C‐S cross‐coupling reaction using novel and green synthesized CuO nanoparticles assisted by Euphorbia maculata extract

In the present study, biosynthesis of CuO nanoparticles using a rapid, eco‐friendly, cost‐effective and efficient method has been reported employing aqueous Euphorbia maculata extract as mild, renewable and non‐toxic reducing and capping agents without adding any surfactants. The biogenic and green method has some benefits compared to conventional physical and chemical methods. It is simple, cheap and environmentally friendly. The biosynthesized CuO NP displayed a color change pattern (from sky blue to black) on preparation and presented its respective broad peak at 365 nm, which was analyzed by UV–Vis spectroscopy. Using the FT‐IR analysis, biomolecules in E. maculata extract which are responsible for bioreduction activity and synthesize of CuO NP, were identified. The XRD, EDX and FESEM results confirmed the successful synthesis of CuO nanoparticles of 18 nm sizes, with spherical and sponge crystal structure. The catalytic activity of biosynthesized CuO NPs was studied in C‐S cross‐coupling reaction. This method has the advantages of high yields, easy work‐up, and simple reusability. The recovered CuO NP can be reused four times without any considerable loss of its catalytic activity.     

Novel palladium nanoparticles supported on β‐cyclodextrin@graphene oxide as magnetically recyclable catalyst for Suzuki–Miyaura cross‐coupling reaction with two different approaches in bio‐based solvents

A novel nanocatalyst was designed and prepared. Initially, the surface of magnetic graphene oxide (M‐GO) was modified using thionyl chloride, tris(hydroxymethyl)aminomethane and acryloyl chloride as linkers which provide reactive C═C bonds for the polymerization of vinylic monomers. Separately, β‐cyclodextrin (β‐CD) was treated with acryloyl chloride to provide a modified β‐CD. Then, in the presence methylenebisacrylamide as a cross‐linker, monomers of modified β‐CD and acrylamide were polymerized on the surface of the pre‐prepared M‐GO. Finally, palladium acetate and sodium borohydride were added to this composite to afford supported palladium nanoparticles. This fabricated nanocomposite was fully characterized using various techniques. The efficiency of this easily separable and reusable heterogeneous catalyst was successfully examined in Suzuki–Miyaura cross‐coupling reactions of aryl halides and boronic acid as well as in modified Suzuki–Miyaura cross‐coupling reactions of N‐acylsuccinimides and boronic acid in green media. The results showed that the nanocatalyst was efficient in coupling reactions for direct formation of the corresponding biphenyl as well as benzophenone derivatives in green media based on bio‐based solvents. In addition, the nanocatalyst was easily separable, using an external magnet, and could be reused several times without significant loss of activity under the optimum reaction conditions.     

Facile synthesis of inorganic–organic Fe2W18Fe4@NiO@CTS hybrid nanocatalyst induced efficient performance in oxidative desulfurization of real fuel

In this work, a new nanocatalyst, Fe₂W₁₈Fe₄@NiO@CTS, was synthesized by the reaction of sandwich‐type polyoxometalate (Fe₂W₁₈Fe₄), nickel oxide (NiO), and chitosan (CTS) via sol–gel method. The assembled nanocatalyst was systematically characterized by FT‐IR, UV–vis, XRD, SEM, and EDX analysis. The catalytic activity of Fe₂W₁₈Fe₄@NiO@CTS was tested on oxidative desulfurization (ODS) of real gasoline and model fuels. The experimental results revealed that the levels of sulfur content and mercaptan compounds of gasoline were lowered with 97% efficiency. Also, the Fe₂W₁₈Fe₄@NiO@CTS nanocatalyst demonstrated an outstanding catalytic performance for the oxidation of dibenzothiophene (DBT) in the model fuel. The major factors that influence the desulfurization efficiency and the kinetic study of the ODS reactions were fully detailed and discussed. The probable ODS pathway was proposed via the electrophilic mechanism on the basis of the electrophilic characteristic of the metal‐oxo‐peroxo intermediates. The prepared nanocatalyst could be reused for 5 successive runs without any appreciable loss in its catalytic activity. As a result, the current study suggested the potential application of the Fe₂W₁₈Fe₄@NiO@CTS hybrid nanocatalyst as an ideal candidate for removal of sulfur compounds from fuel.     

