木质素过氧化物酶在球型介孔材料上的固定化特性研究

在醋酸-醋酸钠缓冲体系(pH=3.5)中以聚乙二醇-聚丙三醇-聚乙二醇三嵌段共聚物(P123)为模板,正硅酸甲酯(TMOS)为硅源,1,3,5-三异丙基苯(TIPB)为扩孔剂合成了具有规则六方形孔道(11.6nm)的微米级球型颗粒.以合成的介孔材料为载体,采用物理吸附法对木质素过氧化物酶(LiP)进行固定化,研究了初始酶量和固定化时间等因素对固定化效果的影响,以及固定化对LiP酶学性质和稳定性的影响.结果表明,当初始酶量(E)与载体量(MS)比为76.8mg/g,固定化反应12h时,固定化LiP可获得最大蛋白质负载量(8.87mg/g)和最大表观活性(41.45U/mg).与游离酶相比,固定化LiP的最适pH和温度均未有明显变化,但pH稳定性和热稳定性都有了不同程度的提高,在4℃条件下保存7周后固定化LiP活性几乎没有损失,且在重复使用6次后,可保留近30%的活性.     

Direct electrochemistry of glucose oxidase and biosensing for glucose based on DNA/chitosan film

Glucose oxidase (GOD) is widely used in the glucose biosensor industry. The amperometric biosensors based on directly electron transfer (DET) between an electrode and immobilized GOD are especially promising. In this article, GOD was immobilized with a DNA/chitosan bio-material film on GC electrode, and the DET of GOD on DNA/chitosan was studied. The cyclic voltammetric results indicated that the GOD immobilized in the DNA/chitosan film underwent DET reaction, and the cyclic voltammogram displayed a pair of well-defined redox peaks with a formal potential of ?0.45 V (vs. Ag/AgCl) at pH 5.5. The response showed a surface-controlled electrode process with an electron transfer rate constant of 0.91 sec^?1 determined in the scan rate range from 10 to 100 mV/sec. The GOD immobilized in DNA/chitosan membrane retained its biocatalytic activity and stability. The immobilized GOD could electrocatalyze the reduction of dissolved oxygen and resulted in a great increase of the reduction peak current. Upon the addition of glucose, the reduction peak current decreased, which could be used for glucose detection with a sensitivity of 0.48 μA/(mmol/L), a linear range from 0.04 to 2.28 mmol/L and a detection limit of 0.04 mmol/L at a signal-to-noise ratio of 3. The sensor could exclude the interference of commonly coexisted uricacid and ascorbic acid.     

AgCl/ZnO/GO光催化降解甲基橙的性能研究

为了提高ZnO对偶氮染料污染物的光催化降解效率,以AgCl和GO（氧化石墨烯）作为改性剂,通过水热法和化学沉积法制备了AgCl/ZnO/GO光催化材料,采用XRD、SEM、XPS、UV-Vis方法对材料的物相组成、微观形貌及光学特性进行表征;以MO（甲基橙）为目标污染物,探究其在可见光下的催化降解性能,考察AgCl含量、催化剂投加量、pH对其可见光催化活性的影响.结果表明:①AgCl的沉积和GO的负载增强了ZnO对可见光的响应能力,提高了光生电子-空穴产生、分离效率,同时增加了材料的分散性及其对MO的吸附率,因此AgCl/ZnO/GO光催化材料对MO有良好的可见光催化降解效率.②AgCl/ZnO/GO对MO的催化降解效率随着AgCl含量的增加而增加,随着催化剂投加量的增加呈先增后降的趋势,溶液pH对其降解效果有一定影响,但不显著.③当AgCl/ZnO（二者物质的量的比）为2:1、AgCl/ZnO/GO投加量为70 mg、pH为7、室温下经过可见光照射50 min后,AgCl/ZnO/GO对质量浓度为10 mg/L的MO的降解率可达98.93%;此外,该催化剂重复使用4次对MO仍具有88%的去除率,显示出良好的稳定性.因此,AgCl/ZnO/GO是一种高效、稳定的可见光光催化剂,在废水净化方面具有良好的应用前景.      

Immobilization of an enzyme from a Fusarium fungus WZ-I for chlorpyrifos degradation

The free enzyme extracted from WZ-I,which was identified as Fusarium LK.ex Fx,could effectively degrade chlorpyrifos,an organophosphate insecticide.The methods of immobilizing this free enzyme and determined its degradation-related characteristics were investigated.The properties of the immobilized enzyme were compared with those of the free enzyme.The optimal immobilization of the enzyme was achieved in a solution of 30 g/L sodium alginate at 4°C for 4-12 hr.The immobilized enzyme showed the maximal activity at pH 8.0,45°C.The maximum initial rate and the substrate concentration of the immobilized enzyme were less than that of the free enzyme.The immobilized enzyme,therefore,had a higher capacity to withstand a broader range of temperatures and pH conditions than the free enzyme.With varying pH and temperatures,the immobilized enzyme was more active than the free enzyme in the degradation reaction.In addition,the immobilized enzyme exhibited only a slight loss in its initial activity,even after three repeated uses.The results showed that the immobilized enzyme was more resistant to different environmental conditions,suggesting that it was viable for future practical use.     

