Ultrasonic and Raman Scattering Spectroscopy of Zinc Thiocyanate Complexes in Water at 25<Superscript>∘</Superscript>C: Kinetics of Complex Formation Determined by Multivariate Analysis

Advances have been made recently in broadening the accessible ultrasonic absorption frequency range and improving the detectability of minor species present in solution using Raman spectroscopy. Development of chemometric techniques in these areas needs to keep pace with the improvement of these experimental methods. Refinements in the analysis of ultrasonic and Raman data based on multivariable least squares and factor analysis, respectively, are examined to investigate the kinetics of zinc thiocyanate complex formation in water. Analysis of ultrasonic absorption relaxation spectra verified that the observed process in aqueous Zn(SCN)₂ involves substitution of water from the first coordination shell of Zn²⁺. Use of a multivariable least-squares error surface is described that enhances the reliability of assigned frequencies of ultrasonic absorption maxima. Factor analysis of Raman scattering data provided direct evidence that at least four complex species, such as Zn(SCN)⁺ and Zn(SCN)₂, are simultaneously present in the aqueous zinc thiocyanate solutions.     

Determination of arsenic in sediments, coal and fly ash slurries after ultrasonic treatment by hydride generation atomic absorption spectrometry and trapping in an iridium-treated graphite tube

A simple and reliable method for the determination of arsenic in sediment and in coal without sample digestion, based on hydride generation from slurry samples is proposed. After grinding the samples to a particle size of 50 μm, the sample powder was mixed with aqua regia and hydrofluoric acid in an ultrasonic bath for 30 min. After diluting the mixture with hydrochloric acid, the slurry was allowed to stand for 48 h, and an aliquot was used for hydride generation with sodium borohydride. More than 80% of the arsenic was leached to the aqueous phase under these conditions, except for one sediment sample with very high silica content. The generated arsine was collected in a graphite tube, treated with 0.5 mg of iridium as a permanent modifier, and the arsenic determination was carried out by electrothermal atomic absorption spectrometry. The same tube could be used for at least 160 cycles without any re-treatment. The greatest advantage of the method was that only a minimum of reagents and sample handling were required, reducing the risks of contamination and/or analyte loss. However, the addition calibration technique had to be used in order to obtain results within the 95% confidence level for 11 certified reference materials, 5 sediments, 5 coals and one coal fly ash. One certified sediment slurry was spiked with the analyte and the resulting addition calibration curve was used for the analysis of the certified sediments. Similarly, one certified coal was used to obtain the addition calibration curve for the coal and coal fly ash samples. The recoveries of the certified values, except for one sediment, were between 91 and 115%. The limits of detection in the samples were 0.54 and 0.7 μg g⁻¹ for the coal and sediment samples, respectively, obtained for 1 ml of slurry containing 1 mg of sample.     

Static ultrasonic oscillations induced degradation and its effect on the linear rheological behavior of novel propylene based plastomer melts

The ultrasonic degradation of novel propylene based plastomer (DP) melts with different melt viscosities was conducted in a “static” ultrasonic device where the samples were taken from various distances from the tip of an ultrasonic probe. The effects of ultrasonic time, oscillation temperature, ultrasonic intensity and the distance from the ultrasonic probe tip on the degradation behavior of DP melts as well as the ultrasonic degradation effect on the linear rheological behavior of DP melts were studied. The results show that the increase of initial melt viscosity of DP (higher molecular weight) has greater impact on the ultrasonic degradation of DP melt. The molecular weight and intrinsic viscosity of DP decrease with the increase of ultrasonic oscillation time and they approach to a limiting value. The molecular weight distribution of DP increases after ultrasonic degradation. Decreasing oscillation temperature and distance from probe tip and increasing ultrasonic intensity lead to an increase in the degradation of DP melt. The linear rheological behavior measurements of the samples obtained near the ultrasonic probe tip show that ultrasonic oscillations decrease the complex viscosity, zero shear viscosity, viscoelastic moduli, cross modulus, relaxation time and the slope of log G′ − log G″ for DP melts.     

Reversed Capillary Electrochromatography: Investigation of Peak Symmetry for Eluting Curves of Solutes

Summary A clean method without use of organic solvents has been developed for isolation and high-performance liquid chromatographic (HPLC) determination of oxytetracycline (OTC) and sulphadimidine (SDD) in cow's milk. Isolation is rapid and simple—homogenization with an inorganic acid solution by means of a handy ultrasonic homogenizer, which is easy-to-use and portable, followed by centrifugation. Reversed-phase HPLC was performed on a C₄ column, with 1.25 mmol L⁻¹ succinic acid solution as mobile phase, and identification was by means of a photodiode-array detector. Separation of the analytes was achieved in less than 8 min. Significant linearity was established over the concentration range of 0.1–1.0 μg mL⁻¹ for both target compounds (r>0.99,P<0.01). Average recoveries of OTC and SDD (each spiked at 0.1–1.0 μg mL⁻¹) were ≥88.8, and inter- and intra-assay variability was ≤2.8%. The total time required for analysis of one sample was <20 min. The limits of quantitation of the method (μg mL⁻¹ in milk) were 0.044 for OTC and 0.023 for SDD. No organic solvent was used at any stage of the analysis.     

