Molybdenum (VI)‐functionalized UiO‐66 provides an efficient heterogeneous nanocatalyst in oxidation reactions

A novel heterogeneous nanocatalyst was established by supporting molybdenum (VI) on Zr₆ nodes in the structure of the well‐known UiO‐66 metal–organic framework (MOF). The structure of the UiO‐66 before and after Mo (VI) immobilization was confirmed with XRD, DR‐FTIR and UV–vis spectroscopy, and the presence and amount of Mo (VI) was identified by X‐ray photoelectron spectroscopy and inductively coupled plasma atomic emission spectroscopy. TEM imaging confirmed the absence of Mo clusters on the MOF surface, while SEM confirmed that the appearance of the MOF has not changed upon immobilizing the Mo (VI) catalyst. BET adsorption measurements were used to confirm the porosity of the catalyst. The catalytic activity of this heterogeneous catalyst was investigated in oxidation of sulfides with H₂O₂ in acetonitrile and oxidative desulfurization of dibenzothiophene. Easy work up, convenient and steady reuse and high activity and selectivity are prominent properties of this new hybrid material.     

Unexpected Factors Affecting the Kinetics of Guest Molecule Release from Investigation of Binary Chemical Systems Trapped in a Single Void of Mesoporous Silica Particles

In this work, we present results for loading of well-defined binary systems (cocrystal, solid solution) and untreated materials (physical mixtures) into the voids of MCM-41 mesoporous silica particles employing three different filling methods. The applied techniques belong to the group of “wet methods” (diffusion supported loading – DiSupLo ) and “solvent-free methods” (mechanical ball-mill loading – MeLo , thermal solvent free – TSF ). As probes for testing the guest1-guest2 interactions inside the MCM-41 pores we employed the benzoic acid ( BA ), perfluorobenzoic acid ( PFBA ), and 4-fluorobenzoic acid ( 4-FBA ). The guests intermolecular contacts and phase changes were monitored employing magic angle spinning (MAS) NMR Spectroscopy techniques and powder X-ray diffraction (PXRD). Since mesoporous silica materials are commonly used in drug delivery system research, special attention has been paid to factors affecting guest release kinetics. It has been proven that not only the content and composition of binary systems, but also the loading technique have a strong impact on the rate of guests release. Innovative methods of visualizing differences in release kinetics are presented.     

Effect of Ultrasonic‐assisted Preparation Methods on Structure,Morphology and Optical Properties of Nanosized Cupric Oxide

Cupric oxide is a p‐type semiconductor with a narrow band‐gap which is suitable for catalysis, electrochemical cells, field emission devices and gas sensor applications. Despite considerable efforts devoted to the preparation of the nanosized CuO, there is a lack of information about ultrasonic‐assisted (US) preparation methods. Nanosized cupric oxide was successfully prepared through different ultrasonic‐assisted (US) preparation methods. Furthermore, the influence of preparation method on the structure, morphology and optical properties of nanosized CuO has been reported. XRD patterns were identical to the single‐phase pure CuO with a monoclinic structure. The enhancement of the crystallinity and crystallite size was observed for the sample prepared through the US thermal decomposition. The absorption band of CuO nanocrystals prepared through the US liquid hydrolysis shows a clear red shift of about 40 nm compared to those obtained with other preparation methods. Our results indicated that almost spherical CuO nanoparticles with an average size of 65 nm were prepared during the US thermal decomposition, while CuO rod‐like nanostructures with an average diameter of about 16 nm were obtained via the US liquid hydrolysis method. The band gap values of nanosized CuO samples were larger than the reported value for the bulk CuO. Synthesized CuO samples by US methods with adjustable and controllable properties make the applicability of cupric oxide even more versatile.     

A Simple,Microwave-Assisted,and Solvent-Free Synthesis of 2-Arylbenzothiazoles by Acetic Acid–Promoted Condensation of Aldehydes with 2-Aminothiophenol in Air

An efficient and simple procedure has been developed for the synthesis of various 2-arylbenzothiazoles by acetic acid–promoted condensation of 2 -aminothiophenol with aromatic aldehydes under microwave irradiation and solvent-free conditions in high yields.     

Atomic force microscopy investigation of surface roughness generated between SiO2 micro-pits in CHF3/Ar plasma

The present paper investigates the surface roughness generated by reactive ion etching (RIE) on the location between silicon dioxide (SiO₂) micro-pits structures. The micro-pit pattern on polymethyl methacrylate (PMMA) mask was created by an electron beam lithography tool. By using PMMA as a polymer resist mask layer for pattern transfer in RIE process, the carbon (C) content in etching process is increased, which leads to decrease of F/C ratio and causes domination of polymerization reactions. This leads to high surface roughness via self-organized nanostructure features generated on SiO₂ surface which was analyzed using atomic force microscopy (AFM) technique. The etching chemistry of CHF₃ plasma on PMMA masking layer and SiO₂ is analyzed to explain the polymerization. The surface root-mean-square (RMS) roughness below 1 nm was achieved by decreasing the RF power to 150 W and process pressure lower than 10 mTorr.     

