Trends in the bioanalytical applications of microfluidic electrocapture

Downscaled analytical tools for sample preparation have offered benefits such as higher throughput, easier automation and lower sample/reagent consumption. Microfluidic electrocapture, which is a newly developed sample preparation/manipulation system, uses an electric field to trap and separate charged species without using any solid sorbent. The feasibility of using microfluidic electrocapture is reported for separation, clean-up, concentration, microreactions and complexation studies of proteins, peptides and other biologically important biomolecules. The instrumentation and applications of microfluidic electrocapture are reviewed and an overview is provided of future perspectives offered by the current and envisaged platforms.     

Application of QR Decomposition Algorithm for Multivariate Calibration in High Overlapping Systems

An accurate and stable algorithm, QR Decomposition Algorithm (QRDA) is initially presented into the chemistry field. The basic principle of QR Multivariate Calibration Algorithm (QRMCA) is investigated, and the complexes system of sodium tripolyphosphate (STPP), sodium sulfate (SS), and sodium Carbonate (SC) with serious overlapping absorption peaks is analyzed by QRMCA. According to our survey, QRDA can avoid matrix inverting, reduce the orders of matrixes, and speed up the operation of matrices. So, it has bright prospects in chemometrics. The process of the QR Decomposition Algorithm (QRDA) was implemented by an orthogonal and upper triangular matrix decomposition that is robust and convenient. Then it was applied to overcome the problem of overlapping spectra of different components in detergent-washing powder.     

Separation optimization of quercetin,hesperetin and chrysin in honey by micellar liquid chromatography and experimental design

The chemometrics approach was applied for the separation optimization of flavonoid markers (quercetin, hesperetin and chrysin) in honey using micellar liquid chromatography (MLC). The investigated method combines SPE of flavonoids from honey using C₁₈ cartridge and their separation and quantification by micellar liquid chromatography. A two level full factorial design was carried out to evaluate the effect of four experimental factors including concentration of SDS, alkyl chain length of the alcohol used as the organic modifier (N), volume percentage of the organic modifier (V_m) and volume percentage of acetic acid (AcOH) in mobile phase on analytes retention times. Experiments for analytes retention times modeling and optimization of separation were performed according to central composite design. Multiple linear regression method was used for the construction of the best model based on experimental retention times. Pareto optimal method was used to find suitable compatibility between resolution and analysis time of analytes in honey. The optimum mobile phase composition for separation and determination of analytes in honey were [SDS]=0.124 mol/L; 7.8% v/v ethanol and 5.0% v/v AcOH. Limits of detection and linear range of flavonoid markers were 0.0079–0.0126, 0.05–50.0 mg/L, respectively.     

Synthesis and characterization of nanocrystalline α-Al2O3 using Al and Fe2O3 (hematite) through mechanical alloying

In this present work, the synthesis of nanocrystalline α-Al₂O₃ using pure aluminum (Al) and Fe₂O₃ (hematite) as the precursors by mechanical alloying technique has been studied. The formation of α-Al₂O₃ nanocrystallites occurs during the solid-state reaction and through the reduction treatment. Also in this paper, effects of milling time on particle size and the lattice strain nanocrystalline α-Al₂O₃ have been investigated. Obtained powders were evaluated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential thermal analysis (DTA), thermal gravimetric analysis (TGA) and X-ray diffraction (XRD). The obtained results indicated that a reduction reaction was completed after 2 h milling in a planetary mill. The crystallite size of obtained α-alumina (α-Al₂O₃) was in general about 12 nm. Finally, the results showed appropriate homogeneity and dispersion of related nanocrystalline.     

