A reversed phase high performance liquid chromatography method for the determination of fumonisins B1 and B2 in food and feed using monolithic column and positive confirmation by liquid chromatography/tandem mass spectrometry

The development of a reversed phase high performance liquid chromatography fluorescence method for the determination of the mycotoxins fumonisin B(1) and fumonisin B(2) by using silica-based monolithic column is described. The samples were first extracted using acetonitrile:water (50:50, v/v) and purified by using a C(18) solid phase extraction-based clean-up column. Then, pre-column derivatization for the analyte using ortho-phthaldialdehyde in the presence of 2-mercaptoethanol was carried out. The developed method involved optimization of mobile phase composition using methanol and phosphate buffer, injection volume, temperature and flow rate. The liquid chromatographic separation was performed using a reversed phase Chromolith(?) RP-18e column (100 mm × 4.6 mm) at 30 °C and eluted with a mobile phase of a mixture of methanol and phosphate buffer pH 3.35 (78:22, v/v) at a flow rate of 1.0 mL min(-1). The fumonisins separation was achieved in about 4 min, compared to approximately 20 min by using a C(18) particle-packed column. The fluorescence excitation and emission were at 335 nm and 440 nm, respectively. The limits of detections were 0.01-0.04 μg g(-1) fumonisin B(1) and fumonisin B(2), respectively. Good recoveries were found for spiked samples (0.1, 0.5, 1.5 μg g(-1) fumonisins B(1) and B(2)), ranging from 84.0 to 106.0% for fumonisin B(1) and from 81.0 to 103.0% for fumonisin B(2). Fifty-three samples were analyzed including 39 food and feeds and 14 inoculated corn and rice. Results show that 12.8% of the food and feed samples were contaminated with fumonisin B(1) (range, 0.01-0.51 μg g(-1)) and fumonisin B(2) (0.05 μg g(-1)). The total fumonisins in these samples however, do not exceed the legal limits established by the European Union of 0.8 μg g(-1). Of the 14 inoculated samples, 57.1% contained fumonisin B(1) (0.16-41.0 μg g(-1)) and fumonisin B(2) (range, 0.22-50.0 μg g(-1)). Positive confirmation of selected samples was carried out using liquid chromatography-tandem mass spectrometry, using triple quadrupole analyzer and operated in the multiple reaction monitoring mode.     

Effect of ionic conductivity of a PAN–PC–LiClO<Subscript>4</Subscript> solid polymeric electrolyte on the performance of a TiO<Subscript>2</Subscript> photoelectrochemical cell

A nanoparticle TiO₂ solid-state photoelectrochemical cell has been fabricated. The effect of ionic conductivity of a solid electrolyte of polyacrylonitrile (PAN)–propylene carbonate (PC)–lithium perchlorate (LiClO₄) on the performance of a photoelectrochemical cell of indium tin oxide (ITO)/TiO₂/PAN–PC–LiClO₄/graphite has been investigated. A nanoparticle TiO₂ film was deposited onto ITO-covered glass substrate by controlled hydrolysis technique. A solid electrolyte of PAN–LiClO₄ with PC plasticizer prepared by solution casting technique was used as a redox couple medium. The room temperature conductivity of the electrolyte was determined by AC impedance spectroscopy technique. A graphite electrode was prepared onto a glass slide by electron beam evaporation technique. The device shows a photovoltaic effect under illumination. The short-circuit current density, J _sc, and open-circuit voltage, V _oc, vary with the conductivity of the electrolyte. The highest J _sc of 2.82 μA cm⁻² and V _oc of 0.56 V were obtained at the conductivity of 4.2 × 10⁻⁴ Scm⁻¹ and at the intensity of 100 mW cm⁻².     