Particle formation mechanism and kinetic model of ultrasonically initiated emulsion polymerization

A general kinetic model of particle formation in an ultrasonically initiated emulsion polymerization system is presented. This model takes into account homogeneous, micelle entry, and monomer droplet nucleation mechanism. The effects of the ultrasound in producing free radical, degrading free radical and influencing the fashion of the nucleation are also considered. Moreover, chain transfer to monomer and termination in the aqueous phase, capture of oligomer radicals by particles, and coagulation of particles are also considered. An analytical solution is obtained for the initial particle stage consideration. This model predicts that, if the desorption of radical from particles can be neglected, the concentration of the total radical in the aqueous phase is directly proportional to the cavitation concentration. Model predictions are in good agreement with experimental data obtained from the literature.     

The extraction,antioxidant and against β-amyloid induced toxicity of polyphenols from Alsophila spinulosa leaves

Alsophila spinulosa is a tree-like fern, and many evidences suggested that plant polyphenols had the potential therapeutic for Alzheimer s disease (AD). Herein, polyphenols (ASP) was isolated from A. spinulosa leaves and its major constituent were isoorientin and vitexin. ASP displayed excellent antioxidant activity and obvious anti-lipid peroxidation capacity in vitro. ASP improved the survival rate of C. elegans under high temperature by enhancing the antioxidant enzymes activities and decreasing the lipid peroxidation level. Moreover, ASP alleviated β-amyloid (Aβ) induced paralysis and reduced Aβ deposition, decreased reactive oxygen species (ROS) accumulation and improved the level of skn-1 mRNA. In addition, ASP decreased the levels of pdk-1 and akt-1 mRNA in P13K/AKT signaling pathway. In conclusion, ASP may be a potential ingredient for the alleviation of AD.     

Novel polyester/SiO2 nanocomposite membranes: Synthesis,properties and morphological studies

In this paper, a new type of soluble polyester/silica (PE/SiO₂) hybrid was prepared by the ultrasonic irradiation process. The coupling agent γ-glycidyloxypropyltrimethoxysilane (GOTMS) was chosen to enhance the compatibility between the polyester (PE) and silica (SiO₂). Furthermore, the effects of the coupling agent on the morphologies and properties of the PE/SiO₂ hybrids were investigated using UV-vis and FT-IR spectroscopies and FE-SEM. The densities and solubilities of the PE/SiO₂ hybrids were also measured. The results show that the size of the silica particle was markedly reduced by the introduction of the coupling agent, which made the PE/SiO₂ hybrid films become transparent. Furthermore, thermal stability, residual solvent in the membrane film and structural ruination of membranes were analyzed by thermal gravimetric analysis (TGA). The effects of SiO₂ nanoparticles on the glass transition temperature (T_g) of the prepared nanocomposites were studied by differential scanning calorimetry (DSC). Moreover, their mechanical properties were also characterized. It can be observed that the Young's moduli (E) of the hybrid films increase linearly with the silica content. The results obtained from gas permeation experiments with a constant pressure setup showed that adding SiO₂ nanoparticles to the polymeric membrane structure increased the permeability of the membranes.     

Distorted wave response of ultrasonic annular stator incorporating non-uniform geometry

The traveling wave ultrasonic stator is normally fabricated with teeth. The tooth geometry improves the driving speed, but it creates natural frequency splitting and mode contamination, especially a distorted traveling wave. A dynamic model of a stepped-plate periodic stator is developed to examine the distortion. The stator is treated as an annular supported by a thin mid plate, and the support stiffness is formulated by using equivalent energy principle. The effects of the tooth and mid plate on the natural frequency and vibration mode are examined by using the perturbation method. The rules governing the frequency splitting, frequency perturbation as well as mode contamination are also identified. The traveling wave response and elliptical trace on stator surface are obtained by using the mode superposition method and they are proved to be distorted due to the tooth geometry. The response at the repeated doublets becomes coupled forward and backward traveling waves, but that at the split doublets becomes coupled forward traveling, standing and backward traveling waves. The results indicate that the tooth mass instead of the stiffness decreases the vibration amplitude and driving speed of the dominant wave, but their effects are different at the repeated and split doublets. Inspection of the model implies that the distortion can be suppressed by using a suitable combination of the wavenumber, tooth count, tooth height and occupying fraction. Numerical calculations are carried out to demonstrate the tooth geometry effect on the transient waveform, driving speed and elliptical trace. The optimization of the tooth geometry that can help achieve a purer traveling wave is discussed.     

Effect of ultrasound on the synthesis of low-modulus zeolites from a metakaolin

It was studied the effect of ultrasonic processing (22 kHz) of the aqueous suspension of metakaolin, sodium hydroxide and alumina with a molar ratio 2Al₂Si₂O₇:12NaOH:2Al₂O₃ on the low-modulus zeolite synthesis processes. To investigate the XRD, SEM, IR, EDS had been used. It was shown that after ultrasonic processing, sodium aluminates are formed, what leads to a change in process of further synthesis. It was found that without ultrasonic processing on the stage of thermal treatment at 650 °C, SOD zeolite (|Na₆|[Al₆Si₆O₂₄]) and sodium aluminosilicate (Na₆Al₄Si₄O₁₇) are synthesized. In the sample after ultrasound during thermal treatment, only sodium aluminosilicates of cubic syngony (Na₆Al₄Si₄O₁₇ and Na₈Al₄Si₄O₁₈) are formed. It was demonstrated that sodium aluminosilicates are precursors for the formation of LTA zeolite (|Na₁₂|[Al₁₂Si₁₂O₄₈]). As a result zeolitization of sodium aluminosilicates after the hydrothermal crystallization in alkaline solution, the sonicated sample contained 97 wt% LTA. Without ultrasonic processing, the product of synthesis contained 50 wt% SOD and 40 wt% LTA.