Photocatalysed degradation of a herbicide derivative, Dinoterb, in aqueous suspension

The photocatalytic degradation of a herbicide derivative, Dinoterb (1), has been investigated in aqueous micellar solution in the presence of titanium dioxide (TiO₂) and air as a function of irradiation time under a variety of conditions using UV and HPLC analysis techniques. The degradation kinetics was studied under different conditions such as different types of TiO₂, catalyst concentration, substrate concentration and reaction pH in the presence of air. The photocatalyst Degussa P25 was found to be more efficient catalyst as compared to other photocatalysts tested. The model compound was found to degrade more efficiently under neutral pH as compared to acidic and alkaline pH. GC/MS analysis of the irradiated samples indicate the formation of 2-isopropyl-4,6-dinitro-phenol as by-product which has been characterized on the basis of molecular ion and mass fragmentation pattern. A probable pathway for its formation has been proposed.     

Development of a new microextraction method based on a dynamic single drop in a narrow-bore tube: application in extraction and preconcentration of some organic pollutants in well water and grape juice samples

A novel sample preparation technique, the microextraction method based on a dynamic single drop in a narrow-bore tube, coupled with gas chromatography-flame ionization detection (GC-FID) is presented in this paper. The most important features of this method are simplicity and high enrichment factors. In this method, a microdrop of an extraction solvent assisted by an air bubble was repeatedly passed through a narrow-bore closed end tube containing aqueous sample. It has been successfully used for the analysis of some pesticides as model analytes in aqueous samples. Parameters affecting the method's performance such as selection of extraction solvent type and volume, number of extractions, volume of aqueous sample (tube length), and salt effect were studied and optimized. Under the optimal conditions, the enrichment factors (EFs) for triazole pesticides were in the range of 141-214 and the limits of detection (LODs) were between 2 and 112 μg L⁻¹. The relative standard deviations (C = 1000 μg L⁻¹, n = 6) were obtained in the range of 2.9-4.5%. The recoveries obtained for the spiked well water and grape juice samples were between 71 and 106%. Low cost, relatively short sample preparation time and less solvent consumption are other advantages of the proposed method.     

Automated flow-based anion-exchange method for high-throughput isolation and real-time monitoring of RuBisCO in plant extracts

In this work, a miniaturized, completely enclosed multisyringe-flow system is proposed for high-throughput purification of RuBisCO from Triticum aestivum extracts. The automated method capitalizes on the uptake of the target protein at 4 °C onto Q-Sepharose Fast Flow strong anion-exchanger packed in a cylindrical microcolumn (105 × 4 mm) followed by a stepwise ionic-strength gradient elution (0-0.8 mol/L NaCl) to eliminate concomitant extract components and retrieve highly purified RuBisCO. The manifold is furnished downstream with a flow-through diode-array UV/vis spectrophotometer for real-time monitoring of the column effluent at the protein-specific wavelength of 280 nm to detect the elution of RuBisCO. Quantitation of RuBisCO and total soluble proteins in the eluate fractions were undertaken using polyacrylamide gel electrophoresis (PAGE) and the spectrophotometric Bradford assay, respectively. A comprehensive investigation of the effect of distinct concentration gradients on the isolation of RuBisCO and experimental conditions (namely, type of resin, column dimensions and mobile-phase flow rate) upon column capacity and analyte breakthrough was effected. The assembled set-up was aimed to critically ascertain the efficiency of preliminary batchwise pre-treatments of crude plant extracts (viz., polyethylenglycol (PEG) precipitation, ammonium sulphate precipitation and sucrose gradient centrifugation) in terms of RuBisCO purification and absolute recovery prior to automated anion-exchange column separation. Under the optimum physical and chemical conditions, the flow-through column system is able to admit crude plant extracts and gives rise to RuBisCO purification yields better than 75%, which might be increased up to 96 ± 9% with a prior PEG fractionation followed by sucrose gradient step.     

