Electrochemically controlled in-tube solid phase microextraction

We report a new in-tube solid phase microextraction approach named electrochemically controlled in-tube solid phase microextraction (EC in-tube SPME). This approach, which combined electrochemistry and in-tube SPME, led to decrease in total analysis time and increase in sensitivity. At first, pyrrole was elctropolymerized on the inner surface of a stainless steel tube. Then, the polypyrrole (PPy)-coated in-tube SPME was coupled on-line to liquid chromatography (HPLC) to achieve automated in-tube SPME–HPLC analysis. After the completion of EC-in-tube SPME–HPLC setup, the PPy-coated tube was used as working electrode for uptake of diclofenac as target analyte. Extraction ability of the tube in presence and in absence of applied electrical field was investigated. It was found that, under the same extraction conditions, the extraction efficiency could be greatly enhanced by using the constant potential. Important factors are also optimized. The detection limit (S/N = 3) and precision were 0.1 μg L⁻¹ and 4.4%, respectively.     

In-tube magnetic solid phase microextraction of some fluoroquinolones based on the use of sodium dodecyl sulfate coated Fe3O4 nanoparticles packed tube

In-tube magnetic solid phase microextraction (in-tube MSPME) of fluoroquinolones from water and urine samples based on the use of sodium dodecyl sulfate (SDS) coated Fe₃O₄ nanoparticles packed tube has been reported. After the preparation of Fe₃O₄ nanoparticles (NPs) by a batch synthesis, these NPs were introduced into a stainless steel tube by a syringe and then a strong magnet was placed around the tube, so that the Fe₃O₄ NPs were remained in the tube and the tube was used in the in-tube SPME-HPLC/UV for the analysis of fluoroquinolones in water and urine samples. Plackett–Burman design was employed for screening the variables significantly affecting the extraction efficiency. Then, the significant factors were more investigated by Box–Behnken design. Calibration curves were linear (R² > 0.990) in the range of 0.1–1000 μg L⁻¹ for ciprofloxacin (CIP) and 0.5–500 μg L⁻¹ for enrofloxacin (ENR) and ofloxacin (OFL), respectively. LODs for all studied fluoroquinolones ranged from 0.01 to 0.05 μg L⁻¹. The main advantages of this method were rapid and easy automation and analysis, short extraction time, high sensitivity, possibility of fully sorbent collection after analysis, wide linear range and no need to organic solvents in extraction.     

Functionalization of Graphene Oxide with 3‐Mercaptopropyltrimethoxysilane and Its Electrocatalytic Activity in Aqueous Medium

In this work, a highly dispersed graphene oxide (GO) was successfully functionalized with 3‐mercaptopropyltrimethoxysilane (MPTS) molecule by silanization method. The chemically generated GO and MPTS functionalized GO (MPTS‐GO) were structurally characterized by thermogravimetric analysis (TGA), X‐ray diffraction analysis (XRD), scanning electron microscope (SEM), energy dispersive X‐ray (EDAX), fourier transform infrared spectroscopy (FT‐IR) and ultraviolet visible spectroscopy (UV‐Vis) techniques. The MPTS‐GO is highly suspensable in water. The thermal and conductivity results for MPTS‐GO are significantly increased compared to GO. Moreover, glassy carbon electrode modified with MPTS‐GO hybrid (MPTS‐GO/GCE) was prepared by casting of the MPTS‐GO solution on GCE. The MPTS‐GO/GCE showed an excellent electrocatalytic activity towards methionine (Met). This was understood from the observed less positive oxidation potential and higher oxidation current when compared to bare GC electrode. The MPTS‐GO has excellent electrocatalytic activity, making it an ideal candidate for sensor applications.     

Synthesis and characterisation of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) Zr(IV) monothiophosphate composite cation exchanger: analytical application in the selective separation of lead metal ions

In this study, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) zirconium(IV) monothiophosphate composite cation exchanger was prepared by sol–gel precipitation method. The presence of sulphur in the cation exchanger enhances affinity towards the heavy metal ions which can improve the selectivity of the material. The selectivity studies showed that the material is selective towards Pb(II) ions. To characterise the material, several physicochemical properties were also studied which includes X-ray, scanning electron microscopy and transmission electron microscopy studies. The ion-exchange behaviour of this cation exchanger was studied by using some of the selected properties like ion-exhange capacity for various metal ions, elution, effect of eluent concentration, thermal effect on ion-exchange capacity (IEC). The results of IEC and physicochemical properties revealed that the material is nanocomposite, crystalline, chemically, mechanically and thermally stable. The analytical ability of this cation exchanger was demonstrated in binary separation of Pb(II) ions from a mixture of other metal ions. The recovery is qualitative and the separations are reproducible.     

