Electrophoretically deposited sulfonated poly(styrene-co-divinylbenzene) on a screw for microextraction of cationic dyes from aqueous solutions

In the present work, a novel solid-phase microextraction on a screw (MES) was employed to extract cationic dyes (malachite green, methylene blue, and rhodamine B) from food samples and fish breeding pool water. The sulfonated poly(styrene-co-divinylbenzene) was electrophoretically deposited on the surface of the grooves of a screw. Then the screw was placed inside a silicon tube as a holder to create a channel to run a test solution through it. The extracted dyes on the coated screw were eluted by a suitable eluent. High-performance liquid chromatography with an ultraviolet/visible detector was utilized for the separation and analysis of the analytes. The effective parameters of the analyte extraction efficiency were optimized. Under optimum conditions, the limits of detection were 0.15 μg/L, and calibration curves were linear in the range of 0.50–250.00 μg/L, with coefficients of determination > 0.989 for all studied dyes. The relative standard deviations of intra and inter-day (n = 3) were in the range of 2.8%–7.0% and 7.0%–9.5%, respectively. The MES was applied as a simple and repeatable method with acceptable relative recoveries (82.0%–103.0%) for the determination of cationic dyes in grape nectar, ice pop, jelly powder, and fish breeding pool water.     

A new effective on chip electromembrane extraction coupled with high performance liquid chromatography for enhancement of extraction efficiency

In the present research, an effective on chip electromembrane extraction (CEME) coupled with high performance liquid chromatography was presented for analysis of nortriptyline (NOR) and amitriptyline (AMI) as basic model analytes from urine samples. The chip consists of two polymethyl methacrylate (PMMA) parts with two craved microfluidic channels in each part. These channels were used as flow path for the sample solution and a thin compartment for the acceptor phase. A porous polypropylene sheet membrane impregnated with an organic solvent was placed between two parts of chip device to separate the channels. Two platinum electrodes were mounted at the bottom of these channels that were connected to a power supply providing the electrical driving force for migration of ionized analytes from sample solution through the porous sheet membrane into the acceptor phase. This new setup provides effective and reproducible extractions with low volume of sample solution. Efficient parameters on CEME of the model analytes were optimized using one variable at a time method. Under the optimized conditions, the calibration curve was linear in the range of 10.0–500 μg L⁻¹ with coefficient of determination (r²) more than 0.9902. The relative standard deviations (RSDs %) for extraction and determination of the analytes were less than 6.8% based on six replicate measurements. LODs less than 4.0 μg L⁻¹ were obtained for both of the model analytes. The preconcentration factors higher than 17.0-fold were obtained. The results demonstrated that CEME would be used efficiently for extraction and determination of AMI and NOR from urine samples.     

Nanostructured polypyrrole for automated and electrochemically controlled in-tube solid-phase microextraction of cationic nitrogen compounds

The authors describe an efficient method for microextraction and preconcentration of trace quantities of cationic nitrogen compounds, specifically of anilines. It relies on a combination of electrochemically controlled solid-phase microextraction and on-line in-tube solid-phase microextraction (SPME) using polypyrrole-coated capillaries. Nanostructured polypyrrole was electrically deposited on the inner surface of a stainless steel tube and used as the extraction phase. It also acts as a polypyrrole electrode that was used as a cation exchanger, and a platinum electrode that was used as the anode. The solution to be extracted is passed over the inner surface of the polypyrrole electrode, upon which cations are extracted by applying a negative potential under flow conditions. This method represents an ideal technique for SPME of protonated anilines because it is fast, easily automated, solvent-free, and inexpensive. Under optimal conditions, the limits of detection are in the 0.10–0.30 μg L‾¹ range. The method works in the 0.10 to 300 μg L‾¹ concentration range. The inter- and intra-assay precisions (RSD%; for n = 3) range from 5.1 to 7.5 % and from 4.7 to 6.0 % at the concentration levels of 2, 10 and 20 μg L‾¹, respectively. The EC-in-tube SPME method was successfully applied to the analysis of methyl-, 4-chloro-, 3-chloro and 3,4-dichloroanilines in (spiked) water samples.

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SMFs-supported Pd nanocatalysts in selective acetylene hydrogenation:Pore structure-dependent deactivation mechanism

In the present study,CNFs,ZnO and Al2O3 were deposited on the SMFs panels to investigate the deactivation mechanism of Pd-based catalysts in selective acetylene hydrogenation reaction.The examined supports were characterized by SEM,NH3-TPD and N2adsorption-desorption isotherms to indicate their intrinsic characteristics.Furthermore,in order to understand the mechanism of deactivation,the resulted green oil was characterized using FTIR and SIM DIS.FTIR results confirmed the presence of more unsaturated constituents and then,more branched hydrocarbons formed upon the reaction over alumina-supported catalyst in comparison with the ones supported on CNFs and ZnO,which in turn,could block the pores mouths.Besides the limited hydrogen transfer,N2 adsorption-desorption isotherms results supported that the lowest pore diameters of Al2O3/SMFs close to the surface led to fast deactivation,compared with the other catalysts,especially at higher temperatures.     

