整体型大孔/介孔PDA/SiO_2复合材料固定化漆酶及其在染料降解中的应用
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摘要
用硬模板法制得具有三维连续贯通孔道结构的整体型大孔/介孔SiO_2,通过多巴胺(DA)在大孔/介孔SiO_2孔道表面的原位氧化聚合,制得聚多巴胺(PDA)功能化修饰的整体型大孔/介孔复合材料(PDA/SiO_2)。应用SEM、BET、FTIR和TG等技术对修饰前后的材料进行表征。以PDA/SiO_2为载体固定诺维信工业级漆酶,系统研究了pH、固定化时间、漆酶初始浓度及温度对漆酶固定化的影响;以偶氮荧光桃红作为模拟污染物,研究了固定化漆酶对染料的催化降解性能。结果显示,在漆酶浓度为80mg/mL、pH为4.0、固定化时间为6h及固定化温度为25℃时,固定化漆酶酶活达到最高(348.9U/g)。在偶氮荧光桃红浓度为10mg/L、pH为7.0、温度为30℃、降解时间为8h时,固定化漆酶对偶氮荧光桃红脱色率≥99.9%,且固定化漆酶易从反应体系中分离,重复使用性能良好。
A monolithic macroporous/mesoporous SiO_2 with three-dimensional(3D) continuous passthrough pore structure was prepared by the hard template method. It was the surface functionalized with polydopamine(PDA) by the in situ oxidation polymerization of dopamine in its micro-channels to obtainthe macroporous/mesoporous composite PDA/SiO_2. Samples were characterized by SEM,BET,FTIR andTG. PDA/SiO_2 was used to immobilize commercial Novozymes laccase; and the effects of pH,immobilizingtime,initial concentration of laccase and temperature on laccase immobilization were investigated. Usingazophloxine as a simulated pollutant, the catalytic performance of the immobilized laccase for thedegradation of dye was studied. The results showed that the activity of immobilized laccase reached themaximum(348.9U/g) under conditions of initial laccase concentration 80mg/mL,pH of 4.0,immobilizingtime of 6h and temperature of 25℃. Up to 99.9% of azophloxine was decolored under azophloxine concentration 10mg/L,pH of 7.0,temperature of 30℃,and degradation time of 8h.The immobilized laccase exhibited good reusability and it can be easily recovered from the reaction system.
A monolithic macroporous/mesoporous SiO_2 with three-dimensional(3D) continuous passthrough pore structure was prepared by the hard template method. It was the surface functionalized with polydopamine(PDA) by the in situ oxidation polymerization of dopamine in its micro-channels to obtainthe macroporous/mesoporous composite PDA/SiO_2. Samples were characterized by SEM,BET,FTIR andTG. PDA/SiO_2 was used to immobilize commercial Novozymes laccase; and the effects of pH,immobilizingtime,initial concentration of laccase and temperature on laccase immobilization were investigated. Usingazophloxine as a simulated pollutant, the catalytic performance of the immobilized laccase for thedegradation of dye was studied. The results showed that the activity of immobilized laccase reached themaximum(348.9U/g) under conditions of initial laccase concentration 80mg/mL,pH of 4.0,immobilizingtime of 6h and temperature of 25℃. Up to 99.9% of azophloxine was decolored under azophloxine concentration 10mg/L,pH of 7.0,temperature of 30℃,and degradation time of 8h.The immobilized laccase exhibited good reusability and it can be easily recovered from the reaction system.
引文
[1] WANG H X, ZHANG W, ZHAO J X, et al.Rapid decolorization ofphenolic azo dyes by immobilized laccase with Fe3O4/SiO2nanoparticles as support[J]. Industrial&Engineering ChemistryResearch, 2013, 52(12):4401-4407.
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[3] LIN Z, YIN Y Q, XIAO Y, et al. An enzyme-inorganic hybridnanoflowers based immobilized enzyme reactor with enhancedenzymatic activity[J]. Journal of Materials Chemistry B, 2015, 3(11):2295-2300.
