Potentiometric studies of oxidation–reduction reactions with redox copolymers

Polymeric oxidants in the bead form that were macroporous styrene/divinylbenzene copolymers containing N‐chlorosulfonamide functional groups (in sodium or hydrogen form) or N‐bromosulfonamide groups (in sodium form) were synthesized and investigated to determine their oxidizing powers. The redox potentials of the N‐chlorosulfonamide/sulfonamide and N‐bromosulfonamide/sulfonamide systems were determined by potentiometric studies at different pH values with aqueous solutions of Na₂SO₃, KCN, and KSCN as reducers. The formal redox potentials of the N‐chlorosulfonamide copolymers were 0.79, 0.44, and ?0.12 V at pH's of 1.8, 8.45, and 13.6, respectively. The formal redox potential of the N‐bromosulfonamide copolymer was about 100 mV higher in comparable conditions and in solutions over pH = 5 (e.g., 0.56 V at pH = 8.56). The comparatively higher oxidizing power of the N‐bromosulfonamide copolymer was particularly evident in a strong alkaline medium (in which the N‐chlorosulfonamide copolymer was not reactive). In contrast, the N‐chlorosulfonamide copolymer showed strong oxidative properties in acidic media (in which the N‐bromosulfonamide copolymer decomposed itself). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Semiflexible random thermotropic copolymers from 8‐(3‐hydroxy phenyl) octanoic acid and 3‐chloro‐4‐hydroxy benzoic acid/3,5‐dibromo‐4‐hydroxy benzoic acid

Two series of semiflexible random thermotropic copolymers containing 8‐(3‐hydroxy phenyl) octanoic acid (HPOA) with either 3‐chloro‐4‐hydroxy benzoic acid or 3,5‐dibromo‐4‐hydroxy benzoic acid were prepared by melt polycondensation techniques. The copolyesters were characterized with Fourier transform infrared spectroscopy, dilute solution viscometry, hot‐stage polarized light microscopy, differential scanning calorimetry, thermogravimetric analysis, and wide‐angle X‐ray diffraction. Studies revealed that the amount of HPOA as a disruptor incorporated into the backbone of substituted 4‐hydroxy benzoic acids had a detrimental effect on the liquid‐crystalline behavior. Mesophase‐transition temperatures were observed between 210 and 250°C, and the optical textures were of typical nematic phases. The degree of crystallinity decreased with an increase in the HPOA content. The thermal stability of the copolymers was in the range of 310–370°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Effect of Li+ ions on structure,properties, and actuation of cellulose electro‐active paper actuator

We have reported an electro‐active paper actuator from regenerated cellulose. After dissolving cellulose fibers with a solution of lithium chloride in N,N‐dimethylacetamide, cellulose was regenerated by combining distillation of cellulose solution along with washing with the mixture of deionized water, isopropyl alcohol, and running water. However, the effect of Li⁺ ions on structure, properties, and the actuation behavior of the actuator was not studied. This article describes the changes in these parameters when the Li⁺ ions are removed by subjecting it to different running water exposure time. The structure and properties of cellulose electro‐active paper and its actuation behavior were studied. As Li⁺ ions content reduced from 4354.17 to 10.26 ppm by increasing the exposure time of running water, crystallinity, Young's modulus, and bending displacement decreased. Details about the investigation have been explained. This elimination of ions is important to increase the piezoelectric effect in EAPap by decreasing the ion migration effect. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis and thermomechanical characterization of polyurethane elastomers extended with α,ω‐alkane diols

A series of polyurethane (PU) elastomers was prepared by the reaction of poly(?‐caprolactone) and 4,4′‐diphenylmethane diisocyanate, which was extended with a series of chain extenders (CEs) having 2–10 methylene units in their structure. The completion of the reaction was confirmed by Fourier transform infrared spectroscopy. The chemical structures of the synthesized PU samples were characterized with Fourier transform infrared, ¹H‐NMR, and ¹³C‐NMR spectroscopy, and the thermal properties were determined by thermogravimetric analysis, DSC, and dynamic mechanical thermal analysis techniques. The mechanical properties were also studied and are discussed. The thermogravimetric analysis and DSC analysis showed that CE length had a considerable effect on the thermal properties of the prepared samples. The dynamic mechanical thermal analysis and damping peaks were also affected by the number of methylene units in the CE length. The elastomer extended with 1,2‐ethane diol exhibited optimum thermal properties, whereas the elastomer based on 1,10‐decane diol displayed the worst thermal properties. Tensile strength and elongation at break decreased with increasing CE length, whereas hardness showed the opposite trend. The glass‐transition temperature moved toward lower temperatures with increasing CE length. The decrease in the glass‐transition temperature and tensile properties were interpreted in terms of decreasing hard segments and increasing chain flexibility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Oil yield and compressibility modeling during microscale expression: Criteria for linseed breeding

