immobilized cobalt chloride within nanoreactors of ?Si-MCM-48 as selective catalyst for epoxidation of alkenes

Summary It was found that immobilized CoCl₂ within nanoreactors of Si-MCM-48 catalyzes the oxidation of 1-octene, styrene, cyclohexene, norbornene, trans-stilbene and trans-2-hexene-1-ol with 35 to 95% conversion and 75 to 100% selectivity to the corresponding epoxides.     

A green and efficient synthesis of isoxazol-5(4<Emphasis Type="Italic">H</Emphasis>)-one derivatives in water and a DFT study

A series of 4-arylmethylene-3-methylisoxazol-5(4H)-one derivatives are obtained via treating ethyl acetoacetate, hydroxylamine hydrochloride and variety of aromatic aldehyde compounds in the presence of antimony trichloride as an efficient catalyst in aqueous media. Mild conditions, safe, short reaction times, commercially available catalyst, environmentally friendly, no uses of organic solvent and high yields are remarkable advantages to this process. (Z)-4-(3-hydroxybenzylidene)-3-methylisoxazol-5(4H)-one, (HBIM), is characterized by theoretical (density functional theory) and experimental (IR, ¹H NMR, CV and UV). The structural parameters, vibrational frequencies, molecular electrostatic potential, frontier molecular orbital analysis (HOMO–LUMO), thermodynamic properties and nonlinear optical properties are found and discussed. UV–Vis spectra are recorded in two organic solvents. Thermal stability of HBIM is studied by thermogravimetric analysis. The molecule orbital contributions are studied using the total and partial density of states (TDOS and PDOS).     

Magnetic Nanoparticle Supported Ionic Liquid Assisted Green Synthesis of Pyrazolopyranopyrimidines and 1,6‐diamino‐2‐oxo‐1,2,3,4‐tetrahydropyridine‐3,5‐ dicarbonitriles

A simple and eco‐friendly green protocol was used for synthesis of pyrazolopyranopyrimidines via four‐component reaction of hydrazine hydrate, ethyl acetoacetate, barbituric acid or dimethyl barbituric acid, and aromatic aldehydes under thermal and solvent‐free conditions in the presence of magnetic nanoparticle supported silica bonded n‐propyl‐4‐aza‐1‐azoniabicyclo[2.2.2]octane chloride (MNPs@DABCO⁺Cl^?) as an efficient, recyclable heterogeneous catalyst. MNPs@DABCO⁺Cl^? also catalyzed the synthesis of 1,6‐diamino‐2‐oxo‐1,2,3,4‐tetrahydropyridine‐3,5‐dicarbonitrile derivatives by four‐component reaction of hydrazine hydrate, malononitrile, ethyl cyanoacetate and ketones under thermal and solvent‐free conditions at 80 °C. These methods are practical and offer many advantages, such as high yields, short reaction times, and simple work‐up.     

Use of volatile organic solvents in headspace liquid‐phase microextraction by direct cooling of the organic drop using a simple cooling capsule

A low‐cost and simple cooling‐assisted headspace liquid‐phase microextraction device for the extraction and determination of 2,6,6‐trimethyl‐1,3 cyclohexadiene‐1‐carboxaldehyde (safranal) in Saffron samples, using volatile organic solvents, was fabricated and evaluated. The main part of the cooling‐assisted headspace liquid‐phase microextraction system was a cooling capsule, with a Teflon microcup to hold the extracting organic solvent, which is able to directly cool down the extraction phase while the sample matrix is simultaneously heated. Different experimental factors such as type of organic extraction solvent, sample temperature, extraction solvent temperature, and extraction time were optimized. The optimal conditions were obtained as: extraction solvent, methanol (10 μL); extraction temperature, 60°C; extraction solvent temperature, 0°C; and extraction time, 20 min. Good linearity of the calibration curve (R² = 0.995) was obtained in the concentration range of 0.01–50.0 μg/mL. The limit of detection was 0.001 μg/mL. The relative standard deviation for 1.0 μg/mL of safranal was 10.7% (n = 6). The proposed cooling‐assisted headspace liquid‐phase microextraction device was coupled (off‐line) to high‐performance liquid chromatography and used for the determination of safranal in Saffron samples. Reasonable agreement was observed between the results of the cooling‐assisted headspace liquid‐phase microextraction high‐performance liquid chromatography method and those obtained by a validated ultrasound‐assisted solvent extraction procedure.     

Characterization of the interaction between a new merocyanine dye and bovine serum albumin

A new merocyanine dye was synthesized, and its acidity constant was determined by spectrophotometric and chemometrics methods. The interactions of the new cyanine dye with bovine serum albumin (BSA) have been studied by fluorescence and UV absorption spectroscopy at pH 7.40. A visual color change from red to blue was observed by addition of BSA to aqueous solution of the dye. The quenching constants and binding parameters (binding constants and number of binding sites) were determined at different temperatures. The calculated thermodynamic parameters confirmed that the binding reaction is mainly entropy-driven, whereas electrostatic interaction plays major role in the reaction. The displacement experiment confirmed binding of the dye to the subdomain IIA (site 1) of albumin. Moreover, synchronous fluorescence spectroscopy studies revealed the dye induces some local conformational change in BSA. The binding distance, r, between donor (serum albumin) and acceptor (dye) was obtained according to Förster’s theory.     

