Thoughening of poly(lactic acid) with silicone rubber

In this study, poly(lactic acid) (PLA) was blended with silicone rubber (SR) to improve its impact strength and toughness by using dynamic crosslinking in the presence of peroxide during melt compounding. The SR to PLA ratio, peroxide and coagent concentrations were taken as experimental parameters. Blends were evaluated in terms of their thermal properties, tensile and impact strengths, dynamic mechanical properties, and micro‐structure. Results showed that PLA was successfully toughened with SR using dynamic crosslinking. Impact strength and energy of fracture in tensile test improved up to 4 and 10 times, respectively. On the other hand, yield strength and stiffness of blends deteriorated by the incorporation of SR. Thermal analysis pointed out that presence of SR decreased the cold crystallization temperature. It was observed from scanning electron microscopy (SEM) that the energy absorbing mechanism under impact loads in PLA/SR blends is tortuosity in the crack patterns. POLYM. ENG. SCI., 54:2029–2036, 2014. © 2013 Society of Plastics Engineers     

Process intensification for heavy oil upgrading using supercritical water

Demand for light hydrocarbons has been steadily increasing in the market with a corresponding decrease in heavy hydrocarbon demand. Therefore, there is a need to develop environmentally friendly and efficient technologies for conversion of heavy molecular weight hydrocarbons. Supercritical fluids (SCF) are attracting increased attention as solvents for green chemistry and among those supercritical water (SCH₂O) is promising for the upgrading of heavy hydrocarbons. Because of a sharp decrease in its dielectric constant, water loses its polarity when brought to the supercritical conditions and its properties starts to resemble the properties of hydrocarbons and becomes an excellent solvent for organic compounds. Moreover, increased ionic product of water leads to an increasing [H₃O⁺] concentration and thus promotes the reactions requiring the addition of an acid. Solvation power enables the extraction of lighter compounds while increased [H₃O⁺] concentration makes the reactive extractions of heavy hydrocarbons possible. As a result of its favorable properties, a wide variety of process intensification studies have been carried out using near critical or SCH₂O such as combined distillation-cracking-fractionation and in some cases even without the utilization of catalysts and/or hydrogen. In this review, recent advances on reactions of hydrocarbons occurring in a SCH₂O environment will be highlighted. Fundamental aspects of these reactions including their thermodynamics and kinetics will be discussed. Experimental and theoretical developments on phase equilibria of relevant water–hydrocarbons systems will be presented.     

Enhancement of hybrid sol–gel coating and industrial application on polished porcelain stoneware tiles and investigation of the performance

The aim of this study was to improve stain resistance and cleanability of polished porcelain tiles by sealing the micro-pores on the tile surface with hybrid sol–gel solution. For this purpose, solutions of a hybrid system based on sol–gel technology were prepared. The obtained solution were applied to polished unglazed tiles and subsequently spread with soft tissue thereon. To achieve complete sealing, both organic and inorganic particles of different sizes were mixed with obtained sol–gel hybrid systems. Coated surfaces were investigated by means of a scanning electron microscope. The stain resistance and the cleanability of the tile surface were tested according to ISO-10545-2014 standard. It has been shown that prepared sealing material permanently prevents formation of stains such as olive oil, green staining paste, iodine solution on the surface of polished porcelain tiles. The remains of stains on the surface can easily be removed from it with a cleaning agent.     

Inactivation of particle-associated microorganisms in wastewater disinfection: modeling of ozone and chlorine reactive diffusive transport in polydispersed suspensions

Occlusion of microorganisms in wastewater particles often governs the overall performance of a disinfection system, and the associated health risks of post-disinfected effluents. Little is currently known on the penetration of chemical oxidants into particles developed in wastewater treatment. In this work, a reactive transport model that incorporates intra- and extra-particle chemical decay, radial intra-particle diffusion, mass transfer resistance at particle surfaces, and non-linear reaction kinetics within a competitive multi-particle size aqueous environment, was used to analyze the penetration of ozone and chlorine into wastewater particles. Individual characteristics from two secondary wastewater treatment facilities were used in model calibration. Simulations revealed that significant ozone transport within particles greater than 6 microm required large initial concentrations to exhaust the preferential reaction with aqueous soluble matter. Chlorinated samples exhibited apparently slower reactions and thus deeper penetration (22-40 microm). Chlorine penetration was less sensitive to variations in the extra-particle reaction and disinfectant concentration than ozone. Model simulations that considered elevated initial concentrations of chemical disinfectants revealed that complete inactivation of all particle size domains was not possible with current disinfection practices (e.g., contact times). Reduction in the health risks associated with wastewater particles requires treatment that efficiently balances particle removal (filtration) and particle inactivation (disinfection).     