SMFs-supported Pd nanocatalysts in selective acetylene hydrogenation: Pore structure-dependent deactivation mechanism

In the present study, CNFs, ZnO and Al₂O₃ were deposited on the SMFs panels to investigate the deactivation mechanism of Pd-based catalysts in selective acetylene hydrogenation reaction. The examined supports were characterized by SEM, NH₃-TPD and N₂ adsorption-desorption isotherms to indicate their intrinsic characteristics. Furthermore, in order to understand the mechanism of deactivation, the resulted green oil was characterized using FTIR and SIM DIS. FTIR results confirmed the presence of more unsaturated constituents and then, more branched hydrocarbons formed upon the reaction over alumina-supported catalyst in comparison with the ones supported on CNFs and ZnO, which in turn, could block the pores mouths. Besides the limited hydrogen transfer, N₂ adsorption-desorption isotherms results supported that the lowest pore diameters of Al₂O₃/SMFs close to the surface led to fast deactivation, compared with the other catalysts, especially at higher temperatures.     

Effects of nitrogen-containing functional groups of reduced graphene oxide as a support for Pd in selective hydrogenation of cinnamaldehyde

Research on Chemical Intermediates - The importance of electronic and chemical properties of nitrogen-doped reduced graphene oxide (NRGO) has attracted more attention in recent years. Various...     

3D Printing in analytical sample preparation

In the last 5 years, additive manufacturing (three‐dimensional printing) has emerged as a highly valuable technology to advance the field of analytical sample preparation. Three‐dimensional printing enabled the cost‐effective and rapid fabrication of devices for sample preparation, especially in flow‐based mode, opening new possibilities for the development of automated analytical methods. Recent advances involve membrane‐based three‐dimensional printed separation devices fabricated by print‐pause‐print and multi‐material three‐dimensional printing, or improved three‐dimensional printed holders for solid‐phase extraction containing sorbent bead packings, extraction disks, fibers, and magnetic particles. Other recent developments rely on the direct three‐dimensional printing of extraction sorbents, the functionalization of commercial three‐dimensional printable resins, or the coating of three‐dimensional printed devices with functional micro/nanomaterials. In addition, improved devices for liquid–liquid extraction such as extraction chambers, or phase separators are opening new possibilities for analytical method development combined with high‐performance liquid chromatography. The present review outlines the current state‐of‐the‐art of three‐dimensional printing in analytical sample preparation.     

Optical and electrochemical DNA nanobiosensors

In the past two decades, nanoscale advanced materials have been explored for biosensing molecules, so new horizons have opened up for identifying and quantifying biomolecules, and possible early diagnosis of diseases.DNA nanobiosensors show promise. This article provides an overview on their optical and electrochemical aspects. We discuss recent progress in this field, describing basic concepts of molecular beacons and quantum dots as optical nano-imaging systems. Also, carbon nanotubes provide a platform for development and advancement of electrochemical DNA nanobiosensors, which are increasingly being implemented as robust tools for detection in biomedical sciences.     

Acid‐induced homogenous liquid‐phase microextraction: Application of medium‐chain carboxylic acid as extraction phase

In this research, a novel homogeneous liquid‐phase microextraction method was successfully developed based on applying octanoic acid as low‐density extraction solvent. The method was applied for extraction and determination of chlorophenols (CPs) as model compounds. Twelve milliliter of the sample solution was poured into a home‐designed glass vial. Sixty microliter of octanoic acid was solved in water sample by adjusting pH and ionic strength. By rapid addition of 75 μL of concentrated HCl (6 M), a cloudy solution was obtained. Phase separation occurred at 5000 rpm for 5 min. After that, 20 μL of the collected phase (approximately 26 μL) was injected into the HPLC‐UV instrument for analysis. The effect of some parameters such as the volume of concentrated HCl (phase separation reagent), ionic strength, extraction time, centrifugation time, and the volume of extracting phase on the extraction efficiency of the CPs were investigated and optimized. The preconcentration factors in a range of 159–218 were obtained under the optimal conditions. The linear range, detection limits (S/N = 3), and precision (n = 3) were 1– 200, 0.3–0.5 μg/L, and 4.6–5.1%, respectively. Tap water, seawater, and river water samples were successfully analyzed for the existence of CPs using the proposed method and satisfactory results were obtained.