Convenient Preparation of Cycloalkenyl Boronic Acid Pinacol Esters

A practical method for the preparation of cycloalkenyl boronic acid pinacol esters is described. These important synthetic intermediates are typically made using more expensive methods like transition metal-catalyzed borylation of alkenyl halides or triflates. In this work, they are obtained from the simple corresponding cycloalkanones, which are subjected to Shapiro reaction conditions followed by trapping with a borate ester. The requisite products are obtained in very good to excellent yields, and the reactions can be scaled up to multigram amounts. By providing a simple alternative to common methods that make use of expensive transition-metal catalysts and formation of sensitive intermediates, this convenient method will be useful for the synthesis of ring-containing partners for Suzuki–Miyaura cross-coupling and other reactions employing boronic esters as substrates.     

Theoretical study of electronic structure of rhodium mononitride and interpretation of experimental spectra

Potential energy curves of 22 electronic states of RhN have been calculated by the complete active space second‐order perturbation theory method. The X¹Σ₀⁺ is assigned as the ground state, and the first excited state a³Π₀+ is 978 cm^?1 higher. The ¹Δ(I) and B¹Σ⁺ states are located at 9521 and 13,046 cm^?1 above the ground state, respectively. The B¹Σ⁺ state should be the excited state located 12,300 cm^?1 above the ground state in the experimental study. Moreover, two excited states, C¹Π and b³Σ⁺, are found 14,963 and 15,082 cm^?1 above the X¹Σ⁺ state, respectively. The transition C¹Π₁–X¹Σ₀⁺ may contribute to the experimentally observed bands headed at 15,071 cm^?1. There are two excited states, D¹Δ and E¹Σ⁺, situate at 20,715 and 23,145 cm^?1 above the X¹Σ⁺ state. The visible bands near 20,000 cm^?1 could be generated by the electronic transitions D¹Δ₂–a³Π₁ and E¹Σ⁺₀–X¹Σ⁺₀ because of the spin–orbit coupling effect. © 2013 Wiley Periodicals, Inc.     

Zinc-Mediated Cyclodimerization of 1,5-Diaryl-1,4-pentadien-3-one in Aqueous Solution Under Ultrasound Irradiation

Synthesis of 2-cinnamoyl-1-styryl-3,4-diarylcyclopentanol via cyclodimerization of 1,5-diaryl-1,4-pentadien-3-one mediated by zinc was carried out in good yields at room temperature in NH₄Cl (aq.) and tetrahydrofuran under ultrasonic irradiation. In comparison with conventional methods, the main advantages of the present procedure are shorter reaction time and better yields.     

Electroless plating of copper on fly ash cenospheres using polyaniline‐Pd activation

The polyaniline of different intrinsic oxidation states, viz., the emeraldine (EM) and the leucoemeraldine (LM) states, were coated on 3‐aminopropyltriethoxy silane modified fly ash cenospheres. Without prior sensitization by SnCl₂ solution, Pd activation by PdCl₂ solution was carried out on EM and LM laden cenospheres, followed by electroless plating of copper (Cu). The topography and composition of the composites were characterized by scanning electron microscopy, X‐ray diffraction, and X‐ray photoelectron spectroscopy, etc. The results indicate that the oxidation state of the LM layer showed a much bigger increase than that of the EM layer in the Pd activation process, while coupled Pd reduction underwent to a more extent on the LM layer. The metallic Pd atoms on the LM and EM layers surface initiated the subsequent electroless plating of Cu, and the coated Cu on LM laden cenospheres had a much more uniform and compact morphology than that on EM laden cenospheres. Copyright © 2012 John Wiley & Sons, Ltd.     

Improved staining of phosphoproteins with high sensitivity in polyacrylamide gels using Stains‐All

An improved Stains‐All (ISA) staining method for phosphoproteins in SDS‐PAGE was described. Down to 0.5–1 ng phosphoproteins (α‐casein, β‐casein, or phosvitin) can be successfully selectively detected by ISA stain, which is approximately 120‐fold higher than that of original Stains‐All stain, but is similar to that of commonly used Pro‐Q Diamond stain. Furthermore, unlike the original Stains‐All protocol that was time consuming and light unstable, ISA stain could be completed within 60 min without resorting to protect the gels from light during the whole staining procedure. According to the results, it is concluded that ISA stain is a rapid, sensitive, specific, and economic staining method for a broad application to the research of phosphoproteins.     

Fluorescent staining of protein in SDS polyacrylamide gels by salicylaldehyde azine

As a noncovalent fluorescence probe, in this study, salicylaldehyde azine (SA) was introduced as a sensitive fluorescence‐based dye for detecting proteins both in 1D and 2D polyacrylamide electrophoresis gels. Down to 0.2 ng of single protein band could be detected within 1 h, which is similar to that of glutaraldehyde‐silver stain, but approximately four times higher than that of SYPRO Ruby fluorescent stain. Furthermore, comparative analysis of the MS compatibility of SA stain with SYPRO Ruby stain indicated that SA stain is compatible with the downstream of protein identification by LC‐MS/MS. Additionally, the probable mechanism of the SA stain was investigated by molecular docking. The results demonstrated that the interaction between SA and protein was mainly contributed by hydrogen bonding and hydrophobic forces.     