Fabrication of a nanoparticle TiO<Subscript>2</Subscript> photoelectrochemical cell utilizing a solid polymeric electrolyte of PAN–PC–LiClO<Subscript>4</Subscript>

A nanoparticle TiO₂ solid-state photoelectrochemical cell utilizing as a solid electrolyte of poly(acrylonitrile)–propylene–carbonate–lithium perchlorate (PAN–PC–LiClO₄) has been fabricated. The performance of the device has been tested in the dark and under illumination of 100-mW cm⁻² light. A nanoparticle TiO₂ film was deposited onto indium tin oxide-covered glass substrate by controlled hydrolysis technique assisted with spin-coating technique. The average grain size for the TiO₂ film is 76 nm. LiClO₄ salt was used as a redox couple. The room temperature conductivity of the electrolyte is 4.2 × 10⁻⁴ S cm⁻¹. A graphite electrode was prepared onto a glass slide by electron beam evaporation technique. The device shows the rectification property in the dark and shows the photovoltaic effect under illumination. The best J _sc and V _oc of the device were 2.82 μA cm⁻² and V _oc of 0.58 V, respectively, obtained at the conductivity of 4.2 × 10⁻⁴ S cm⁻¹ and intensity of 100 mW cm⁻². The J _sc was improved by about three times by introducing nanoparticle TiO₂ and by using a solid electrolyte of PAN–PC–LiClO₄ replacing PVC–PC–LiClO₄ in the device. The current transport mechanism of the cell is also presented in this paper.     

Film thickness effects on calibrations of a narrowband thermochromic liquid crystal

Thermochromic liquid crystals (TLCs) have been widely employed by researchers in heat transfer and fluid flow communities as a reliable and non-intrusive temperature measurement tool due to their unique optical properties such as birefringence, optical activity, circular dichroism and selective reflection of colours in the visible spectrum as function of temperature. The use of narrowband TLCs are attractive for temperature and heat transfer measurements due to their higher precision in temperature measurements and due to the fact that narrowband TLCs are less affected by variations in illumination-viewing angles and illumination disturbances. Narrowband TLCs have been used with full intensity-matching methods to provide robust image processing for measurements of thermal parameters in transient heat transfer tests. Calibration of narrowband TLCs is necessary in order to obtain the intensity-temperature relationship of the TLCs. Film thickness is one of the factors which affects calibrations of TLCs. In this research, film thicknesses of 10, 20, 30, 40 and 50 μm were investigated on green intensity-based calibrations of R35C1W TLC during heating and cooling. Results showed an increase in magnitude of peak green intensity with increasing film thickness, with a percentage increase of nearly 18% when film thickness increased from 10 to 50 μm. Results also showed an inconsistent shift in temperature at which peak green intensity occurs, with a maximum shift of 0.40 °C, suggesting that film thickness effects may be insignificant for narrowband TLCs compared with wideband TLCs. A theoretical method for estimating the volume of TLC coating required to achieve a desired film thickness has also been described in this paper, based on the surface area and dry solids content of the TLC. The method is easily implemented and applicable for sprayable TLC coatings.     

Lipase immobilized on poly(VP-co-HEMA) hydrogel for esterification reaction

Lipase from Candida rugosa was immobilized by entrapment on poly(N-vinyl-2-pyrrolidone-co-2-hydroxyethyl methacrylate)(poly[VP-co-HEMA]) hydrogel, and divinylbenzene was the crosslinking agent. The immobilized enzymes were used in the esterification reaction of oleic acid and butanol in hexane. The activities of the immobilized enzymes and the leaching ability of the enzyme from the support with respect to the different compositions of the hydrogels were investigated. The thermal, solvent, and storage stability of the immobilized lipases was also determined. Increasing the percentage of composition of VP from 0 to 90, which corresponds to the increase in the hydrophilicity of the hydrogels, increased the activity of the immobilized enzyme. Lipase immobilized on VP(%):HEMA(%) 90∶10 exhibited the highest activity. Lipase immobilized on VP(%):HEMA(%) 50∶50 showed the highest thermal, solvent, storage, and operational stability compared to lipase immobilized on other compositions of hydrogels as well as the native lipase.     

