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1.
In this study, a combined use of biopolymer chitosan and oxidoreductase polyphenol oxidase (PPO) was applied to the removal of bisphenol A (BPA) as an endocrine disrupting chemical from aqueous solutions. The optimum conditions for the enzymatic quinone oxidation of BPA were determined to be pH 7.0 and 40°C. Quinone derivatives generated were chemisorbed on chitosan beads, and BPA was completely removed at 4–7 h. The removal time was shortened with an increase in the amount of dispersed chitosan beads or the PPO concentration. In addition, the initial velocity of quinone oxidation increased with an increase in the amount of chitosan beads. The use of chitosan in the form of porous beads was more effective than the use of chitosan in the form of solutions or powder. It was found that an important factor for this procedure was a high‐specific surface area of chitosan beads and heterogeneous reaction of quinone derivatives enzymatically generated with chitosan. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

2.
Mushroom tyrosinase was covalently immobilized on a poly(acrylic acid)‐type, weakly acidic cation‐exchange resin (Daiaion WK10, Mitsubishi Chemical Corp., Tokyo, Japan) with 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide hydrochloride salt as a water‐soluble carbodiimide. Ion‐exchange resins immobilized with tyrosinase were packed in one column, and crosslinked chitosan beads prepared with epichlorohydrin were packed in another column. The enzymatic activity was modified by covalent immobilization, and the immobilized tyrosinase had a high activity in the temperature range of 30–45°C and in the pH range of 7–10. When solutions of various alkylphenols were circulated through the two columns packed with tyrosinase‐immobilized ion‐exchange resins and crosslinked chitosan beads at 45°C and pH 7 (the optimum conditions determined for p‐cresol), alkylphenols were effectively removed through quinone oxidation with immobilized tyrosinase and subsequent quinone adsorption on chitosan beads. The use of chemically crosslinked chitosan beads in place of commercially available chitosan beads was effective in removing alkylphenols from aqueous solutions in shorter treatment times. The removal efficiency increased with an increase in the amount of crosslinked chitosan beads packed in the column because the rate of quinone adsorption became higher than the rate of enzymatic quinone generation. The activity of tyrosinase was iteratively used by covalent immobilization on ion‐exchange resins. One of the most important findings obtained in this study is the fact that linear and branched alkylphenols suspected of weak endocrine‐disrupting effects were effectively removed from aqueous solutions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

3.
BACKGROUND: Endocrine disruptors, as in the case of bisphenol A (BPA), are increasingly found in aqueous effluents. The degree of mineralization of a bisphenol A (BPA) aqueous solution after applying several oxidation treatments has been investigated. RESULTS: UV‐C photolysis of BPA allowed calculation of the quantum yield, ϕλ=254 = 0.045 ± 0.005 mol Einstein−1 but only 15% of the initial organic carbon content (TOC) was eliminated. Better results (80% conversion) were obtained after TiO2 addition. Ozone inmediately reacts with BPA. Again, TiO2 addition in the presence of O3 was capable of increasing the mineralization level (60%). The photolytic ozonation of BPA was capable of completely eliminating TOC. The presence of activated carbon in the O3/UV and O3/UV/TiO2 systems significantly enhanced the TOC removal reaction rate (100% conversion in 20 min). CONCLUSIONS: Processes such as ozonation or photolysis are capable of efficiently removing BPA from water however, mineralization levels are rather low. Addition of TiO2 to O3 or UV‐C significantly enhances TOC removal. The remaining organics still account for an average 20–40% of the initial organic carbon. The combination of O3/UV‐C is capable of completely mineralizing BPA. Activated carbon and/or TiO2 addition to the system O3/UV‐C improves the TOC depletion rate. Copyright © 2008 Society of Chemical Industry  相似文献   

