Specific Fluorescence Probe for Direct Recognition of Dimethoate Using Molecularly Imprinting Polymer on ZnO Quantum Dots

ZnO quantum dots (QDs) based molecularly imprinting polymer (MIP)-coated composite was described for specific detection of the dimethoate (DM) as a template. The MIP was synthesized by simple self-assembly of 3-aminopropyl triethoxysilane (APTES) monomers and tetraethyl ortho-silicate as cross linking agent in the presence of template molecules. The used imprinting course can improve the tendency of the prepared QDs toward the DM template molecules. The MIP-coated ZnO QDs showed a strong fluorescence emission which undergoes a quenching effect in the presence of DM. So, a selective probe could be designed based on these composites to recognize DM in water samples. Under optimized experimental conditions, a linear relationship between the emission intensity of MIP-coated ZnO QDs and concentration of DM, in the range of 0.02–3.2 mg L^?1 with a detection limit of 0.006 mg L^?1. Combination of high specificity of MIP element and distinct fluorescence features of ZnO QDs provides a sensitive and selective recognizing method for pesticide detection. The developed method was successfully applied for the determination of DM contamination in environmental water samples.     

Perfect quantum excitation energy transport via single edge perturbation in a complete network

We consider quantum excitation energy transport (EET) in a network of two-state nodes in the Markovian approximation by employing the Lindblad formulation. We find that EET from an initial site, where the excitation is inserted to the sink, is generally inefficient due to the inhibition of transport by localization of the excitation wave packet in a symmetric, fully-connected network. We demonstrate that the EET efficiency can be significantly increased up to ≈100% by perturbing hopping transport between the initial node and the one connected directly to the sink, while the rate of energy transport is highest at a finite value of the hopping parameter. We also show that prohibiting hopping between the other nodes which are not directly linked to the sink does not improve the efficiency. We show that external dephasing noise in the network plays a constructive role for EET in the presence of localization in the network, while in the absence of localization it reduces the efficiency of EET. We also consider the influence of off-diagonal disorder in the hopping parameters of the network.     

A Heuristic Insight on End-Point Calculation and a New Phase Interference Parameter in Two-Phase Relative Permeability Curves for Horizontal Fracture Flow

Relative permeability curves of two-phase flow in a fracture have been a subject of study in recent years. The importance of these curves have been widely observed in multidisciplines, such as water subsurface resources, geothermal energy and underground hydrocarbon resources, especially fractured oil and gas reservoirs. Extensive experimental studies have been cited alongside the numerical studies in this area. However, simple analytical and practical solutions are still attractive. In the current study, wettability effects and phase interference explicitly were tried to be implemented in a simple analytical formula. The wettability effects are represented by residual saturations which resulted in direct calculation of relative permeability end points. In addition, the phase interference part affected the shape of the curves that allowed to quantify the degree of phase interference from no phase interference, assigned as zero, to ultimate phase interference, assigned as infinity. The results were compared and validated with the available experimental data in the literature. The proposed formulation is applicable for both smooth and rough fracture assemblies.     

Biomimetic Bottlebrush Polymer Coatings for Fabrication of Ultralow Fouling Surfaces

Demand for long‐lasting antifouling surfaces has steered the development of accessible, novel, biocompatible and environmentally friendly materials. Inspired by lubricin (LUB), a component of mammalian synovial fluid with excellent antifouling properties, three block polymers offering stability, efficacy, and ease of use were designed. The bottlebrush‐structured polymers adsorbed strongly on silica surfaces in less than 10 minutes by a simple drop casting or online exposure method and were extremely stable in high‐salinity solutions and across a wide pH range. Antifouling properties against proteins and bacteria were evaluated with different techniques and ultralow fouling properties demonstrated. With serum albumin and lysozyme adsorption <0.2 ng cm^?2, the polymers were 50 and 25 times more effective than LUB and known ultralow fouling coatings. The antifouling properties were also tested under MPa compression pressures by direct force measurements using surface forces apparatus. The findings suggest that these polymers are among the most robust and efficient antifouling agents currently known.     

A green non-acid-catalyzed process for direct N=N–C group formation: comprehensive study,modeling, and optimization

The aim of this work is to introduce, model, and optimize a new non-acid-catalyzed system for a direct N\(=\)N–C bond formation. By reacting naphthols or phenol with anilines in the presence of the sodium nitrite as nitrosonium (\(\hbox {NO}^{+})\) source and triethylammonium acetate (TEAA), a N\(=\)N–C group can be formed in non-acid media. Modeling and optimization of the reaction conditions were investigated by response surface method. Sodium nitrite, TEAA, and water were chosen as variables, and reaction yield was also monitored. Analysis of variance indicates that a second-order polynomial model with F value of 35.7, a P value of 0.0001, and regression coefficient of 0.93 is able to predict the response. Based on the model, the optimum process conditions were introduced as 2.2 mmol sodium nitrite, 2.2 mL of TEAA, and 0.5 mL \(\hbox {H}_{2}\hbox {O}\) at room temperature. A quadratic (second-order) polynomial model, by analysis of variance, was able to predict the response for a direct N=N–C group formation. Predicted response values were in good agreement with the experimental values. Electrochemistry studies were done to introduce new Michael acceptor moieties. Broad scope, high yields, short reaction time, and mild conditions are some advantages of the presented method.     

