MOFs for desulfurization of fuel oil: Recent advances and future insights

Nowadays, desulfurization of fuel oil has raised concern globally because of strict industrial and environmental legislations. Albeit hydrodesulfurization (HDS) has been extensively used in oil refineries to produce low sulfur oil (< 10 ppm) but not been proven as effective method for the removal of dibenzothiophene (DBT), benzothiophene (TH) and their derivatives. Subsequently, adsorptive desulfurization (ADS) and oxidative desulfurization (ODS) methods have been developed to achieve high removal efficiency. In the past decade, metal–organic frameworks (MOFs) and its composites as oxidative catalysts, as well as adsorbents, have attracted the researchers owing to high surface area, tunable properties, and reusable. The present review comprises use of MOFs and their composites for the removal of sulfur from fuel oil via ODS and ADS processes. Additionally, physicochemical properties of MOFs, mechanism, pros and cons of both process, regeneration, and future challenges have been discussed briefly. Moreover, current limitations and future prospective are also discussed.     

Evaluation of spectral dispersion of optical constants of a-Se films from their normal-incidence transmittance spectra using Swanepoel algebraic envelope approach

Spectral dispersions of index of refraction \({n(\lambda )}\) and extinction coefficient \({\kappa (\lambda )}\) of undoped amorphous selenium (a-Se) films of three thicknesses (d?≈?0.5, 0.75, and 1.0 µm) were evaluated by analyzing experimental room-temperature normal-incidence transmittance-wavelength (\({{T_{{\text{exp}}}}(\lambda )} - \lambda\)) data (λ =?400–1100 µm) of their air-supported {a-Se film/thick glass slide}-stacks using Swanepoel’s transmission envelope theory of uniform films. Above a wavelength \({{\lambda _c}\,\, \approx \,\,640\;{\text{nm}}}\), as-measured \({{T_{{\text{exp}}}}(\lambda )}\,\, - \,\lambda\) spectra display well-resolved maxima and minima, with minor shrinkage in transparent and weak absorption regions (750–1100 nm). Below \({\lambda _{\text{c}}}\), a smeared sharp decline of \({{T_{{\text{exp}}}}(\lambda )}\) with decreasing λ, signifying strong absorption in a-Se films and existence of band-tail localized states. For λ > λ _c, the \({n\,(\lambda )}\, - \,\lambda\) data retrieved from algebraic envelope procedures followed a Sellmeier-like dispersion relation, with the best-fit values of high-frequency dielectric constant \({{\varepsilon _\infty }\, \approx \,\,{\text{4.9}}}\), static index of refraction \({{n_{\text{0}}} = n\left( {E\, \to \,{\text{0}}} \right)\,\, \approx \,\,{\text{2.43}}}\), and resonance wavelength \({{\lambda _0}\, \approx \,490\,\,{\text{nm}}}\), which may be assigned to onset of photogeneration in a-Se. Urbach-like dependency of absorption coefficient \({\alpha (h{{\nu }})}\) of a-Se films on photon energy \({h{{\nu }}}\) was realized with an Urbach-tail breadth of 85 meV. All achieved optical parameters were found to be slightly dependent on film thickness. Findings of present algebraic analysis are consistent with reported literature results obtained on the basis of other optical analytical approaches.     

Aligned rank tests in measurement error model

Aligned rank tests are introduced in the linear regression model with possible measurement errors. Unknown nuisance parameters are estimated first and then classical rank tests are applied on the residuals. Two situations are discussed: testing about an intercept in the linear regression model considering the slope parameter as nuisance and testing of parallelism of several regression lines, i.e. whether the slope parameters of all lines are equal. Theoretical results are derived and the simulation study is also made to illustrate good performance of introduced tests.     

