Structural and Electrical Characterization of Polypyrrole and Cobalt Aluminum Oxide Nanocomposites

To investigate electrical properties of conducting polypyrrole (PPy) and cobalt aluminum oxide (CAO) nanocomposites, impedance analyzer in frequency range of 100 Hz to 5 MHz is used. In this work, PPy/CAO nanocomposites were synthesized by chemical oxidation polymerization method in different weight percent of CAO in PPy. The dielectric properties and AC conductivity studies were carried out for different nanocomposites in temperature range of room temperature to 180 °C. With the increase in frequency, the dielectric constant for all the nanocomposites was observed to decrease. AC conductivity of PPy was improved by addition of CAO nanopowder.

Simulation of the Reactive Rotational Molding Using Smoothed Particle Hydrodynamics

Reactive rotational molding (RRM) is a process to manufacture hollow plastic parts with reactive material has several advantages compared to conventional roto molding of thermoplastic powders: process cycle time is shorter; raw material is less expensive because polymerization occurs during processing and high-performance polymers may be used such as thermosets, thermoplastics or blends. However, several phenomena occur during this process which makes the optimization of the process quite complex. In this study, we have used a mixture of isocyanate and polyol as a reactive system. The chemical transformation of this system to polyurethane has been studied by thermal analysis and rheology tests. Thanks to these results of the curing process and rheological measurements, the kinetic and rheokinetik of polyurethane was identified. Smoothed Particle Hydrodynamics, a Lagrangian meshless method, was chosen to simulate reactive fluid flow in 2 and 3D configurations of the polyurethane during the process taking into account the chemical, and chemiorehological results obtained experimentally in this study.

Fabrication of Immune-Affinity Monolithic Array for Detection of α-Fetoprotein and Carcinoembryonic Antigen

In this paper, we presented a highly sensitive immune-affinity monolithic array for detection of α-fetoprotein (AFP) and carcinoembryonic antigen (CEA). Firstly, the epoxy functionalized monolith arrays were fabricated using UV initiated copolymerization method. Scanning electron microscopy (SEM) image showed that the poly(BABEA-co-GMA) monolith exhibited a well-controlled skeletal and well-distributed porous structure. Then, AFP and CEA immune-affinity monolithic arrays were prepared by immobilization of AFP and CEA antibodies on epoxy functionalized monolith arrays. With a non-competitive immune response format, the presented AFP and CEA immune-affinity arrays were demonstrated as an inexpensive, flexible, homogeneous and stable array for detection of AFP and CEA.

Performance Comparison of Different Regression Methods for a Polymerization Process with Adaptive Sampling

Developing complete mechanistic models for polymerization reactors is not easy, because complex reactions occur simultaneously; there is a large number of kinetic parameters involved and sometimes the chemical and physical phenomena for mixtures involving polymers are poorly understood. To overcome these difficulties, empirical models based on sampled data can be used instead, namely regression methods typical of machine learning field. They have the ability to learn the trends of a process without any knowledge about its particular physical and chemical laws. Therefore, they are useful for modeling complex processes, such as the free radical polymerization of methyl methacrylate achieved in a batch bulk process. The goal is to generate accurate predictions of monomer conversion, numerical average molecular weight and gravimetrical average molecular weight. This process is associated with non-linear gel and glass effects. For this purpose, an adaptive sampling technique is presented, which can select more samples around the regions where the values have a higher variation. Several machine learning methods are used for the modeling and their performance is compared: support vector machines, k-nearest neighbor, k-nearest neighbor and random forest, as well as an original algorithm, large margin nearest neighbor regression. The suggested method provides very good results compared to the other well-known regression algorithms.

