Production from ilmenite of TiO2-supported catalysts for selective catalytic reduction of NO with NH3

Economic production of titanium dioxide (yield >98 %) from ilmenite has been achieved by use of a modified sulfate reduction process. A series of samples were prepared by varying the concentration of titanium dioxide nuclei (0.2, 0.3, and 0.6 %) and further impregnation with antimony and vanadia. The structural and acidic properties of the samples were comprehensively studied by X-ray diffraction (XRD), transmission electron microscopy, BJH pore size distribution, and temperature-programmed desorption of NH₃. The XRD results revealed the presence of intense peaks from anatase titanium dioxide. Enhancement of surface area was observed for second-time filtered samples, possibly because of loss of iron from the bulk. As a result, formation of additional micropores was apparent from N₂ adsorption and desorption isotherms. Among all the antimony and vanadia-doped samples, the first-time filtered sample with the low concentration of nuclei (0.2 %) had the highest catalytic activity at low temperatures, owing to its larger pore size and abundant acidic species.     

Enhancement of naringenin solution concentration by solid dispersion in cellulose derivative matrices

Naringenin (Nar) is an important bioactive flavonoid with poor organic solubility and oral bioavailability. It is highly promising for treatment of conditions including diabetes, hyperlipidemia, and hepatitis C infection. Amorphous solid dispersion (ASD) of Nar is an appealing way to enhance its solubility, and carboxylated cellulose esters are attractive polymers for this purpose because of their ability to stabilize drugs against crystallization in both solid and solution phases, while restricting drug release to the pH of the small intestine (ca. 6.8). We demonstrate that ASDs of Nar can be formed using such carboxylated cellulose derivatives as cellulose acetate adipate propionate (CAAdP), carboxymethylcellulose acetate butyrate (CMCAB) and hydroxypropylmethylcellulose acetate succinate (HPMCAS). We compare Nar solution concentrations and release profiles from these cellulosic ASDs to those from pure crystalline Nar, and to Nar ASD in poly(vinylpyrrolidinone) (PVP). We show that all polymers in this study form ASDs with Nar, that the PVP ASDs release Nar at both gastric (1.2) and small intestine (6.8) pH, and that the cellulosic polymers release Nar selectively at neutral pH. Solution concentrations of Nar are significantly enhanced from these ASDs. These preliminary studies indicate that HPMCAS, CAAdP, and CMCAB are practical ASD polymers for Nar due to their ability to generate and stabilize high solution concentrations, and their pH-triggered drug release.     

Improved methods for the synthesis and isolation of imidazolium based ionic salts

Solvent-free reactions were used for the synthesis of a series of imidazolium-based ionic salts: 3,3′-[pyridine-2,6-diylbis(methylene)]bis(1-R-1H-imidazol-3-ium)chloride; (R = methyl, ethyl, butyl, isobutyl, hexyl, and benzyl). A simple and effective filtration process was used to isolate all the products in high purity and with yields ?93% within a 24 h period. The highly pure ionic compounds which are precursors to N-heterocyclic carbene ligands used in catalysis were fully characterized as gray-white hygroscopic salts.     

Enhancement in Aqueous Solubility of Mefenamic Acid using Micellar Solutions of Various Surfactants

Journal of Solution Chemistry - The development of a meaningful dissolution procedure for drug products with limited water solubility has been a challenge to both the pharmaceutical industry and...     

Influence of supporting ligand microenvironment on the aqueous stability and visible light-induced CO-release reactivity of zinc flavonolato species

The visible light-induced CO-release reactivity of the zinc flavonolato complex [(6-Ph₂TPA)Zn(3-Hfl)]ClO₄ (1) has been investigated in 1?:?1 H₂O?:?DMSO. Additionally, the effect of ligand secondary microenvironment on the aqueous stability and visible light-induced CO-release reactivity of zinc flavonolato species has been evaluated through the preparation, characterization, and examination of the photochemistry of compounds supported by chelate ligands with differing secondary appendages, [(TPA)Zn(3-Hfl)]ClO₄ (3; TPA = tris-2-(pyridylmethyl)amine) and [(bnpapa)Zn(3-Hfl)]ClO₄ (4; bnpapa = N,N-bis((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine)). Compound 3 undergoes reaction in 1?:?1 H₂O?:?DMSO resulting in the release of the free neutral flavonol. Irradiation of acetonitrile solutions of 3 and 4 at 419 nm under aerobic conditions results in quantitative, photoinduced CO-release. However, the reaction quantum yields under these conditions are lower than that exhibited by 1, with 4 exhibiting an especially low quantum yield. Overall, the results of this study indicate that positioning a zinc flavonolato moiety within a hydrophobic microenvironment is an important design strategy toward further developing such compounds as CO-release agents for use in biological systems.     

A novel synthesis of 1,2,4-oxadiazoles and isoxazoles

A novel synthesis of 1,2,4-oxadiazoles and isoxazoles is described by utilizing the reactions between amidoximes and α,β-alkynic aldehydes and/or ketones. Conjugate addition products, obtained from amidoximes and α,β-alkynic aldehydes and/or ketones, afford 1,2,4-oxadiazoles and isoxazoles when treated with bases and acids, respectively. 1,2,4-Oxadiazoles can also be synthesized directly from amidoximes and α,β-alkynic aldehydes in a one-pot manner under basic conditions. The reactions are general for a variety of starting compounds and tolerate the presence of aryl, heteroaryl and alkyl groups.     

