Co-immobilized microbial biosensor for BOD estimation based on sol-gel derived composite material

A novel type of biochemical oxygen demand (BOD) biosensor was developed for water monitor, based on co-immobilizing of Trichosporon cutaneum and Bacillus subtilis in the sol-gel derived composite material which is composed of silica and the grafting copolymer of poly (vinyl alcohol) and 4-vinylpyridine (PVA-g-P(4-VP)). Factors that influence the performance of the resulting biosensor were examined. The biodegradable substrate spectrum could be expanded by the co-immobilized microorganisms. The biosensor prepared also exhibited good reproducibility and long-term stability. Good agreement was obtained between the results of the sensor BOD measurement and those obtained from conventional BOD5 method for water samples.

Functionalization of an ethylene-propylene copolymer with allyl (3-isocyanate-4-tolyl) carbamate

An ethylene-propylene copolymer (EPM) was functionalized with an iso cyanate-bearing unsaturated monomer, allyl(3-isocyanate-4-tolyl) carbamate (TAI), with dicumyl peroxide as an initiator in a xylene solution. Fourier transform infrared (FTIR) was used to confirm the formation of EPM-g-TAI. The peak at 2273 cm(-1), characteristic of -NCO groups in EPM-g-TAI, revealed evidence of grafting. The grafting degree was determined with both chemical titration and FTIR. The grafting degree could be adjusted, and the maximum was over 6 wt % without any gelation. The molar mass distribution of EPM-g-TAI was narrower than that of EPM. The rheological behavior of both EPM-g-TAI and EPM was investigated with a rotational rheometer. The apparent viscosity of EPM-g-TAI was higher than that of EPM and increased with an increasing grafting degree of TAI. Surface analysis by contact-angle measurements showed that contact angles of EPM-g-TAI samples to a given polar liquid decreased with an increasing grafting degree of TAI. We also obtained the dispersion component of the surface free energy (gamma(S)(d)), the polar component of the surface free energy (gamma(S)(d)), and the total surface free energy (gamma(S) = gamma(S)(d) + gamma(S)(p)) of the grafted EPM. These parameters increased with the enhancement of the grafting degree, which gave us a quantitative estimation of the polar contribution of the grafted TAI to the total surface free energy of EPM-g-TAI.

Capillary electrophoresis with solid-state electrochemiluminescence detector

We report capillary electrophoresis coupling to a solid-state electrochemiluminescence (ECL) detector for the first time. The solid-state ECL detector was fabricated by immobilizing the ECL reagent tris(2,2'-bipyridyf)ruthenium (TBR) in poly-(p-styrenesulfonate)-silica-poly(vinyl alcohol) grafting 4-vinylpyridine copolymer films. The excellent stability of the solid-state ECL detector in the phosphate solution satisfied application in CE. The CE with solid-state ECL detector system was characterized using tripropylamine (TPA) and proline. The influences of detection potential, the concentration of TBR in the film, and pH value of ECL buffer were investigated. The linear range for TPA and proline was 0.005-10 muM and 5-10 mM with correlation coefficients of 0.997 and 0.998, respectively. The detection limit (signal-to-noise ratio S/N = 3) was estimated to be 0.002 and 2.0 muM for TPA and proline, respectively. The relative standard deviations for 1.0 pm TPA and 1.0 mm proline were 8.7% and 7.5% with theoretical plate numbers of 70 000 and 16 000, respectively. Compared with the CE-ECL of TBR in aqueous solution, the CE coupling with solid-state ECL detector system gave the same sensitivity of analysis.

A novel preparation method of maleic anhydride grafted syndiotactic polystyrene and its blend performance with nylon6

This work is intended to provide a method for the preparation of maleic anhydride grafted syndiotactic polystyrene (sPS-g-MA). In particular, a novel solid reaction method by a radical grafting approach is investigated. The grafting reaction is performed at a solid state, where the syndiotactic polystyrene (sPS) is swollen in solvent at relatively low temperature compared to the conventional melt modification method. The formation of sPS-g-MA is directly confirmed by Fourier transform infrared spectroscopy and by the morphology observation of sPS/polyamide-6 (Nylon6) blends, when sPS-g-MA is used as a reactive compatibilizer.

Morphology and thermal and mechanical properties of PBT/HIPS and PBT/HIPS-g-GMA blends

The modification of high-impact polystyrene (HIPS) was accomplished by melt-grafting glycidyl methacrylate (GMA) on its molecular chains. Fourier transform infrared spectroscopy and electron spectroscopy for chemical analysis were used to characterize the formation of HIPS-g-GMA copolymers. The content of GMA in HIPS-g-GMA copolymer was determined by using the titration method. The effect of the concentrations of GMA and dicumyl peroxide on the degree of grafting was studied. A total of 1.9% of GMA can be grafted on HIPS. HIPS-g-GNU was used to prepare binary blends with poly(buthylene terephthalate) (PBT), and the evidence of reactions between the grafting copolymer and PBT in the blends was confirmed by scanning electron microscopy (SEM), dynamic mechanical analysis, and its mechanical properties. The SEM result showed that the domain size in PBT/HIPS-g-GMA blends was reduced significantly compared with that in PBT/HIPS blends; moreover, the improved strength was measured in PBT/HIPS-g-GMA blends and results from good interfacial adhesion. The reaction between ester groups of PBT and epoxy groups of HIPS-g-GMA can depress crystallinity and the crystal perfection of PBT.