Oxidation of Amitriptyline by Bromamine-T in Acidic Buffer Medium: A Kinetic and Mechanistic Approach

The kinetics of the oxidation of amitriptyline (AT) by sodium N-bromotoluene sulphonamide (C6H5SO2NBrNa) has been studied in an acidic buffer medium of pH 1.2 at 303 K. The oxidation reaction of AT was followed spectrophotometrically at maximum wavelength, 410 nm. The reaction rate shows a first order dependence each on concentration of AT and concentration of sodium N-bromotoluene sulphonamide. The reaction also shows an inverse fractional order dependence at low or high concentration of HCl. The dielectric constant of the solvent shows negative effect on the rate of reaction. The addition of halide ions and the reduction product of BAT have no significant effect on the rate. The rate is unchanged with the variation in the ionic strength (NaClO4) of the medium. Addition of reaction mixtures to be aqueous acrylamide solution did not initiate polymerization, indicating the absence of free radical species. The stoichiometry of the reaction was found to be 1:1 and oxidation product of AT is identified. The Michaelis-Menton type of kinetics has been proposed. The CH3C6H5SO2NHBr has been assumed to be the reactive oxidizing species. Thermodynamical parameters were computed by studying the reactions at different temperatures. A mechanism consistent with observed kinetics is presented.

UV-Cured Coatings Based on Acrylated Epoxidized Soybean Oil and Epoxy Carboxylate

During the past two decades, photoinitiated polymerization has been attracting a great interest in terms of scientific and industrial activity. The wide recognition of UV treatment in the polymer industry results not only from its many practical applications but also from its advantage for low-cost processes. Unlike most thermal curing systems, radiation-curable systems can polymerize at room temperature without additional heat, and the curing is completed in a very short time. The advantage of cationic UV technology is that post-cure can continue in the ‘dark’ after radiation. In this study, bio-based acrylated epoxidized soybean oil (AESO) was cured with UV radiation using radicalic photoinitiator Irgacure 184. Triarylsulphonium hexafluoroantimonate was used as cationic photoinitiator for curing of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. The effect of curing time and the amount of initiators on the curing degree and thermal properties were investigated. The thermal properties of the coating were analyzed after crosslinking UV irradiation. The level of crosslinking in the coating was evaluated by FTIR analysis. Cationic UV-cured coatings demonstrated excellent adhesion and corrosion resistance properties. Therefore, our study holds a great potential with its simple and low-cost applications.

Polydopamine Nanoparticle as a Stable and Capacious Nano-Reservoir of Rifampicin

Application of nanoscience in biomedical field has come across as a new era. This study involves the synthesis of nano drug carrier with antibiotic loading. Based on the founding that polydopamine (PDA) nanoparticles could be formed via self-polymerization of dopamine at alkaline pH, one-step synthesis of rifampicin coupled polydopamine (PDA-R) nanoparticles was achieved by adding rifampicin into the dopamine solution. The successful yield of PDA nanoparticles with or without the presence of rifampicin during the polymerization process was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. Drug loading was monitored by UV-vis spectroscopy and the loading efficiency of rifampicin was calculated to be 76%. Such highly capacious nano-reservoir was found very stable with little drug leakage at pH 3.

Dynamic Fault Diagnosis for Semi-Batch Reactor under Closed-Loop Control via Independent Radial Basis Function Neural Network

In this paper, a robust fault detection and isolation (FDI) scheme is developed to monitor a multivariable nonlinear chemical process called the Chylla-Haase polymerization reactor, when it is under the cascade PI control. The scheme employs a radial basis function neural network (RBFNN) in an independent mode to model the process dynamics, and using the weighted sum-squared prediction error as the residual. The Recursive Orthogonal Least Squares algorithm (ROLS) is employed to train the model to overcome the training difficulty of the independent mode of the network. Then, another RBFNN is used as a fault classifier to isolate faults from different features involved in the residual vector. Several actuator and sensor faults are simulated in a nonlinear simulation of the reactor in Simulink. The scheme is used to detect and isolate the faults on-line. The simulation results show the effectiveness of the scheme even the process is subjected to disturbances and uncertainties including significant changes in the monomer feed rate, fouling factor, impurity factor, ambient temperature, and measurement noise. The simulation results are presented to illustrate the effectiveness and robustness of the proposed method.