Chemical preparation and characterization of fibrous poly(3-methylthiophene) decorated by TiO2 nanoparticles

In this article, we report on the chemical oxidative polymerization of 3-methylthiophene (3MTh) in a concentrated TiO₂/CHCl₃ homogeneous suspension with an oxidant/monomer mole ratio of 3 at room temperature. According to the scanning electron microscopy images, in this condition, poly(3-methylthiophene) (P3MTh) was prepared with fibrous morphology decorated by nano-dimensional TiO₂ particles. P3MTh/TiO₂ was also characterized by Fourier transform infrared spectroscopy and X-ray diffraction techniques. It was found that no aggregation of nanoparticles occurred during the polymerization process. In addition, the thermal stability of P3MTh/TiO₂ nanocomposite was investigated by thermogravimetric analysis and compared with that of an analogously prepared neat P3MTh. The thermal degradation of P3MTh in the temperature range of 300–550°C decreases significantly due to the presence of the TiO₂ nanoparticles in the polymer composite.     

ECG compression method based on adaptive quantization of main wavelet packet subbands

In this study, a new compression algorithm for ECG signal is proposed based on selecting important subbands of wavelet packet transform (WPT) and applying subband-dependent quantization algorithm. To this end, first WPT was applied on ECG signal and then more important subbands are selected according to their Shannon entropy. In the next step, content-based quantization and denoising method are applied to the coefficients of the selected subbands. Finally, arithmetic coding is employed to produce compressed data. The performance of the proposed compression method is evaluated using compression rate (CR), percentage root-mean-square difference (PRD) as signal distortion, and wavelet energy-based diagnostic distortion (WEDD) as diagnostic distortion measures on MIT-BIH Arrhythmia database. The average CR of the proposed method is 29.1, its average PRD is <2.9 % and WEDD is <3.2 %. These results demonstrated that the proposed method has a good performance compared to the state-of-the-art compression algorithms.     

Metal‐Organic‐Framework‐Coated Optical Fibers as Light‐Triggered Drug Delivery Vehicles

Physical delivery of anticancer drugs in controlled anatomic locations can complement the advances being made in chemo‐selective therapies. To this end, an optical fiber catheter is coated in a thin layer of metal organic framework UiO‐66 and the anticancer drug 5‐Fluorouracil (5‐FU) is deposited within the pores. Delivery of light of appropriate wavelength through the fiber catheter is found to trigger the release of 5‐FU on demand, offering a new route to localized drug administration. The system exhibits great potential with as much as 110 × 10^?6 m of 5‐FU delivered within 1 min from one fiber.     

Label-free and sensitive impedimetric nanosensor for the detection of cocaine based on a supramolecular complexation with β-cyclodextrin,immobilized on a nanostructured polymer film

Cocaine, a powerful addictive stimulant drug, has a variety of adverse effects on the body, thus its sensitive detection is very important. Here, we report on a simple, label-free, and sensitive impedimetric sensor for determination of cocaine based on its affinity to form an inclusion complex with β-cyclodextrin (β-CD). First, we prepared nanostructured poly N-acetylaniline film via electropolymerization of its monomer on a glassy carbon electrode (PNAANI/GC), subsequently overoxidized it, and conjugated β-CD to the polymer backbone. The designed and synthesized nanostructured PNAANI film serves a dual function in the sensor: on one hand, it maintains a high effective surface area on a geometrically small electrode that significantly enhances the number of β-CD molecules immobilized on the electrode; on the other hand, it provides an upright-oriented β-CD conjugation to the polymer backbone, thus all the β-CD receptors are actively involved in responding to the target. Sensitivity of the sensor was further enhanced by preconcentration of cocaine on the modified electrode surface. We attributed the changes in the interfacial charge transfer resistance (R _ct) of the electrode to cocaine concentration. Under optimized condition (pH 7.4, 5-min accumulation at an open circuit voltage), the sensor responded to cocaine concentration in the range of 100 nM–1.0 mM with a detection limit of 50 nM. Selectivity of the sensor for cocaine relative to some potential inferring compounds was also investigated, and the results were promising. The proposed approach exhibited an extended dynamic range, low detection limit, good sensitivity, and a desirable selectivity, which provides an efficient application prospect for on-field cocaine sensing.     

Molecularly imprinted stir bar sorptive extraction coupled with high-performance liquid chromatography for trace analysis of naphthalene sulfonates in seawater

In this paper, a novel molecularly imprinted polymer coated stir bar has been used to selectively extract naphthalene sulfonates (NS_s) directly from seawater sample. 1-Naphthalene sulfonic acid (1-NS) was used as template molecule. The effects of different parameters were optimized on the extraction efficiency and the optimum conditions were established as: the absorption and desorption times were fixed, respectively, at 10 and 15 min, stirring speed was 700 rpm, pH was adjusted to 4.1, amount of NaCl was 1 mol L^?1 and extraction process was performed at a temperature of 50 °C. The linear ranges were 2–250 µg L^?1 for 3,6-NDS-1-OH (1-naphthol-3,6-disulfonic acid), 4–250 µg L^?1 for 2-NS (2-naphthalene sulfonate) and 3–250 µg L^?1 for 1-NS. The detection limits were within the range of 0.32–0.95 µg L^?1. Under optimum conditions, the detection limits of the NSs were 0.84, 0.95 and 0.32 µg L^?1 with the enrichment factor of 117-, 41- and 77-fold for 2-NS, 1-NS, and 6-NDS-1-OH, respectively. The repeatability of the method was satisfactory (0.53 ≤ RSD ≤6.0 %, n = 10). The method has been successfully applied for the analysis of trace amounts of three naphthalene sulfonates in seawater of Chabahar Bay.