4.
An investigation was undertaken on the application of dilute chitosan solutions gelled by melB tyrosinase‐catalyzed reaction with 3,4‐dihydroxyphenethylamine (dopamine). The tyrosinase‐catalyzed reaction with dopamine conferred water‐resistant adhesive properties to the semi‐dilute chitosan solutions. The viscosity of the chitosan solutions highly increased by the tyrosinase‐catalyzed quinone conversion and the subsequent nonenzymatic reactions of o‐quinones with amino groups of the chitosan chains. The viscosity of chitosan solutions highly increased in shorter reaction times by addition of melB tyrosinase. Therefore, in this study, the gelation of a chitosan solution was carried out without poly(ethylene glycol) (PEG), which was added for the gelation of chitosan solutions using mushroom tyrosinase. The highly viscous, gel‐like modified chitosan materials were allowed to spread onto the surfaces of the glass slides, which were tightly lapped together and were held under water. Tensile shear adhesive strength of over 400 kPa was observed for the modified chitosan samples. An increase in either amino group concentration of the chitosan solutions or molecular mass of the chitosan samples used effectively led to an increase in adhesive strength of the glass slides. Adhesive strength obtained by chitosan materials gelled enzymatically was higher than that obtained by a chitosan gel prepared with glutaraldehyde as a chemical crosslinking agent. In addition, the use of melB tyrosinase led to a sharp increase in adhesive strength in shorter reaction times without other additives such as PEG. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

5.
An investigation was undertaken on the application of dilute chitosan solutions gelled by tyrosinase‐catalyzed reaction with 3,4‐dihydroxyphenethylamine (dopamine). The tyrosinase‐catalyzed reaction with dopamine conferred water‐resistant adhesive properties to the semidilute chitosan solutions. The viscosity of the chitosan solutions increased highly by the tyrosinase‐catalyzed reaction and the subsequent reactions between o‐quinone compounds and chitosan. These highly viscous, gel‐like modified chitosan materials were allowed to spread onto the surfaces of the glass slides, which were tightly lapped together and held them in water. Tensile shear adhesive strength of over 400 kPa was observed for the modified chitosan samples. The increase in the amino group concentration of the chitosan solutions and the molecular mass of the chitosan used effectively led to the increase in adhesive strength of the glass slides. In addition, in the case where the chitosan solution was gelled by the enzymatic reaction with dopamine in the presence of poly(ethylene glycol), adhesive strength sharply increased at shorter reaction times concomitantly with the increase in the viscosity of the chitosan solutions because the tyrosinase activity effectively was retained by poly(ethylene glycol). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1818–1827, 2007  相似文献   

6.
The efficiency of protein chemical modification on tyrosine residues with N‐methylluminol derivatives was drastically improved by using horseradish peroxidase (HRP). In the previous method, based on the use of hemin and H2O2, oxidative side reactions such as cysteine oxidation were problematic for functionalization of proteins selectively on tyrosine residues. Oxidative activation of N‐methylluminol derivatives with a minimum amount of H2O2 prevented the occurrence of oxidative side reactions under HRP‐catalyzed conditions. As probes for HRP‐catalyzed protein modification, N‐methylluminol derivatives showed much higher efficiency than tyramide without inducing oligomerization of probe molecules. Tyrosine modification also proceeded in the presence of β‐nicotinamide adenine dinucleotide (NADH, H2O2‐free conditions).  相似文献   

7.
《分离科学与技术》2012,47(1):111-122
Abstract

A possibility of Cr(VI) removal by the adsorption method is discussed in the paper. An adsorbent were hydrogel chitosan beads are produced by the phase inversion method (by changing pH). The possibility of removing Cr(VI) ions by both pure chitosan hydrogel and its chelate compounds (chitosan cross‐linked with Cu(II) and Ag(I) ions) was investigated. The adsorption proceeded from the solutions of potassium dichromate and ammonium dichromate (NH4)2Cr2O7 and K2Cr2O7. The process rates and adsorption isotherms were determined and described by relevant equations. The process rate was described by the pseudo‐ and second‐order equations, and adsorption equilibria by the Langmuir equations. A slight advantageous change in adsorption properties of chitosan beads was revealed after cross‐linking (for chromium concentration up to 10 g/dm3). A maximum adsorption was 1.1 gCr/g chitosan. Results of the studies show that chitosan hydrogel proves useful in the removal of Cr(VI) ions, additionally, cross‐linking with Cu(II) and Ag(I) ions has an advantageous effect in the case of low‐concentrated solutions.  相似文献   