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[10] ZHENG X B, WANG Q, JIANG Y J, et al. Biomimetic synthesis ofmagnetic composite particles for laccase immobilization[J]. Industrial&Engineering Chemistry Research, 2012, 51(30):10140-10146.
[11] ANSARI S A, Husain Q. Potential applications of enzymesimmobilized on/in nano materials:a review[J]. Biotechnology Advances,2012, 30(3):512.
[12] KALKAN N A, AKSOY S, AKSOY E A, et al. Preparation of chitosan-coated magnetite nanoparticles and application for immobilization oflaccase[J]. Journal of Applied Polymer Science, 2012, 123(2):707-716.
[13]王磊,陈诚,田美娟,等.介孔SiO2的改性及对诺维信漆酶的交联固定化[J].无机化学学报, 2013, 29(4):677-688.WANG L, CHEN C, TIAN M J, et al. Modified mesoporous silica:synthesis and immobilization function for novozymes laccase[J].Chinese Journal of Inorganic Chemistry, 2013, 29(4):677-688.
[14] XU R, ZHOU Q J, LI F T, et al. Laccase immobilization on chitosan/poly(vinyl alcohol)composite nanofibrous membranes for 2, 4-dichlorophenol removal[J]. Chemical Engineering Journal, 2013, 222(15):321-329.
[15] JIANG Y J, WANG Y P, WANG H, et al. Facile immobilization ofenzyme on three dimensionally ordered macroporous silica via abiomimetic coating[J]. New Journal of Chemistry, 2015, 39(2):978-984.
[16]刘晓贞,李云,梁云霄,等.二氧化硅/壳聚糖大孔复合材料固定化漆酶及其对2, 4-二氯苯酚的降解[J].高校化学工程学报, 2016, 30(1):201-209.LIU X Z, LI Y, LIANG Y X, et al. Laccase immobilization with silica/chitosan macroporous composites and its application in 2, 4-dichlorophenol degradation[J]. Journal of Chemical Engineering ofChinese Universities, 2016, 30(1):201-209.
[17]张笛,邓满凤,赵赫,等.多巴胺包埋磁性SiO2固定化漆酶催化去除4-氯酚[J].化工学报, 2015, 66(9):3705-3711.ZHANG D, DENG M F, ZHAO H, et al. Immobilization of laccase onmagnetic SiO2through dopamine self-polymerization for 4-CP removal[J]. CIESC Journal, 2015, 66(9):3705-3711.
[18] CHO J H, SHANMUGANATHAN K, ELLISON C J. Bioinspiredcatecholic copolymers for antifouling surface coatings[J]. ACS AppliedMaterials&Interfaces, 2013, 5(9):3794.
[19] LIU N, WU H, MCDOWELL M T, et al. A yolk-shell design forstabilized and scalable Li-ion battery alloy anodes[J]. Nano Letters,2012, 12(6):3315.
[20] SAFARI M, GHIACI M, JAFARI-ASL M, et al. Nanohybrid organicinorganic chitosan/dopamine/TiO2, composites with controlled drug-delivery properties[J]. Applied Surface Science, 2015, 342:26-33.
[21]?ORMAN M E,?ZTüRK N, BERELI N, et al. Preparation ofnanoparticles which contains histidine for immobilization of Trametes versicolor, laccase[J]. Journal of Molecular Catalysis B:Enzymatic,2010, 63(1/2):102-107.
[22] MALININ A S, RAKHNYANSKAYA A A, BACHEVA A V, et al.Activity of an enzyme immobilized on polyelectrolyte multilayers[J].Polymer Science, 2011, 53(1):52-56.
[23] VAIDYA B K, INGAVLE G C, PONRATHNAM S, et al.Immobilization of Candida rugosa lipase on poly(allyl glycidyl ether-co-ethylene glycol dimethacrylate)macroporous polymer particles[J].Bioresource Technology, 2008, 99(9):3623-3629.
[24]丁莉.漆酶对染料降解的研究[D].苏州:苏州大学, 2007.DING L. Study on decoloration of dyestuffs by laccase[D]. Suzhou:Soochow University, 2007.
