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.     

Mathematical simulation and long-term monitoring of leachate components from two different landfill cells

In this study we monitored for 920 days the sulfate (SO(4)(2-)), chloride (Cl(-)), chemical oxygen demand (COD) and biological oxygen demand (BOD) parameters in leachate produced in two large-scale test cells at the Odayeri Sanitary Landfill, Istanbul, Turkey. We present a mathematical model of these parameter concentrations in leachates of two test cells with one being the control (C1) and the other (C2) leachate recirculation. The relationship between these parameters and refuse age is simulated by a mathematical formula. The unknown constants of the simulation formula are solved by the least squares method, which minimizes the squared total of deviation from the model of the actual data using a MATLAB computer program. A good fit was obtained between the measured data and model simulations. COD concentrations in leachate from C1 and C2 rapidly attained their maximum values of 75 and 70 g/l, respectively, after 1 month of landfilling. BOD to COD ratios are around 0.8 for both test cells during the acidogenic phase; this ratio then decreased to 0.06. A sharp decrease in the concentration of Cl(-) from 14 to 15 g/l was observed after approximately 2 months of operation, followed by a slow decrease. SO(4)(2-) concentrations rapidly reached a maximum value of 2000 mg/l within 45 days; development of anaerobic conditions caused a sharp decrease to around 75 mg/l for C2 and 450 mg/l for C1 after 5 months of operation. The results showed that there appeared to be little improvement in leachate quality by leachate recirculation in terms of COD and BOD values, however, it is determined that the pollution loads more rapidly reached minimum values within the C2 test cell.     

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.     

Biosorption characteristics of Bacillus sp. ATS-2 immobilized in silica gel for removal of Pb(II)

The bacterial strain Bacillus sp. ATS-2 isolated from Pb(II) polluted soil was immobilized with a silica matrix and Pb(II) biosorption properties of immobilized biosorbent were examined. Optimum biosorption conditions were investigated in the fixed bed column with the variation in the parameters of pH, bed length, flow rate and influent concentration. The Pb(II) biosorption equilibrium was attained within 60 min and the maximum biosorption yield for silica gel immobilized Bacillus sp. ATS-2 was determined as 91.73% at pH 4.0. The higher biosorption yields were observed at flow rates of 60 and 180 ml h(-1). The optimum bed length for the column was found as 10 cm. Data obtained from batch studies were evaluated by Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherm models. The maximum monolayer capacity of Bacillus sp. ATS-2 for Pb(II) was 2.36 x 10(-5) mol g(-1). The involvement of the functional groups on the surface of immobilized cells in biosorption process was also evaluated by FTIR spectral analysis.     

Synthesis,characterization, conductivity,band gap,and kinetic of thermal degradation of poly‐4‐[(2‐mercaptophenyl) imino methyl] phenol

The oxidative polycondensation reaction conditions of 4‐[(2‐mercaptophenyl) imino methyl] phenol (2‐MPIMP) were studied in an aqueous acidic medium between 40 and 90°C by using oxidants such as air, H₂O₂, and NaOCl. The structures of the synthesized monomer and polymer were confirmed by FTIR, ¹H NMR, ¹³C NMR, and elemental analysis. The characterization was made by TGA‐DTA, size exclusion chromatography (SEC) and solubility tests. At the optimum reaction conditions, the yield of poly‐4‐[(2‐mercaptophenyl) imino methyl]phenol (P‐2‐MPIMP) was found to be 92% for NaOCl oxidant, 84% for H₂O₂ oxidant 54% for air oxidant. According to the SEC analysis, the number‐average molecular weight (M_n), weight‐average molecular weight (M_w), and polydispersity index values of P‐2‐MPIMP were found to be 1700 g mol^?1, 1900 g mol^?1, and 1.118, using H₂O₂; 3100 g mol^?1, 3400 g mol^?1, and 1.097, using air; and 6750 g mol^?1, 6900 g mol^?1, and 1.022, using NaOCl, respectively. According to TG analysis, the weight losses of 2‐MPIMP and P‐2‐MPIMP were found to be 95.93% and 76.41% at 1000°C, respectively. P‐2‐MPIMP showed higher stability against thermal decomposition. Also, electrical conductivity of the P‐2‐MPIMP was measured, showing that the polymer is a typical semiconductor. The highest occupied molecular orbital, the lowest unoccupied molecular orbital, and the electrochemical energy gaps (E′_g) of 2‐MPIMP and P‐2‐MPIMP were found to be ?6.13, ?6.09; ?2.65, ?2.67; and 3.48, 3.42 eV, respectively. Kinetic and thermodynamic parameters of these compounds investigated by MacCallum‐Tanner and van Krevelen methods. The values of the apparent activation energies of thermal decomposition (E_a), the reaction order (n), pre‐exponential factor (A), the entropy change (ΔS*), enthalpy change (ΔH*), and free energy change (ΔG*) were calculated from the TGA curves of compounds. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(vinylbenzylchloride) beads grafted with polymer brushes carrying hydrazine ligand for reversible enzyme immobilization

Poly(glycidylmethacrylate), p(GMA), brush grafted poly(vinylbenzyl chloride/ethyleneglycol dimethacrylate), p(VBC/EGDMA), beads were prepared by suspension polymerization and the beads were grafted with poly(glycidyl methacrylate), p(GMA), via surface‐initiated atom transfer radical polymerization aiming to construct a material surface with fibrous polymer. The epoxy groups of the fibrous polymer were reacted with hydrazine (HDZ) to create affinity binding site on the support for adsorption of protein. The influence of pH, and initial invertase concentration on the immobilization capacity of the p(VBC/EGDMA‐g‐GMA)‐HDZ beads has been investigated. Maximum invertase immobilization onto hydrazine functionalized beads was found to be 86.7 mg/g at pH 4.0. The experimental equilibrium data obtained invertase adsorption onto p(VBC/EGDMA‐g‐GMA)‐HDZ affinity beads fitted well to the Langmuir isotherm model. It was shown that the relative activity of immobilized invertase was higher than that of the free enzyme over broader pH and temperature ranges. The K_m and V_max values of the immobilized invertase were larger than those of the free enzyme. After inactivation of enzyme, p(VBC/EGDMA‐g‐GMA)‐HDZ beads can be easily regenerated and reloaded with the enzyme for repeated use. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009