CO2 reforming of methane over nickel catalysts supported on nanocrystalline MgAl2O4 with high surface area

In this paper dry reforming of methane (DRM) was carried out over nanocrystalline MgAl2O4-supported Ni catalysts with various Ni loadings. Nanocrystalline MgAl2O4 spinel with high specific surface area was synthesized by a co-precipitation method with the addition of pluronic P123 triblock copolymer as surfactant, and employed as catalyst support. The prepared samples were characterized by X-ray diffraction (XRD), N2 adsorption, H2 chemisorption, temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), temperature- programmed desorption (TPD) and transmission and scanning electron microscopies (TEM, SEM) techniques. The obtained results showed that the catalyst support has a nanocrystalline structure (crystal size: about 5 nm) with a high specific surface area (175 m2 g-1) and a mesoporous structure. Increasing in nickel content decreased the specific surface area and nickel dispersion. The prepared catalysts showed high catalytic activity and stability during the reaction. SEM analysis revealed that whisker type carbon deposited over the spent catalysts and increasing in nickel loading increased the amount of deposited carbon. The nickel catalyst with 7 wt% of nickel showed the highest catalytic activity.     

Preparation and characterization of Ni(II)/polyacrylonitrile and carbon nanotube composite modified electrode and application for carbohydrates electrocatalytic oxidation

A nickel(II) into porous polyacrylonitrile–carbon nanotubes composite modified glassy carbon electrode (Ni/PAN-CNT/GCE) was fabricated by simple drop-casting and immersing technique. The unique electrochemical activity of Ni/PAN-CNT composite modified glassy carbon electrode was illustrated in 0.10?M NaOH using cyclic voltammetry. The Ni/PAN-CNT/GCE exhibits the characteristic of improved reversibility and enhanced current responses of the Ni(III)/Ni(II) couple compared with Ni/PAN/GCE and Ni/CNT/GCE. The results of electrochemical impedance spectroscopy and scanning electron microscopy indicated the successful immobilization for PAN-CNT composite film. Kinetic parameters such as the electron transfer coefficient, α, and rate constant, k _s, of the electrode reaction were determined. Ni/PAN-CNT/GCE also shows good electrocatalytic activity toward the oxidation of carbohydrates (glucose, sucrose, fructose, and sorbitol). The electrocatalytic response showed a wide linear range (10–1,500, 12–3,200, 7–3,500, and 16–4,200?μM for glucose, sucrose, fructose, and sorbitol, respectively) as well as its experimental limit of detection can be achieved 6, 7, 5, and 11?μM for glucose, sucrose, fructose, and sorbitol, respectively. The modified electrode for carbohydrates determination is of the property of simple preparation, good stability, and high sensitivity.     

EIS and adjunct electrical modeling for material selection by evaluating two mild steels for use in super-alkaline mineral processing

The production of metal concentrates during mineral processing of ferrous and non-ferrous metals involves a variety of highly corrosive chemicals which deteriorate common mild steel as the material of choice in the construction of such lines, through rapid propagation of localized pitting in susceptible parts, often in sensitive areas. This requires unscheduled maintenance and plant shut down. In order to test the corrosion resistance of different available materials as replacement materials, polarization and electrochemical impedance spectroscopy (EIS) tests were carried out. The EIS numerical outputs were then transformed into an equivalent electric circuit using Z-View software, and the predictive behavior was contrasted with actual performance after long-term immersion, depicted through SEM, EDS, XRD and weight change observations. Also, results of pits and cracks, obtained with climax software-enhanced polarization resistance, and reduced capacitance added to much diminished current densities, verified the acceptable performance of CK₄₅ compared with high priced stainless steel substitutes with comparable operational life. Therefore, CK₄₅ can be a suitable alternative in steel constructions which are exposed to super-alkaline and corrosive environments.     

Fabrication of Chitosan‐Multiwall Carbon Nanotube Nanocomposite Containing Ferri/Ferrocyanide: Application for Simultaneous Detection of D‐Penicillamine and Tryptophan

We report a simple and effective strategy for fabrication of the nanocomposite containing chitosan (CS) and multiwall carbon nanotube (MWNT) coated on a glassy carbon electrode (GCE). The characterization of the modified electrode (CS‐MWNT/GC) was carried out using scanning electron microscopy (SEM) and UV–vis absorption spectroscopy. The electrochemical behavior of CS‐MWNT/GC electrode was investigated and compared with the electrochemical behavior of chitosan modified GC (CS/GC), multiwalled carbon nanotube modified GC (MWNT/GC) and unmodified GC using cyclic voltammetry (CV) and electron impedance spectroscopy (EIS). The chitosan films are electrochemically inactive; similar background charging currents are observed at bare GC. The chitosan films are permeable to anionic Fe(CN)₆^3?/4? (FC) redox couple. Electrochemical parameters, including apparent diffusion coefficient for the Fe(CN)₆^3?/4? redox probe at FC/CS‐MWNT/GC electrode is comparable to values reported for cast chitosan films. This modified electrode also showed electrocatalytic effect for the simultaneous determination of D‐penicillamine (D‐PA) and tryptophan (Trp). The detection limit of 0.9 μM and 4.0 μM for D‐PA and Trp, respectively, makes this nanocomposite very suitable for determination of them with good sensitivity.     