Miniaturized optical chemosensor for flow-based assays

A cost-effective, highly compact, and versatile optoelectronic device constructed of two ordinary light emitting diodes compatible with optosensing films has been developed. This fibreless device containing chemoreceptor, semiconductor light source, and detector integrated in a miniaturized flow-through cell of low microliter internal volume works as a complete photometric chemical sensor suitable for detection in flow analysis. The operation of the developed device under nonstationary programmable-flow conditions offered by sequential injection analysis has been demonstrated using Prussian Blue film as a model optical chemoreceptor. The unique spectroelectrochemical properties of the sensing material enable its use for optical sensing of redox species, whereby ascorbic acid and hydrogen peroxide have been chosen as model analytes. The reported SI-sensor system features fast and reproducible determination of both analytes in the submillimolar range of concentrations. The construction concept demonstrated in this work can be easily applied to other kinds of optical sensors based on absorbance sensing films.     

Determination of Imidacloprid in Tomato Grown in Greenhouse Based on Copper(II) Phthalocyanine Modified Carbon Ceramic Electrode by Differential Pulse Voltammetry

A new sol‐gel derived electrocatalytic carbon ceramic electrode was prepared by incorporating copper(II) phthalocyanine (CuPc) in a carbon ceramic network. This electrode was used as a sensitive electrochemical sensor for determination of the insecticide Imidacloprid (1‐(6‐chloro‐3‐pyridylmethyl)‐N‐nitro‐imidazolidin‐2‐ylideneamine) by differential pulse voltammetry (DPV). The resulting modified electrode exhibits a cathodic peak potential shifted positively and an increasing in cathodic peak current in comparison with unmodified electrode. The redox properties of this modified electrode at various pH values and CuPc percentage were investigated. The catalytic current obtained from differential pulse voltammetry is linearly dependent on Imidacloprid concentration over the two linear ranges of 0.67‐17 μM and 17‐93 μM with correlation coefficient of R² = 0.9999 and R² = 0.990, respectively. The detection limit for Imidacloprid was found to be 0.28 μM according to lower linear range. Possible interferences from several common pesticides were also evaluated. The inherent stability, high sensitivity, low detection limit and low cost for each preparation are advantages of this sensor. Determination of Imidacloprid in commercial formulation and residual Imidacloprid in tomato grown in greenhouse (protected cultivation) was also conducted. The results obtained from commercial formulation were completely consistent with those obtained through the standard high‐performance liquid chromatography (HPLC) method.     

A Hexagonally Ordered Nanoporous Silica-Based Fiber Coating for SPME of Polycyclic Aromatic Hydrocarbons from Water Followed by GC–MS

A highly porous fiber coating material was prepared and functionalized with 3-amino propyl triethoxysilane (APTES) on hexagonally ordered nanoporous silica (SBA-15). Applicability of this coating was assessed employing a laboratory made solid-phase microextraction (SPME) device and gas chromatography–mass spectrometry for the simultaneous sampling and determination of trace polycyclic aromatic hydrocarbons (PAHs) from aqueous sample solutions. A one at the time optimization strategy was applied to investigate and optimize important extraction parameters such as extraction temperature, extraction time, ionic strength and sonication time. In the optimum conditions, the relative standard deviations for deionized water, spiked with selected PAHs were between 3.3 and 7.7% (n = 3), and detection limits for the studied compounds were 4.2 and 26.1 pg mL⁻¹. No significant change was observed in the extraction efficiency of the new SPME fiber, over 50 extractions. The proposed method was successfully applied to the extraction and determination of PAHs in the waste water samples.

     

Molecular tectonics: design of enantiomerically pure helical tubular crystals with controlled channel size and orientation

The combination of four enantiomerically pure organic tectons composed of a rigid chiral backbone bearing two terminal pyridyl coordinating sites with ZnSiF(6) behaving as an infinite pillar leads to the formation of tubular 2-D enantiomerically pure helical channels with controlled size and orientation.     

Photoreactive gold(I) macrocycles with diphosphine and trans,trans-muconate ligands

A pair of trans,trans-muconate ligands have been successfully aligned in two novel Au(I) macrocycles by design from phosphino metal precursors that undergo photochemical cycloaddition reactions quantitatively, resulting in the formation of cyclooctadiene derivatives.     

A Legendre-based computational method for solving a class of Itô stochastic delay differential equations

Numerical Algorithms - This paper provides a numerical method for solving a class of Itô stochastic delay differential equations (SDDEs). The method’s novelty is its use of the spectral...