8.
This study investigated a dual function system combining powdered activated carbon (PAC) and TiO2 for the removal of trace organics together with the in-situ regeneration of PAC. The combined system with PAC adsorption and TiO2 photo-oxidation for in-situ regeneration of the PAC was studied as a batch process. Bisphenol A (BPA), an endocrine disrupting compound present at low concentration levels, was used as a model compound. When UV light and 0.5 l min− 1 of oxygen were introduced to the PAC/TiO2 batch system, the removal of BPA was 2.3 to 3.1 times faster than that of neat TiO2 oxidation in the pH range of 4 to 10. However, mass transfer of the adsorbed BPA by diffusion from the PAC to oxidation sites on the surface of the TiO2 was found to be limited because PAC has a strong affinity to adsorb BPA. During in-situ regeneration of PAC by TiO2 photo-oxidation at pH 7 for 6 h, the removal of BPA from the PAC which was fully saturated with BPA was about 50%. The regeneration of the PAC was improved by increasing the UV-irradiation time (4 h to 12 h) and the light intensity (0.13 mW cm− 2 to 0.425 mW cm− 2), but it was not enhanced by increasing temperature, operating at basic conditions, or adding H2O2. The results suggest that a process with in-situ regeneration of PAC by TiO2 oxidation may be feasible.  相似文献   

9.
Fe/AC催化过氧化氢降解双酚A   总被引:2,自引:1,他引:2       下载免费PDF全文
周文  程治良  全学军  陈波 《化工学报》2013,64(3):936-942
传统Fenton反应存在对液相pH要求较高、Fe3+回收困难以及难以重复使用等问题。基于"活性离子固载化,酸性环境局部化"的设计思路,通过对活性炭(AC)表面酸化改性,制备得到载铁活性炭(Fe/AC)催化剂。研究了Fe/AC制备工艺与其性能之间的关系,结果表明,在载Fe3+量44.05 mg·g-1、煅烧温度200℃的制备工艺下可得到催化活性较高、稳定性好的Fe/AC催化剂。用性能优良的Fe/AC催化H2O2降解双酚A(BPA),其较佳催化反应条件为:反应时间60 min、反应温度20℃、溶液pH值为4.0≤pH≤8.0、Fe3+/H2O2摩尔比为0.007~0.012、30% H2O2用量为0.04 ml H2O2·(mg BPA)-1。本工作制备得到的Fe/AC催化剂具有较好的重复使用性能,在实际废水处理领域具有较大的应用前景。  相似文献   

10.
This paper reports the application of chitosan–Fe3O4 (CS–Fe3O4) nanocomposite modified glassy carbon electrodes for the amperometric determination of bisphenol A (BPA). We observed that the CS–Fe3O4 nanocomposite could remarkably enhance the current response and decrease its oxidation overpotential in the electrochemical detection. Experimental parameters, such as the amount of the CS–Fe3O4, the accumulation potential and time, the pH value of buffer solution etc. were optimized. Under the optimized conditions, the oxidation peak current was proportional to BPA concentration in the range between 5.0 × 10−8 and 3.0 × 10−5 mol dm−3 with the correlation coefficient of 0.9992 and the limit of detection of 8.0 × 10−9 mol dm−3 (S/N = 3). The proposed sensors were successfully employed to determine BPA in real plastic products and the recoveries were between 92.0% and 06.2%. This strategy might open more opportunities for the electrochemical determination of BPA in practical applications. Additionally, the leaching studies of BPA on incubation time using the as-prepared modified electrode were successfully carried out.  相似文献   

