New phosphonium molybdate-promoted green,fast and selective catalytic procedure for the synthesis of trisubstituted imidazoles

The compound 1,1′-(ethane,1,2-diyl)ditriphenylphosphonium hexamolybdate dimethylsulfoxide {C₂H₄[P(C₆H₅)₃]₂}{Mo₆O₁₉}·SO (CH₃)₂ ( I ) was prepared, and ¹H-NMR, ¹³C-NMR, Fourier transform-infrared, differential scanning calorimetry and single crystal X-ray diffraction analysis were used to characterize the titled compound. Crystallographic data showed that compound I crystallized in the monoclinic crystal system in C2/c space group. The compound ( I ) was used for selective synthesis of 2,4,5-tri aryl imidazole derivatives under solvent-free conditions efficiently. Because of hindrance of the catalyst, the yields of products for aldehydes bearing para substituents are higher than the aldehydes bearing ortho substituents, and for aromatic aldehydes with meta substituents are very low.     

Oxidation reactions catalysed by molybdenum(VI) complexes grafted on UiO‐66 metal–organic framework as an elegant nanoreactor

A heterogeneous catalyst was synthesized by immobilizing Mo(CO)₃ in a UiO‐66 metal–organic framework. The benzene ring of the organic linker in UiO‐66 was modified via liquid‐phase deposition of molybdenum hexacarbonyl, Mo(CO)₆, as starting precursor to form the (arene)Mo(CO)₃ species inside the framework. The structure of this catalyst was characterized using X‐ray diffraction, and chemical integrity was confirmed using Fourier transform infrared and diffuse reflectance UV–visible spectroscopic methods. The metal content was analysed with inductively coupled plasma. Field emission scanning electron microscopy was used to measure particle size and N₂ adsorption measurements to characterize the specific surface area. This catalytic system was efficiently applied for epoxidation of alkenes and oxidation of sulfides. The Mo‐containing metal–organic framework was reused several times without any appreciable loss of its efficiency.     

Study of mechanics of physically transient electronics: A step toward controlled transiency

Transient electronics is a class of electronic devices designed to maintain stable operation for a desired and preset amount of time; and, undergo fast and complete degradation and deconstruction once transiency is triggered. Controlled and programmed transiency in solvent‐triggered devices is strongly dependent on chemical and physical interactions between the solvent and the device, as well as those within the device itself, among its constituent components. Mechanics of transiency of prototypical transient circuits demonstrate strong dependence of the transiency characteristics on that of the substrate. In the present study, we demonstrate the control of transiency through the dissolution behavior of a substrate for the devices with electronic parts composed of colloidal units. It is observed that the physical circuit–substrate interactions are the dominating factors in defining the overall transiency behavior of the device. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 517–524     

Ru(III) complex anchored onto amino-functionalized MIL-101(Cr) framework via post-synthetic modification: an efficient heterogeneous catalyst for ring opening of epoxides

In this work, the metallo Schiff base-functionalized metal–organic framework was prepared by post-synthetic method and used as an electron-deficient catalyst for the alcoholysis of epoxides. In this manner, the aminated MIL-101 was modified with 2-pyridine carboxaldehyde and then the prepared Schiff base reacted with RuCl₃. This new catalyst, MIL-101–NH₂–PC–Ru, was characterized by Fourier transform infrared, UV–Vis spectroscopic techniques, X-ray diffraction, BET, inductively coupled plasma atomic emission spectroscopy and field-emission scanning electron microscopy. In the presence of this heterogeneous catalyst, ring opening of epoxides was performed under mild condition to show the significant ability and successful applications of Lewis acid containing catalysts in corporation with metal–organic frameworks. The reusability of the catalyst was also investigated. No noticeable decrease in the catalytic activity was found after four consecutive times.     

