Sonolytic degradation of halogenated organic compounds in groundwater: mass transfer effects

Organic pollutants in liquid exposed to acoustic waves behave differently according to their physical and chemical properties. Laboratory batch experiments of sonication for the degradation of trichloroethylene (TCE) and ethylene dibromide (EDB) were carried out in groundwater at 20 kHz, and 12.5 and 35 W/cm(2). A theoretical model for the batch sonication system was derived to examine the mass transfer dependency of the ultrasonic degradation. Experimental results were supported with model predictions suggesting that both liquid phase diffusion coefficient and Henry's law constant are important parameters for the sonolytic degradation of the halogenated organic compounds in groundwater. When compared with the effect of the diffusion coefficient, Henry's constant exerts a greater influence on sonolytic degradation. When Henry's constant exceeds a value of 1 (volume/volume ratio), however, it no longer has much influence on the degradation process. The results also suggest that degradation is enhanced with an increase in ultrasonic power probably due to a greater bubble residence time and the formation of larger bubble at high-energy intensities.     

Immobilization of novel the semicarbazone derivatives of calix[4]arene onto magnetite nanoparticles for removal of Cr(VI) ion

A series of novel the semicarbazone derivatives of calix[4]arene have been synthesized and then immobilized onto amino functionalized magnetic nanoparticles. Magnetic Fe₃O₄ nanoparticles were prepared by the chemical co-precipitation of Fe(III) and Fe(II) ions and the nanoparticles were modified directly by 3-aminopropyltriethoxy silane (APTES) to introduce reactive amine groups onto the particles’ surface. The characterization of the prepared compounds was made by FT-IR, elemental analysis, TGA/DTG and NMR techniques. The sorption properties of the new calix[4]arene based magnetic sorbents toward Cr(VI) ion were also studied. The results showed that the prepared magnetic nanoparticles were effective sorbents for the removal of Cr(VI) ion. Also, Langmuir and Freundlich isotherm models were applied for Cr(VI) ion sorption by using MN-C2 and it was found that the experimental data confirmed to Langmiur isotherm model.     

Temperature dependent electrical characteristics of Sn/p-Si Schottky diodes

Current-voltage and capacitance-voltage characteristics of Sn/p-Si Schottky diodes measured in the temperature range 80-320 K are presented and analysed. Anomalous strong temperature dependencies of the ideality factor and apparent barrier height were obtained. There was also a considerable difference between the apparent barrier heights obtained from current-voltage and capacitance-voltage characteristics. These anomalies are explained by the domination of the current by a high level of thermionic-field emission, and by the presence of deep levels near the Sn/Si interface, which yield a reduction of free hole concentration and a significant temperature dependence of the charge stored near the metal-semiconductor (MS) interface. The evaluation of temperature dependence of forward current for thermionic-field emission resulted in the following parameters: characteristic energy E₀₀ = 9.8 meV, Schottky barrier height at zero bias Φ_b0 = 0.802 eV, bias coefficient of barrier height β = 0, and effective Richardson constant A* = 37.32 A cm⁻² K⁻².     

Comparison of separation performance of polysaccaride-based chiral stationary phases in enantioseparation of 1-(4-chlorobenzhydryl)piperazine benzamide derivatives by HPLC

Analytical high-performance liquid chromatographic enantioseparation of 1-(4-chlorobenzhydryl) piperazine benzamide derivatives was accomplished on different chiral stationary phases. The enantiomers of the compounds were resolved by normal-phase chromatography on silica-based amylose tris(3,5-dimethylphenylcarbamate) (Chiralpak AD-H), cellulose tris(3,5-dimethylphenylcarbamate) (Chiralcel OD-H) and cellulose tris(4-methylbenzoate) (Chiralcel OJ) columns with mobile phases consisting of mixtures of n-hexane and ethanol in different proportions (90: 10, 80: 20). The mobile phase and the chiral stationary phase were varied to achieve the best resolution. The effect of the concentration of ethanol in the mobile phase was studied. The resolution obtained on the three columns was significant.     

Evaluation of new silica‐based humic acid stationary phase for the separation of tocopherols in cold‐pressed oils by normal‐phase high‐performance liquid chromatography

A new humic acid stationary phase was prepared by immobilizing humic acid onto aminopropyl silica via an amide linkage formation and used, for the first time, for the separation and quantification of the tocopherol compounds in cold‐pressed oil samples under normal‐phase high‐performance liquid chromatography conditions. Parameters affecting the chromatographic separation such as mobile phase composition and flow rate were optimized. By evaluating the calculations of capacity factor, asymmetry factor, resolution, selectivity factor, and theoretical plate number, the best separation was obtained with isocratic elution of n‐hexane and isopropyl alcohol (99:1% v/v) at a flow rate of 1.0 mL/min. The effluent was monitored by a fluorescence detector set at excitation and emission wavelengths 295 and 330 nm, respectively. All compounds were separated in 20 min. The method was validated according to international guidelines and found to be linear in a wide concentration range, also the mean recovery of the compounds ranged from 97.9 to 99.2%, with a CV less than 2.7% in all cases. The results showed that the developed stationary phase is suitable for the separation and quantification of the tocopherol compounds in real oil samples.     

