Tetrafluorobenzyne thermochemistry: experiment and theory

Gas-phase thermodynamic properties of 1,2,3,4-tetrafluorobenzyne (1 H-(2)) were determined by Fourier transform mass spectrometry and ab initio and density functional theory methods. 1,2,3,4-Tetrafluorobenzyne radical anion was generated by abstraction of a proton and a hydrogen atom upon reaction of 1,2,3,4-tetrafluorobenzene (1) with O(-.). The resulting structure was confirmed by converting it to a species which could be independently prepared. Bracketing results provided the proton affinity of 1,2,3,4-tetrafluorobenzyne radical anion and the electron affinities of 1,2,3,4-tetrafluorobenzyne and 1,2,3,4-tetrafluorophenyl radical. These measured values were combined in a thermodynamic cycle to provide the heat of hydrogenation of 1 H(2) (DeltaH degree (hyd) = 367 +/- 18 kJ mol(-1)) and the first and second CH bond dissociation energies of 1 (481 +/- 11 and 321 +/- 13 kJ mol(-1)). The same approach failed for the meta and para isomers, but their energetics were examined using B3LYP and CCSD(T) computations.     

Mathematical modeling of a slurry reactor for DME direct synthesis from syngas

In this paper,an axial dispersion mathematical model is developed to simulate a three-phase slurry bubble column reactor for direct synthesis of dimethyl ether(DME) from syngas.This large-scale reactor is modeled using mass and energy balances,catalyst sedimentation andsingle-bubble as well as two-bubbles class flow hydrodynamics.A comparison between the two hydrodynamic models through pilot plantexperimental data from the literature shows that heterogeneous two-bubbles flow model is in better agreement with the experimental data thanhomogeneous single-bubble gas flow model.Also,by investigating the heterogeneous gas flow and axial dispersion model for small bubblesas well as the large bubbles and slurry(i.e.including paraffins and the catalyst) phase,the temperature profile along the reactor is obtained.Acomparison between isothermal and non-isothermal reactors reveals no obvious performance difference between them.The optimum values ofreactor diameter and height were obtained at 7 m and 50 m,respectively.The effects of operating variables on the axial catalyst distribution,DME productivity and CO conversion are also investigated in this research.     

Excess molar volume,viscosity, and refractive index study for the ternary mixture {2-methyl-2-butanol (1) + tetrahydrofuran (2) + propylamine (3)} at different temperatures. Application of the ERAS-model and Peng–Robinson–Stryjek–Vera equation of state

Densities, viscosities, and refractive indices of the ternary mixture consist of {2-methyl-2-butanol (1) + tetrahydrofuran (THF) (2) + propylamine (3)} at a temperature of 298.15 K and related binary mixtures were measured at temperatures of (288.15, 298.15, and 308.15) K at ambient pressure. Data were used to calculate the excess molar volumes and the deviations of the viscosity and refractive index. The Redlich–Kister and the Cibulka equations were used for correlating binary and ternary properties, respectively. The ERAS-model has been applied for describing the binary and ternary excess molar volumes and also Peng–Robinson–Stryjek–Vera (PRSV) equation of state (EOS) has been used to predict the binary and ternary excess molar volumes and viscosities.     

Organocatalytic synthesis of amides from nitriles via the Ritter reaction

A simple, inexpensive, environmentally friendly, and efficient route for the synthesis of a wide variety of amides in high yields via the Ritter reaction of alcohols with nitriles has been demonstrated. Pentafluorophenyl ammonium triflate (PFPAT) is used as an organocatalyst and is air-stable, cost-effective, easy to handle, and easily removed from the reaction mixtures.     

Magnetic Solid Phase Extraction Coupled with HPLC Towards Removal of Pigments and Impurities from Leaf-derived Paclitaxel Extractions of Taxus baccata and Optimization via Response Surface Methodology

A reusable and cost-effective magnetic graphite oxide (Fe₃O₄NPs@GO) nanocomposite was fabricated and applied for pre-purification of paclitaxel from leaf-derived crude extract of Taxus baccata. Furthermore, the potential roles of three crucial criteria (i.e., adsorbent dosage, sorption temperature and agitation/shaking power) on the two responses [i.e., efficiency of plant pigments removal (EPPR) and efficiency of taxol purity (ETP)] were examined and simultaneously optimized through response surface methodology. The nanocomposite was accurately characterized using TEM, AFM, BET, FT-IR, Raman and VSM. Moreover, for both proposed second-degree polynomial regression models, highly significant correlations were achieved between the experimental and predicted data (p < 0.0001). Meanwhile, the optimum conditions to simultaneously acquire the maximum EPPR (94.0 %) and ETP (11.4 %) were recorded as adsorbent dosage of 37.7 g L⁻¹, sorption temperature of 30.7 °C and agitation power of 153.1 rpm; and the predictive results were confirmed using experimental rechecking survey. Interestingly, upon five consecutive treatments, the nanocomposite still exhibited substantial potency in eliminating large amounts of plant pigments and impurities (up to 90 %), without significant reduction on sorption capacity and magnetism thereof. Our results demonstrated that the current nanocomposite, as SPE sorbent for MSPE, could be a simple, fast and reusable approach for HPLC-based purification studies of paclitaxel, and probably other plant secondary metabolites.