Expression of miRNAs Targeting <Emphasis Type="Italic">mTOR</Emphasis> and <Emphasis Type="Italic">S6K1</Emphasis> Genes of mTOR Signaling Pathway Including miR-96, miR-557, and miR-3182 in Triple-Negative Breast Cancer

Triple-negative breast cancer (TNBC) is a highly aggressive form of breast cancer. Aberrant expression of genes in mTOR pathway and their targeting miRNAs plays an important role in TNBC. The aim of this study was to determine the expression of mTOR and S6K1 and their targeting miRNAs in breast cancer cell lines and clinical samples. miRNAs targeting 3′-UTR of mTOR and S6K1 mRNAs were predicted using bioinformatic algorithms. MDA-MB-231, MCF-7, and MCF-10A as well as 20 TNBC samples were analyzed for gene and miRNA expression using quantitative real-time PCR (RT-qPCR). A receiver operating characteristic (ROC) curve analysis was performed for evaluation of candidate miRNAs as diagnostic biomarkers. miR-96 and miR-557 targeting mTOR and S6K1 mRNAs, respectively, were selected, and miR-3182 was selected as the miRNA targeting both genes. The miRNAs were down-regulated in cell lines, while their target mRNAs were up-regulated. Similar findings were observed in clinical samples. The ROC curve analysis revealed decline in expression of these miRNAs. We suggest that miR-96, miR-557, and miR-3182 can be used as inhibitory agents for mTOR and S6K1 in TNBC-targeted therapy.     

Switchable phase transition behavior of thermoresponsive substrates for cell sheet engineering

Recently, there are significant interests in the development of biomaterials with nonlinear response to an external stimulus. Thermoresponsive polymers as a well-known class of stimuli-responsive materials represent reversible hydrophilicity/hydrophobicity characteristics around a critical temperature. This switchable behavior applies for nondestructive cellular detachment from cultivation substrates. In this study, poly (N-isopropylacrylamide) (PNIPAAm)-grafted dishes were made up to harvest retinal pigmented epithelial (RPE) and periodontal ligament cell (PDLC) sheets. Wettability assessments verified that all functionalized surfaces were inverted from hydrophilic to hydrophobic state when the temperature rises from lower critical solution temperature (LCST) at 37 °C. Other physicochemical characteristics such as chemical composition, grafting thickness, and surface topography were investigated through attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and atomic force microscopy (AFM). ATR-FTIR results showed typical peaks of amide group corresponding to successful PNIPAAm polymerization. AFM microscopy results also proved creating a rough PNIPAAm layer with thickness of 29.2 nm after grafting process in the mixture of methanol and water. Cell culture experiments showed an irreversible cellular attachment/detachment from modified surfaces upon temperature changes. These results introduced thermoresponsive TCPS to noninvasively harvest RPE and PDLCs sheets especially for application in scaffold-free tissue engineering decorations. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1567–1576     

Thiozonation and thiozonolysis of triatomic sulfur (S<Subscript>3</Subscript>) on the C<Subscript>70</Subscript> fullerene: a DFT study

Density functional theory calculations have been carried out to investigate the [2?+?x] x?=?1, 2, and 3 cycloaddition reactions (paths A, B, and C) of triatomic sulfur (S₃) with the C₇₀ fullerene in terms of geometry, energies, and electronic structures. The thiozonation (S₃) on the hexagon–hexagon and hexagon–pentagon bonds of the C₇₀ fullerene through 1,3-dipolar reaction, i.e., [2?+?3] cycloaddition, is generally exothermic, while through the chelotrope additions, i.e., [2?+?1] cycloaddition, are endothermic. The results indicate that the 1,3-dipolar cycloaddition is the most preferable path. Having more negative values of reaction energies E_r together with the lower barrier heights, thiozonation of the hexagon–hexagon bonds is thermodynamically and kinetically more favorable than hexagon–pentagon ones. Moreover, the addition of thiozone to the hexagon–hexagon bonds near the pole area of the C₇₀ leads to more negative reaction energies. Therefore, it is established that the arrangement and position of C=C bonds play an important role in the thiozonation of C₇₀ fullerene. Thiozonolysis of triatomic sulfur (S₃) indicates that S–S bond cleavage has not occurred, instead a sulfur bridge over a C–C bond or a four-membered ring of 1,2-dithietane-1-sulfide is preferred to be formed.     

Reaction of barbituric/thiobarbituric acid with phosphines or phosphites and dialkyl acetylenedicarboxylates for synthesis of phosphorus zwitterions or phosphonate derivatives

Abstract

A three-component reaction between barbituric/thiobarbituric acid, phosphines, and dialkyl acetylenedicarboxylates in dry acetonitrile led to the formation of barbiturate/thiobarbiturate-functionalized stable zwitterionic salts in a one-pot process. When trialkyl phosphites were used instead of phosphines, barbiturate/thiobarbiturate-functionalized phosphonates were obtained in good yields.     

The effect of different drying methods on band gap energy and femtosecond LIDT of nano-porous anti-reflective silica thin films

In this work, nano-porous anti-reflective silica thin films are deposited on the quartz samples by dip-coating in silica sol–gel. After dip-coating, the samples are divided into three groups and each group is heated in an oven with a different drying method. The effect of the heating methods on the morphology and optical properties of the coated layers are studied by SEM imaging and measuring optical transmission of the samples. Then based on the transmission data and calculation of absorption coefficient of the layers, the band gap energy of the silica thin films is calculated. In addition, laser induced damage threshold (LIDT) of the samples are measured by using 35 fs, 100 mJ femtosecond laser pulses. It can be seen that there is a distinct correlation between band gap energy and LIDT of the samples which both of them have been affected by heating method of the coated samples.