Graphene oxide‐catalyzed CSp3–H activation of methylarenes in aqueous medium: A unified metal‐free access to amides and benzimidazoles

Graphene oxide (GO)‐catalyzed selective synthesis of amides via C_Sp3–H activation of methylarenes and consequent C–N bond formation with anilines under aqueous medium has been described. Oxygen functionality allied with GO surface played a dual role both as acid catalyst and oxidizing agent to some extent. However, GO has a copious effect on the reaction, shown by a high TOF value with TBHP as co‐oxidant. The decisive role of carboxylic acid functional groups on GO nanosheets in this metal‐free strategy has been confirmed and was monitored by various analytic techniques viz. Fourier transform‐infrared, UV–Vis, Raman and XPS. A plausible mechanism was proposed by control experiments and by the isolation of the intermediate. Over‐oxidation of methylarenes was not detected, and high recyclability of the carbocatalyst with its heterogeneous behavior facilitated the isolation and purification of the desired products. We have further explored the utility of this process for the chemoselective synthesis of benzimidazoles.     

Extended phase diagram of La1-xCaxMnO3 by interfacial engineering

The interfacial enhanced ferromagnetism in maganite/ruthenate system is regarded as a promising path to broaden the potential of oxide-based electronic device applications. Here, we systematically studied the physical properties of LaLa_1-xCa_xMnO₃/SrRuO₃ superlattices and compared them with the LaLa_1-xCa_xMnO₃ thin films and bulk compounds. The LaLa_1-xCa_xMnO₃/SrRuO₃ superlattices exhibit significant enhancement of Curie temperature (T_C) beyond the corresponding thin films and bulks. Based on these results, we constructed an extended phase diagram of LaLa_1-xCa_xMnO₃ under interfacial engineering. We considered the interfacial charge transfer and structural proximity effects as the origin of the interface-induced high T_C. The structural characterizations revealed a pronounced increase of B-O-B bond angle, which could be the main driving force for the high T_C in the superlattices. Our work inspires a deeper understanding of the collective effects of interfacial charge transfer and structural proximity on the physical properties of oxide heterostructures.     

Development and application of chip calorimeter as an X-ray detector

Radiotherapy for cancer patients requires accurate measurement of the absorbed dose of radiation in a treatment planning step. Various types of radiation detectors are currently utilized for dose measurement. Among them, calorimeters are known to be the most precise detector for measuring absorbed dose, but their on-site application is limited by the large size of the equipment. We developed a miniaturized chip calorimeter for application as a radiation detector. The calorimetric radiation detector was built using micro/nano fabrication techniques, and consists of an SU-8 photoresist absorber and high-sensitivity vanadium oxide (VO_x) thermistors. The thermistors had a temperature resolution of 135 μK, and the calorimeter showed a thermal conductance of 11 μW/K. The detector was irradiated with various X-ray dose rates from a linear accelerator, and the absorbed dose to SU-8 was measured. The detector responses showed high linearity with dose rates, demonstrating the feasibility of the radiation detector for practical uses.     

Identifying a perovskite phase in rare-earth nickelates using X-ray photoelectron spectroscopy

We demonstrate a practical way to identify the presence of a perovskite phase in rare-earth nickelates (RNiO₃) using X-ray photoelectron spectroscopy (XPS). By varying the calcination temperature, we prepared RNiO₃ powders with different degrees of chemical reaction. We found that perovskite RNiO₃ becomes predominant after high-temperature calcination (≥1,000 °C) in X-ray diffraction and XPS (at Ni 3p and O 1s edges) measurements. While the observed spectra at the Ni 3p edge are similar for all powders, a sizable difference was observed in the O 1s-edge spectra depending on the calcination temperature. With the formation of a perovskite phase with a trivalent Ni³⁺ state, an XPS peak corresponding to oxygen ions in the perovskite lattice distinctly emerges. Our work shows that the Ni³⁺ state cannot be determined by analyzing the Ni 3p edge solely and rather, the O 1s edge should be simultaneously monitored for explicit identification.     

Amides and Heparin‐Like Polymer Co‐Functionalized Graphene Oxide Based Core @ Polyethersulfone Based Shell Beads for Bilirubin Adsorption

Excessive bilirubin in the body of patient with liver dysfunction or metabolic obstruction may cause jaundice with irreversible brain damage, and new type of adsorbent for bilirubin is under frequent investigation. Herein, graphene oxide based core @ polyethersulfone‐based shell beads are fabricated by phase inversion method, amides and heparin‐like polymer are introduced to functionalize the core‐shell beads. The beads are successfully prepared with obvious core‐shell structure, adequate thermostability and porous shell. Clotting times and protein adsorption are investigated to inspect the hemocompatibility property of the beads. The adsorption of bilirubin is systematically investigated by evaluating the effects of contacting time, initial concentration and temperature on the adsorption, which exhibits improved bilirubin adsorption amount for the beads with amides contained cores or/and shells. It is worth believing that the amides and heparin‐like polymer co‐functionalized core‐shell beads may be utilized in the field of hemoperfusion for bilirubin adsorption.