Efficient Allylic Oxidation of Olefins Catalyzed by Polymer Supported Metal Schiff Base Complexes with Peroxides

Three homogeneous Cu(II), Co(II) and Ni(II) complexes of a Schiff base ligand and their heterogeneous complexes supported on poly(4-aminostyrene) were prepared and characterized by using elemental analysis, fourier transform infrared spectroscopy, UV–Vis diffuse reflectance spectroscopy, thermogravimetric analysis and scanning electron microscopy. The catalytic performance of both homogeneous and heterogeneous complexes was evaluated in the liquid phase oxidation of cyclohexene, styrene and trans-stilbene in acetonitrile with tert-butylhydroperoxide or hydrogen peroxide as the oxidant. All types of catalyst were active in oxidation; and, the complexes produce allylic oxidation products in all cases. Immobilized complexes are slightly more active than their homogeneous complexes. The polymer-supported Cu(II) complex shows a higher catalytic activity than the other metal species. The activities of the immobilized catalysts remained nearly the same after five cycles, suggesting the true heterogeneous nature of the catalyst.     

Damage detection by the distribution of predicted constraint forces

Damage causes the deterioration of dynamic and static performance of intact structures. Regarding the measured static displacement or modal displacement data as constraints for describing damaged responses, this study derives analytical equations to estimate constraint forces in the satisfaction of constraints. The constraint forces are forces required for describing the flexural shape of the damaged beam under static and dynamic loadings. Based on the concept that the occurrence of damage causes the change of force mechanism, this work proposes an analytical method to detect damage from the distribution of constraint forces. When compared to the displacement curvature and the frequency response function (FRF) curvature methods using 2% noise, the results have shown that the proposed method is less sensitive to noise and is more effective in detecting multiple damaged areas in the beam of short span length and their intensity at low levels of damage.     

Effects of Moisture and pH on Supercritical Fluid Extraction of Cocoa Butter

The effects of moisture content and alkali treatment on cocoa butter extraction using supercritical fluid were studied. Ground cocoa nibs were examined at moisture contents of 1.95 %, 3.91 %, 5.87 %, 9.79 % and 17.64 % and the pH of the cocoa liquor was maintained at 5.0–5.9, 6.8–7.2 and 7.5–7.9. Cocoa butter was successfully extracted, using supercritical carbon dioxide (SC-CO₂) for the moisture content study and SC-CO₂ with 25 % ethanol as a cosolvent for the pH-level alkali treatment study, at 35 MPa, 60 °C and 2 ml/min. The results showed that increases in moisture content and pH level significantly (p?<?0.05) increase the yield efficiency. A moisture content of 9.79 % and pH-alkali treatment at 7.5–7.9 produced the highest yield (60.36 % and 73.70 % at 20 and 18 h extraction time, respectively). Triglycerides (TG) and fatty acids (FAs) were similar to those found in cocoa butter obtained using the Soxhlet method. Saturated and short-chain TG and FA constituents were more soluble than unsaturated and long-chain constituents.     

Electrical conductivity and electric modulus of stable Kevlar® fiber loaded HAF/NBR rubber composite

DC, AC conductivities and dielectric properties of high abrasion furnace carbon black (HAF)/acrylonitrile butadiene rubber (NBR) composite have been studied with varying the aramide Stable Kevlar^® fiber content, temperature, and frequency. Generally, the electrical conductivity was decreased with increasing Stable Kevlar^® fiber content, which was confirmed by the positron annihilation lifetime spectroscopy. Negative temperature coefficient of conductivity (NTCC) behavior between 353 and 413 K was detected, except for the composite containing 10 phr Kevlar which showed positive temperature coefficient of conductivity (PTCC) behavior above 383 K. These NTCC and PTCC behaviors were further manifested by differential scanning calorimetry (DSC). For the composite with 10 phr Kevlar, the interfacial polarization between the fibers and the polymeric composite can be ascribed to Maxwell‐Wagner‐Sillars mechanism. The (MWS) relaxation disappeared for higher fibers content. The analysis of the electric modulus in the frequency range from 1 kHz to 1 MHz shows that the interfacial relaxation obeys Cole–Davison distribution of relaxation times. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Nanoencapsulation of Alpha-linolenic Acid with Modified Emulsion Diffusion Method

Nanocapsules of alpha-linolenic acid (α-LA) were prepared by a modified emulsion diffusion technique with encapsulation efficiency of 93%. Polylactic acid (PLA) was used as the encapsulating polymer with acetone and ethyl acetate as organic solvents, and Tween 20, gelatin and Pluronic-F68 in water as stabilizers. Two ratios of organic to aqueous phases were used with each solvent and stabilizer. Nanocapsule dispersions with a particle size less than 100 nm and a zeta potential as high as 33 mV were obtained as verified by scanning electron microscopy and the dynamic light scattering technique respectively. Both particle size and zeta potential were influenced by such preparation conditions as the type of stabilizer, type of organic solvent and the organic to aqueous phase ratio. Acetone was superior to ethyl acetate, and Tween 20 was superior to each of Pluronic-F68 and gelatin in obtaining smaller, less aggregated nanocapsules. An organic to aqueous phase ratio of 1:5 was shown to be more suitable for the formation of smaller nanocapsules, particularly when acetone was used as the organic solvent.     