Engineering hairy cellulose nanocrystals for chemotherapy drug capture

Cancer is one of the leading causes of death worldwide, affecting millions of people every year. Although chemotherapy remains one of the most common cancer treatments in the world, the severe side effects of chemotherapy drugs impose serious concerns to cancer patients. In many cases, the chemotherapy can be localized to maximize the drug effects; however, the drug systemic circulation induces undesirable side effects. Here, we have developed a highly efficient cellulose-based nanoadsorbent that can capture more than 6,000 milligrams of doxorubicin (DOX), one of the most widely used chemotherapy drugs, per gram of the adsorbent at physiological conditions. Such drug capture capacity is more than 3,200% higher than other nanoadsorbents, such as DNA-based platforms. We show how anionic hairy cellulose nanocrystals, also known as electrosterically stabilized nanocrystalline cellulose (ENCC), bind to positively charged drugs in human serum and capture DOX immediately without imposing any cytotoxicity and hemolytic effects. We elucidate how ENCC provides a remarkable platform for biodetoxification at varying pH, ionic strength, ion type, and protein concentration. The outcome of this research may pave the way for developing the next-generation in vitro and in vivo drug capture additives and devices.     

An iron Schiff base complex loaded mesoporous silica nanoreactor as a catalyst for the synthesis of pyrazine-based heterocycles

An iron Schiff base complex was encapsulated in SBA-15 mesoporous silica to afford a Fe(III)-Schiff base/SBA-15 heterogeneous nanocatalyst for the synthesis of pyridopyrazine and quinoxaline heterocycles. These reactions proceeded in water with excellent yields. The catalyst was characterized by physico-chemical and spectroscopic methods and found to retain the characteristic channel structures of the SBA-15, allowing good accessibility of the encapsulated metal complex.     

Synthesis and characterization of new cross-linked terpolymer systems containing silyl group

A series of acrylic terpolymers containing silyl pendant groups was prepared by free radical cross-linking copolymerization. Me₃Si, Et₃Si and t-BuMe₂Si together with cubane-1, 4-dicarboxylic acid (CDA) were covalently linked with 2-hydroxyethyl methacrylate (HEMA). The silyl-linked HEMA are abbreviated as TMSiEMA, TESiEMA and TBSiEMA respectively. Cubane-1, 4-dicarboxylic acid (CDA) linked to two HEMA group is the cross-linking agent (CA). Free radical cross-linking terpolymerization of the methyl methacrylate (MMA) and methacrylic acid (MAA) with two different molar ratios of organosilyl monomers and CA was carried out at 60–70 ^∘C. The compositions of the cross-linked three-dimensional polymers were determined by FT-IR spectroscopy. The glass transition temperature (Tg) of the network polymers was determined calorimetrically. The Tg of network terpolymers increases with increasing of cross-linking degree. Equilibrium swelling studies were carried out in enzyme-free simulated gastric and intestinal fluids (SGF and SIF, respectively). The gels swelled more in SIF than in SGF. The swelling behaviour of the copolymers was dependent on the content of MAA groups and caused a decrease in gel swelling in pH 1 or an increase in gel swelling in pH 7.4. Based on the great difference in swelling ratio at pH 1 and 7.4 for P-1, P-6 and P-10 appear to be good candidates for colon-specific drug delivery.     

An efficient three-component reaction involving [3 + 1 + 1] furannulation leading to furanonaphthoquinones in water

An efficient and clean green synthesis of highly substituted linear naphtho[2,3-b]-furan-4,9-dione derivatives, starting from 2-hydroxy-1,4-naphthoquinone, alkyl isocyanides and a variety of aldehydes, is described. This new method provides the first example of an efficient regioselective synthetic method for the synthesis of linear naphtho[2,3-b]-furan-4,9-dione ring systems by formation of three bonds. This [3 + 1 + 1] furannulation strategy affords furanonaphthoquinones in moderate to high yields, using water as a cheap, non-toxic, environmentally friendly solvent, in a one-step reaction, without the need of complicated work-up procedures.