(Cu/Ni)–Al layered double hydroxides@Fe3O4 as efficient magnetic nanocomposite photocatalyst for visible-light degradation of methylene blue

Research on Chemical Intermediates - A new magnetic nanocomposite based on layered double hydroxides (LDHs) was synthesized by coprecipitation of (Cu/Ni)–Al LDHs and nano-Fe3O4 and...     

In situ forming PLGA implant for 90 days controlled release of leuprolide acetate for treatment of prostate cancer

In prostate cancer, hormone therapy via leuprolide acetate drug (LUP) is used to lower the level of testosterone down to castration level to effectively control the development of prostate cancer. The objective of this study was to evaluate the effective parameters in degradation and controlled release of an injectable in situ formed polymeric implant, loaded with leuprolide acetate, in order to achieve an optimum formulation for sustained drug release for 90 days with minimum burst release. The main problem associating with such implants is their high burst release. Designing an injectable implant with sustained and minimum burst release has thus become an attractive challenge in drug delivery field. Effects of type of poly(lactic‐co‐glycolic acid) 75:25 copolymers (RG752, RG756) and addition of nano‐hydroxyapatite (HA) particles on degradation rates of the implants and release profiles were examined in vitro and in vivo in a rabbit animal model. Results showed that implants containing polymers with higher molecular weights had significantly lower weight loss and molecular weight reduction. Adding nanoparticles of hydroxyapatite into poly(lactic‐co‐glycolic acid) implants caused further reduction in degradation rates, leading to a more sustained drug release in vivo, with reduced burst release. Different conventional kinetic models were applied to drug release and degradation data. The degradation data fit well to the first‐order degradation model. Higuchi model was the best kinetic release model fitted to the experimental in vitro release data. This study led to an optimum formulation (RG756:RG752 3:1 + 5% HA) with sustained leuprolide release and testosterone suppression over a 90‐day period with significant decrease of burst release phase (50%, p < 0.001) compared with the conventional Eligard formulation. The histopathology test showed that the formulated implant had no effects of toxicity or tissue necrosis in organs of the animal model. Copyright © 2017 John Wiley & Sons, Ltd.     

Positive solutions for nonlinear fractional differential equations

Positivity - We study the existence and uniqueness of positive solutions of the nonlinear fractional differential equation $$\begin{aligned} \left\{ \begin{array}{l} ^{C}D^{\alpha }x\left( t\right)...     

Unirationality of the Hurwitz space $$\varvec{\mathcal {H}_{9,8}}$$

In this paper we prove that the Hurwitz space \(\mathcal {H}_{9,8}\), which parameterizes 8-sheeted covers of \({\mathbb P }^1\) by curves of genus 9, is unirational. Our construction leads to an explicit Macaulay2 code, which will randomly produce a nodal curve of degree 8 of geometric genus 9 with 12 double points and together with a pencil of degree 8.     

Mixed two‐grid finite difference methods for solving one‐dimensional and two‐dimensional Fitzhugh–Nagumo equations

The aim of this paper is to propose mixed two‐grid finite difference methods to obtain the numerical solution of the one‐dimensional and two‐dimensional Fitzhugh–Nagumo equations. The finite difference equations at all interior grid points form a large‐sparse linear system, which needs to be solved efficiently. The solution cost of this sparse linear system usually dominates the total cost of solving the discretized partial differential equation. The proposed method is based on applying a family of finite difference methods for discretizing the spatial and time derivatives. The obtained system has been solved by two‐grid method, where the two‐grid method is used for solving the large‐sparse linear systems. Also, in the proposed method, the spectral radius with local Fourier analysis is calculated for different values of h and Δt. The numerical examples show the efficiency of this algorithm for solving the one‐dimensional and two‐dimensional Fitzhugh–Nagumo equations. Copyright © 2016 John Wiley & Sons, Ltd.