11.
Turnip roots, which are readily available in Mexico, are a good source of peroxidase, and because of their kinetic and biochemical properties have a high potential as an economic alternative to horseradish peroxidase (HRP). The efficiency of using turnip peroxidase (TP) to remove several different phenolic compounds as water‐insoluble polymers from synthetic wastewater was investigated. The phenol derivatives studied included phenol, 2‐chlorophenol, 3‐chlorophenol, o‐cresol, m‐cresol, 2,4‐dichlorophenol and bisphenol‐A. The effect of pH, substrate concentration, amount of enzyme activity, reaction time and added polyethylene glycol (PEG) was investigated in order to optimize reaction conditions. A removal efficiency ≥85% was achieved for 0.5 mmol dm?3 phenol derivatives at pH values between 4 and 8, after a contact time of 3 h at 25 °C with 1.28 U dm?3 of TP and 0.8 mmol dm?3 H2O2. Addition of PEG (100–200 mg dm?3) significantly reduced the reaction time required (to 10 min) to obtain >95% removal efficiency and up to 230% increase in remaining TP activity. A relatively low enzyme activity (0.228 U dm?3) was required to remove >95% of three phenolic solutions in the presence of 100–200 mg dm?3 PEG. TP showed efficient and fast removal of aromatic compounds from synthetic wastewaters in the presence of hydrogen peroxide and PEG. These results demonstrate that TP has good potential for the treatment of phenolic‐contaminated solutions. © 2002 Society of Chemical Industry  相似文献   

12.
Molecularly imprinted polymers (MIP) with high performance in selectively recognizing bisphenol A (BPA) were prepared by using a novel and facile surface molecular‐imprinting technique. Vinyl‐functionalized, monodispersed silica spheres were synthesized by a one‐step emulsion reaction in aqueous solution. Then, BPA surface molecularly imprinted polymers (SMIP) were prepared by polymerization with 4‐vinylpyridine as the functional monomer and ethylene glycol dimethacrylate as the crosslinker. Maximal sorption capacity (Qmax) of the resulting SMIP was up to 600 μmol g?1, while that of nonimprinted polymers was only 314.68 μmol g?1. Kinetic binding study showed that sorption capacity reached 70% of Qmax in 20 min and sorption equilibrium at 80 min. SMIP had excellent accessibility and affinity toward BPA, for the selectivity coefficients of SMIP for BPA in respect to phenol, p‐tert‐butylphenol, and o‐phenylphenol were 3.39, 3.35, and 3.02, respectively. The reusage process verified the SMIP owning admirably stable adsorption capacity toward BPA for eight times. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

13.
The aim of this study was to prepare magnetic beads that could be used for the removal of heavy‐metal ions from synthetic solutions. Magnetic poly(ethylene glycol dimethacrylate–1‐vinyl‐1,2,4‐triazole) [m‐poly(EGDMA–VTAZ)] beads were produced by suspension polymerization in the presence of a magnetite Fe3O4 nanopowder. The specific surface area of the m‐poly(EGDMA–VTAZ) beads was 74.8 m2/g with a diameter range of 150–200 μm, and the swelling ratio was 84%. The average Fe3O4 content of the resulting m‐poly(EGDMA–VTAZ) beads was 14.8%. The maximum binding capacities of the m‐poly(EGDMA–VTAZ) beads from aquous solution were 284.3 mg/g for Hg2+, 193.8 mg/g for Pb2+, 151.5 mg/g for Cu2+, 128.1 mg/g for Cd2+, and 99.4 mg/g for Zn2+. The affinity order on a mass basis was Hg2+ > Pb2+ > Cu2+ > Cd2+> Zn2+. The binding capacities from synthetic waste water were 178.1 mg/g for Hg2+, 132.4 mg/g for Pb2+, 83.5 mg/g for Cu2+, 54.1 mg/g for Cd2+, and 32.4 mg/g for Zn2+. The magnetic beads could be regenerated (up to ca. 97%) by a treatment with 0.1M HNO3. These features make m‐poly(EGDMA–VTAZ) beads potential supports for heavy‐metal removal under a magnetic field. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

