A palladium-catalyzed one-pot procedure for the regioselective dimerization and cyanation of indoles

A one-pot method for the regioselective dimerization and cyanation of indoles has been developed. The reaction uses safe and nontoxic K₄[Fe(CN)₆]·3H₂O as the cyanating agent which introduces selectively a cyano group into the 3-position of biindoles with high efficiency.     

Thermal stability and surface structure of Mo/CeO<Subscript>2</Subscript> and Ce-doped Mo/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

In order to explore the influence of CeO₂ on the structure and surface characteristics of molybdena, an investigation was undertaken by using N₂ adsorption (BET method), thermal analysis and in-situ diffuse reflectance infrared (DRIFT) techniques. In this work, the Mo/CeO₂ and Ce-Mo/Al₂O₃ samples were prepared by impregnation and co-precipitation methods with high Mo loadings. Combining the results one may notice that the presence of ceria led to the increase of polymerized surface Mo species so as to forming Mo-O-Ce linkages besides the formation of coupled O=Mo=O bonds indicative of polymeric MoO₃. From thermal analysis, it can be inferred that Mo/Al₂O₃ is the thermally most stable material in the temperature range used in the experiment (up to 900°C), whereas Ce-Mo/Al₂O₃ and Mo/CeO₂ samples undergo morphological modifications above 700°C resulting in lattice defects, which motivate the mobility of Mo and Ce ions and thus enhance the possibility of interaction between them. Additionally, their activity towards CO adsorption needs reduced ceria and molybdena containing coordinatively unsaturated sites (CUS), oxygen vacancies and hydroxyl groups to form various carbonate species.     

Evaluating the Effect of four Hosting Ionophores on the Performance of Anion Selective Potentiometric Sensor

A systematically designed practical approach was carried out for the optimization of an anion selective electrode for the determination of an anionic laxative, docusate sodium (DS). The PVC membrane composition and the sensor assembly were systematically optimized. Different sensors were fabricated using tetradodecylammonium bromide (TDAB), tridodecylmethylammonium bromide, tetraheptylammonium bromide as ion exchangers. The effect of ionophore was evaluated using four different host‐guest ionophores, namely; calix[8]arene, β‐cylodextrin, hydroxypropyl‐β‐cylodextrin and carboxymethyl‐β‐cylodextrin to reach the optimum membrane composition. Sensors were constructed in both liquid membrane and solid contact sensor‐assemblies. The slope, linear range, LOQ and response time for each sensor was calculated to assess their performance characteristics. Best Nernstian slope of ?61.38 mV/decade and lowest quantification limit of 7.62×10^?7 M was achieved by the sensor containing TDAB as ion exchanger and Calix[8]arene as ionophore in the PVC matrix using the gold wire solid contact sensor assembly. Electrode selectivity was assured in the presence of DS potential degradation product, common interfering ions and industrial excipients of tablet and gel formulations. Validation was carried out regarding the ICH validation parameters.     

Hyperelastic characterization of the interlamellar domain and interphase layer in semicrystalline polyethylene

The interphase layer in semicrystalline polyethylene (PE) serves as the transition between the crystalline lamellae and the amorphous domains and is recognized as the third constituent of PE. When PE undergoes large deformations, this interphase layer together with the amorphous phase behaves hyperelastically. Because of the metastable nature and nanometric size of the interphase and its intimate mechanical coupling to the neighboring crystal and amorphous domains, detailed characterization of its hyperelastic properties have eluded detailed experimental evaluation. To extract these properties, a combined algorithm is proposed based on applying the constitutive relations of an isotropic, compressible, hyperelastic continuum to the molecular dynamics simulation results of a PE stack from Lee and Rutledge (Macromolecules 2011, 3096–3108). The simulation element is incrementally deformed to a large strain, during which the stress–strain information is recorded. Assuming a neo‐Hookean model, the tensorial constitutive equation is derived. The hyperelastic parameters for the central amorphous phase, the interphase layer, and the interlamellar domain are identified with the help of the optimization notion and a set of nonnegative objective functions. The identified hyperelastic parameters for the interlamellar domain are in good agreement with the ones estimated experimentally and frequently used in the literature for the noncrystalline phase. The specifically developed sensitivity analysis indicates that the shear modulus is identified with a higher degree of certainty, in contrast to the bulk modulus. It is also revealed that the presented continuum mechanics analysis is able to capture the melting/recrystallization and rotation of crystalline chains that take place during the deformation. The evolutions of the boundaries of the hyperelastic elements are also identified concurrently with the hyperelastic parameters as the by‐product of the presented methodology. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1692–1704     

Iron(III) Trifluoroacetate: Chemoselective and Recyclable Lewis Acid Catalyst for Diacetylation of Aldehydes,Thioacetalization and Transthioacetalization of Carbonyl Compounds and Aerobic Coupling of Thiols

