Facile one-pot synthesis of novel dicyanoanilines fused to tetrahydro-4H-thiopyran-4-one ring via Et3N/H2O catalyzed pseudo four-component reaction

A facile procedure is developed for one-pot synthesis of a new group of dicyanoanilines. Tetrahydro-4H-thiopyran-4-one, 1, undergoes a pseudo four-component reaction with various aldehydes bearing different groups and two equivalents of malononitrile in aqueous media in the presence of triethylamine (Et₃N). As a result, novel thiopyran-fused dicyanoanilines 4 are formed efficiently in the reaction mixtures in 90–97% yield within 9–12?h mixing at 40°C. Due to the polarity of the medium, products precipitate in the mixture spontaneously allowing for easy purification by recrystallization avoiding cumbersome chromatographic separations. Characterization of the products was performed by spectroscopic methods and, in one case, was further supported by X-ray crystallographic experiments.     

Preparation of immunomagnetic beads coupled with a rhodamine hydrazine immunosensor for the detection of Mycobacterium avium subspecies paratuberculosis in bovine feces,milk, and colostrum

The aim of this study was to develop and evaluate a method for detecting Mycobacterium avium ssp. paratuberculosis (MAP) bacteria in bovine fecal, milk, and colostrum samples using immunomagnetic beads (IMB) and a rhodamine hydrazone immunosensor. Immunomagnetic beads were prepared by using purified antibodies from hyperimmunized sera that were coupled to Fe nanoparticles with diethylene triamine pentaacetic acid (DTPA) or ethyl (dimethyl aminopropyl) carbodiimide (EDC)-N-hydroxy succinimide (NHS) as linkers. Rhodamine hydrazone particles were synthesized and coupled to IgY anti-MAP antibodies using DTPA or EDC-NHS linkers. Separation efficiency of the IMB was tested on bovine fecal, milk, and colostrum samples experimentally contaminated with MAP. The studied methods were evaluated on their ability to detect MAP and separate bacteria in complex mediums. The ELISA results indicated 95% efficacy in antibody coupling to IMB, with the DTPA-IMB method being more efficient than the EDC-NHS-IMB method. By using the DTPA-IMB method, MAP bacteria were successfully recovered from fecal, milk, and colostrum samples. The DTPA-IMB method used in combination with the rhodamine hydrazone immunosensor had a limit of detection equal to 30 and 30,000 MAP cells/mL using chromogenic and fluorescent properties, respectively. Combining the DTPA-IMB separation method with the rhodamine hydrazone immunosensor provides a fast, sensitive, and cost-beneficial method for detecting MAP in bovine feces, milk, and colostrum.     

Mathematical Modeling and Genetic Algorithm Optimization of Reactive Absorption of H2S

A rate‐based mathematical model was developed for the reactive absorption of H₂S in NaOH, with NaOCl or H₂O₂ as the chemical oxidant solutions in a packed column. A modified mass transfer coefficient in the gas phase was obtained by genetic algorithm and implemented in the model to correct the assumption of instantaneous reactions. The effects of different operating variables including the inlet H₂S concentration, inlet gas mass flux, initial NaOH, concentrations of the chemical oxidants in the scrubbing solutions, and liquid‐to‐gas ratio on the H₂S removal efficiency were studied. A genetic algorithm was employed to optimize the operating variables in order to obtain maximum removal efficiency of H₂S. The model results were in good agreement with the experimental data.     

A comparative study of CO<Subscript>2</Subscript> and CH<Subscript>4</Subscript> adsorption using activated carbon prepared from pine cone by phosphoric acid activation

Adsorption of pure carbon dioxide and methane was examined on activated carbon prepared from pine cone by chemical activation with H₃PO₄ to determine the potential for the separation of CO₂ from CH₄. The prepared adsorbent was characterized by N₂ adsorption-desorption, elemental analysis, FTIR, SEM and TEM. The equilibrium adsorption of CO₂ and CH₄ on AC was determined at 298, 308 and 318 K and pressure range of 1–16 bar. The experimental data of both gases were analyzed using Langmuir and Freundlich models. For CO₂, the Langmuir isotherm presented a perfect fit, whereas the isotherm of CH₄ was well described by Freundlich model. The selectivity of CO₂ over CH₄ by AC (CO₂: CH₄=50: 50, 298K, 5 bar), predicted by ideal adsorbed solution theory (IAST) model, was achieved at 1.68. These data demonstrated that pine cone-based AC prepared in this study can be successfully used in separation of CO₂ from CH₄.     

Two-dimensional spin coating with a vertical centrifugal force and the effect of artificial gravity on surface leveling

This study focuses on an innovative method for spin coating called the two-dimensional (2D) spin coating method. Using a centrifugal force applied by a rotary machine perpendicular to the wafer surface body, a vertical centrifuge force (VCF) was generated. The VCF allowed controllable artificial gravity acceleration to be generated and caused the coating to face this elevated gravity acceleration to adjust and normalize the high and low surface tension stresses. Previous surface leveling mathematics were analyzed and modified. The modified calculations indicate that the effect of additional gravity exerted on the liquid’s surface can reduce the amplitude of surface leveling. To experimentally investigate this phenomenon, a 2D spin coater was designed and manufactured. Higher artificial gravity overcame some common coating defects, such as cloudiness, edge beading, inner layer bubbling, and unsmooth surface leveling. Photoresist (AZP4620) was used as the coating material. The surface roughness was analyzed by atomic force microscopy (AFM) and the layer properties were also imaged by scanning electron microscopy (SEM). The AFM results (average and root-mean-square roughness) indicated a decrease in surface leveling amplitude by increasing the VCF. SEM images showed condensed layers without any porosity or rupture. The experimental results agreed with the simulations and calculated values.     

