Studies on the synthesis of diacetyl over oxidation zeolite catalysts

Diacetyl (2,3-butanedione) synthesis from methyl ethyl ketone over oxidation zeolites using O₂ as oxidant was studied. Various zeolites with Fe, V and Ti as active sites were employed. VS-1, Ti-NCL, Ti-MCM-41 and FeBEA type materials were synthesized and characterized by BET, FTIR, XRD, pyridine adsorption and template desorption. The detailed study of the effect of reaction temperature, the effect of concentration of oxygen and the addition of water was realized. The most active catalyst was zeolites with V as oxidation center.     

Approximation for scheduling on uniform nonsimultaneous parallel machines

We consider the problem of scheduling on uniform machines which may not start processing at the same time with the purpose of minimizing the maximum completion time. We propose using a variant of the MULTIFIT algorithm, LMULTIFIT, which generates schedules which end within 1.382 times the optimal maximum completion time for the general problem, and within \(\sqrt{6}/2\) times the optimal maximum completion time for problem instances with two machines. Both developments represent improvements over previous results. We prove that LMULTIFIT worst-case bounds for scheduling on simultaneous uniform machines are also LMULTIFIT worst-case approximation bounds for scheduling on nonsimultaneous uniform machines and show that worst-case approximation bounds of MULTIFIT variants for simultaneous uniform machines from previous literature also apply to LMULTIFIT. We also comment on how a PTAS for scheduling on a constant number of uniform machines with fixed jobs can be used to obtain a PTAS for scheduling on a constant number of uniform nonsimultaneous parallel machines.     

Effect of γ-radiation on green onion DNA integrity: Role of ascorbic acid and polyphenols against nucleic acid damage

The effect of γ-radiation on green onion DNA integrity, phenol content, oxygen radical absorbance capacity, employing pyrogallol red and fluorescein as probes, as well as ascorbic acid content has been evaluated. Measurements using thiazole orange-DNA fluorescence and agarose gel electrophoresis show that γ-radiation does not lead to an apparent DNA change in green onion. However, it was readily cleaved upon irradiation from the previously isolated nucleic acid. Furthermore, green onion exposure to γ-radiation produces slight increases in the polyphenol concentrations (163–188 μM Trolox eq.) and a decrease in the oxygen radical absorbance using fluorescein (from 245 to 200 Trolox eq.) Interestingly, a high ascorbic acid content (364 μM), which decreases by 40% after γ-ray exposure was measured by using pyrogallol-red-based oxygen radical absorbance capacity induction times from green onion aqueous extracts. Thus, our results suggest that ascorbic acid present in green onion plays a fundamental role in the plant antioxidant response toward γ-radiation exposure, while polyphenols remain largely unchanged, as revealed from oxygen radical absorbance capacity, employing pyrogallol red.     

Numerical Simulation of Water Flow from the Coal Seam Floor in a Deep Longwall Mine in China

The study of groundwater flow from the coal seam floor is critical to safe mining operations in China. We developed a numerical simulation model to describe flood water pathways during mining, using the field conditions present at the no. 4196 west work face in the Panxi longwall coal mine, Shandong Province, China, Groundwater flow analysis revealed unusual values for the failure depth of the coal seam floor. The high ground stress and underground pressure, excavation length, width of working face, poor mechanical properties of aquitards, and expansion of fractures by groundwater infiltration all contribute to groundwater flow into the mine. The modeling results predict the time and longwall locations associated with the maximum likelihood of flood occurrence. Such results can be used by decision makers to improve mine design and safety.     

Nucleation behavior of blended high‐melting fractions of milk fat as affected by emulsifiers

The effect of highly hydrophobic emulsifiers, the palmitic sucrose ester P‐170 (hydrophilic/lipophilic balance (HLB) = 1.0), the stearic sucrose ester S‐170 (HLB = 1.0), the polyglycerol ester decaglycerol decastearate DAS 7S (HLB = 3.7) and the polyglycerol ester decaglycerol dodecabehenate DDB 750 (HLB = 2.6), on the nucleation of a high melting point milk fat fraction (HMF) and its blends with sunflower oil (SFO) was investigated by polarized laser light turbidimetry, X‐ray diffractometry and polarized light microscopy (PLM). Addition of polyglycerol esters accelerated nucleation, giving shorter induction times for the same supercooling. On the contrary, sucrose esters inhibited nucleation since induction times were elongated in all conditions selected. Addition of emulsifiers modified the polymorphic behavior in the blends with SFO. The β' form was promoted especially with the addition of S‐170. DAS 7S and DDB 750 promoted crystallization. PLM images showed many small crystals that did not appear in HMF images. Addition of P‐170 and S‐170 delayed nucleation and inhibited crystal growth. Crystals were notoriously smaller than the ones that appeared in HMF images. The Fisher–Turnbull model was used to calculate activation free energies of nucleation. In all cases, sucrose esters elevated the energy barrier for nucleation. Polyglycerol esters, however, if they had an effect on the energy barrier, lowered the values.     

