Kinetic study of in situ normal and AGET atom transfer radical copolymerization of n–butyl acrylate and styrene: Effect of nanoclay loading and catalyst concentration

The effect of clay nanolayers and catalyst concentration on the kinetics of atom transfer radical copolymerization of styrene and butyl acrylate initiated by activators generated by electron transfer (AGET initiation system) or an alkyl halide (normal initiation system) was studied. Monomer conversion was studied by attenuated total reflection–Fourier transform infrared spectroscopy, and also proton nuclear magnetic resonance (¹H NMR) spectroscopy was utilized to evaluate the heterogeneity in the composition of poly(styrene‐co‐butyl acrylate) chains. A decrease in the copolymerization rate of styrene and butyl acrylate in the presence of clay platelets was observed since clay layers confine the accessibility of monomer and growing radical chains. Considering the linear first‐order kinetics of the polymerization, successful AGET and normal atom transfer radical polymerization (ATRP) in the presence of clay nanolayers were carried out. Consequently, poly(styrene‐co‐butyl acrylate) chains with narrow molecular weight distribution and low polydispersity indices (1.13–1.15) were obtained. The linearity of ln([M]₀/[M]) versus time and molecular weight distribution against conversion plots indicates that the proportion of propagating radicals is almost constant during the polymerization, which is the result of insignificant contribution of termination and transfer reactions. Controlled synthesis of poly(styrene‐co‐butyl acrylate)/clay is implemented with the diminishing catalyst concentration of copper(I) bromide/N,N,N′,N′′,N′′‐pentamethyl diethylene triamine without affecting the copolymerization rate of normal ATRP. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 789–799, 2012     

New predictor-corrector approach for nonlinear fractional differential equations: error analysis and stability

In this paper, the predictor-corrector approach is used to propose two algorithms for the numerical solution of linear and non-linear fractional differential equations (FDE). The fractional order derivative is taken to be in the sense of Caputo and its properties are used to transform FDE into a Volterra-type integral equation. Simpson''s 3/8 rule is used to develop new numerical schemes to obtain the approximate solution of the integral equation associated with the given FDE. The error and stability analysis for the two methods are presented. The proposed methods are compared with the ones available in the literature. Numerical simulation is performed to demonstrate the validity and applicability of both the proposed techniques. As an application, the problem of dynamics of the new fractional order non-linear chaotic system introduced by Bhalekar and Daftardar-Gejji is investigated by means of the obtained numerical algorithms.     

Adaptive neural network-based saturated control of robotic exoskeletons

In this paper, novel adaptive neural network (NN) controllers with input saturation are presented for n-link robotic exoskeletons. The controllers consist of a state feedback controller and an output feedback controller. Through utilizing auxiliary dynamics, the controllers provide a new framework for input saturated control of these robotic systems which can feature the global stability for state feedback control. To compensate for the unknown dynamics of the system, adaptive schemes based on NNs are exploited. Furthermore, adaptive robust terms are utilized to deal with unknown external disturbances. Stability studies show that the closed-loop system is globally uniformly ultimately bounded (UUB) with the state feedback controller, where the global property of the NN-based controller is achieved exploiting a smooth switching function and a robust control term. Also, the system is semi-globally UUB with the output feedback controller. Effectiveness of the controllers is validated by simulations and experimental tests.     

Modulated large-pore mesoporous silica as an efficient base catalyst for the Henry reaction

In this study, mesoporous silica materials with tuned pores and surface areas were successfully synthesized by adjusting the amount of applied hexane and controlling the hydrothermal temperature. The synthesized silica materials were then functionalized by an amine group to produce solid base catalysts and be applicable as efficient heterogeneous base catalysts for the Henry reaction. The mesoporous silica catalysts possessing large-pores and surface area expose their active catalytic sites and thereby improve contacts with reactants fulfilling the reactions expeditiously in comparison with solid base catalysts possessing small-pores and surface area. The results indicated that the yield of the products is significantly dependent on the structure of the applied solid base catalysts. The modulated large-pore solid base catalysts presented high catalytic activity in Henry reactions and could be reused for five consecutive cycles.     

Simultaneous extraction of acidic and basic drugs via on-chip electromembrane extraction

In the present work, a on-chip electromembrane extraction (CEME) was designed and employed for simultaneous extraction of mefenamic acid (MEF) and diclofenac (DIC), as acidic model analytes, and betaxolol (BET), as a basic model analyte, followed by HPLC-UV. The CEME consists of two polymethyl methacrylate (PMMA) parts which each part consists of two separated microfluidic channels. A polypropylene sheet membrane impregnated with an organic solvent was sandwiched between the parts. One of the parts was used as the flow path for the sample solution and the other one as holder for the acceptor phases. The separated microfluidic channels of the sample solution part were connected to each other using a small piece of a capillary tube and the sample solution was pumped through them by means of a micro-syringe pump. However, the acceptor phases of the acidic and basic analytes were separately kept stagnant in the two microfluidic channels during the extraction process. A d.c. potential was applied for migration of the analytes from sample solution through the organic membrane into the acceptor phases. All effective variables on the extraction efficiency of the analytes were optimized. Under the optimized conditions, preconcentration factors higher than 15 were achieved and the calibration curves were linear in the range of 10–500 μg L⁻¹ (r² > 0.9982). RSD% values (n = 4) and LODs were less than 7.1% and 5.0 μg L⁻¹. The results demonstrated that CEME could efficiently be used for the simultaneous analysis of acidic and basic analytes in biological samples.     

Enhancing effects of nanoparticles on polymer-OLED performances

We have previously reported that the silane coating of magnetic nanoparticles (MNPs) of maghemite phase could be used to protect iron oxide cores during plasma heat treatment, and even help to reduce their phase to magnetite with higher magnetization. In this work, an additional layer of an electrically conductive polypyrrole was added on top of the silane-coated MNPs, producing core?Cshell particles with sizes ranging from 150 to 500?nm. A microwave plasma heat treatment was used to convert the amorphous, already-conductive polypyrrole coatings into a more electrically conductive graphitic structure, while simultaneously reducing the iron oxide phase to magnetite. The treatment produced core?Cshell particles with better microwave absorption properties over the frequency of 1?C18?GHz, with a maximum reflection loss (absorption) of these MNPs at ?37?dB at 10.3?GHz for samples containing 70?wt% of plasma-treated core?Cshell nanoparticles embedded in wax. By comparison, the maximum absorption for the same amount of untreated nanoparticles was only ?18?dB at 7.5?GHz. The improved electromagnetic wave absorption properties were due to higher electrical conductivity of the more ordered, graphitic-like polypyrrole shell structures. This relatively simple protocol could thus be used to synthesize highly magnetic and conductive nanocomposites for electromagnetic interference shielding applications, particularly at the high frequency range.     

On Holomorphic Hypercomplex Connections

The main purpose of this paper is to study some properties of integrable commutative hypercomplex structures endowed with a holomorphic torsion-free affine connection whose curvature tensor satisfies the purity condition with respect to the covariantly constant structure affinors.