Copper iodide nanoparticles-decorated porous polysulfonamide gel: As effective catalyst for decarboxylative synthesis of N-Arylsulfonamides

A porous cross-linked poly (ethyleneamine)-polysulfonamide (PEA-PSA) as a novel organic support system is synthesized in the presence of silica template by nanocasting technique. The paper demonstrates immobilization of CuI nanoparticles inside the pores (PEA-PSA@CuI) for the facile recovery and recycling of these nanoparticles. The presence of porous PEA-PSA and PEA-PSA@CuI nanocomposites was confirmed using FT-IR spectroscopy, FE-SEM, EDX, TGA, XRD, TEM, BET, XPS, WDX, ¹H NMR, and ICP-OES techniques. The PEA-PSA@CuI along with Ag(I)/K₂S₂O₈ was implemented as a reusable cooperative catalyst-oxidant system in the N-arylation of p-toluenesulfonamide with substituted carboxylic acids in mild condition. So, the novel decarboxylative cross-coupling catalyzed by copper and silver has been developed. Aromatic, secondary and tertiary aliphatic acids underwent high efficient decarboxylative processes with p-toluenesulfonamide to afford the corresponding products. This method provides a practical approach for the flexible synthesis of sulfonamides from the readily affordable substrates. The catalyst is highly reusable and efficient, especially in terms of time and yield of the desired product.     

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.

     

One‐pot synthesis of 1‐ and 5‐substituted 1H‐tetrazoles using 1,4‐dihydroxyanthraquinone–copper(II) supported on superparamagnetic Fe3O4@SiO2 magnetic porous nanospheres as a recyclable catalyst

An effective one‐pot, convenient process for the synthesis of 1‐ and 5‐substituted 1H‐tetrazoles from nitriles and amines is described using1,4‐dihydroxyanthraquinone–copper(II) supported on Fe₃O₄@SiO₂ magnetic porous nanospheres as a novel recyclable catalyst. The application of this catalyst allows the synthesis of a variety of tetrazoles in good to excellent yields. The preparation of the magnetic nanocatalyst with core–shell structure is presented by using nano‐Fe₃O₄ as the core, tetraethoxysilane as the silica source and poly(vinyl alcohol) as the surfactant, and then Fe₃O₄@SiO₂ was coated with 1,4‐dihydroxyanthraquinone–copper(II) nanoparticles. The new catalyst was characterized using Fourier transform infrared spectroscopy, X‐ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, dynamic light scattering, thermogravimetric analysis, vibration sample magnetometry, X‐ray photoelectron spectroscopy, nitrogen adsorption–desorption isotherm analysis and inductively coupled plasma analysis. This new procedure offers several advantages such as short reaction times, excellent yields, operational simplicity, practicability and applicability to various substrates and absence of any tedious workup or purification. In addition, the excellent catalytic performance, thermal stability and separation of the catalyst make it a good heterogeneous system and a useful alternative to other heterogeneous catalysts. Also, the catalyst could be magnetically separated and reused six times without significant loss of catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.     

Chiral Chromium Salen@rGO as Multipurpose and Recyclable Heterogeneous Catalyst

The first immobilization of a pyrene-tagged chromium salen complex through π-π noncovalent interactions on reduced graphene oxide (rGO) is described. A very robust supported catalytic system is obtained to promote asymmetric catalysis in repeated cycles, without loss of activity or enantioselectivity. This specific behavior was demonstrated in two different catalytic reactions (up to ten reuses) promoted by chromium salen complexes, the cyclohexene oxide ring-opening reaction and the hetero-Diels-Alder cycloaddition between various aldehydes and Danishefsky's diene. Furthermore, the chiral chromium salen@rGO has been found to be compatible with a multi-substrate type use, in which the structure of the substrate involved is modified each time the catalyst is reused.     

A computational study of the electronic structure and the chemical activity of curcumin and some novel curcuminoids by density functional theory

Structural modification of curcumin represents a strategy to improve its stability, water solubility, pharmaceutical properties and bioactivity. In this context, numerous structural analogues of curcumin, including curcuminoids, have been developed. In this paper, the precise density functional theory computations were used for investigating the electronic and geometrical structure of curcumin and some of its derivatives. The chemical activity of the considered molecules was investigated with the help of the global softness and hardness concepts. Among the studied molecules, bisdemethoxycurcumin had the most chemical activity and hexahydrocurcumin had the most stable structure. Among two isomers of the curcumin, the enol isomer was found to be active.     

Monitoring the effects of homogeneity methanol/water/monomer on the mode of polymerization of styrene: dispersion polymerization versus emulsion polymerization

The polymerization of styrene (St) was carried out with varying amounts of methanol in aqueous medium. As methanol content decreased (to 50 %), the phase of polymerization mixture (methanol/water/monomer) changed to a heterogeneous state; the homogeneous state was obtained in samples that contain 75 and 100 % methanol. In order to verify the mechanism of polymerization in heterogeneous and homogeneous mixtures, the nucleus formation rate during polymerization, the stability equilibrium of the media and seeded particles, and the size of particles and their growth in polymerization were experimentally being monitored. With the homogeneous mixture in 75 wt% methanol, dumbbell, triangle, and peanut-like particles have been formed. On the other hand, the characteristics of the polymerization products were different from those typically obtained in the emulsion polymerization and in the sample with 100 wt% methanol dispersion polymerization. In the sample with 100 % methanol and in one with 50 % methanol, monodispersed spherical particles are formed in the final conversion. Thus, homogeneity in the aqueous methanol mixture can be a critical factor in determining the polymerization modes between dispersion and emulsion polymerization.     

Microleakage and antibacterial properties of ZnO and ZnO:Ag nanopowders prepared via a sol–gel method for endodontic sealer application

A novel method, recently proved useful for the synthesis of nanoparticles, has been now used for the preparation of very stable silver iodide–trihexyl(tetradecyl)phosphonium chloride ionanofluids. Only the ionic liquid and the AgI bulk powder were needed. Synthesized nanofluids are much more stable than those obtained by simple dispersion of the nanoparticles in the base fluid. The ionanofluids were synthesized at different concentrations (up to 50 % w/w) and characterized in terms of physical, electrical, and thermal properties (density, viscosity, refractive index, electric conductivity, and specific heat capacity). A very high increase in the electric conductivity of the base ionic liquid was expected due to the high concentration of nanoparticles achieved. Nonetheless, it was not found, probably due to the reduction of ions mobility caused by the increase of the viscosity in ionanofluids with concentrations over 20 % w/w. An appropriate characterization of nanoparticles composing the nanofluids was carried out (UV–Vis absorbance, shape and size distribution). The diameter of the particles was measured and calculated by different techniques and approximations, obtaining a value of 2–4 nm. They were spherical, well-defined, and not agglomerated, with a narrow size distribution. The X-ray powder diffraction confirmed that no structural change took place in the transformation of the bulk solid to nanoparticles.     

Entropic order quantity (EnOQ) model for deteriorating items

Jaber et al. [M.Y. Jaber, R.Y. Nuwayhid, M.A. Rosen, Price-driven economic order systems from a thermodynamic point of view, Int. J. Prod. Res. 42 (24) (2004) 5167–5184] suggested that it might be possible to improve production systems performance by applying the first and second laws of thermodynamics to reduce system entropy (or disorder). They then used these laws to modify the economic order quantity (EOQ) model to derive an equivalent entropic order quantity (EnOQ). The results suggested that larger quantities should be ordered than is suggested by the classical EOQ model.