14.
On the basis of the present study, the details of the recovery of cutting oil from oil‐in‐water emulsion using the modified forms of biopolymer chitosan viz., chitosan beads (CB), carboxylated chitosan beads (CCB), and lanthanum incorporated carboxylated chitosan beads (La‐CCB). Various oil sorption experiments were conducted using an extractive gravimetric method by optimizing various parameters such as contact time, pH, sorbent dosage, and initial oil concentration for maximum sorption. It was found that the oil removal percentage was comparatively less in the case of CB and CCB when compared with La‐CCB, which showed 85% of oil removal at acidic condition. The obtained adsorption equilibrium data was explained with Freundlich, Langmuir, D–R, and Tempkin isotherms to find the best fit for the sorption process. Thermodynamic parameters such as ΔG0, ΔH0, and ΔS0 were calculated in order to understand the nature of sorption process. The surface morphology and sorption of oil on the beads were confirmed by FTIR, SEM with EDAX, XRD, TGA, and DSC analysis. This work provides a potential platform for the expansion of oil removal technology. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43218.  相似文献   

15.
《分离科学与技术》2012,47(7):1521-1534
Abstract

Aqueous solutions of Acid Blue 74, Acid Orange 10, and Acid Violet 19 were subjected to Fenton/Fenton‐like oxidation and its combination with lime coagulation. The analysis indicated no dependence of chemical oxidation efficacy on dye concentration in the range of 0.1–1 g L?1. Complete or nearly complete (higher than 95%) color removal of all treated samples was observed. Dye:H2O2 weight ratio of 1∶2 proved optimal for treatment of all dye solutions by means of Fenton/Fenton‐like oxidation. Moderate doses of hydrogen peroxide led to the improvement of biodegradability of dye solutions. No formation of any toxic intermediates during the oxidation of Acid Orange 10 and Acid Violet 19 was detected. Only a slight toxicity increase was observed after Acid Blue 74 degradation by Fenton chemistry. H2O2/Fe3+ system with pH adjusted to 3 proved the most effective oxidation process. The combination of Fenton chemistry and subsequent lime coagulation was the most feasible treatment method of removing COD and UV254 and UVmax absorbance of dye solutions. Combined oxidation and coagulation was more effective for Acid Blue 74 and Acid Orange 10 elimination than for Acid Violet 19.  相似文献   

16.
In the present study, the treatability of aqueous DEP solution employing H2O2/UV-C oxidation and the changes in acute and/or chronic toxicity of untreated and H2O2/UV-C treated DEP solutions was investigated. For DEP removal and its ultimate oxidation (mineralization), an optimum initial H2O2 concentration of 40 mM was required. The HO? bimolecular reaction rate constant of DEP was found as 2.33 ± 0.27×108 M?1 s?1. Activated sludge inhibition experiments inferred that H2O2/UV-C treated DEP solutions were composed of a mixture of oxidation intermediates which exhibited higher degree of inhibition to heterotrophic biomass with respect to DEP. According to the results obtained in this work, the complete mineralization of DEP by H2O2/UV-C process would be a better option.  相似文献   

17.
Fungicidal and Insecticidal Activity of O-Acyl Chitosan Derivatives   总被引:1,自引:0,他引:1  
Summary A series of O-(acyl) chitosan (OAC) derivatives with a degree of substitution (DS) between 0.02 and 0.28 were synthesized by reaction of alkanoic acid derivatives with chitosan in the presence of H2SO4 as a catalyst. The reaction was performed at 80 °C for 4 h with different mol ratios of alkanoic acids to chitosan. The synthesized compounds were analyzed by 1H- and 13C-NMR spectroscopy. A high DS was obtained with O-(butyroyl) chitosan (DS 0.28) at a mol ratio of (1:5) chitosan to butyric acid. Their fungicidal activity against the grey mould Botrytis cinerea (Leotiales: Sclerotiniaceae) and the rice leaf blast pathogen Pyricularia grisea (Teleomorph: Magnaportha grisea) has been evaluated. O-(decanoyl) chitosan at mol ratio of 1:2 (chitosan to decanoic acid) was the most active compound against B. cinerea (EC50=1.02 g.l-1) and O-(hexanoyl) chitosan displayed the highest activity against P. grisea (EC50=1.11 g.l-1). It has been mentioned that some derivatives also repressed spore formation at rather high concentrations (1.0, 2.0 and 5.0 g.l-1). The insecticidal activity has been screened at 5 g.kg-1 artificial diet against the larvae of the cotton leafworm Spodoptera littoralis (Lepidoptera: Noctuidae). The results revealed that all of the synthesized derivatives showed high inhibition of growth of the larvae of S. littoralis compared to chitosan (7% growth inhibition) and the most active one was O-(decanoyl) chitosan (64% growth inhibition) after 5 days of feeding on treated artificial diet.  相似文献   