     

Fuzzy quasi C*-algebra

At the present paper, the new concepts of fuzzy quasi norm, fuzzy Banach space, fuzzy quasi continuity and fuzzy quasi boundedness is introduced. Furthermore, we define the fuzzy quasi operator norm and also it is shown that the set all of fuzzy quasi bounded operator from X to Y is fuzzy quasi Banach space. Finally, we have introduced and investigated some notions and some results on *-algebra theory.     

A dynamic pricing approach for returned products in integrated forward/reverse logistics network design

During the last decade, the stringent pressures from environmental and social requirements have spurred an interest in designing a reverse logistics network. In this paper, we address the problem of designing and planning a multi-echelon, multi-period, multi-commodity and capacitated integrated forward/reverse logistics network. Returned products are categorized with respect to their quality levels, and a different acquisition price is offered for each return type. Furthermore, the reservation incentive of customers, the expected price of customers for one unit of used product described by uniform distribution, is applied to model the customers’ return willingness. Due to the fact that the remaining worthwhile value in the used products is the corporation’s key motivation for buying them from customers, a dynamic pricing approach is developed to determine the acquisition price for these products and based on it determine the percentage of returned products collected from customer zones. The used products’ acquisition prices at each time period are determined based on the customers’ return willingness by each collection center.     

2-Imino 2<Emphasis Type="Italic">H</Emphasis>-chromene and 2-(phenylimino) 2<Emphasis Type="Italic">H</Emphasis>-chromene 3-aryl carboxamide derivatives as novel cytotoxic agents: synthesis,biological assay,and molecular docking study

The inhibition of AKR₁B₁₀ has been recognized as a potential therapeutic approach to the treatment of various types of cancers. A novel series of compounds with imino-2H-chromen and phenylimino-2H-chromen scaffolds were synthesized by Knoevenagel condensation reaction. The in vitro cytotoxic activity of synthesized compounds was evaluated against MOLT-4 and SK-OV-3 cells. Among the tested compounds, N-(3,4-dimethoxyphenyl)-2-(phenylimino)-2H-chromene-3-carboxamide (8g) demonstrated potent inhibitory activity against both examined cell lines. The results of the molecular docking study suggested that this compound is involved in critical hydrogen-bonding interactions with the Val301 and Lue302 of AKR₁B₁₀ catalytic site.     

Extending the time range of luminescence dating using red TL (RTL) from volcanic quartz

The potential of red thermoluminescence (RTL) emission from quartz, as a dosimeter for baked sediments and volcanic deposits, has received some attention over the past decade. While there have been some important observations relating to signal stability, saturation characteristics and emission wavebands, there has not been a systematic analysis of RTL properties of older (i.e., >1 Ma), quartz-bearing known age volcanic deposits. We have undertaken such an analysis using independently-dated silicic volcanic deposits from New Zealand, ranging in age from 300 ka through to 1.6 Ma. We observed a complex RTL emission in most volcanic quartzes, which consists of a number of discrete high temperature (i.e, >220°C) TL peaks. Isothermal analysis indicates a stable dating trap (E=2.03 eV; S=4.20×10¹⁵) which is stable at ambient (c. 20°C) temperatures for >10⁹ a. We confirm the slow onset of saturation with dose, and the limited extent of sensitivity changes due to dosing and TL readout. As such, there is much potential for exploiting the dosimeter in dating studies and we present the results from a modified single aliquot regenerative (SAR) procedures which indicate that there is a good agreement between RTL dating and other methods over time scales 10⁵–10⁶ a. This paper presents a summary of the most important related results of our findings and outlines the configuration of photomultiplier and filter combinations which maximizes RTL detection for temperatures up to 500°C.     

Small scale effects on buckling and postbuckling behaviors of axially loaded FGM nanoshells based on nonlocal strain gradient elasticity theory

By means of a comprehensive theory of elasticity, namely, a nonlocal strain gradient continuum theory, size-dependent nonlinear axial instability characteristics of cylindrical nanoshells made of functionally graded material (FGM) are examined. To take small scale effects into consideration in a more accurate way, a nonlocal stress field parameter and an internal length scale parameter are incorporated simultaneously into an exponential shear deformation shell theory. The variation of material properties associated with FGM nanoshells is supposed along the shell thickness, and it is modeled based on the Mori-Tanaka homogenization scheme. With a boundary layer theory of shell buckling and a perturbation-based solving process, the nonlocal strain gradient load-deflection and load-shortening stability paths are derived explicitly. It is observed that the strain gradient size effect causes to the increases of both the critical axial buckling load and the width of snap-through phenomenon related to the postbuckling regime, while the nonlocal size dependency leads to the decreases of them. Moreover, the influence of the nonlocal type of small scale effect on the axial instability characteristics of FGM nanoshells is more than that of the strain gradient one.