Ru-catalyzed highly enantioselective hydrogenation of α-keto Weinreb amides

Asymmetric hydrogenation of α-keto Weinreb amides has been realized with [Ru((S)-Sunphos)(benzene)Cl]Cl as the catalyst and CeCl 3·7H2O as the additive.A series of enantiopure α-hydroxy Weinreb amides(up to 97% ee) have been obtained.Catalytic amount of CeCl3·7H2O is essential for the high reactivity and enantioselectivity and the ratio of CeCl3·7H2O to [Ru((S)-Sunphos)(benzene)Cl]Cl plays an important role in the hydrogenation reaction.     

A TLC Study of the lipophilicity of thirty-two acetylcholinesterase inhibitors — 1,2,3,4-tetrahydroacridine and 2,3-dihydro-1H-cyclopenta[b]quinoline derivatives

The lipophilicity of thirty-two novel acetylcholinesterase (AChE) inhibitors — 1,2,3,4-tetrahydroacridine and 2,3-dihydro-1H-cyclopenta[b]quinoline derivatives was studied by thin layer chromatography. The analyzed compounds were chromatographed on RP-18, RP-8, RP-2, CN and NH₂ stationary phases with dioxane — citric buffer pH 3.0 binary mobile phases containing different proportions of dioxane. R_M values for pure water were extrapolated from the linear Soczewiński-Wachtmeister equation and six compounds with known literature log P values were used as reference calibration data set for computation of experimental log P values. The obtained results were compared with computationally calculated partition coefficients values (AlogPs, AClogP, AlogP, MlogP, KOWWIN, XlogP2, XlogP3) by PCA and significant differences between them were observed.     

ZnII and CuII complexes generated from 5‐(pyridin‐4‐yl)‐3‐[2‐(pyridin‐4‐yl)ethyl]‐1,3,4‐oxadiazole‐2(3H)‐thione

A new 1,3,4‐oxadiazole‐containing bispyridyl ligand, namely 5‐(pyridin‐4‐yl)‐3‐[2‐(pyridin‐4‐yl)ethyl]‐1,3,4‐oxadiazole‐2(3H)‐thione (L), has been used to create the novel complexes tetranitratobis{μ‐5‐(pyridin‐4‐yl)‐3‐[2‐(pyridin‐4‐yl)ethyl]‐1,3,4‐oxadiazole‐2(3H)‐thione}zinc(II), [Zn₂(NO₃)₄(C₁₄H₁₂N₄OS)₂], (I), and catena‐poly[[[dinitratocopper(II)]‐bis{μ‐5‐(pyridin‐4‐yl)‐3‐[2‐(pyridin‐4‐yl)ethyl]‐1,3,4‐oxadiazole‐2(3H)‐thione}] nitrate acetonitrile sesquisolvate dichloromethane sesquisolvate], {[Cu(NO₃)(C₁₄H₁₂N₄OS)₂]NO₃·1.5CH₃CN·1.5CH₂Cl₂}_n, (II). Compound (I) presents a distorted rectangular centrosymmetric Zn₂L₂ ring (dimensions 9.56 × 7.06 Å), where each Zn^II centre lies in a {ZnN₂O₄} coordination environment. These binuclear zinc metallocycles are linked into a two‐dimensional network through nonclassical C—H...O hydrogen bonds. The resulting sheets lie parallel to the ac plane. Compound (II), which crystallizes as a nonmerohedral twin, is a coordination polymer with double chains of Cu^II centres linked by bridging L ligands, propagating parallel to the crystallographic a axis. The Cu^II centres adopt a distorted square‐pyramidal CuN₄O coordination environment with apical O atoms. The chains in (II) are interlinked via two kinds of π–π stacking interactions along [01]. In addition, the structure of (II) contains channels parallel to the crystallographic a direction. The guest components in these channels consist of dichloromethane and acetonitrile solvent molecules and uncoordinated nitrate anions.     

Promotion effect of adsorbed water/OH on the catalytic performance of Ag/activated carbon catalysts for CO preferential oxidation in excess H2

Activated carbon (AC) supported silver catalysts were prepared by incipient wetness impregnation method and their catalytic performance for CO preferential oxidation (PROX) in excess H₂ was evaluated. Ag/AC catalysts, after reduction in H₂ at low temperatures (≤200 °C) following heat treatment in He at 200 °C (He200H200), exhibited the best catalytic properties. Temperature-programmed desorption (TPD), X-ray diffraction (XRD) and temperature-programmed reduction (TPR) results indicated that silver oxides were produced during heat treatment in He at 200 °C which were reduced to metal silver nanoparticles in H₂ at low temperatures (≤200 °C), simultaneously generating the adsorbed water/OH. CO conversion was enhanced 40% after water treatment following heat treatment in He at 600 °C. These results imply that the metal silver nanoparticles are the active species and the adsorbed water/OH has noticeable promotion effects on CO oxidation. However, the promotion effect is still limited compared to gold catalysts under the similar conditions, which may be the reason of low selectivity to CO oxidation in PROX over silver catalysts. The reported Ag/AC-S-He catalyst after He200H₂00 treatment displayed similar PROX of CO reaction properties to Ag/SiO₂. This means that Ag/AC catalyst is also an efficient low-temperature CO oxidation catalyst.     