Photoelectrochemistry of poly(3-methylthiophene), I: Surface morphology and thickness effect

Photocyclovoltammetric experiments with films of poly(3-methylthiophene) under polychromatic light irradiation show a p-type semiconductor behavior in the reduced state, with a flat band potential of 0.18 V. The photocurrent depends on film thickness and surface morphology. Films with different thickness were characterized by scanning electron microscopy, indicating a globular morphology with globule sizes changing according to the charge density used during polymer deposition. The highest photocurrent is observed for the lowest globule diameter. These films were also irradiated with monochromatic light from the electrolyte side and from the substrate side. A higher photocurrent and a photocurrent spectrum matching the absorption spectrum of the reduced form of the polymer is observed on irradiation from the electrolyte side of a 0.7 μm thick film. In contrast, for irradiation from the electrode side, the photocurrent is lower and the spectrum shows a peak at lower energy. These results were interpreted in terms of a delocalized space charge zone, different kinetics for charge transfer and mass transport across the solvent swollen polymer film and different depth of penetration of the light as a function of wavelength.     

CO(2) Adsorption on Activated Carbon Honeycomb-Monoliths: A Comparison of Langmuir and Tóth Models

Activated carbon honeycomb-monoliths with different textural properties were prepared by chemical activation of African palm shells with H(3)PO(4), ZnCl(2) and CaCl(2) aqueous solutions of various concentrations. The adsorbents obtained were characterized by N(2) adsorption at 77 K, and their carbon dioxide adsorption capacities were measured at 273 K and 1 Bar in volumetric adsorption equipment. The experimental adsorption isotherms were fitted to Langmuir and Tóth models, and a better fit was observed to Tóth equation with a correlation coefficient of 0.999. The maximum experimental values for adsorption capacity at the highest pressure (2.627-5.756 mmol·g(-1)) are between the calculated data in the two models.     

Dodecatungstocobaltate supported over ZSM-5 zeolite as novel solid catalyst in selective sulfide oxidation

The catalytic behavior of a Keggin type potassium dodecatungstocobaltate (II) salt supported on ZSM-5 zeolite for wet peroxide oxidation of 2-(methylthio)benzothiazole, as a model organic sulfide, was thoroughly studied. Microporous ZSM-5 zeolite was obtained by the hydrothermal crystallization method. The Keggin salt was incorporated in the MFI zeolite matrix by the wet impregnation method followed by calcination at 350 °C. Catalysts were further characterized by X ray diffraction, UV–Vis diffuse reflectance spectroscopy and scanning electron microscopy-EDAX techniques. Supported and bulk Keggin dodecatungstocobaltate (II) were compared with pure H-ZSM-5 zeolite as catalysts for the sulfide oxidation. When the reaction was not catalyzed, just a 9 mol% of sulfide conversion was obtained. Reaction parameters, such as nature of the solvent, hydrogen peroxide concentration, reaction time, catalyst mass, substrate initial concentration and reaction temperature, were evaluated to reach the optimum reaction conditions, considering substrate conversion and sulfoxide and sulfone selectivities. Catalyst stability in several oxidation cycles was also examined.     

Preparation and magnetoelectric properties of NiFe2O4–PZT composites obtained in-situ by gel-combustion method

Magnetoelectric composites of xNiFe₂O₄–(1 ? x)Pb(Zr,Ti)O₃ with x = 2, 5, 10, 20, 30% were prepared by citrate–nitrate combustion using PZT-based template powders. In order to ensure a better connectivity of dissimilar phases, we have used chemical methods for preparation in situ composites, followed by adequate sintering procedure. The structural, microstructural and functional properties of di-phase magnetoelectric composites of NiFe₂O₄–PZT are reported. The XRD analysis is demonstrating the synthesis of pure ferrite phase directly on the ferroelectric templates. An excellent mixing was obtained in the composite powders, as proved by a detailed SEM analysis.The magnetic and dielectric behaviors of the ceramic composites vary with the ratio of the two phases. The dielectric behavior is greatly influenced by the magnetic phase. The magnetoelectric (ME) coefficient was measured as a function of applied DC magnetic field. The maximum ME coefficient (dE/dH) varies from 0.0011 mV/(cm Oe) to 0.5 mV/(cm Oe) with increasing of NF addition.     

Comparison of the stability of palm olein and a palm olein/canola oil blend during deep‐fat frying of chicken nuggets and French fries

Stability of palm olein (PO) and a blend 50% palm olein/50% canola oil (POC) during deep‐fat frying at 180 °C of French fries (FF) or chicken nuggets (CN) was studied through the determination of physical and chemical parameters in the fresh and used oils. Degradation at the end of the study resulted in total polar compounds of 12–13.5% for PO and 11.5–14.5% for POC and viscosity of 65–123.3 cP for PO and 63–72.8 cP for POC. Lower peroxide values (5.33–6.32) were obtained for the blend (PO had 5.21–8.55). Food type affected colour parameters and p‐anisidine value of the oils. For CN, the lowest fat content and higher hardness were obtained when they were fried in PO. CN caused a faster deterioration in the oils, in comparison with FF, especially in POC. Gas chromatography allowed to observe differences in fatty acids composition for both used oils.