Chemical vapor deposition of poly(3‐alkylthiophene) nanoparticles on fabric: Chemical and electrochemical characterization

Chemical vapor deposition of poly(3‐methylthiophene) and poly (3‐hexylthiophene) as conductive polymers on the surface of polyester fabrics was successfully obtained. Fourier transform infrared spectroscopy confirmed the formation of polymers on surface of fabrics (the fingerprint of polythiophenes, υ 600–1500 cm^?1). The uniformity of deposition and nanoparticles (average size of 60 nm) were proved with scanning electron microscopy. Electrochemical impedance spectroscopy showed that P3HT‐coated samples offer higher conductivity in compared to P3MT‐coated samples. The impedance modulus of P3HT‐coated samples was lowered nine times to that of row materials and reached to c8000 Ω. The samples have also shown electrochromic properties under electrical current, changing its color from yellowish green at 0 V to dark green at +12 V for poly (3‐hexylthiophene) samples and from brown at 0 V to red at +12 V for poly(3‐methylthiophene)‐coated fabrics (V = 0 V, λ = 450 nm; V = 12 V, λ = 650 nm). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40673.     

Explaining the Difference Between Real Part and Virtual Design of 3D Printed Porous Polymer at the Microstructural Level

The combination of experimental and numerical approaches is attempted to shed more light on 3D microstructural imperfections and mechanical performance of 3D printed acrylonitrile butadiene styrene parts. The starting point is the virtual building of airy structures using a reverse engineering approach. This approach combines microstructure generator, finite element model, and optimization strategy to propose virtual airy structures satisfying structural and mechanical criteria up to a desired porosity content of 60%. Optimal structures are printed using fused deposition modeling and X‐ray microtomography is used to assess all microstructural defects. Compression testing is performed for load levels above 50% of reduction in sample height. The main outcome of this work is the demonstration of small amount of process induced porosity inducing high pore connectivity. The interdependence of process induced and desired porosity reveals genuine microstructural effects that are only characteristics of 3D printed materials.

     

Effect of nano-sized calcium carbonate on cure kinetics and properties of polyester/epoxy blend powder coatings

Today's strict environmental laws pose significant challenges for coating's formulators to look for eco-friendly products. Powder coatings, particularly polyester/epoxy blends have demonstrated their ability as alternatives to traditional solvent-borne coatings. Recently, the use of nanoparticles such as nano-CaCO₃ (nCaCO₃) has been suggested as a beneficial strategy towards powder coating application with improved properties. Here, we study the effect of nCaCO₃ on morphology, cure behavior, adhesion and hardness of polyester/epoxy systems. The nanoparticles shape, size and dispersion state were investigated through X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) methods. Furthermore, isothermal cure characterization of the neat and filled systems was performed using a torque rheometer. The most important finding based on the rheological studies was the catalytic effect of nCaCO₃ on cure reaction of polyester/epoxy, leading to the shorter curing time. Moreover, the kinetic analyses of rheograms revealed a marked decrease in the activation energy of the cure process upon raising nCaCO₃ content. Interestingly, pull-off adhesion and hardness tests showed that the hardness and adhesion strength were dramatically increased by the addition of nCaCO₃ into the polyester/epoxy system compared to pure blend resin. Therefore, considering the strong competition in powder coating market, the use of nCaCO₃ as a commercial and inexpensive nanofiller is necessary not only to reduce the dwell time which has benefits in terms of the energy consumption and economics, but also to improve the performance of final polyester/epoxy coating.     

Synthesis of Chemically Cross-Linked Hydroxypropyl Methyl Cellulose Hydrogels and their Application in Controlled Release of 5-Amino Salicylic Acid

The objective of this study was to achieve the colon-specific delivery of an anti-ulcerative colitis drug using hydroxypropyl methyl cellulose (HPMC) hydrogels. HPMC hydrogels containing poly ethylene glycol (PEG) as cross-links have been prepared by reacting HPMC sodium salt with polyethylene glycol dichloride.

The effect of cross-linking agent on swelling behavior of HPMC-PEG hydrogels, were investigated. Swelling parameters such as equilibrium degree of swelling, swelling ratio and network parameter such as molecular mass between cross-links (M_c) were determined. The cross-linking concentrations were 0.5%, 1%, 1.5%, and 2% (based on weight of HPMC). The equilibrium swelling ratio (Q) of cross-linked HPMC hydrogels increases from 13.2 to 27.1 as the cross-linker percentage increases from 0.5% to 2%. 5-Aminosalicylic acid (5-ASA) was used as a model of an anti-inflammatory drug. Cross-linked HPMC hydrogels were found to be a promising drug delivery system for the drugs to be delivered to the colon.