Chemical Characterization and Prebiotic Effect of Water-Soluble Polysaccharides from Zizyphus lotus Leaves

In order to investigate the prebiotic potential of oligosaccharides prepared by chemical hydrolysis of water-soluble polysaccharides (WSP) from Zizyphus lotus leaves, the effect of oligosaccharides on bacterial growth was studied. The chemical composition of WSP was evaluated by colorimetric assays revealed the average values: 7.05±0.73% proteins and 86.21±0.74% carbohydrates, among them 64.81±0.42% is neutral sugar and the rest 16.25±1.62% is uronic acids. The characterization of monosaccharides was determined by high performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD) was found to be composed of galactose (23.95%), glucose (21.30%), rhamnose (20.28%), arabinose (9.55%), and glucuronic acid (22.95%). The effects of oligosaccharides on the growth of lactic acid bacteria were compared with those of fructooligosaccharide (RP95). The oligosaccharides concentration was 1g/L of Man, Rogosa, Sharpe broth. Bacterial growth was assessed during 2, 4.5, 6.5, 9, 12, 16 and 24 h by measuring the optical density of the cultures at 600 nm (OD600) and pH values. During fermentation, pH in broth cultures decreased from 6.7 to 5.87±0.15. The enumeration of lactic acid bacteria indicated that oligosaccharides led to a significant increase in bacteria (P≤0.05) compared to the control. The fermentative metabolism appeared to be faster on RP95 than on oligosaccharides from Zizyphus lotus leaves. Both RP95 and oligosaccharides showed clear prebiotic effects, but had differences in fermentation kinetics because of to the different degree of polymerization. This study shows the prebiotic effectiveness of oligosaccharides, and provides proof for the selection of leaves of Zizyphus lotus for use as functional food ingredients.

Preparation and Characterization of Chitosan / Polyacrylic Acid / Ag-Nanoparticles Composite Membranes

Chitosan polyacrylic acid composite membranes were prepared by a bulk polymerization method in presence of N, N'- methylene bisacrylamide (crosslinker) and ammonium persulphate as initiator. Membranes prepared from this copolymer in presence and absence of Ag nanoparticles were characterized by measuring mechanical and physical properties, water up-take and antibacterial properties. The results obtained indicated that the prepared membranes have antibacterial properties which increase with adding Ag nanoparticles.

A Thermodynamic Study of Parameters That Affect the Nitration of Glycerol with Nitric Acid

Biodiesel production from vegetable oil will produce glycerol as by-product about 10% of the biodiesel production. The amount of glycerol that was produced needed alternative way to handling immediately so as to not become the waste that polluted environment. One of the solutions was to process glycerol to polyglycidyl nitrate (PGN). PGN is synthesized from glycerol by three-step reactions i.e. nitration of glycerol, cyclization of 13- dinitroglycerine and polymerization of glycosyl nitrate. Optimum condition of nitration of glycerol with nitric acid has not been known. Thermodynamic feasibility should be done before run experiments in the laboratory. The aim of this study was to determine the parameters those affect nitration of glycerol and nitric acid and chose the operation condition. Many parameters were simulated to verify its possibility to experiment under conditions which would get the highest conversion of 1, 3-dinitroglycerine and which was the ideal condition to get it. The parameters that need to be studied to obtain the highest conversion of 1, 3-dinitroglycerine were mol ratio of nitric acid/glycerol, reaction temperature, mol ratio of glycerol/dichloromethane and pressure. The highest conversion was obtained in the range of mol ratio of nitric acid /glycerol between 2/1 – 5/1, reaction temperature of 5-25oC and pressure of 1 atm. The parameters that need to be studied further to obtain the highest conversion of 1.3 DNG are mol ratio of nitric acid/glycerol and reaction temperature.