Sulfonated carbon catalyzed oxidation of aldehydes to carboxylic acids by hydrogen peroxide

Sulfonated carbon as a strong and stable solid acid catalyst exhibited excellent catalytic performance in various acid-catalyzed reactions. Here, sulfonated carbon, as catalyst for oxidation reaction, was prepared via the carbonization of starch followed by sulfonation with concentrated sulfuric acid. N₂ physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray fluorescence and acid-base titration were used to characterize the obtained materials. The catalytic activity of sulfonated carbon was studied in the oxidation of aldehydes to carboxylic acids using 30 wt% H₂O₂ as oxidant. This oxidation protocol works well for various aldehydes including aromatic and aliphatic aldehydes. The sulfonated carbon can be recycled for three times without obvious loss of activity.     

Direct conversion of fructose-based carbohydrates to 5-ethoxymethylfurfural catalyzed by AlCl3·6H2O/BF3·(Et)2O in ethanol

Direct conversion of fructose-based carbohydrates to 5-ethoxymethylfurfural (EMF) catalyzed by Lewis acid in ethanol was investigated. It was found that BF₃·(Et)₂O was favorable for 5-hydroxymethylfurfural (HMF) etherification to EMF. BF₃·(Et)₂O combination with AlCl₃·6H₂O with the molar ratio of 1 was an effective catalyst system for synthesis of EMF from fructose-based carbohydrates. 55.0%, 45.4% and 23.9% of EMF yields were obtained from fructose, inulin and sucrose under optimized conditions, respectively.     

Amperometric detection of nitrite based on Dawson-type vanodotungstophosphate and carbon nanotubes

A nitrite sensor based on Dawson vanodotungstophosphates α₂-K₇P₂VW₁₇O₆₂·18H₂O (P₂W₁₇V) and carbon nanotubes (CNTs) was prepared by electrostatic layer-by-layer self-assembly technique. The sensor {PEI/PSS/[PDDA/P₂W₁₇V-CNTs]_n} was characterized by UV–vis spectroscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM) and X-ray photoelectron spectra (XPS). The electron transfer and sensing ability of this sensor were explored using cyclic voltammetry (CV) and electrochemical impedance spectra (EIS) technology. The results show that the incorporation of CNTs and P₂W₁₇V into the composite film endowed the modified electrode with fast transfer rate and high electrocatalytic activity towards oxidation of nitrite. This nitrite sensor with 10 bilayers has a broad linear range of 5 × 10⁻⁸ to 2.13 × 10⁻³ M, a low detection limit of 0.0367 μM (S N⁻¹ = 3), a high sensitivity of 0.35 mA mM⁻¹ NO₂⁻, an excellent anti-interference property in the presence of other potential interfering species and a good stable. It was successfully employed for determination of nitrite in real towards.     

High sensitivity chemiluminescence enzyme immunoassay for detecting staphylococcal enterotoxin A in multi-matrices

In this study, detection of staphylococcal enterotoxin A (SEA) in multi-matrices using a highly sensitive and specific microplate chemiluminescence enzyme immunoassay (CLEIA) has been established. A pair of monoclonal antibodies (mAbs) was selected from 37 anti-SEA mAbs by pairwise analysis, and the experimental conditions of the CLEIA were optimized. This CLEIA exhibited high performance with a wide dynamic range from 6.4 pg mL⁻¹ to 1600 pg mL⁻¹, and the measured low limit of detection (LOD) was 3.2 pg mL⁻¹. No cross-reactivity was observed when this method was applied to test SEB, SEC1, and SED. It has also been successfully applied for analyzing SEA in a variety of environmental, biological, and clinical matrices, such as sewage, tap water, river water, roast beef, peanut butter, cured ham, 10% nonfat dry milk, milk, orange juice, human urine, and serum. Thus, the highly sensitive and SEA-specific CLEIA should make it attractive for quantifying SEA in public health and diagnosis in near future.     

Electrochemical immunosensor based on nanoporpus gold loading thionine for carcinoembryonic antigen

Nanoporous gold (NPG) has recently received considerable attention in analytical electrochemistry because of its good conductivity and large specific surface area. A facile layer-by-layer assembly technique fabricated NPG was used to construct an electrochemical immunosensor for carcinoembryonic antigen (CEA). NPG was fabricated on glassy carbon (GC) electrode by alternatively assembling gold nanoparticles (AuNPs) and silver nanoparticles (AgNPs) using 1,4-benzenedimethanethiol as a cross-linker, and then AgNPs were dissolved with HNO₃. The thionine was absorbed into the NPG and then gold nanostructure was electrodeposited on the surface through the electrochemical reduction of gold chloride tetrahydrate (HAuCl₄). The anti-CEA was directly adsorbed on gold nanostructure fixed on the GC electrode. The linear range of the immunosensor was from 10 pg mL⁻¹ to 100 ng mL⁻¹ with a detection limit of 3 pg mL⁻¹ (S/N = 3). The proposed immunosensor has high sensitivity, wide linear range, low detection limit, and good selectivity. The present method could be widely applied to construct other immunosensors.