18.
Multiporous TiO2/Ti film electrodes were prepared by different anodic oxidation processes at low voltage, in which the micro-structured TiO2 thick films were prepared in H2SO4–H2O2–H3PO4–HF solution for 2 h and the nano-structured TiO2 thin films were prepared in H3PO4–HF solution for 30 min with post-calcination. Both types of TiO2/Ti films were characterized by scanning electron microscopy and X-ray diffraction analysis. The photocatalytic (PC) and photoelectrocatalytic (PEC) reactivity of the TiO2/Ti electrodes were evaluated in terms of bisphenol A (BPA) degradation in aqueous solution. The experimental results demonstrated that the nano-structured TiO2/Ti thin-film electrodes had higher reactivity in the BPA degradation reaction. The PEC degradation of BPA was further studied using different cathodes, either a reticulated vitreous carbon (RVC) electrode or a platinum (Pt) electrode. The experimental results confirmed that the efficiency of BPA degradation could be significantly enhanced in the TiO2/Ti–RVC reaction system due to the generation of H2O2 on the RVC cathode. It is believed that such a H2O2-assisted TiO2 PEC oxidation process may have good potential for water and wastewater treatment.  相似文献   

19.
The effects of environmentally relevant bisphenol A (BPA) concentrations (0.3, 1 and 3 μg L−1) were tested at 2, 4, 6 and 8 days, on intermediate leaves, of the seagrass Cymodocea nodosa. Hydrogen peroxide (H2O2) production, lipid peroxidation, protein, phenolic content and antioxidant enzyme activities were investigated. Increased H2O2 formation was detected even at the lowest BPA treatments from the beginning of the experiment and both the enzymatic and non-enzymatic antioxidant defense mechanisms were activated upon application of BPA. Elevated H2O2 levels that were detected as a response to increasing BPA concentrations and incubation time, led to the decrease of protein content on the 4th day even at the two lower BPA concentrations, and to the increase of the lipid peroxidation at the highest concentration. However, on the 6th day of BPA exposure, protein content did not differ from the control, indicating the ability of both the enzymatic and non-enzymatic mechanisms (such as superoxide dismutase (SOD) and phenolics) to counteract the BPA-derived oxidative stress. The early response of the protein content determined that the Low Effect Concentration (LOEC) of BPA is 0.3 μg L−1 and that the protein content meets the requirements to be considered as a possible early warning “biomarker” for C. nodosa against BPA toxicity.  相似文献   

20.
A novel bisphenol A (BPA) sensor based on amperometric detection has been developed by using molecularly imprinted polymers (MIPs) and gold nanoparticles. The sensitive layer was prepared by electropolymerization of 2-aminothiophenol on a gold nanoparticles-modified glassy carbon electrode in the presence of BPA as a template. Cyclic voltammetry was used to monitor the process of electropolymerization. The properties of the layer were studied in the presence of Fe(CN)6 3−/Fe(CN)6 4− redox couples. The template and the non-binding molecules were removed by washing with H2SO4 (0.65 mol L−1) solution. The linear response range of the sensor was between 8.0 × 10−6–6.0 × 10−2 mol L−1, with a detection limit of 1.38 × 10−7 mol L−1 (S/N = 3). The proposed MIPs sensor exhibited good selectivity for BPA. The stability and repeatability of the MIPs senor were found to be satisfactory. The results from real sample analysis confirmed the applicability of the MIPs sensor to quantitative analysis.  相似文献   

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