Seven linseed varieties were harvested at seven times before complete maturity. Microscale oilseed expressions were subsequently carried out on it. A pressure of 10 MPa was applied for 1 h under uniaxial stress. The results were characterized in terms of oil, water and mucilage content, harvest date and oil yield. The piston displacement versus time (creep curves) was described by a four‐Kelvin‐Voigt elements viscoelastic model. Parameters were derived from the model, such as the mechanical properties of seeds (compressibility moduli), showing that the viscoelastic model fits well the experimental data (R² ≈ 0.999). The modeling parameters were combined with some biochemical data in order to predict the kinetics of oil extraction.     

Oxidation of oleuropein studied by EPR and spectrophotometry

The autoxidation at alkaline pH and enzymatic oxidation by mushroom tyrosinase of oleuropein, the dominant biophenol present in the fruits and leaves of Olea europea, was followed by both electron paramagnetic resonance (EPR) and absorption spectroscopy. For comparison, the same oxidation processes were applied to 4‐methylcatechol, a simple polyphenol present in olive mill wastewaters. EPR spectra of stable o‐semiquinone radicals produced during autoxidation at pH 12 and short‐lived o‐semiquinone free radicals produced during autoxidation at pH 9.0 or tyrosinase action and stabilized by chelation with a diamagnetic metal ion (Mg²⁺) were recorded for both polyphenols, and the corresponding hyperfine splitting constants were determined. The UV‐Vis spectral characteristics of the oxidation of polyphenols were highly dependent on the type of polyphenol, oxidant type and the pH of the reaction. The kinetic behavior of tyrosinase in the presence of oleuropein and 4‐methylcatechol was followed by recording spectral changes at 400 nm (absorption maximum) over time. The tysosinase activity with oleuropein showed a pronounced pH optimum at pH 6.5 and a minor one around pH 8. From the data analysis of the initial rate at pH 6.5, the kinetic parameters K_m = 0.34 ± 0.03 mM and V_max = 0.029 ± 0.002 ΔA₄₀₀ min^–1 were determined for oleuropein.     

Accelerator Analysis of Tributyltin Adsorbed onto the Surface of a Tributyltin Resistant Marine Pseudoalteromonas sp. Cell

Tributyltin (TBT) released into seawater from ship hulls is a stable marine pollutant and obviously remains in marine environments. We isolated a TBT resistant marine Pseudoalteromonas sp. TBT1 from sediment of a ship’s ballast water. The isolate (10^{9.3 ± 0.2} colony-forming units mL⁻¹) adsorbed TBT in proportion to the concentrations of TBTCl externally added up to 3 mM, where the number of TBT adsorbed by a single cell was estimated to be 10^8.2. The value was reduced to about one-fifth when the lysozyme-treated cells were used. The surface of ethanol treated cells became rough, but the capacity of TBT adsorption was the same as that for native cells. These results indicate that the function of the cell surface, rather than that structure, plays an important role to the adsorption of TBT. The adsorption state of TBT seems to be multi-layer when the number of more than 10^6.8 TBT molecules is adsorbed by a single cell.     

Aerobic degradation by white‐rot fungi of trichloroethylene (TCE) and mixtures of TCE and perchloroethylene (PCE)

BACKGROUND: Trichloroethylene (TCE) and perchloroethylene (PCE) are considered among the most important groundwater pollutants around the world. These compounds are usually found together in polluted environments but little is known about the ability of microorganisms to simultaneously degrade TCE and PCE. RESULTS: Data showed that several species of white‐rot fungi, including Trametes versicolor, Ganoderma lucidum, and Irpex lacteus, degrade substantial levels of TCE in pure culture. T. versicolor was chosen for further study since it degraded higher levels of TCE than the other organisms. Initial glucose concentration and reoxygenation of samples increased the amount of TCE dechlorination, but no significant difference in percentage TCE degradation was observed. T. versicolor was able to degrade 34.1 and 47.7% of PCE and TCE added as mixtures (containing 5 and 10 mg L⁻¹, respectively). CONCLUSIONS: The degradation ability of TCE was extended to other species of white‐rot fungi. Percentage degradation as well as chloride release from mixtures of TCE and PCE showed that T. versicolor degrades mixtures of TCE and PCE almost as well as its ability to degrade individually added TCE or PCE. The results suggest the potential promise of T. versicolor for bioremediation of TCE and PCE in the environment. Copyright © 2008 Society of Chemical Industry