Inhibitor and Activator: Dual Role of Subsurface Sulfide Enables Selective and Efficient Electro-Oxidation of Methanol to Formate on CuS@CuO Core-Shell Nanosheet Arrays.

Selective electro-oxidation of aliphatic alcohols into value-added carboxylates at lower potentials than that of the oxygen evolution reaction (OER) is an environmentally and economically desirable anode reaction for clean energy storage and conversion technologies. However, it is challenging to achieve both high selectivity and high activity of the catalysts for the electro-oxidation of alcohols, such as the methanol oxidation reaction (MOR). Herein, a monolithic CuS@CuO/copper-foam electrode for the MOR with superior catalytic activity and almost 100% selectivity for formate is reported. In the core-shell CuS@CuO nanosheet arrays, the surface CuO directly catalyzes MOR, while the subsurface sulfide not only serves as an inhibitor to attenuate the oxidative power of the surface CuO to achieve selective oxidation of methanol to formate and prevent over-oxidation of formate to CO2 but also serves as an activator to form more surface O defects as active sites and enhances the methanol adsorption and charge transfer to achieve superior catalytic activity. CuS@CuO/copper-foam electrodes can be prepared on a large scale by electro-oxidation of copper-foam at ambient conditions and can be readily utilized in clean energy technologies.

In situ grown oxygen-vacancy-rich copper oxide nanosheets on a copper foam electrode afford the selective oxidation of alcohols to value-added chemicals.

Selective oxidation of low-molecular-weight aliphatic alcohols like methanol and ethanol into carboxylates in acid/base hybrid electrolytic cells offers reduced process operating costs for the generation of fuels and value-added chemicals, which is environmentally and economically more desirable than their full oxidation to CO2. Herein, we report the in-situ fabrication of oxygen-vacancies-rich CuO nanosheets on a copper foam (CF) via a simple ultrasonication-assisted acid-etching method. The CuO/CF monolith electrode enables efficient and selective electrooxidation of ethanol and methanol into value-added acetate and formate with ~100% selectivity. First principles calculations reveal that oxygen vacancies in CuO nanosheets efficiently regulate the surface chemistry and electronic structure, provide abundant active sites, and enhance charge transfer that facilitates the adsorption of reactant molecules on the catalyst surface. The as-prepared CuO/CF monolith electrode shows excellent stability for alcohol oxidation at current densities >200 mA·cm2 for 24 h. Moreover, the abundant oxygen vacancies significantly enhance the intrinsic indicators of the catalyst in terms of specific activity and outstanding turnover frequencies of 5.8k s-1 and 6k s-1 for acetate and formate normalized by their respective faradaic efficiencies at an applied potential of 1.82 V vs. RHE.

Ultrasonically Surface-Activated Nickel Foam as a Highly Efficient Monolith Electrode for the Catalytic Oxidation of Methanol to Formate.

Most of the current electrocatalysts for the methanol oxidation reaction are precious group metals such as Pt, Pd, and Ru. However, their use is limited due to their high cost, scarcity, and issues with carbon monoxide poisoning. We developed a simple method to prepare a nickel foam (NF)-based monolith electrode with a NiO nanosheet array structure as an efficient electrocatalyst toward the oxidation of methanol to produce formate. By a simple ultrasonic acid treatment and air oxidation at room temperature, an inert NF was converted to NiO/NF as a catalytically active electrode due to the uniform NiO nanosheet array that was rapidly formed on the surface of NiO/NF. In alkaline electrolytes containing methanol, the as-prepared NiO/NF catalysts exhibited a lower methanol oxidation reaction (MOR) potential of +1.53 V vs RHE at 100 mA cm-2 compared to that of inert NF samples. The difference in potentials between the EMOR and the EOER at that current density was found to be 280 mV, indicating that methanol oxidation occurred at lower potentials as compared to the oxygen evolution reaction (OER). We also observed that the NiO/NF could also efficiently catalyze the oxidation of CO without being poisoned by it. NiO/NF retained close to 100% of its initial activity after 20,000 s of methanol oxidation tests at high current densities above 200 mA cm-2. Because of the simple synthesis method and the enhanced catalytic performance and stability of NiO/NF, this allows methanol to be used as an OER masking agent for the energy-efficient generation of value-added products such as formic acid and hydrogen.

Anti-malarial, cytotoxicity and molecular docking studies of quinolinyl chalcones as potential anti-malarial agent.

The quinolinyl chalcones series (A1-A14) were screened for antimalarial activity. According to in vitro antimalarial studies, many quinolinyl chalcones are potentially active against CQ-sensitive and resistance P. falciparum strains with no toxicity against Vero cell lines. The most active quinolinyl chalcones A4 (with IC50 0.031 µM) made a stable A4-heme complex with - 25 kcal/mole binding energy and also showed strong π-π interaction at 3.5 Å. Thus, the stable A4-heme complex formation suggested that these quinolinyl chalcones act as a blocker for heme polymerization. The docking results of quinolinyl chalcones with Pf-DHFR showed that the halogenated benzene part of quinolinyl chalcones made strong interaction with Pf-DHFR as compared to quinoline part. A strong A4-Pf-DHFR complex was formed with low binding energy (- 11.04 kcal/mole). The ADMET properties of quinolinyl chalcones were also studied. The in vivo antimalarial studies also confirmed the A4 as an active antimalarial agent.

Anti-HIV cytotoxicity enzyme inhibition and molecular docking studies of quinoline based chalcones as potential non-nucleoside reverse transcriptase inhibitors (NNRT).

A series of fourteen (A1 - A14) qunioline based chalcones were screened for reverse transcriptase inhibitors (RT) and found potentially active against RT. Bioassay, theoretical and dockings studies with RT (the enzyme required for reverse transcription of viral RNA) results showed that the type and positions of the substituents seemed to be critical for their inhibition against RT. The bromo and chloro substituted chalcone displayed high degree of inhibition against RT. The A4 andA6 showed high interaction with RT, contributing high free binding energy (ΔG -9.30 and -9.13kcal) and RT inhibition value (IC50 0.10µg/ml and 0.11µg/ml).