Nonisothermal crystallization and melting behavior of poly(3-hydroxybutyrate) and maleated poly(3-hydroxybutyrate)

Nonisothermal crystallization and melting behavior of poly(3-hydroxybutyrate) (PHB) and maleated PHB were investigated by differential scanning calorimetry using various cooling rates. The results show that the crystallization behavior of maleated PHB from the melt greatly depends on cooling rates and its degree of grafting. With the increase in cooling rate, the crystallization process for PHB and maleated PHB begins at lower temperature. For maleated PHB, the introduction of maleic anhydride group hinders its crystallization, causing crystallization and nucleation rates to decrease, and crystallite size distribution becomes wider. The Avrami analysis, modified by Jeziorny, was used to describe the nonisothermal crystallization of PHB and maleated PHB. Double melting peaks for maleated PHB were observed, which was caused by recrystallization during the heating process.

Preparation of the HIPS/MA graft copolymer and its compatibilization in PA6/HIPS blends

The graft copolymer of high impact polystyrene (HIPS) grafted with malice anhydride (MA) (HIPS-g-MA) was prepared with melt mixing in the presence of a free-radical initiator. The grafting reaction was confirmed by IR analyses and the amount of MA grafted on HIPS was evaluated by a titration method. 1-5 wt% of MA can be grafted on HIPS. HIPS-g-MA is miscible with HIPS. Its anhydride group can react with the PA6 during melt mixing the two components. The compatibility of HIPS-g-MA in the HIPS/PA6 blends was evident. Evidence of reactions in the blends was confirmed in the morphology and mechanical properties of the blends. A significant reduction in domain size was observed because of the compatibilization of HIPS-g-MA in the blends of HIPS and PA6. The tensile mechanical properties of the prepared blends were investigated and the fracture surfaces of the blends were examined by means of the scanning electron microscope (SEM). The improved adhesion in a 16%HIPS/75%PA6 blend with 9%HIPS-g-MA copolymer was detected. The morphology of fibrillar ligaments formed by PA6 connecting HIPS particles was observed.

Thermally crosslinkable poly(phenylene sulfide)/poly (ether sulfone)/polymerization of monomer reactant-polyimide blends

The effects of thermally crosslinkable polymerization of monomer reactant-polyimide (POI) on the miscibility, morphology, and crystallization of partially miscible poly(ether sulfone) (PES)/poly(phenylene sulfide) (PPS) blends were investigated with differential scanning calorimetry and scanning electron microscopy. The addition of POI led to a significant reduction in the size of PPS particles, and the interfacial tension between PPS and crosslinked POI was smaller than that between PES and crosslinked POI. During melt blending, crosslinking and grafting reactions of POI with PES and PPS homopolymers were detected; however, the reaction activity of POI with PPS was much higher than that with PES. The crosslinking and grafting reactions were developed further when blends were annealed at higher temperatures. Moreover, POI was an effective nucleation agent of the crystallization of PPS, but crosslinking and grafting hindered the crystallization of PPS. The final effect of POI on the crystallinity of the PPS phase was determined by competition between the two contradictory factors. The crosslinking and grafting reactions between the two components was controlled by the dosage of POI in the blends, the premixing sequence of POI with the two components, the annealing time, and the temperature.

Silica sol-gel composite film as an encapsulation matrix for the construction of an amperometric tyrosinase-based biosensor

An amperometric tyrosinase enzyme electrode for the determination of phenols was developed by a simple and effective immobilization method using sol-gel techniques. A grafting copolymer was introduced into sol-gel solution and the composition of the resultant organic-inorganic composite material was optimized, the tyrosinase retained its activity in the sol-gel thin film and its response to several phenol compounds was determined at 0 mV vs. Ag/AgCl (sat. KCI). The dependences of the current response on pH, oxygen level and temperature were studied, and the stability of the biosensor was also evaluated. The sensitivity of the biosensor for catechol, phenol and p-cresol was 59.6, 23.1 and 39.4 muA/mM, respectively. The enzyme electrode maintained 73% of its original activity after intermittent use for three weeks when storing in a dry state at 4 degreesC. (C) 2000 Elsevier Science S.A. All rights reserved.

Amperometric quantification of polar organic solvents based on a tyrosinase biosensor

A novel amperometric biosensor for quantification of the electrochemically inert polar organic solvents based on tyrosinase electrode was preliminarily reported. The biosensor was fabricated by simply syringing an aqueous solution of tyrosinase/PVAVP (PVAVP: copolymer of poly(vinyl alcohol) grafting with 4-vinylpyridine) onto glassy carbon electrode surface followed by drying the modified electrode at +4 degrees C in a refrigerator. The current generated from electrochemical reduction of quinone is a probe signal. The biosensor can be used for quantification of polar organic solvents, and its mechanism was characterized with in situ steady-state amperometry-quartz crystal microbalance experiments. The detection limit, sensitivity, and dynamic range for certain organic solvents are dependent on the kind and concentration of the substrate probe and the hydrophobicity of the immobilization matrix. The response time for all the tested organic solvents is less than 2 min.