Synthesis and Properties of Chitosan-Graft Polyacrylamide/Gelatin Superabsorbent Composites for Wastewater Purification

Superabsorbent polymers received much attention and are used in many fields because of their superior characters to traditional absorbents, e.g., sponge and cotton. So, it is very important but challenging to prepare highly and fast-swelling superabsorbents. A reliable, efficient and low-cost technique for removing heavy metal ions from wastewater is the adsorption using bio-adsorbents obtained from biological materials, such as polysaccharides-based hydrogels superabsorbents. In this study, novel multi-functional superabsorbent composites type semi-interpenetrating polymer networks (Semi-IPNs) were prepared via graft polymerization of acrylamide onto chitosan backbone in presence of gelatin, CTS-g-PAAm/Ge, using potassium persulfate and N,N’-methylene bisacrylamide as initiator and crosslinker, respectively. These hydrogels were also partially hydrolyzed to achieve superabsorbents with ampholytic properties and uppermost swelling capacity. The formation of the grafted network was evidenced by Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Thermogravimetric Analysis (TGA). The porous structures were observed by Scanning Electron Microscope (SEM). From TGA analysis, it was concluded that the incorporation of the Ge in the CTS-g-PAAm network has marginally affected its thermal stability. The effect of gelatin content on the swelling capacities of these superabsorbent composites was examined in various media (distilled water, saline and pH-solutions). The water absorbency was enhanced by adding Ge in the network, where the optimum value was reached at 2 wt. % of Ge. Their hydrolysis has not only greatly optimized their absorption capacity but also improved the swelling kinetic.These materials have also showed reswelling ability. We believe that these super-absorbing materials would be very effective for the adsorption of harmful metal ions from wastewater.

Synthesis and Performance of Polyamide Forward Osmosis Membrane for Natural Organic Matter (NOM) Removal

Forward Osmosis (FO) polyamide thin-film composite membranes have been prepared by interfacial polymerization using commercial UF polyethersulfoneas membrane support. Different interfacial polymerization times (10s, 30s and 60s) in the organic solution containing trimesoyl chloride (TMC) at constant m-phenylenediamine (MPD) concentration (2% w/v) were studied. The synthesized polyamide membranes then tested for treatment of natural organic matter (NOM) and compared to commercial Cellulose TriAcetate (CTA) membrane. It was found that membrane prepared with higher reaction time (30s and 60s) exhibited better membrane performance (flux and humic acid removal) over commercial CTA membrane.

Quartz Crystal Microbalance Based Hydrophobic Nanosensor for Lysozyme Detection

A quartz crystal microbalance (QCM) nanosensor was developed to detect lysozyme enzyme by functionalizing its gold surface with the attachment of poly(methacroyl-L-phenylalanine) (PMAPA) nanoparticles. PMAPA was chosen as a hydrophobic matrix. The hydrophobic nanoparticles were synthesized by micro-emulsion polymerization method. Hydrophobic QCM nanosensor was tested for real time detection of lysozyme enzyme from aqueous solution. The kinetic and affinity studies were determined by using lysozyme solutions with different concentrations. The responses related with mass (Δm) and frequency (Δf) shifts were used to evaluate adsorption properties.   

Mathematical Modeling for Continuous Reactive Extrusion of Poly Lactic Acid formation by Ring Opening Polymerization Considering Metal/Organic Catalyst and Alternative Energies

PLA emerged as a promising polymer because of its property as a compostable, biodegradable thermoplastic made from renewable sources. PLA can be polymerized from monomers (Lactide or Lactic acid) obtained by fermentation processes from renewable sources such as corn starch or sugarcane. For PLA synthesis, ring opening polymerization (ROP) of Lactide monomer is one of the preferred methods. In the literature, the technique mainly developed for ROP of PLA is based on metal/bimetallic catalyst (Sn, Zn and Al) or other organic catalysts in suitable solvent. However, the PLA synthesized using such catalysts may contain trace elements of the catalyst which may cause toxicity. This work estimated the usefulness and drawbacks of using different catalysts as well as effect of alternative energies and future aspects for PLA production.

Copolymers of Pyrrole and α,ω-Dithienyl Terminated Poly(ethylene glycol)

This work presents synthesis of α,ω-dithienyl terminated poly(ethylene glycol) (PEGTh) capable for further chain extension by either chemical or electrochemical polymeriztion. PEGTh was characterized by FTIR and 1H-NMR. Further copolymerization of PEGTh and pyrrole (Py) was performed by chemical oxidative polymerization using ceric (IV) salt as an oxidant (PPy-PEGTh). PEG without end group modification was used directly to prepare copolymers with Py by Ce (IV) salt (PPy-PEG). Block copolymers with mole ratio of pyrrole to PEGTh (PEG) 50:1 and 10:1 were synthesized. The electrical conductivities of copolymers PPy-PEGTh and PPy-PEG were determined by four point probe technique. Influence of the synthetic route and content of the insulating segment on conductivity and yield of the copolymers were investigated.

