Antioxidant activity of phenolic compounds in 2,2′-azobis (2-amidinopropane) dihydrochloride (AAPH)-induced oxidation: Synergistic and antagonistic effects

Interactions between phenolic antioxidants in binary systems were determined by adding two antioxidants simultaneously in equimolar proportions to an aqueous dispersion of linoleic acid that was then subjected to 2,2′-azobis (2-amidinopropane) dihydrochloride-induced oxidation and by evaluating the protective effect of the antioxidant mixture. The antioxidant power of the mixture was then compared with the expected antioxidant activity calculated by the sum of efficiencies of each compound separately, relative to their proportions in the mixture. If it was higher, a synergy was pointed out whereas a lower value was representative of an antagonism. Thus, synergistic effects were observed between rosmarinic acid and quercetin, or rosmarinic acid and caffeic acid, whereas antagonistic effects were obtained with the following mixtures: α-tocopherol/caffeic acid; α-tocopherol/rosmarinic acid; (+)-catechin/caffeic acid; and caffeic acid/quercetin. These mixture effects are partly explained by regeneration mechanisms between antioxidants, depending on the chemical structure of molecules and on the possible formation of stable intermolecular complexes.     

Effect of temperature gradient on competitive growth behavior of Si and YSi2 in a Si–Y eutectic alloy prepared by Bridgeman method

The Si–Y eutectic alloy has been prepared by Bridgeman method where the high temperature gradient (G_E) can be obtained by means of double heating combining with liquid metal cooling. The microstructures of longitudinal section and cross section at different G_E have been observed. It can be seen clearly that the YSi₂ phase presents the evolution process of thick banded shape, island shape, reticular shape and fine strip shape as G_E increases from 90 K/cm to 200 K/cm. Based on the interface growth temperature model, it can be concluded that the interface growth temperatures of Si phase and YSi₂ phase both will decrease linearly with increasing G_E while that of eutectic structure will keep a constant of 1485.6 K. Two critical temperature gradients G_EC1 = 52 K/cm and G_EC2 = 111 K/cm have been calculated. Eutectic coupling growth will take the dominant position when the actual G_E is greater than G_EC2. The primary Si phase will begin to form as G_E is smaller than G_EC2 and will be thicker as G_E is smaller than G_EC1. The coupling effect of withdrawal rate and G_E on the microstructures of the Si–Y alloy also has been analyzed comprehensively.     

Polymerization,grafting and adsorption in the presence of inorganic substrates: Thermal polymerization of styrene with untreated and γ-irradiated silica gel as a case study

The search for innovative and well-defined organic–inorganic hybrid materials demands that the interplay between polymerization reactions, chemical reactivity, and physical adsorption be fully understood. We examine the case study of the thermal polymerization of styrene in the presence of silica, and the effect of pre-irradiation of silica with γ-rays. The effect of adsorption of styrene-derived radical species on the silica support and polymerization conditions on free and grafted (unextractable) polystyrenes and on polymerization mechanism is discussed on the basis of previous literature findings and new data. Evidence is provided of silica derivatization with various species besides polystyrene (¹³C CPMAS NMR), including products from a β-scission of the adsorbed radical intermediates ensuing oxygen donation from the silica network. The polymerization mechanism can be cationic as well as radical, depending on reaction conditions, and the cationic route prevails in the grafting of polystyrene from silica, resulting in a bimodal molecular weight distribution.     

Synthesis,structure and properties of the first dinuclear copper(II) complex as a structural model for the phenolic intermediate in tyrosinase–cresolase activity

The synthesis, X-ray crystal structure and spectroscopic and electrochemical properties of the new dinuclear copper(II) complex [Cu₂(Hbtppnol)CH₃COO](ClO₄)₂ (1), employing the novel unsymmetric dinucleating ligand N-(2-hydroxybenzyl)-N,N′,N′-tris(2-pyridylmethyl)-1,3-diaminopropan-2-ol (H₂btppnol), are presented. This complex could be a relevant model for the axial interaction of a phenolic substrate to tyrosinase during cresolase activity.     