Preparation and properties of semiconductor CuO nanoparticles via a simple precipitation method at different reaction temperatures

Preparation and properties of CuO nanoparticles as an important p-type semiconductor via a simple precipitation method at different reaction temperatures varying from 10 to 115°C using copper acetate as a starting material have been reported. In addition, we investigated the influence of the ultrasonic irradiation through synthesizing the nanosized CuO at 60°C. Samples were characterized by XRD, FT-IR, SEM, TEM and UV-Vis techniques. XRD patterns of samples were identical to the single-phase pure CuO with a monoclinic structure. FT-IR spectra exhibited sharp peaks at around 519 and 598?cm^?1 which can be assigned to vibrations of the Cu-O bond. Results indicated that properties of samples had great dependence on the temperature and ultrasonic irradiation. The crystallite size and crystallization increased with increasing the temperature from 10 to 115°C. The band gap of samples was estimated to be in the range of 1.9–2.9?eV that is larger than the reported value for the bulk CuO (1.85?eV). This study provides a simple method for the preparation of nanosized CuO with a better surface uniformity and a narrow size distribution. Synthesized CuO samples with adjustable and controllable optical properties make the applicability of copper oxide even more versatile.     

Synthesis of ZnO Nanoparticles Based on Zn Complex Achieved from L‐leucine

In the present study, ZnO nanoparticle preparation in a water‐base medium without using toxic chemicals was investigated. Zinc (II) acetate dehydrate, L? leucine and 5? sulfosalicylaldehyde sodium salt were utilized as the starting materials. X? ray diffraction analyses proved that ZnO was achieved as a unique phase. The highest value of crystallinity was obtained at 600 °C and the minimum values of crystallite size and lattice strain were reported at 400 and 500 °C, respectively. The photoluminescence spectroscopy showed that firing at 500 °C leads to decrease the point defects in ZnO structure. SEM and TEM images confirmed the relation between the firing temperature, the degree of crystallinity and the crystallite size. Firing at 400 °C leads to form ZnO nanoparticles with a size distribution ranging from 15 to 50 nm with cubic, circle and hexagonal shapes. By increasing the temperature to 500 °C, the nanoparticles dimensions increase to 30–60 nm. The particle size of sample ‘c’ is more than 50 nm. The optimum temperature to achieve the goal of this research, namely a high crystallinity and low structure defects, was found to be 500 °C.     

Coalescence of particle-laden fluid interfaces

Colloidal particles are capable of stabilizing emulsions and, thus, slowing or preventing their complete breakdown into phase-separated systems. Direct observations of the dynamics of such particles on both water and oil droplets are reported as two colloid-laden interfaces are brought into contact with each other. As coalescence proceeds, the complementary systems, representing oil-in-water and water-in-oil emulsions, exhibit contrasting mechanisms for the formation of ring and disk structures by the particles as they serve to temporarily stabilize the approaching surfaces. An explanation of such behavior leads to a better understanding of the stabilization and breaking mechanisms of so-called Pickering emulsions.     

Nucleophilic addition to 3-substituted pyridinium salts: expedient syntheses of (-)-L-733,061 and (-)-CP-99,994

[reaction: see text] The addition of nucleophiles to 3-substituted pyridinium salts prepared from N-methylbenzamide and various pyridines has been investigated. Good to excellent regioselectivities favoring the 2,3-disubstituted 1,2-dihydropyridines were observed. The resulting 1,2-dihydropyridines led to the corresponding 2,3-disubstituted pyridines upon treatment with Mn(OAc)3/NaIO4. This methodology was also successfully applied to the enantioselective syntheses of (-)-L-733,061 and (-)-CP-99,994, two members of a new class of highly potent, nonpeptide, Substance P antagonists.     

Spectral characterization of novel ternary zinc(II) complexes containing 1,10-phenanthroline and Schiff bases derived from amino acids and salicylaldehyde-5-sulfonates

A series of new ternary zinc(II) complexes [Zn(L(1-10))(phen)], where phen is 1,10-phenanthroline and H(2)L(1-10)=tridentate Schiff base ligands derived from the condensation of amino acids (glycine, l-phenylalanine, l-valine, l-alanine, and l-leucine) and salicylaldehyde-5-sulfonates (sodium salicylaldehyde-5-sulfonate and sodium 3-methoxy-salicylaldehyde-5-sulfonate), have been synthesized. The complexes were characterized by elemental analysis, IR, UV-vis, (1)H NMR, and (13)C NMR spectra. The IR spectra of the complexes showed large differences between nu(as)(COO) and nu(s)(COO), Deltanu (nu(as)(COO)-nu(s)(COO)) of 191-225 cm(-1), indicating a monodentate coordination of the carboxylate group. Spectral data showed that in these ternary complexes the zinc atom is coordinated with the Schiff base ligand acts as a tridentate ONO moiety, coordinating to the metal through its phenolic oxygen, imine nitrogen, and carboxyl oxygen, and also with the neutral planar chelating ligand, 1,10-phenanthroline, coordinating through nitrogens.