[25]杨波,杜丹,孙也,等.漆酶对活性黑KN-B和直接大红染料的脱色性能[J].环境工程学报, 2013, 7(12):4835-4840.YANG B, DU D, SUN Y, et al. Decolorization performance of reactiveblack KN-B and direct red dyes with laccase[J]. Chinese Journal ofEnvironmental Engineering, 2013, 7(12):4835-4840.
[26]房伟,方泽民,常飞,等.重组海洋细菌漆酶Lac15脱色人工合成纺织染料的潜力[J].生物工程学报, 2012, 28(8):973-980.FANG W, FANG Z M, CHANG F, et al. Dye decolorization bybacterial laccase Lac15[J]. Chinese Journal of Biotechnology, 2012, 28(8):973-980.
[27] SATHISHKUMAR P, CHAE J C, UNNITHAN A R, et al. Laccase-poly(lactic-co-glycolic acid)(PLGA)nanofiber:highly stable, reusable,and efficacious for the transformation of diclofenac[J]. Enzyme&Microbial Technology, 2012, 51(2):113-118.
[2] LLORET L, EIBES G, FEIJOO G, et al. Immobilization of laccase byencapsulation in a sol-gel matrix and its characterization and use forthe removal of estrogens[J]. Biotechnology Progress, 2011, 27(6):1570.
[3] LIN Z, YIN Y Q, XIAO Y, et al. An enzyme-inorganic hybridnanoflowers based immobilized enzyme reactor with enhancedenzymatic activity[J]. Journal of Materials Chemistry B, 2015, 3(11):2295-2300.
[4] LIESE A, HILTERHAUS L. Evaluation of immobilized enzymes forindustrial applications[J]. Cheminform, 2013, 44(38):6236-6249.
[5] WANG T N, LU L, LI G F, et al. Decolorization of the azo dye reactiveblack 5 using laccase mediator system[J]. African Journal ofBiotechnology, 2011, 10(75):17186-17191.
[6] ZENG X K, CAI Y J, LIAO X R, et al. Anthraquinone dye assisted thedecolorization of azo dyes by a novel trametes trogii laccase[J]. ProcessBiochemistry, 2012, 47(1):160-163.
[7] RIVA S. Laccases:blue enzyme for green chemistry[J]. Trends inBiotechnology, 2006, 24:219-226.
[8]赖超凤,李爽,彭丽丽,等.漆酶及其在有机合成中应用的研究进展[J].化工进展, 2010, 29(7):1300.LAI C F, LI S, PENG L L, et al. Progress of applications of laccase inorganic synthesis[J]. Chemical Industry and Engineering Progress,2010, 29(7):1300.
[9]朱显峰,秦仁炳,余晨晨,等.蜜环菌漆酶对蒽醌类染料的脱色条件优化[J].环境科学, 2012, 33(2):495-498.ZHU X F, QIN R B, YU C C, et al. Optimization on decolorationconditions of anthraquinone dyes by laccase from Amillariella mellea[J]. Environmental Science, 2012, 33(2):495-498.
[10] ZHENG X B, WANG Q, JIANG Y J, et al. Biomimetic synthesis ofmagnetic composite particles for laccase immobilization[J]. Industrial&Engineering Chemistry Research, 2012, 51(30):10140-10146.
[11] ANSARI S A, Husain Q. Potential applications of enzymesimmobilized on/in nano materials:a review[J]. Biotechnology Advances,2012, 30(3):512.
[12] KALKAN N A, AKSOY S, AKSOY E A, et al. Preparation of chitosan-coated magnetite nanoparticles and application for immobilization oflaccase[J]. Journal of Applied Polymer Science, 2012, 123(2):707-716.
[13]王磊,陈诚,田美娟,等.介孔SiO2的改性及对诺维信漆酶的交联固定化[J].无机化学学报, 2013, 29(4):677-688.WANG L, CHEN C, TIAN M J, et al. Modified mesoporous silica:synthesis and immobilization function for novozymes laccase[J].Chinese Journal of Inorganic Chemistry, 2013, 29(4):677-688.