Influence of Emulsifiers on Acrylate Latex Blends

The poly(methyl methacrylate/butyl acrylate/acrylic acid) [P(MMA/BA/AA)] and poly (styrene/butyl acrylate/acrylic acid) [P(St/BA/AA)] latexes were synthesized using the emulsifier octylphenol polyoxyethylene(10) ether (OP-10) and ammonium sulfate allyloxy nonylphenoxy poly(ethyleneoxy)(10) ether(DNS-86). The optimum amount of OP-10 and DNS-86 was 1.5% and 2.5% respectively. The P(MMA/BA/AA) and P(St/BA/AA) latex containing 1.5% OP-10 or 2.5% DNS-86 were blended pairwise. The performances of latex blends and parent latexes as a function of emulsifiers content in parent latexes were determined. The results indicated that the stability of latex blends is favorable, and particle size distribution was more uniform and thermal stability was improved after blending.     

Immobilization and sustained release of cefalexin on MCF nano-mesoporous material

Abstract

Mesocellular foams (MCF) silica nanometer mesoporous molecular sieve was successfully synthesized by hydrothermal route. This method used poly(ethylene glycol)-block-poly(propyl glycol)-block-poly(ethylene glycol) as template, tetraethyl orthosilicate as silica source and 1, 3, 5-trimethylbenzene as pore-expanding agent to prepare nano mesoporous MCF in acidic medium. The MCF mesoporous material was characterized by powder X-ray diffraction (XRD), infrared (IR) spectroscopy, low temperature nitrogen adsorption-desorption at 77?K, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The effects of pH, temperature, adsorbent dosage, cefalexin dosage and contact time on the immobilization of cefalexin were studied. Under the optimized conditions, MCF has the best effect on the drug immobilization. The maximum immobilization amount of cefalexin in MCF nano-mesoporous material is 498.8?mg/g. The behavior of adsorption of cefalexin by MCF belongs to multilayer heterogeneous adsorption, which accords with the Freundlich adsorption isotherm. In the adsorption process, all the ΔH⁰, ΔS⁰ and Gibbs free energy change ΔG⁰ are less than zero, indicating that the adsorption process is spontaneous, exothermic entropy decreasing reaction at ordinary temperature. Kinetic investigation showed that the adsorption process of cefalexin on MCF belongs to the pseudo-second-order kinetic process. The release laws of composite material cephalexin-MCF in the simulated body fluid, gastric and intestinal fluid were investigated, respectively. The maximum cumulative release rate in simulated body fluid was 99.4% at 18?h. The maximum cumulative release rate in the simulated gastric juice was 48.7% at 6?h and in the simulated intestinal fluid the maximum cumulative release rate of 61.9% was achieved at 8?h. These release processes satisfy the zero-order ordered kinetic process.     

Alignment of liquid crystals induced by a photopolymerized self‐assembled film

An alignment film derived from a photopolymerized self‐assembled film may be used to orient nematic liquid crystals after irradiating the film with linearly polarized UV (LPUV). A photosensitive cationic amphiphile was first synthesized containing two double bonds and which could be polymerized by UV. A layer‐by‐layer self‐assembled multilayer film was next prepared in an aqueous solution of the cationic amphiphile and poly(sodium 4‐styrenesulphonate); the UV‐Vis spectra showed that each layer of the LBL multilayer film was uniform. When the film was irradiated by LPUV, the photosensitive double bonds underwent [2+2] cycloaddition along the vector direction of LPUV. The polarized UV‐Vis absorption spectra also provided evidence that the film was anisotropic, i.e. the photopolymerization was along a certain direction. The anisotropic film was used as an alignment layer for nematic liquid crystals, and observations under a polarizing microscope indicated that the alignment of the liquid crystals was good, as expected, and that the orientation direction of the liquid crystals was always perpendicular to the electric vector of the irradiating LPUV.     

A pre-enrichment procedure using diethyldithiocarbamate-modified TiO2 nanoparticles for the analysis of biological and natural water samples by ICP-AES

In this article, a new method that utilizes a diethyldithiocarbamate-modified nanometre TiO₂ (TiO₂–DDTC) as solid-phase extractant has been developed for simultaneous preconcentration of trace Cu(II), Pb(II), Zn(II), and Cd(II) prior to measurement by inductively coupled plasma atomic emission spectrometry (ICP-AES). The separation/preconcentration conditions of analytes, which include the effects of pH, sample flow rate and volume, elution conditions, and interfering ions on the recovery of the analytes, were investigated. At pH 5, the adsorption capacity of modified nanometre TiO₂–DDTC was found to be 6.2, 19, 4.7, and 6.0?mg/g for Cu(II), Pb(II), Zn(II), and Cd(II), respectively. According to the definition of IUPAC, the detection limits (3σ) of this method for Cu(II), Pb(II), Zn(II), and Cd(II) were 0.41, 1.7, 0.39, and 0.52?ng/mL, respectively. The proposed method achieved satisfied results when applied to the determinations of trace Cu(II), Pb(II), Zn(II), and Cd(II) in biological and natural water samples.