Layering Optimization of the SrFe0.9Ti0.1O3−δ–Ce0.8Sm0.2O1.9 Composite Cathode

Cathode thickness plays a major role in establishing an active area for an oxygen reduction reaction in energy converter devices, such as solid oxide fuel cells. In this work, we prepared SrFe_0.9Ti_0.1O_3−δ–Ce_0.8Sm_0.2O_1.9 composite cathodes with different layers (1×, 3×, 5×, 7×, and 9× layer). The microstructural and electrochemical performance of each cell was then explored through scanning electron microscopy and electrochemical impedance spectroscopy (EIS). EIS analysis showed that the area-specific resistance (ASR) decreased from 0.65 Ωcm² to 0.12 Ωcm² with the increase in the number of layers from a 1× to a 7×. However, the ASR started to slightly increase at the 9× layer to 2.95 Ωcm² due to a higher loss of electrode polarization resulting from insufficient gas diffusion and transport. Therefore, increasing the number of cathode layers could increase the performance of the cathode by enlarging the active area for the reaction up to the threshold point.     

Reductive alkylation of lipase

Candida rugosa lipase was modified via reductive alkylation to increase its hydrophobicity to work better in organic solvents. The free amino group of lysines was alkylated using propionaldehyde with different degrees of modification obtained (49 and 86%). Far-ultraviolet circular dichroism (CD) spectroscopy of the lipase in aqueous solvent showed that such chemical modifications at the enzyme surface caused a loss in secondary and tertiary structure that is attributed to the enzyme unfolding. Using molecular modeling, we propose that in an aqueous environment the loss in protein structure of the modified lipase is owing to disruption of stabilizing salt bridges, particularly of surface lysines. Indeed, molecular modeling and simulation of a salt bridge formed by Lys-75 to Asp-79, in a nonpolar environment, suggests the adoption of a more flexible alkylated lysine that may explain higher lipase activity in organic solvents on alkylation.     

Chemical Constituents of Polyalthia rumphii

Chemistry of Natural Compounds -     

Effect of TiO2 nanostructure morphology on the performance of a photoelectrochemical cell of ITO/TiO2/electrolyte/platinum

The morphology of photovoltaic material is able to influence of the performance of photoelectrochemical cell. Polyvinylpyrrolidone (PVP), cetyltrimethylammonium bromide (CTAB), and hexamethylenetetramine (HMT) surfactant were used to modify the morphology nanostructure of TiO₂ films by a simple technique, namely, liquid phase deposition during their growth process. It was found that the untreated surfactant TiO₂ film produces the morphology with the mixture nanosphere and nanoflower. The film treated with PVP, CTAB, and HMT produce the nanostructure shape of nanoflower, nanowire, and nanorod, respectively. These TiO₂ samples were utilized as photovoltaic materials in a photoelectrochemical cell of ITO/TiO₂/electrolyte/platinum. It was found that the photovoltaic parameters such as short-circuit current density (J _sc), open-circuit voltage (V _oc) and fill factor are influenced by the morphology in terms of shape and particle size of the TiO₂ nanostructure. The cell utilizing the TiO₂ nanowire treated with PVP possesses the highest J _sc and V _oc of 0.100 mAcm^?2 and 0.44 V. The length of the TiO₂ nanowire is 6?±?2 nm, while the cell with the untreated surfactant TiO₂ sample demonstrates the lowest performance. It was also found that the J _sc and V _oc increase with the decrease in the length of the TiO₂ nanostructures. The smallest length of TiO₂ possesses the best interfacial contact at TiO₂/electrolyte containing iodide/triiodide redox couple. Thus, the redox reaction is optimized at this interface.     

Preparation of highly oriented poly-diacetylene films with ion beam irradiation

Abstract

Substituting metallic or rare-earth atoms or removing O in the superconductor YBa₂Cu₃O₇ usually has a strong effect on the superconducting properties. We have made extensive XAFS studies on Co, Fe, Ni, Zn, Gd, and Pr substituted materials including some thin film samples. In nearly all cases, significant distortions are found. Although the lattice constant change is small (< 0.05 Å) the local distortions can be significant larger (～ 0.1 to 0.3 Å). The observed large local distortions of the lattice together with a change in the charge distribution at a site indicate that the interior of the unit cell is easily distorted. The correlation of a strong Tc suppression with large local distortions suggests that distortions of the nearby layers must play a significant role in models for superconductivity in high Tc materials.