Effect of the design of a feedstock injection device in a fluidized-bed reactor on the efficiency of the reaction using the dehydrogenation of <Emphasis Type="Italic">iso</Emphasis>-paraffins in a fluidized chromia–alumina catalyst bed as an example

Mathematical modeling is performed for the operation of two units of industrial chemical fluidized-bed reactors with different gas feedstock injection devices, i.e, three toroidal rings with nozzles in unit 1 and a false bottom with nozzles distributed over it in unit 2. Efficiency is analyzed (using the target product (iso-butylene) yield) for the operation of the two units over 4 months under industrial conditions and revealed the higher efficiency of unit 2. To dedetrmine the reasons for different product yields in the two units, a numerical solution is found by mathematical modeling to obtain characteristic pictures of catalyst particle concentrations and temperature fields in these units. It is concluded that unit 2 is characterized by a more uniform and dense distribution of the catalyst along with more uniform heating of the reactor. Pictures of the principal catalyst circulation flows are plotted to explain the considerable difference between the catalyst concentrations and gas temperature fields. Based on the numerical solution, the operational efficiency of the two units is subjected to comparative analysis, which showed good agreement with the results from an analysis of industrial reactors. The approach used in this work could be used in designing new units and optimizing existing units.     

Effects of conservation tillage,crop residue and cropping systems on changes in soil organic matter and maize–legume production: a case study in Teso District

The effects of conservation tillage, crop residue and cropping systems on the changes in soil organic matter (SOM) and overall maize–legume production were investigated in western Kenya. The experiment was a split-split plot design with three replicates with crop residue management as main plots, cropping systems as sub-plots and nutrient levels as sub-sub plots. Nitrogen was applied in each treatment at two rates (0 and 60 kg N ha⁻¹). Phosphorus was applied at 60 kg P/ha in all plots except two intercropped plots. Inorganic fertilizer (N and P) showed significant effects on yields with plots receiving 60 kg P ha⁻¹ + 60 kg N ha⁻¹ giving higher yields of 5.23 t ha⁻¹ compared to control plots whose yields were as low as 1.8 t ha⁻¹ during the third season. Crop residues had an additive effect on crop production, soil organic carbon and soil total nitrogen. Crop rotation gave higher yields hence an attractive option to farmers. Long-term studies are needed to show the effects of crop residue, cropping systems and nutrient input on sustainability of SOM and crop productivity.     

Enzymatic synthesis of poly(ε-caprolactone): thermal properties, recovery, and reuse of lipase B from Candida antarctica immobilized on macroporous acrylic resin particles

Candida is a genus of yeast, and lipase B isolated from Candida antarctica (CALB) has been utilized as a biocatalyst for the synthesis of a variety of organic compounds including polyesters and polylactones. Among the various immobilization media reported in the literature, the porous acrylic resin utilized in Novozym-435 has been widely studied. Here, we report the enzyme recovery and reuse for the synthesis of poly(ε-caprolactone) in toluene at 70 °C for 4 h per cycle for up to 10 reaction cycles, which consistently resulted in polymers with a weight-average molecular weight, M _w , of ~50,000 g mol^?1 and a polydispersity index of ~1.4. In addition, the thermal properties of the resin particles used in Novozym-435, with and without the enzyme, were evaluated by TGA and DSC analysis. The effect of mechanical agitation on the enzyme stability, recovery, and reuse was also discussed. These results may have significance to enzymatic polymer synthesis as well as to the enzyme immobilization on acrylic resins and other matrices.     

Experimental and modeling studies on the enantio-separation of 3,5-dinitrobenzoyl-(R),(S)-leucine by continuous liquid–liquid extraction in a cascade of centrifugal contactor separators

The continuous enantioselective liquid–liquid extraction of aqueous 3,5-dinitrobenzoyl-(R),(S)-leucine (A_R,S) using O-(1-t-butylcarbamoyl)-11-octadecylsulfinyl-10,11-dihydro-quinine (C, a cinchona alkaloid) as extractant in 1,2-dichloroethane (DCE) was studied experimentally in a countercurrently operated pilot scale cascade of six centrifugal contactor separators (CCS) at 294 K. The extractant was efficiently recovered by back-extraction in a single CCS allowing the cascade to be run continuously for 10 h. The steady-state ee of A_R (ee_R) in the raffinate was 42% at a 99% yield, the A_S was obtained with high purity (98% ee_S) and a yield of 55% in the back-extraction raffinate. In total 2.23 g of A_S was obtained at steady-state operation from 8.11 g racemate feed. Deterioration of the ee in time was not observed, demonstrating the robustness of the chemistry. The experiments were modeled using an equilibrium stage approach. The correlation between model and experiment was satisfactory. The model was applied to optimize the production of both enantiomers in >97% ee. At zero reflux, 12 stages are required for 99% ee for both enantiomers. Application of a reflux allows a 25% reduction of the total liquid flow through the system by reduction of the wash feed as well as a reduction in the number of stages from 12 to 11. With a configuration of 12 CINC-V02’s operating at an aqueous feed flow of 360 mL/min, the model predicts that 17.7 kg racemate per week may be separated into both enantiomers with 99% ee using only 60 g of extractant.     