[14] XU R, ZHOU Q J, LI F T, et al. Laccase immobilization on chitosan/poly(vinyl alcohol)composite nanofibrous membranes for 2, 4-dichlorophenol removal[J]. Chemical Engineering Journal, 2013, 222(15):321-329.
[15] JIANG Y J, WANG Y P, WANG H, et al. Facile immobilization ofenzyme on three dimensionally ordered macroporous silica via abiomimetic coating[J]. New Journal of Chemistry, 2015, 39(2):978-984.
[16]刘晓贞,李云,梁云霄,等.二氧化硅/壳聚糖大孔复合材料固定化漆酶及其对2, 4-二氯苯酚的降解[J].高校化学工程学报, 2016, 30(1):201-209.LIU X Z, LI Y, LIANG Y X, et al. Laccase immobilization with silica/chitosan macroporous composites and its application in 2, 4-dichlorophenol degradation[J]. Journal of Chemical Engineering ofChinese Universities, 2016, 30(1):201-209.
[17]张笛,邓满凤,赵赫,等.多巴胺包埋磁性SiO2固定化漆酶催化去除4-氯酚[J].化工学报, 2015, 66(9):3705-3711.ZHANG D, DENG M F, ZHAO H, et al. Immobilization of laccase onmagnetic SiO2through dopamine self-polymerization for 4-CP removal[J]. CIESC Journal, 2015, 66(9):3705-3711.
[18] CHO J H, SHANMUGANATHAN K, ELLISON C J. Bioinspiredcatecholic copolymers for antifouling surface coatings[J]. ACS AppliedMaterials&Interfaces, 2013, 5(9):3794.
[19] LIU N, WU H, MCDOWELL M T, et al. A yolk-shell design forstabilized and scalable Li-ion battery alloy anodes[J]. Nano Letters,2012, 12(6):3315.
[20] SAFARI M, GHIACI M, JAFARI-ASL M, et al. Nanohybrid organicinorganic chitosan/dopamine/TiO2, composites with controlled drug-delivery properties[J]. Applied Surface Science, 2015, 342:26-33.
[21]?ORMAN M E,?ZTüRK N, BERELI N, et al. Preparation ofnanoparticles which contains histidine for immobilization of Trametes versicolor, laccase[J]. Journal of Molecular Catalysis B:Enzymatic,2010, 63(1/2):102-107.
[22] MALININ A S, RAKHNYANSKAYA A A, BACHEVA A V, et al.Activity of an enzyme immobilized on polyelectrolyte multilayers[J].Polymer Science, 2011, 53(1):52-56.
[23] VAIDYA B K, INGAVLE G C, PONRATHNAM S, et al.Immobilization of Candida rugosa lipase on poly(allyl glycidyl ether-co-ethylene glycol dimethacrylate)macroporous polymer particles[J].Bioresource Technology, 2008, 99(9):3623-3629.
[24]丁莉.漆酶对染料降解的研究[D].苏州:苏州大学, 2007.DING L. Study on decoloration of dyestuffs by laccase[D]. Suzhou:Soochow University, 2007.
[25]杨波,杜丹,孙也,等.漆酶对活性黑KN-B和直接大红染料的脱色性能[J].环境工程学报, 2013, 7(12):4835-4840.YANG B, DU D, SUN Y, et al. Decolorization performance of reactiveblack KN-B and direct red dyes with laccase[J]. Chinese Journal ofEnvironmental Engineering, 2013, 7(12):4835-4840.
[26]房伟,方泽民,常飞,等.重组海洋细菌漆酶Lac15脱色人工合成纺织染料的潜力[J].生物工程学报, 2012, 28(8):973-980.FANG W, FANG Z M, CHANG F, et al. Dye decolorization bybacterial laccase Lac15[J]. Chinese Journal of Biotechnology, 2012, 28(8):973-980.
[27] SATHISHKUMAR P, CHAE J C, UNNITHAN A R, et al. Laccase-poly(lactic-co-glycolic acid)(PLGA)nanofiber:highly stable, reusable,and efficacious for the transformation of diclofenac[J]. Enzyme&Microbial Technology, 2012, 51(2):113-118.