Toughening PA1010 with a functionalized saturated polyolefin elastomer

Polyamide (PA)1010 is blended with a saturated polyolefin elastomer, ethylene-cu-olefin copolymer (EOCP). To improve the compatibility of PA1010 with EOCP, different grafting rates of EOCP with maleic anhydride (MA) are used. The reaction between PA1010 and EOCP-g-MA during extrusion is verified through an extraction test. Mechanical properties, such as notched Izod impact strength, elongation at break, etc., are examined as a function of grafting rate and weight fraction of elastomer. It was found that in the scale of grafting rate (0.13-0.92 wt %), 0.51 wt % is an extreme point for several mechanical properties. Elastomer domains of PA1010/ EOCP-g-MA blends show a finer and more uniform dispersion in the matrix than that of PA1010/EOCP blends. For the same grafting rate, the average sizes of elastomer particles are almost independent on the contents of elastomer, but for different grafting rates, the particle sizes are decreased with increasing grafting rate. The copolymer formed during extrusion strengthens the interfacial adhesion and acts as an emulsifier to prevent the aggregation of elastomer in the process of blending. (C) 2000 John Wiley & Sons, Inc.

Effect of compatibilization on the properties of HIPS/PA1010 blends

Blends consisting of high-impact polystyrene (HIPS) as the matrix and polyamide 1010 (PA1010) as the dispersed phase were prepared by mixing. The grafting copolymers of HIPS and maleic anhydride (MA), the compatibilizer precursors of the blends, were synthesized. The contents of the IMA in the grafting copolymers are 4.7 wt % and 1.6 wt %, and were assigned as HAM and LMA, respectively. Different blend morphologies were observed by scanning electron microscopy (SEM); the domain size of the PA1010 dispersed phase in the HIPS matrix of compatibilized blends decreased comparing with that of uncompatibilized blends. For the blend with 25 wt % HIPS-g-MA component, the T-c of PA1010 shifts towards lower temperature, from 178 to 83 degrees C. It is found that HIPS-g-MA used as the third component has profound effect on the mechanical properties of the resulting blends. This behavior has been attributed to the chemical reaction taking place in situ during the mixing between the two components of PA1010 and HIPS-g-MA. (C) 2000 John Wiley & Sons, Inc.

Chlorohydrin water swellable rubber compatibilized by an amphiphilic craft copolymer. I. Synthesis and characterization of compatibilizer PVA-g-PBA

The graft copolymerization of butyl acrylate onto poly(vinyl alcohol) with eerie ammonium nitrate as redox initiator in a aqueous medium has been investigated. The formation of graft copolymer was confirmed by means of IR, scanning electron microscopy (SEM), and wide-angle X-ray diffraction (WAXD). The percentage of mononer conversion and percentage of grafting varied with concentrations of initiator, nitric acid, monomer, macromolecular backbone (X-n = 1750, M = 80 000), reaction temperature and reaction time. Some inorganic salts and organic solvents have a great influence upon grafting. The reaction mechanism has been explored, and rate equations for the reaction are established. (C) 2000 John Wiley & Sons, Inc.

Amperometric tyrosinase biosensor based on a sol-gel-derived titanium oxide-copolymer composite matrix for detection of phenolic compounds

A new type of tyrosinase biosensor was developed for the detection of phenolic compounds, based on the immobilization of tyrosinase in a sol-gel-derived composite matrix that is composed of titanium oxide sol and a grafting copolymer of poly(vinyl alcohol) with 4-vinylpyridine. Tyrosinase entrapped in the composite matrix can retain its activity to a large extent owing to the good biocompatibility of the matrix. The parameters of the fabrication process and the variables of the experimental conditions for the enzyme electrode were optimized. The resulting sensor exhibited a fast response (20 s), high sensitivity (145.5 muA mmol(-1) 1) and good storage stability. A detection limit of 0.5 muM catechol was obtained at a signal-to-noise ratio of 3.

Amperometric biosensor for hydrogen peroxide based on sol-gel/hydrogel composite thin film

A reagentless amperometric hydrogen peroxide biosensor was developed. Horseradish peroxidase (HRP) was immobilized in a novel sol-gel organic-inorganic hybrid matrix that is composed of silica sol and a grafting copolymer of poly(vinyl alcohol) with 4-vinylpyridine (PVA-g-PVP). Tetrathiafulvalene (TTF) was employed as a mediator and could lower the operating potential to -50 mV (versus Ag/AgCl). The sensor achieved 95% of the steady-state current in 15 s. Linear calibration for hydrogen peroxide was up to 1.3 mM with the detection limit of 2.5 x 10(-7)M. The enzyme electrode retained about 94% of its initial activity after 30 days of storage in a dry state at 4 degreesC.