Co catalysts supported on SiO2 and γ-Al2O3 applied to ethanol steam reforming: Effect of the solvent used in the catalyst preparation method

Cobalt catalysts were prepared on supports of SiO₂ and γ-Al₂O₃ by the impregnation method, using a solution of Co precursor in methanol. The samples were characterized by XRD, TPR, and Raman spectroscopy and tested in ethanol steam reforming. According to the XRD results, impregnation with the methanolic solution led to smaller metal crystallites than with aqueous solution, on the SiO₂ support. On γ-Al₂O₃, all the samples exhibited small crystallites, with either solvent, due to a higher Co-support interaction that inhibits the reduction of Co species. The TPR results were consistent with XRD results and the samples supported on γ-Al₂O₃ showed a lower degree of reduction. In the steam reforming of ethanol, catalysts supported on SiO₂ and prepared with the methanolic solution showed the best H₂, CO₂ and CO selectivity. Those supported on γ-Al₂O₃ showed lower H₂ selectivity.     

Direct conversion of syngas to DME as a green fuel in a high pressure microreactor: Influence of slurry solid content on characteristics and reactivity of washcoated CuO–ZnO–Al2O3/HZSM-5 nanocatalyst

Microchannels of a stainless steel microreactor were successfully washcoated with slurry of Cu–ZnO–Al₂O₃/HZSM-5 (CZAZ) nanocatalyst with different concentrations (10, 20 and 30 wt.%). The properties of nanocatalyst and the washcoated microchannels were investigated by XRD, FESEM, N₂ physisorption, FTIR, EDX-Dot mapping and EDX-Line mapping analysis. The best adherence was observed for 20 wt.% catalyst which has a uniform coating, almost no cracks and homogenous dispersion of copper and zinc. Trend of weight gain during 10 soaks in catalyst slurry was very slow for 10 wt.% but faster for 20 and 30 wt.%. Low amount of weight gain was observed for the last soaks of catalyst slurry in the case of 30 wt.% washcoating. The performance of microreactor with different slurry concentrations were evaluated in direct synthesis of DME at 200–300 °C, 60–150 cm³/min and 40 bar. Regardless of slurry concentration, the microreactor exhibited a better reactivity in comparison to fixed-bed reactor performance. Among three different slurry concentrations, 20 wt.% catalyst slurry revealed the best reactivity in direct DME synthesis. The reduction in reactor performance at higher flow rates was significant in the fixed-bed reactor while microreactor, particularly 20 wt.% washcoated channels, revealed less drastic reduction.     

Inhibiting HDS and HYD reactions with quinoline on Co(Ni)–PMo(W)/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts: Effect of active phase composition on stability in the hydrotreatment of a model petroleum raw material

Со(Ni)–PMo(W)/Al₂O₃ catalysts are prepared using Keggin heteropoly acids H₃PMo(W)₁₂O₄₀ and cobalt (nickel) citrate. The physicochemical properties of the catalysts are studied via low-temperature nitrogen adsorption, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. Their catalytic properties are determined in the hydrotreatment of a model raw material containing dibenzothiophene, naphthalene, and different amounts of quinoline (up to 1000 ppm of nitrogen), and in the hydrotreatment of a straight-run diesel fraction and vacuum gas oil. The composition of Со(Ni)–PMo(W)/Al₂O₃ catalysts plays an important role in the hydrotreatment of a complex hydrocarbon raw material. Ni–PW/Al₂O₃ catalyst is more resistant to organonitrogen inhibitors than Ni(Co)–PMo/Al₂O₃ samples with more reactive active sites. Ni–PW/Al₂O₃ catalyst provides the greatest depth of conversion for sulfur- and nitrogen-containing compounds and polycyclic aromatic hydrocarbons in the hydrotreatment of vacuum gas oil.