Development of a New Polymeric Material with Controlled Surface Micro-Morphology Aimed for Biosensors Applications

Compositions of different molar ratios of polymethylmethacrylate-co-methacrylic acid (PMMA-co-MAA) were synthesized via free-radical polymerization. Polymer coated surfaces have been produced on silicon wafers. Coated samples were analyzed by atomic force microscopy (AFM). The results have shown that the roughness of the surfaces have increased by increasing the molar ratio of monomer methacrylic acid (MAA). This study reveals that the gradual increase in surface roughness is due to the fact that carboxylic functional groups have been generated by MAA segments. Such surfaces can be desirable platforms for fabrication of the biosensors for detection of the viruses and diseases.

Heterophase Polymerization of Pyrrole and Thienyl End Capped Ethoxylated Nonyl Phenol by Iron (III) Chloride

This study presents synthesis of novel block copolymers of thienyl end capped ethoxylated nonyl phenol and pyrrole via chemical oxidative polymerization. Ethoxylated nonyl phenol (ENP) was reacted with 2-thiophenecarbonyl chloride in order to synthesize a macromonomer containing thienyl end-group (ENPThC). Then copolymers of ENP-ThC and pyrrole were synthesized by chemical oxidative polymerization using iron (III) chloride as an oxidant. ENP-ThC served both as a macromonomer and an emulsifier for pyrrole with poor solubility in water. The synthesized block copolymers (ENP-ThC-b-PPy) were characterized by spectroscopic analysis and the electrical conductivities were investigated with 4-point probe technique.

Kinetic Modeling of Transesterification of Triacetin Using Synthesized Ion Exchange Resin (SIERs)

Strong anion exchange resins with QN+OH-, have the potential to be developed and employed as heterogeneous catalyst for transesterification, as they are chemically stable to leaching of the functional group. Nine different SIERs (SIER1-9) with QN+OH-were prepared by suspension polymerization of vinylbenzyl chloridedivinylbenzene (VBC-DVB) copolymers in the presence of n-heptane (pore-forming agent). The amine group was successfully grafted into the polymeric resin beads through functionalization with trimethylamine. These SIERs are then used as a catalyst for the transesterification of triacetin with methanol. A set of differential equations that represents the Langmuir-Hinshelwood-Hougen- Watson (LHHW) and Eley-Rideal (ER) models for the transesterification reaction were developed. These kinetic models of LHHW and ER were fitted to the experimental data. Overall, the synthesized ion exchange resin-catalyzed reaction were welldescribed by the Eley-Rideal model compared to LHHW models, with sum of square error (SSE) of 0.742 and 0.996, respectively.

Removal of Tartrazine Dye form Aqueous Solutions by Adsorption on the Surface of Polyaniline/Iron Oxide Composite

In this work, a polyaniline/Iron oxide (PANI/Fe2O3) composite was chemically prepared by oxidative polymerization of aniline in acid medium, in presence of ammonium persulphate as an oxidant and amount of Fe2O3. The composite was characterized by a scanning electron microscopy (SEM). The prepared composite has been used as adsorbent to remove Tartrazine dye form aqueous solutions. The effects of initial dye concentration and temperature on the adsorption capacity of PANI/Fe2O3 for Tartrazine dye have been studied in this paper. The Langmuir and Freundlich adsorption models have been used for the mathematical description of adsorption equilibrium data. The best fit is obtained using the Freundlich isotherm with an R2 value of 0.998. The change of Gibbs energy, enthalpy, and entropy of adsorption has been also evaluated for the adsorption of Tartrazine onto PANI/ Fe2O3. It has been proved according the results that the adsorption process is endothermic in nature.