A novel technique based on diffuse reflectance near-infrared spectrometry and back-propagation artificial neural network for estimation of particle size in TiO2 nano particle samples

Determination of particle size is one of the critical parameters in nanotechnology. The relationship between particle size and diffuse reflectance (DR) spectra in near-infrared region has been applied to introduce a method for estimation of particle size. Back-propagation artificial neural network (BP-ANN) as a nonlinear model was applied to estimate average particle size based on near-infrared diffuse reflectance spectra. Thirty five different nano TiO₂ samples with different particle size were analyzed by DR-FTNIR spectrometry and the obtained data were processed by BP-ANN. The network was trained by 30 samples and was evaluated by the remaining 5 samples. In order to establish whether the new method is applicable for estimation of particle size of nano structured samples, the optimized model was applied to analyze 44 nano TiO₂ samples. It was observed that ANN using the back-propagation algorithm is capable of generalization and could correctly predict the average particle size of nano-sized particles.     

Determination of Flavonoid Markers in Honey with SPE and LC using Experimental Design

Determination of flavonoid markers quercetin, hesperetin, and chrysin, found in north Iranian citrus honey samples, was carried out by solid phase extraction (SPE) and isocratic liquid chromatographic separation using central composite design. Optimum conditions for SPE were achieved using 10 mL methanol/water (13:87, v/v, pH = 7) as the washing solvent and 4 mL methanol for elution. Good clean-up and high recovery >90% were observed for all analytes. The use of water/ACN/THF/AcOH (54:36:5:5, v/v) was found to serve as the optimum mobile phase composition and allowed for the separation of analytes from endogenous compounds present in honey. SPE parameters, such as maximum loading capacity and breakthrough volume, were also determined for each analyte. Limit of detection, linear range, recovery, repeatability of retention times, and peak heights were 3.11 × 10⁻⁸–4.44 × 10⁻⁸ g g⁻¹, 0.50–50.0 μg mL⁻¹ (R ² > 0.99), 90.7–96.9%, 3.0–3.6%, and 1.0–2.6%, respectively. Precision of the overall analytical procedure, estimated by five replicate measurements for quercetin, hesperetin and chrysin in citrus honey, as well as the relative standard deviations were 4.3%, 3.8%, and 5.5%, respectively.

     

Synthesis of molecularly imprinted polypyrrole as an adsorbent for solid‐phase extraction of warfarin from human plasma and urine

The aim of this work was to develop a method for the clean‐up and preconcentration of warfarin from biological sample employing a new molecularly imprinted polymer (MIP) as a selective adsorbent for solid‐phase extraction (SPE). This MIP was synthesized using warfarin as a template, pyrrole as a functional monomer and vinyl triethoxysilane as a cross‐linker. The molar ratio of 1:4:20 (template–functional monomer–cross‐linker) showed the best results. Nonimprinted polymers (NIPs) were prepared and treated with the same method, but in the absence of warfarin. The prepared polymer was characterized by Fourier transmission infrared spectrometry and scanning electron microscopy. An adsorption process (SPE) for the removal of warfarin using the fabricated MIPs and NIPs was evaluated under various conditions. Effective parameters on warfarin extraction, for example, type and volume of elution solvent, pH of sample solution, breakthrough volume and maximum loading capacity, were studied. The limits of detection were in the range of 0.0035–0.0050 µg mL^?1. Linearity of the method was determined in the range of 0.0165–10.0000 µg mL^?1 for plasma and 0.0115–10.0000 µg mL^?1 for urine with coefficients of determination (R²) ranging from 0.9975 to 0.9985. The recoveries for plasma and urine samples were >95%. Copyright © 2015 John Wiley & Sons, Ltd.     

Anodic electrodeposition of Ag1− x Cu x O microcrystals

We demonstrate the anodic electrodeposition of copper-doped AgO at high pH using a silver counter-electrode. Precipitates from a mixture of nitrates and NaOH provided source material for the deposition, and application of a moderate anodic voltage (0.9 V) to the substrate led to deposition of crystalline nanoparticles with incorporated copper. Further increase of the NaOH concentration reduced the amount of copper in the crystals, and higher voltages degraded the crystal quality. XRD confirms the underlying structure to be that of AgO, and Auger and energy dispersive x-ray analyses confirm copper concentrations of approximately 3 % in the crystals.