Reactions of some new thienothiophene derivatives

Facile and convenient syntheses of bisdimethylthieno[2,3-b]thiophen-2,5-diyl bis(oxazole-2-amine), bis(1H-imidazol-2-amine), bis((3a)-H-indole),[1,2-a]pyrimidine), bis(1H-imidazo[1,2-b][1,2,4]triazole) and bis(9H-benzo[d]imidazo[1,2-a]imidazole) derivatives incorporating a thieno[2,3-b]thiophene moiety from the versatile and readily accessible 1,1'(3,4-dimethylthieno[2,3-b]thiophene-2,5-diyl)-bis(2-bromo-ethanone) (1) are described.     

Improved Method for the Total Synthesis of Azaperone and Investigation of Its Electrochemical Behavior in Aqueous Solution

Azaperone, with anti-anxiety and anti-aggressive activities used in veterinary medicine, is a member of the butyrophenone class. It is ordinarily utilized for a wide range of indications, such as sedation, obstetrics, and anesthesia. In this research, an improved synthetic route is presented for azaperone using a phase-transfer catalyst(PTC). In general, it was synthesized as a dopamine antagonist in four steps. The bis(2-chloroethyl) amine intermediate is easily obtained after the conversion of the alcohol groups into the chloride leaving group using thionyl chloride(95% yields). The alkylation of commercially available 2-amino pyridine in the presence of PTC was then carried out, giving 1-(pyridin-2-yl) piperazine with 75% yield. 1-(Pyridin-2-yl) piperazine was finally alkylated using 4-chloro-1-(4-fluorophenyl) butan-1-one to achieve azaperone with 60% yield. The butyrophenone intermediate was obtained via the Friedel-Crafts reaction of fluorobenzene with 4-chlorobutyryl chloride in the presence of AlCl₃. High efficiency, gentle reaction conditions, and fast and simple procedure are the advantages of this method. Also, the electrochemical oxidation behaviour of azaperone was investigated using cyclic and differential pulse voltammetry techniques. Cyclic voltammetric studies indicated an irreversible process for azaperone electro-oxidation with a peak potential of 0.78 V in a phosphate buffer solution(pH=7.0) vs. Ag/AgCl(saturated KCl) electrode. The value of the peak current vs. the azaperone concentration was enhanced linearly in the range of 10―70 μmol/L, and the detection limit was found to be 3.33 μmol/L.     

Experimental violation of Bell's inequality in spatial-parity space

We report the first experimental violation of Bell's inequality in the spatial domain using the Einstein-Podolsky-Rosen state. Two-photon states generated via optical spontaneous parametric down-conversion are shown to be entangled in the parity of their one-dimensional transverse spatial profile. Superpositions of Bell states are prepared by manipulation of the optical pump's transverse spatial parity-a classical parameter. The Bell-operator measurements are made possible by devising simple optical arrangements that perform rotations in the one-dimensional spatial-parity space of each photon of an entangled pair and projective measurements onto a basis of even-odd functions. A Bell-operator value of 2.389+/-0.016 is recorded, a violation of the inequality by more than 24 standard deviations.     

Luminescent amphiphilic nanogels by terpyridine-Zn(II) complexation of polymeric micelles

In this work, we investigated terpyridine (tpy)/Zn(II) complexation for the crosslinking of polymeric micelles of the branched poly(ethylene oxide)–poly(propylene oxide) block copolymer Tetronic® 1107 (T1107) in water and produce physically stable amphiphilic luminescent nanogels. Nanoparticles displayed a size of 235 ± 25 and 318 ± 57 nm before and after Zn(II) crosslinking, respectively, as measured by dynamic light scattering. High-resolution scanning electron microscopy analysis revealed the multimicellar nature of the crosslinked nanoparticles. In addition, Zn(II) complexation prevented nanoparticle disassembly after extreme dilution below the critical micellar concentration and reduced the minimum concentration required for the reverse thermal gelation of concentrated aqueous T1107 systems. The cell compatibility and uptake were initially assessed in the murine macrophage cell line RAW 264.7. Results showed that complexation increases the cell compatibility of the nanoparticles with respect to the non-complexed counterparts. In addition, non-crosslinked nanoparticles accumulated in the cell membrane, while the complexed ones were internalized, as observed by confocal laser scanning fluorescence microscopy. Then, the antiproliferative activity of the crosslinked nanoparticles was confirmed in the rhabdomyosarcoma cell line Rh30; their inhibitory concentration 50 (IC₅₀) being 101 μg/mL (6.7 μM). Finally, the encapsulation and release of the hydrophobic antiretroviral efavirenz was characterized in vitro. Complexation slightly reduced the release kinetics with respect to the pristine nanoparticles. Overall results demonstrate the promise of this simple modification strategy to produce amphiphilic nanogels with a set of advantageous physicochemical, optical, and biological properties.     