Independent isomeric-yield ratio of 89m,gNb from 93Nb(γ, 4n), natZr(p,xn), and 89Y(α, 4n) reactions

The independent isomeric-yield ratios of ^89m,gNb for the ⁹³Nb(γ, 4n) ^89m,gNb reaction with bremsstrahlung energies of 45-, 50-, 55-, 60-, and 70-MeV were measured by the activation and the off-line γ-ray spectrometric technique at 100 MeV electron linac of the Pohang accelerator laboratory. The isomeric-yield ratios of ^89m,gNb for the ^natZr(p, xn) ^89m,gNb and the ⁸⁹Y(α, 4n) ^89m,gNb reactions were measured by using a stacked-foil activation technique with the proton energies of 19–45 MeV and alpha energies of 38.9-, 40.5-, and 42.5-MeV at the MC-50 cyclotron of Korea Institute of Radiological and Medical Sciences. The measured isomeric-yield ratio of ^89m,gNb from the ⁹³Nb(γ, 4n), ^natZr(p, xn), and ⁸⁹Y(α, 4n) reactions were compared with the similar literature data in the ⁸⁹Y(³He, 3n) reaction. It was found that the isomeric yield ratio of ^89m,gNb increases with projectile energy, which indicate the effect of excitation energy. However, for the similar compound nucleus with the same excitation energy, the isomeric-yield ratios of ^89m,gNb in the ⁸⁹Y(α, 4n) and ⁸⁹Y(³He, 3n) reactions are higher than those in the ⁹³Nb(γ, 4n) and ^natZr(p, xn) reactions, which indicates the role of input angular momentum. The isomeric-yield ratios of ^89m,gNb in the ⁹³Nb(γ, 4n), ^natZr(p, xn), ⁸⁹Y(α, 4n), and ⁸⁹Y(³He, 3n) reactions were also calculated theoretically using computer code TALYS 1.4. The theoretical isomeric-yield ratios of ^89m,gNb from four reactions increase with excitation energy. However, the theoretical value are significantly higher than the experimental data in the ⁹³Nb(γ, 4n) and ^natZr(p, xn) reactions but slightly lower or comparable in the ⁸⁹Y(α, 4n) rand ⁸⁹Y(³He, 3n) reactions.     

Characterization of poly(2-vinylpyridine)-block-poly(methyl methacrylate) copolymers and blends of their homopolymers by liquid chromatography at critical conditions

Poly(2-vinylpyridine)s (P2VPs) are important polymers with extensive applications in modern day material science. P2VP is an exceptional case for liquid chromatography because of certain polar interactions with most of the stationary phases. In the present study, we established the critical adsorption point (CAP) of P2VP for the first time. The effectiveness of the method is demonstrated by analyses of blends and block copolymers of P2VP and PMMA. The CAP of PMMA is established for determination of molar mass of P2VP component of above mentioned blends and block copolymers. The methods successfully demonstrate the separation of both types of homopolymers from the rest of the samples in conjunction with the determination of molar mass distribution of noncritical block or component. Graphical Abstract

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Synthesis,spectroscopic characterization,X-ray crystal structure,biological screening and catalytic studies of organotin(IV) carboxylates of 3-(4-cyanophenyl) acrylic acid

A series of six organotin(IV) carboxylates [Me₂SnL₂] (1), [n-Bu₂SnL₂] (2), [n-Oct₂SnL₂] (3), [Me₃SnL] (4), n-Bu₃SnL (5) and [Ph₃SnL] (6), where L = 3-(4-cyanophenyl) acrylic acid have been synthesized and characterized by elemental analysis, FT-IR and NMR (¹H, ¹³C). The complex (4) was also analyzed by single crystal X-ray analysis which showed distorted trigonal bipyramidal geometry with polymeric bridging behavior. The complexes 1–6 were screened for antimicrobial activities and cytotoxicity. The results showed significant activity with few exceptions. The catalytic activity of complexes was assessed in transesterification reaction of Brassica campestris oil (triglycerides) to produce biodiesel (fatty acid methyl esters). The results showed that triorganotin(IV) complexes exhibited good catalytic activity than their di-analogues.     

Imidazole,pyrimidine and diazepine containing heteroaryl-substituted heterocyclic salts as efficient ligand precursors for Mizoroki–Heck coupling reaction: synthesis,structural characterization and catalytic activities

The nine new heteroaryl-substituted imidazolidinium (1a–c), pyrimidinium (2a–c) and diazepinium (3a–c) salts as N-heterocyclic carbene (NHC) precursors were synthesized in good yields and entirely characterized using elemental analyses and conventional spectroscopic methods. In situ formed complexes from heterocyclic salts (1–3), Pd(OAc)₂ and in the presence of KOBu ^t as a base were tested as catalysts for the Mizoroki–Heck coupling reaction in an aqueous media and very high yields were achieved. 1,3-Di(5-methylthiophen-2-ylmethyl)pyrimidinium hexafluorophosphate salt (2b) was structurally characterized by single-crystal X-ray diffraction. In the 2b compound (C₁₆H₂₁N₂S₂)⁺[PF₆]^?, the terminal thiophene rings are twisted with a dihedral angle of 72.8(3)°. In the pyrimidine ring, the three successive C atoms between the N atoms are disordered over two positions [occupancy ratio 0.753(12):0.247(12)]. In the crystal, neighboring molecules are linked by C–H…F hydrogen bonds, running along the b axis.