikov-type hydroarylation of vinyl arenes and trisubstituted olefins with indoles.     

Discovery,Development, and Patent Trends on Molnupiravir: A Prospective Oral Treatment for COVID-19

The COVID-19 pandemic needs no introduction at present. Only a few treatments are available for this disease, including remdesivir and favipiravir. Accordingly, the pharmaceutical industry is striving to develop new treatments for COVID-19. Molnupiravir, an orally active RdRp inhibitor, is in a phase 3 clinical trial against COVID-19. The objective of this review article is to enlighten the researchers working on COVID-19 about the discovery, recent developments, and patents related to molnupiravir. Molnupiravir was originally developed for the treatment of influenza at Emory University, USA. However, this drug has also demonstrated activity against a variety of viruses, including SARS-CoV-2. Now it is being jointly developed by Emory University, Ridgeback Biotherapeutics, and Merck to treat COVID-19. The published clinical data indicate a good safety profile, tolerability, and oral bioavailability of molnupiravir in humans. The patient-compliant oral dosage form of molnupiravir may hit the market in the first or second quarter of 2022. The patent data of molnupiravir revealed its granted compound patent and process-related patent applications. We also anticipate patent filing related to oral dosage forms, inhalers, and a combination of molnupiravir with marketed drugs like remdesivir, favipiravir, and baricitinib. The current pandemic demands a patient compliant, safe, tolerable, and orally effective COVID-19 treatment. The authors believe that molnupiravir meets these requirements and is a breakthrough COVID-19 treatment.     

Tin oxide dependence of the CO2 reduction efficiency on tin electrodes and enhanced activity for tin/tin oxide thin-film catalysts

The importance of tin oxide (SnO(x)) to the efficiency of CO(2) reduction on Sn was evaluated by comparing the activity of Sn electrodes that had been subjected to different pre-electrolysis treatments. In aqueous NaHCO(3) solution saturated with CO(2), a Sn electrode with a native SnO(x) layer exhibited potential-dependent CO(2) reduction activity consistent with previously reported activity. In contrast, an electrode etched to expose fresh Sn(0) surface exhibited higher overall current densities but almost exclusive H(2) evolution over the entire 0.5 V range of potentials examined. Subsequently, a thin-film catalyst was prepared by simultaneous electrodeposition of Sn(0) and SnO(x) on a Ti electrode. This catalyst exhibited up to 8-fold higher partial current density and 4-fold higher faradaic efficiency for CO(2) reduction than a Sn electrode with a native SnO(x) layer. Our results implicate the participation of SnO(x) in the CO(2) reduction pathway on Sn electrodes and suggest that metal/metal oxide composite materials are promising catalysts for sustainable fuel synthesis.     

Null charts and naked singularities in spherically symmetric,homothetic spacetimes

We give a unified derivation of a null chart for all spherically symmetric, homothetic spacetimes. These spacetimes contain an interesting class of naked singularities which we are also able to elucidate. Much use is made of graphical representation; in particular a chart of the spacetimes based on their homothetic group motions is introduced. Dust spacetimes, and two homogeneous examples with non-zero pressure (flat Robertson-Walker and a Kantowski-Sachs example) are studied in detail. We show the horizon structure in the null atlas, in comoving coordinates, in terms of the areal radius and comoving time, and in the homothetic diagrams. The critical delay between comoving observers for the onset of nakedness is interpreted in terms of a decreasing mass concentration in the spirit of Thorne's hoop conjecture. We also give a simple criterion for the existence of apparent horizons isolating the various singularities, and study in detail how this criterion is circumvented in the naked examples. We conclude that this type of naked singularity is a consequence of the imposed homothetic symmetry, by showing it to be generally present and timelike in the homothetic group chart even when it is not visible at comoving infinity (before the onset of criticality). It is the delayed final collapse of initially distant observers in inhomogeneous spacetimes that causes the initial singularity to become visible at comoving infinity. We conclude that these examples do not present an obstacle to the Event Horizon Conjecture as summarized by W. Israel (1984). That is, one can formulate criteria for the formation of apparent horizons that do not imply that all singularities are necessarily so enclosed. It is still possible that all singularities stronger than homothetic are isolated by an apparent horizon, in the spirit of Tipler's conjecture.On leave from Department of Physics, Queen's University, Kingston, Ontario, Canada     

Selective Homogeneous Palladium(0)-Catalyzed Hydrogenation of Alkynes to (Z)-Alkenes

Zero-valent palladium precatalysts containing rigid bidentate bis(arylimino)acenaphthene ligands (shown schematically) facilitate the highly stereoselective homogeneous catalytic hydrogenation of alkynes to (Z)-alkenes. Internal, terminal, aryl-substituted, and cyclic alkynes are suitable substrates, as are some enynes, which are chemoselectively hydrogenated to dienes. E=CO(2)Me; R(1), R(2)=4-OCH(3), 4-CH(3), 2,6-(CH(3))(2).     