The improvement of numerical modeling in the solution of incompressible viscous flow problems using finite element method based on spherical Hankel shape functions

In this paper, the finite element method with new spherical Hankel shape functions is developed for simulating 2‐dimensional incompressible viscous fluid problems. In order to approximate the hydrodynamic variables, the finite element method based on new shape functions is reformulated. The governing equations are the Navier‐Stokes equations solved by the finite element method with the classic Lagrange and spherical Hankel shape functions. The new shape functions are derived using the first and second kinds of Bessel functions. In addition, these functions have properties such as piecewise continuity. For the enrichment of Hankel radial basis functions, polynomial terms are added to the functional expansion that only employs spherical Hankel radial basis functions in the approximation. In addition, the participation of spherical Bessel function fields has enhanced the robustness and efficiency of the interpolation. To demonstrate the efficiency and accuracy of these shape functions, 4 benchmark tests in fluid mechanics are considered. Then, the present model results are compared with the classic finite element results and available analytical and numerical solutions. The results show that the proposed method, even with less number of elements, is more accurate than the classic finite element method.     

Synthesis of ZnO2 nanoparticles by laser ablation in liquid and their annealing transformation into ZnO nanoparticles

A pulsed laser emitting UV radiations generated by the third harmonic of Nd:YAG was applied for the synthesis of nano-structured ZnO₂ and ZnO. For the synthesis of nanoparticles of ZnO₂, a high-purity metallic plate of Zn target was fixed at the bottom of a glass cell, in the presence of deionized water mixed with oxidizing agent H₂O₂, under repeated laser irradiation. The optical properties, size and the morphology of the synthesized ZnO₂ and ZnO by laser ablation was influenced strongly by post-annealing conditions which is not previously reported. By annealing ZnO₂ at 200 °C for 8 h, the product (ZnO₂) synthesized primarily was converted completely to ZnO. By variation of the annealing temperatures from 200 to 600 °C, the grain size of ZnO changes from 5 to 19 nm with a change in lattice parameters, the band gap and some other optical properties of nano-ZnO.     

Determination of quinocide as impurity in primaquine tablets by capillary zone electrophoresis

A capillary zone electrophoretic method has been developed and validated for the determination of the impurity quinocide (QC) in the antimalarial drug primaquine (PQ). Different buffer additives such as native cyclodextrins and crown ethers were evaluated. Promising results were obtained when either β‐cyclodextrin (β‐CD) or 18‐crown‐6 ether (18C6) were used. Their separation conditions such as type of buffer and its pH, buffer additive concentration, applied voltage capillary temperature and injection time were optimized. The use of 18C6 offers slight advantages over β‐CD such as faster elution times and improved resolution. Nevertheless, migration times of less than 5 min and resolution factors (R_s) in the range of 2–4 were obtained when both additives were used. The method was validated with respect to selectivity, linearity, limits of detection and quantitation, analytical precision (intra‐ and inter‐day variability) and repeatability. Concentrations of 2.12 and 2.71% (w/w) of QC were found in pharmaceutical preparations of PQ from two different manufacturers. A possible mechanism for the successful separation of the isomers is also discussed. Copyright © 2008 John Wiley & Sons, Ltd.