Application of Monte Carlo simulation method to polymerization kinetics over Ziegler–Natta catalysts

In the current work, the Monte Carlo simulation method was applied to ethylene polymerization over Ziegler–Natta catalysts. As expected, polymerization over each center of a Ziegler–Natta catalyst leads to a polymer having a Schultz–Flory molecular weight distribution. Notwithstanding, the total molecular weight distribution obtained by all catalyst centers together is at least twice as broad as that of each center. As another interesting finding, the introduction of hydrogen to the reaction deactivates the catalyst active centers and thereby reduces the catalyst activity. Nevertheless, it does not mainly affect the polymerization kinetics. In addition, the polymer molecular weight falls as hydrogen is added to the reaction since it acts as a strong transfer agent. The same effect is seen when cocatalyst concentration increases. Hydrogen also widens the polymer molecular weight distribution. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 45–56, 2009     

Multivariate optimization of hydrodistillation-headspace solvent microextraction of thymol and carvacrol from Thymus transcaspicus

In this paper multivariate response surface methodology (RSM) has been used for the optimization of hydrodistillation-headspace solvent microextraction (HD-HSME) of thymol and carvacrol in Thymus transcaspicus. Quantitative determination of compounds of interest was performed simultaneously using gas chromatography coupled with flame ionization detector (GC-FID). Parameters affecting the extraction efficiency were assessed and the optimized values were 5 min, 2 μL and 3 min for the extraction time, micro-drop volume and cooling time after extraction, respectively. The amounts of analyte extracted increased with plant weight. The calibration curves were linear in the ranges of 6.25-81.25 and 1.25-87.50 mg L⁻¹ for thymol and carvacrol, respectively. Limit of detection (LOD) for thymol and carvacrol was 1.87 and 0.23 mg L⁻¹, respectively. Within-day and between-day precisions for both analytes were calculated in three different concentrations and recoveries obtained were in the range of 89-101% and 95-116% for thymol and carvacrol, respectively.     

Polypyrrole–montmorillonite nanocomposite as sorbent for solid‐phase microextraction of phenolic compounds in water

A fiber‐coated polypyrrole–montmorillonite nanocomposite was prepared for solid‐phase microextraction. The fiber coating can be prepared easily; it is mechanically stable and exhibits relatively high thermal stability. The prepared fiber was evaluated for the extraction of some phenolic compounds from aqueous sample solutions by gas chromatography–mass spectrometry. The effects of the extraction and desorption parameters including extraction time, extraction temperature, stirring rate, ionic strength, pH and desorption temperature and time have been studied. At optimum conditions, the repeatability for one fiber (n = 5), expressed as % relative standard deviation was between 6.5 and 7.8% for the phenolic compounds. The detection limits for the studied phenolic compounds were between 0.05–1.3 ng/mL. The developed method offers the advantage of being simple to use, with shorter analysis time, lower cost, thermal stability of the fibers, and high relative recovery in comparison to conventional methods of analysis.     

Kinetic spectrophotometric method for the determination of trace amounts of oxalate by an activation effect.

A new, simple and inexpensive kinetic catalytic spectrophotometric method for the determination of oxalate is described. The method is based on an activation effect of oxalate on a catalytic effect of iron(II) on the oxidation of iodide by bromate. The reaction is monitored by measuring the absorbance of triiodide ion at lambda max = 352 nm. A calibration graph was obtained from 0.10 - 7.0 microg cm(-3) of oxalate with a detection limit of 0.080 microg cm(-3). The standard deviations for ten replicate determinations of 0.50, 1.0 and 5.0 microg cm(-3) of oxalate were 4.0, 2.6 and 1.8%, respectively. The applicability of the method was demonstrated by the determination of oxalate ion in real samples.     

Application of H-point standard addition method and partial least squares to the simultaneous kinetic-potentiometric determination of hydrazine and phenylhydrazine

Simultaneous determination of hydrazine (HZ) and phenylhydrazine (PHZ) by H-point standard addition method (HPSAM) and partial least squares (PLS) regression was carried out based on kinetic data from novel potentiometry methods. The rate of chloride ion production in the reaction of HZ and PHZ with N-chlorosuccinimide (NCS) was monitored by a chloride ion-selective electrode. The experimental data show the good ability of ion-selective electrodes (ISEs) as detectors not only for the direct determination of chloride ion but also for simultaneous kinetic-potentiometric analysis using HPSAM and PLS methods. The methods are based on the differences observed in the production rate of chloride ions. The results show that simultaneous determination of HZ and PHZ can be performed in concentration ranges of 0.5 - 20.0 and 0.8 - 25.0 microg mL(-1), respectively. The total relative standard error for applying the PLS method to 8 synthetic samples in the concentration ranges of 1.0 - 16.0 microg mL(-1) for HZ and 2.0 - 16.0 microg mL(-1) for PHZ was 3.96. In order for the selectivity of the method to be assessed, we evaluated the effects of certain foreign ions upon the reaction rate and assessed the selectivity of the method. Both methods (PLS and HPSAM) were evaluated using a set of synthetic sample mixtures and then applied for simultaneous determination of HZ and PHZ in water samples.