Electrochemical copolymerization and characterization of dianilines linked by polyether bridge with aniline

Copolymer of aniline and triethylene glycol bis(o-aminophenyl) ether was synthesized by constant potential electrolysis. Cyclic voltammogram of the copolymer films recorded in the monomer-free electrolytic solution revealed that the redox behavior of the films approaches to that of poly(triethylene glycol bis(o-aminophenyl) ether) with increasing amount of triethylene glycol bis(o-aminophenyl) in the feed ratio. Copolymerization was investigated by in situ recording the changes in the electronic absorption spectrum during electrolysis. The free standing copolymer film was characterized utilizing Fourier transform infrared spectrometer, and spectroelectrochemical behavior of the copolymer was investigated via in situ UV–vis spectroscopic technique. Besides the electron spin resonance study of the copolymer film, the different morphologies of the polymers were examined by scanning electron microscopy and the copolymerization was confirmed. The temperature dependence conductivity of the copolymer film was measured by four-probe technique in the temperature range of 100–300 K, and the calculated parameters showed that conduction mechanism fits to variable range hopping.     

New polymers from plant oil derivatives and styrene‐maleic anhydride copolymers

In this study, styrene maleic anhydride copolymer (SMA2000, Styrene : Maleic Anhydride 2 : 1) is grafted and/or crosslinked with epoxidized methyl oleate, epoxidized soybean oil, methyl ricinoleate (MR), castor oil (CO), and soybean oil diglyceride. Base catalyzed epoxy‐anhydride and alcohol‐anhydride polyesters were synthesized by using the anhydride on SMA, the epoxy or secondary alcohol groups on the triglyceride based monomers. The characterizations of the products were done by DMA, TGA, and IR spectroscopy. SMA‐epoxidized soy oil and SMA‐CO polymers are crosslinked rigid infusible polymers. SMA‐epoxidized soy oil and SMA‐CO showed T_g's at 70 and 66°C, respectively. Dynamic moduli of the two polymers were 11.73 and 3.34 Mpa respectively. SMA‐epoxidized methyl oleate, poly[styrene‐co‐(maleic anhydride)]‐graft‐(methyl ricinoleate), and SMA‐soy oil diglyceride polymers were soluble and thermoplastic polymers and were characterized by TGA, GPC, DSC, NMR, and IR spectroscopy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A method for evaluating dynamic functional network connectivity and task-modulation: application to schizophrenia

Objective

In this paper, we develop a dynamic functional network connectivity (FNC) analysis approach using correlations between windowed time-courses of different brain networks (components) estimated via spatial independent component analysis (sICA). We apply the developed method to fMRI data to evaluate it and to study task-modulation of functional connections.

Materials and methods

We study the theoretical basis of the approach, perform a simulation analysis and apply it to fMRI data from schizophrenia patients (SP) and healthy controls (HC). Analyses on the fMRI data include: (a) group sICA to determine regions of significant task-related activity, (b) static and dynamic FNC analysis among these networks by using maximal lagged-correlation and time–frequency analysis, and (c) HC–SP group differences in functional network connections and in task-modulation of these connections.

Results

This new approach enables an assessment of task-modulation of connectivity and identifies meaningful inter-component linkages and differences between the two study groups during performance of an auditory oddball task (AOT). The static FNC results revealed that connectivities involving medial visual–frontal, medial temporal–medial visual, parietal–medial temporal, parietal–medial visual and medial temporal–anterior temporal were significantly greater in HC, whereas only the right lateral fronto-parietal (RLFP)–orbitofrontal connection was significantly greater in SP. The dynamic FNC revealed that task-modulation of motor–frontal, RLFP–medial temporal and posterior default mode (pDM)–parietal connections were significantly greater in SP, and task modulation of orbitofrontal–pDM and medial temporal–frontal connections were significantly greater in HC (all P < 0.05).

Conclusion

The task-modulation of dynamic FNC provided findings and differences between the two groups that are consistent with the existing hypothesis that schizophrenia patients show less segregated motor, sensory, cognitive functions and less segregated default mode network activity when engaged with a task. Dynamic FNC, based on sICA, provided additional results which are different than, but complementary to, those of static FNC. For example, it revealed dynamic changes in default mode network connectivities with other regions which were significantly different in schizophrenia in terms of task-modulation, findings which were not possible to discover by static FNC.     