Assessment of aquatic toxicity and oxygen depletion during aerobic biodegradation of vegetable oil: effect of oil loading and mixing regime

The potential ecological impacts of aerobic biodegradation of vegetable oils on contaminated water columns was investigated in the laboratory at different oil loadings (100, 333, and 1,000 gal acre(-1)) and mixing regimes (fully, moderately, and nonmixed microcosms). The impacts were estimated by use of the Microtox assay and dissolved oxygen concentration measurements. The results of the Microtox assay showed no major toxicity at the 100 gal acre(-1) loading. Furthermore, oxygen was not completely depleted from the water column at this oil coverage. At higher oil loadings, oxygen was fully depleted from the mixed and nonmixed water columns. A transient toxicity in the aqueous phase was observed in the case of the moderately mixed microcosms at 333 gal acre(-1) and was maintained at moderate levels (EC(50) ～ 30%) in the nonmixed microcosms. A substantial increase in toxicity (EC(50) ～ 10%) was observed in both mixing conditions when the initial oil loading was increased to 1,000 gal acre(-1). At all oil loadings, significant toxicity (EC(50) < 2%) was found in the solid phase due to the strong partition of lipids to the biomass. Long and medium chains fatty acids associated with the measured toxicity were detected in both liquid and solid phases.     

In situ electropolymerization of conducting polypyrrole/carbon nanotubes composites on stainless steel: Role of carbon nanotubes types

In situ electropolymerization was used to prepare polypyrrole-oxidized multi-walled carbon nanotubes and polypyrrole-oxidized single-walled carbon nanotubes composites on a stainless steel surface from 0.1 M oxalic acid by using cyclic voltammetry. The electropolymerization process was investigated and discussed, and the results showed that the addition of the oxidized carbon nanotubes greatly enhanced the electropolymerization process, especially in the case of oxidized single walled carbon nanotubes. The results also showed that increasing the pyrrole monomer concentration leads to increasing the amount of polypyrrole electrodeposited, and this is more pronounced in the presence of the carbon nanotubes. The electropolymerization process was mainly under diffusion control as the process was inhibited by increasing the scan rate. In general, the presence of oxidized carbon nanotubes improved the electropolymerization of the polypyrrole and greatly enhanced its thermal and morphological properties.     

Numerical Simulation of Natural Convection in a Parallelogrammic Enclosure Containing Volumetric Heat Source with Non‐uniformly Heated Left Sidewall

The influence of the external Rayleigh number, inclination angle, and internal Rayleigh number on natural convection within an air‐filled parallelogrammic enclosure containing a volumetric source has been investigated numerically. The left sidewall of the enclosure is subjected to a non‐uniformly hot temperature and the right sidewall experiences a uniform cold temperature while the remaining top and bottom walls are kept adiabatic. The physical problems are represented mathematically by various sets of governing equations along with the corresponding boundary conditions. Buoyancy forces are taken into account during the analysis of the present investigation. By using the finite volume method, the dimensionless governing equations are discretized numerically based on a non‐uniform collocated grid system. Results are obtained for a wide range of external Rayleigh numbers varying from 10³ to 10⁶ with internal Rayleigh numbers varying from (0) to (10⁸) while the left sidewall from vertical is varied as 0, 30, –30, 60, and ?60^°, respectively. In the present study, the obtained results are presented in terms of streamlines, isotherms, and average Nusselt number along the hot and cold sidewalls. Two pairs of rotating vortices are observed due to the non‐uniform heating process while the shape of this rotating vortices is sensitive to the inclination angle. Furthermore, the flow field circulation and the average Nusselt number increase remarkably with the increase in the external Rayleigh number. The results of the present work are compared with other published results and give excellent agreement. © 2013 Wiley Periodicals, Inc. Heat Trans Asian Res, 43(6): 542–560, 2014; Published online 11 November 2013 in Wiley Online Library ( wileyonlinelibrary.com/journal/htj ). DOI 10.1002/htj.21096     

Interaction between chronic arsenic exposure via drinking water and plasma lactate dehydrogenase activity

Arsenic is a potent environmental pollutant that has caused one of the largest public health poisonings in the history of human civilization, affecting tens of millions of people worldwide especially in Bangladesh. Lactate dehydrogenase (LDH) in blood plays an important role in predicting cell or organ damage and as an important clue to the diagnosis of a variety of cancers. However, effect of chronic arsenic exposure on the LDH level in blood has not yet been documented. Since the chronic arsenic exposure is associated with organ damages and multi-site cancers, this research aimed at assaying the plasma level of LDH activity in the population who were exposed to arsenic chronically in Bangladesh. A total of 185 individuals living in arsenic-exposed areas and 121 individuals living in non-exposed area in Bangladesh were recruited as study subjects. Arsenic content in drinking water, hair and nails were estimated by Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) and LDH activity was assayed by a spectrophotometer. Significant increase in LDH activity was observed with increasing concentrations of arsenic in water, hair and nails. Further, the study subjects were split into four groups based on the three ways of each exposure metrics (water, hair and nail arsenic concentrations) where the study subjects in the non-exposed area were used as a reference (lowest exposure) group. LDH activity was found to be increased in the higher exposure groups of water and hair arsenic concentrations. LDH activity was also increased at low to medium exposure groups of nail arsenic concentrations.Thus, the elevated plasma LDH activity might be helpful for the early prognosis of organ or tissue damage in the individuals who were exposed to arsenic chronically.