Use of aminoprophyl silica-immobilized humic acid for Cu(II) ions removal from aqueous solution by using a continuously monitored solid phase extraction technique in a column arrangement

Humic acid (HA) which originated from Leonardite was purified and immobilized onto aminoprophyl silica (APS). Afterwards, the remaining amino groups on the silica are successfully end-capped using acetic anhydride in DMF media and this material was used for Cu(II) ions removal from aqueous solution by using continuously solid phase extraction (SPE) technique in a column arrangement. The sorption characteristics of Cu(II)-immobilized humic acid (ImHA) system were investigated at various experimental conditions, and output was observed by a UV detector. All solid phase extraction (SPE) steps were monitored through breakthrough curves used to visualize distribution of Cu(II) concentration between mobile phase and solid phase. In addition to this, the solutions collected from stripping steps were analyzed in atomic absorption spectrophotometry (AAS) and the amount of adsorbed Cu(II) ions was calculated. It was found that there was a high correlation (R² = 1) between the peak area and AAS data of stripping steps. Sorption characteristics were evaluated by using Freundlich, Langmuir, and Dubinin–Radushkevich (D-R) adsorption isotherms, as well as by Scatchard plot analysis. Thus, the sorption characteristics and usability of ImHA as a solid phase for SPE of Cu(II) ions was evaluated in detail. From the obtained results, it was seen that sorption mechanism of Cu(II) fits to Langmuir model on a large scale, sorption was thought to be localized. From D-R isotherm mean free energy of sorption (E) was calculated (17.68 kJ mol⁻¹), and it was deduced that chemical interactions were more effective than physical interactions for Cu(II). This investigation provides a new, environmentally friendly and cost-effective possibility to remove Cu(II) ions from aqueous solution by using the new APS-ImHA material.     

Series resistance calculation for the Metal-Insulator-Semiconductor Schottky barrier diodes

An accurate way of determining the series resistance R_s of Schottky Barrier Diodes (SBDs) with and without the interfacial oxide layer using forward current-voltage (I–V) characteristics is discussed both theoretically and experimentally by taking into account the applied voltage drop across the interfacial layerV _i. For the experimental discussion, the forward biasI–V characteristics of the SBDs with and without the oxide layer fabricated by LEC (the Liquid-Encapsulated Czochralski) GaAs were performed. The SBD without the oxide layer was fabricated to confirm a novel calculation method. For the theoretical discussion, an expression ofV _i was obtained by considering effects of the layer thickness and the interface state density parameters on forward biasI–V of the SBDs. The valueR _s of the SBD with interfacial oxide layer was seen to be larger than that of the SBD without the interfacial oxide layer due to contribution of this layer to the series resistance. According to the obtained theoretical formula, the value ofV _i for the SBD with the oxide layer was calculated and it was subtracted from the applied voltage values V and then the value ofR _s was recalculated. Thus, it has been shown that this new value ofR _s is in much closer agreement with that determined for the SBD without the oxide layer as predicted. Furthermore, the curves of the interface states energy distribution of each sample are determined. It was concluded that the shape of the density distribution curve and order of magnitude of the density of the interface states in the considered energy range are in close agreement with those obtained by others for Au/n-GaAs Schottky diodes by Schottky capacitance spectroscopy.     

Calix[n]arene Carboxylic Acid Derivatives as Regulators of Enzymatic Reactions: Enhanced Enantioselectivity in Lipase-Catalyzed Hydrolysis of (R/S)-Naproxen Methyl Ester

Candida rugosa lipase was immobilized with a sol–gel encapsulation procedure in the presence and absence of a calix[n]arene carboxylic acid derivative grafted onto magnetic nanoparticles or in the presence of the calix[n]arene carboxylic acid derivative with Fe₃O₄ magnetic nanoparticles as an additive. Through the enantioselective hydrolysis of racemic naproxen methyl ester and the hydrolysis of p-nitrophenylpalmitate, the relative enzyme activity was evaluated and tested. These results show that the encapsulated lipase without supports has lower conversion and enantioselectivity compared to the Calix[n]COOH-based encapsulated lipase. It has also been observed that the Calix[4]COOH-based encapsulated lipase has excellent enantioselectivity (enantiomeric ratio (E)?>?400) as compared to encapsulated-free lipase enantioselectivity (E?=?137), and it also has an enantiomeric excess value of ~98 % for S-naproxen.     

The effect of series resistance on capacitance-voltage characteristics of Schottky barrier diodes

The capacitance-voltage (C-V) and current-voltage (I-V) characteristics of the Ti/p-Si Schottky barrier diodes (SBDs) have been investigated taking into account the effect of the interface states and series resistance of the device. The forward C-V measurements have been carried out in the range frequency of 0.3-2 MHz (at six different frequencies). It is seen that the forward C-V plots exhibit anomalous peaks in the presence of a series resistance. It has been experimentally determined that the peak positions in the C-V plot shift towards lower voltages and the peak value of the capacitance decreases with increasing frequency. In addition to, the effect of series resistance on the capacitance is found appreciable at higher frequencies due to the capacitance decreases with increasing frequency.