The in vitro effects of some pesticides on carbonic anhydrase activity of Oncorhynchus mykiss and Cyprinus carpio carpio fish

Systemic carbonic anhydrase (CA) inhibitors are among the most powerful agents to lower intraocular pressure. Unfortunately, their use is frequently accompanied by undesired side effects. Some are due to the relatively large amounts of drug that have to be systematically administered to inhibit the CA in the ciliary processes. The aim of the present work was to study in vitro effects of some pesticides on CA enzyme obtained from blood of fish, which play a key role in salt- and osmoregulation and acid-base balance in the fish, Oncorhynchus mykiss and Cyprinus carpio carpio living in freshwaters, and compared with CA inhibitors. CA activities were significantly inhibited by pesticides and inhibitors. I(50) values of O. mykiss CA enzyme inhibited by lambda-cyhalothrin, deltametrin, diozinon, dorzolamide and brinzolamide were 6.05 x 10(-4), 1.48 x 10(-5), 6.84 x 10(-3), 3.82 x 10(-5) and 1.80 x 10(-6) mol/l, and that for C. c. carpio 6.86 x 10(-4), 4.70 x 10(-4), 3.92 x 10(-3), 8.34 x 10(-6) and 1.42 x 10(-6) mol/l, respectively. The pesticides used in this study inhibited the CA activity from different fish species to various degrees. It was found that the most effective inhibitor of CA enzyme within pesticides used was detrametrin. These findings observed in vitro could be useful in the understanding of the toxic effects that pesticides elicit on aquatic organisms in vivo.     

Production of granular activated carbon from waste Rosa canina sp. seeds and its adsorption characteristics for dye

An activated carbon was developed from Rosa canina sp. seeds, characterized and used for the removal of methylene blue (basic dye) from aqueous solutions. Adsorption studies were carried out at 20 degrees C and various initial dye concentrations (20, 40, 60, 80, and 100 mg/L) for different times (15, 30, 60, and 120 min). The adsorption isotherm was obtained from data. The results indicate that the adsorption isotherm of methylene blue is typically S-shaped. The shape of isotherm is believed to reflect three distinct modes of adsorption. In region 1, the adsorption of methylene blue is carried out mainly by ion exchange. In region 2 by polarizations of pi-electrons established at cyclic parts of the previously adsorbed methylene blue molecules is occurred. However, it is not observed any change at the sign of the surface charge although zeta potential value is decreased with increase of amount adsorbed. In region 3, the slope of the isotherm is reduced, because adsorption now must overcome electrostatic repulsion between oncoming ions and the similarly charged solid. Adsorption in this fashion is usually complete when the surface is covered with a monolayer of methylene blue. To reveal the adsorptive characteristics of the produced active carbon, porosity and BET surface area measurements were made. Structural analysis was performed using SEM-EDS. The produced active carbon has the specific surface area of 799.2 m2 g-1 and the iodine number of 495 mg/g.     

Effect of the temperature and mobile phase composition on the retention behavior of nitroanilines on ligand-exchange stationary phase

This paper deals with the separation of isomers of nitroaniline by liquid chromatography using the ligand-exchange technique. The chromatographic separations were performed on the ligand-exchanger sporopollenin. The sporopollenin used as support of stationary phase was modified with carboxylated-ethylenediamine matrix and was loaded with cobalt(II) ions. Using the column packed with cobalt(II) loaded carboxylated diaminoethyl sporopollenin [Co(II)-CDAE-S], the retention behavior of 3- and 4-nitroanilines was investigated. The mobile phase used, was a mixture of 0.05 M NH(4)OH in ethanol-water. The resolution was strongly affected by the presence of ammonium hydroxide in the mobile phase and a concentration of 0.05 M was shown to be necessary for the separation of analytes. To study the effects of temperature on the resolution, column runs were also performed at various temperatures (15-60 degrees C). With increasing temperature, a decreased interaction between the solutes and the ligand-exchanger was observed. Consequently, the best results were obtained using a mixture of 0.05 M NH(4)OH in ethanol-water (10:90, v/v) as the mobile phase at a column temperature of 35 degrees C. Ligand-exchange chromatography on the Co(II)-CDAE-S could be a useful alternative method for the separation of nitroaniline.