Iron(III) trifluoroacetate [Fe(CF3CO2)3] was found to be a recyclable, highly efficient and chemoselective Lewis acid catalyst for protection of a variety of carbonyl compounds as thioacetals under nearly neutral conditions. With the use of this catalyst, 1,3-dithiolanes and 1,3-dithianes were obtained in high yields from various aldehydes. Under the same conditions ketones were similarly but more slowly thioketalized. This difference in reactivity between aldehydes and ketones was successfully utilized for the selective thioacetalization of aldehydes in the presence of ketones and also for the chemoselective conversion of β-diketone into the corresponding dithioacetal. Transthioacetalization of O,O-acetals and O,O-ketals into cyclic thioacetals was also achieved by using this catalyst. Additionally, iron(III) trifluoroacetate has been found to be efficient catalyst for the addition of acetic anhydride to both aromatic and aliphatic aldehydes to afford 1,1-diacetates (gem diacetates). Aerobic dimerization of thiols was achieved by this reagent mediated by sodium iodide and air atmosphere.     

Study of hydrogen bonds in N-methylacetamide by DFT calculations of oxygen, nitrogen, and hydrogen solid-state NMR parameters

Solid-state nuclear magnetic resonance (NMR) parameters of ¹⁷O, ¹⁴N/¹⁵N, and ²H/¹H nuclei were evaluated in two available neutron crystalline structures of N-methylacetamide (NMA) at 250 and 276 K, NMA-I and NMA-II, respectively. Density functional theory calculations were performed by B3LYP method and 6-311++G** and IGLO-II type basis sets to calculate the electric field gradient (EFG) and chemical shielding (CS) tensors at the sites of mentioned nuclei. In order to investigate hydrogen bonds (HBs) effects on NMR tensors, calculations were performed on four-model systems of NMA: an optimized isolated gas-phase, crystalline monomers, crystalline dimers, and crystalline trimers. Comparing the calculated results reveal the influence of N–H···O=C and C–H···O=C HB types on the NMR tensors which are observable by the evaluated parameters including quadrupole coupling constant, C _Q, and isotropic CS, σ _iso. Furthermore, the results demonstrate more influence of HB on the EFG and CS tensors of NMA at 276 K rather than that of 250 K.     

Easily prepared azopyridines as potent and recyclable reagents for facile esterification reactions. An efficient modified mitsunobu reaction

The 2,2'-, 3,3'-, and 4,4'-azopyridines (azpy) and their alkyl pyridinium ionic liquids were studied as a new class of electron-deficient reagents for Mitsunobu esterification reactions. Among these compounds, 4,4'-azopyridine was found to be the most suitable one for esterification and thioesterification reactions. This new reagent promises to provide general and complementary solutions for separation problems in Mitsunobu reactions without restricting the reaction scope and facilitates the isolation of its hydrazine byproduct. The pyridine hydrazine byproduct can be simply recycled to its azopyridine by an oxidation reaction.     

Synthesis and application of a novel functionalized magnetic MIL-101(Cr) nanocomposite for determination of aflatoxins in pistachio samples

Research on Chemical Intermediates - Herein, a novel method entitled magnetic solid-phase extraction based on MIL-101(Cr)/Fe3O4@SiO2@propylthiouracil composite was developed using the magnetite...     

A new triterpene and protective effect of Periploca somaliensis Browicz fruits against CCl4-induced injury on human hepatoma cell line (Huh7)

The potential hepatoprotective effect of the methanolic extract of Periploca somaliensis Browicz fruits, its different fractions (n-hexane, chloroform and n-butanol) and the major isolated compound ursolic acid was evaluated using the human hepatoma cell line (Huh7) based on the changes in the activity of aspartate aminotransferase, alanine transaminase, glutathione and superoxide dismutase. Each sample was tested at three different concentrations (1000, 100 and 10 μg/mL). All tested samples exhibited a potent concentration-independent cytoprotective effect relative to silymarin as a reference standard. Chromatographic fractionation of the chloroform-soluble fraction of the methanol extract of P. somaliensis Browicz fruits afforded two known triterpenes, namely ursolic acid, and 11α,12α-epoxy-3β-hydroxy-olean-13β,28-olide, and a newly discovered one, namely 3β-hydroxy-urs-11-en-13β,28-olide. The structures of the isolated compounds were elucidated by the analysis of 1D and 2D NMR spectral data.     

Click Chemistry Based Synthesis of Novel Architectures Bearing Sugar Unit at the Pyridothienopyrimidines

Novel conjugates of pyridothienopyrimidinones and carbohydrates or other moieties linked by 1,2,3‐triazoles were synthesized. After establishing the pyridothienopyrimidone ring systems by ring closure, propargyl group was introduced by O‐alkylation or N‐alkylation. Cu‐catalyzed cycloaddition of the propargyl product with azido group gave the corresponding 1,2,3‐triazoles in high yields. A remarkable case of the catalyzed ring closure to build a pyrimidinone moiety with two diastereomers was observed. Theoretical calculations were performed on the studied diastereomers, and it was found that the S‐isomer is more stable than the corresponding R‐isomer by about 2 kcal/mol.