Multistep small-molecule synthesis programmed by DNA templates

The translation of DNA sequences into synthetic products is a key requirement of our approach to evolving synthetic molecules through iterated cycles of translation, selection, and amplification. Here we report general linker and purification strategies for sequence-specific DNA-templated synthesis that collectively enable the product of a DNA-templated reaction to be isolated and to undergo subsequent DNA-templated reactions. Using these strategies, we have achieved the first multistep nucleic acid-templated small-molecule syntheses to generate two different molecules. In addition to representing a method for translating DNA templates sequence-specifically into corresponding multistep synthetic products, our findings also provide experimental support for previously proposed models invoking multistep nucleic acid-templated synthesis as mediating the prebiotic translation of replicable information into the earliest functional molecules.     

Synthesis and characterization of (RPh3P)3[Bi3I12] (R = Me,Ph) iodobismuthate complexes for photocatalytic degradation of organic pollutants

Research on Chemical Intermediates - Phosphonium iodobismuthates(III) (MePh3P)3[Bi3I12] (1) and (Ph4P)3[Bi3I12] (2) were prepared, and X-ray crystal structures were determined for both complexes....     

Mechanistic studies of the oxygen evolution reaction by a cobalt-phosphate catalyst at neutral pH

The mechanism of the oxygen evolution reaction (OER) by catalysts prepared by electrodepositions from Co(2+) solutions in phosphate electrolytes (Co-Pi) was studied at neutral pH by electrokinetic and (18)O isotope experiments. Low-potential electrodepositions enabled the controlled preparation of ultrathin Co-Pi catalyst films (<100 nm) that could be studied kinetically in the absence of mass transport and charge transport limitations to the OER. The Co-Pi catalysts exhibit a Tafel slope approximately equal to 2.3 × RT/F for the production of oxygen from water in neutral solutions. The electrochemical rate law exhibits an inverse first order dependence on proton activity and a zeroth order dependence on phosphate for [Pi] ≥ 0.03 M. In the absence of phosphate buffer, the Tafel slope is increased ～3-fold and the overall activity is greatly diminished. Together, these electrokinetic studies suggest a mechanism involving a rapid, one electron, one proton equilibrium between Co(III)-OH and Co(IV)-O in which a phosphate species is the proton acceptor, followed by a chemical turnover-limiting process involving oxygen-oxygen bond coupling.     

Infrared study of UV-irradiated tungsten trioxide powders containing adsorbed dimethyl methyl phosphonate and trimethyl phosphate

The photodecomposition of dimethyl methylphosphonate (DMMP) and trimethyl phosphate (TMP) adsorbed on monoclinic WO₃ powders when irradiated by ultraviolet light (UV) in air, oxygen, and under evacuation was investigated using infrared spectroscopy (IR). The IR spectra show that DMMP decomposes into methyl phosphonate upon exposure to 254 nm UV for 2 h at room temperature in air. The same decomposition of DMMP occurs only at temperatures above 300°C without UV illumination. TMP differs from DMMP in that the photodecomposition product is not the same as the decomposition product obtained by heating above 300°C. Thermal decomposition leads to formation of a phosphate on the surface, whereas photodecomposition leads to the same adsorbed methyl phosphonate as found for the thermal or photodecomposition of DMMP. Since TMP does not contain a P-CH₃ bond, the formation of a methyl phosphonate on the surface after UV illumination involves a mechanism where CH₃ groups migrate from the methoxy group to the phosphorous central atom. No decomposition is observed at room temperature when DMMP or TMP adsorbed on WO₃ is irradiated under vacuum or in nitrogen atmosphere. Therefore, the photodecomposition of either DMMP or TMP adsorbed on WO₃ at room temperature does not involve a reaction with the lattice oxygen but rather a reaction with the oxygen radicals produced by the decomposition of ozone.