生物炭对土壤酶活和细菌群落的影响及其作用机制

生物炭因其独特的理化性质能够提高土壤碳氮矿化速率及改善土壤微生态环境,因此探索生物炭调控土壤微生态环境与土壤酶活及其作用机制对改善土壤质量具有重要意义.采用大田试验方式研究不同生物炭施用水平0（CK2）、0.6（T1）、0.9（T2）、1.2（T3）和1.5（T4）t·hm^-2以及完全空白对照（CK1：不施任何肥料和生物炭）对土壤养分、土壤酶活和细菌群落结构的影响.结果表明,生物炭施用后土壤容重降低,pH值、速效磷、速效钾、有机质含量和碳氮比均升高,较CK2处理提高的范围分别为0.32%~5.83%、14.09%~23.16%、0%~38.70%、7.49%~14.16%和4.06%~10.13%.随着生物炭用量的增加,4个土壤酶活性均呈现先升高后降低的趋势;蔗糖酶（INV）、脲酶（URE）、过氧化氢酶（CAT）和中性磷酸酶（NPH）分别较CK2处理提高的范围为63.73%~166.37%、117.52%~174.03%、12.98%~23.59%和60.84%~119.71%.与此相对应的细菌多样性显著提升,尤其是增加了芽单胞菌门（Gemmatimonadetes）和变形菌门（Proteobacteria）等促生菌的丰度;减少酸杆菌门（Acidobacteria）、放线菌门（Actinobacteria）的丰度.相关性分析表明土壤碳氮比是影响土壤酶活性的关键因素,且土壤酶活又与细菌多样性存在显著的正相关关系;上述4种土壤酶活与芽单胞菌门（Gemmatimonadetes）的相对丰度呈现极显著正相关关系（P<0.01）,其中CAT是影响细菌群落结构的关键因子.本研究揭示了生物炭对土壤酶活及微生物菌落影响作用机制,为生物炭调控土壤酶体系和微生态生物学环境提供了理论依据.     

固定化蛋白酶对废水中蛋白质的水解效果与机理

采用吸附方法将蛋白酶固定于活性炭、大孔树脂和硅胶载体上,分别研究了3种载体蛋白酶固定化效果,酶活性以及对淀粉加工黄浆废水中蛋白质的水解效果.批次试验结果表明,3种载体蛋白酶固定效果分别为:硅胶20.31%,大孔树脂37.85%,活性炭61.95%;酶活性最高时pH均为5.5;酶活性分别为3.6mg/min、21.48mg/min和18.68mg/min .水解后,大孔树脂和活性炭固定酶的水解产物氨基酸总量分别较水解前增加21.26倍和14.6倍;产物中检出1 6种氨基酸,较水解前增加2种.以大孔树脂为载体构建固定化酶反应器进行连续进水试验,结果表明:进水中蛋白质浓度明显影响反应器的水解效果,当其蛋白质浓度与反应器的酶浓度匹配时(500mg/L) ,反应器能获得80 %蛋白质水解率和36.1%有机物水解酸化率.挥发性水解产物组成以乙醇和乙酸为主,分别占50.3%,33.3%.为乙醇型水解.     

Thiolsulfonate functionalized polystyrene resin： Preparation and application in the isolation and identification of electrophilic mutagens

A new approach for isolation and identification of elecrtophilic mutagens from complex matrix was developed.Thiosulfonic anion was immobilized onto polystyrene beads and used as separation media.Potassium polystyryl-thiosulfonate,prepared from polystyryl- sulfonyl chloride and KHS,was observed to selectively react with model electrophilic mutagens such as alkyl halides,α-chloroketones andα-chloroesters to produce polystyryl-thiosulfonic esters.After separation from other nonreactive organic compounds,the beads then reacted with ethanethiol to produce unsymmetrical ethyl disulfides which are easily detected by GC/MS.For one mutagenic compound,only one unsymmetrical disulfide was found to contain its structure part.Thus,the structure of the parent mutagens could be deduced from that of the unsymmetrical disulfides.The degree of functionaiization of the potassium polystyryl-thiosulfonate resin was 1.11 mmol/g.Its reactivity was discussed and its recycling method was reported here.     

快速高效去除微囊藻的GO/QPEI复合纳米材料

本研究合成了一种新型高效的去除铜绿微囊藻(Microcystis aeruginosa)的氧化石墨烯/季铵盐聚乙烯亚胺(GO/QPEI)纳米复合材料.GO/QPEI在pH为4~10的条件下都具有高效去除M.aeruginosa的能力,其去除能力在2 min内可达96%以上.GO/QPEI对微囊藻的吸附更符合Freundlich方程,最大吸附量为5.58×1011cells·mg-1.吸附动力学表明GO/QPEI的假二级吸附反应.GO纳米片和QPEI的协同效应是其高效去除微囊藻的主要机制.     

四种酰胺类除草剂对土壤酶活性的影响

在实验室控制条件下,研究了酰胺类除草剂丁草胺、乙草胺、丙草胺和异丙甲草胺在田间推荐用量下,对土壤过氧化氢酶活性和脱氢酶活性的影响.结果表明,培养初期,4种除草剂对2种酶活性有不同程度的抑制作用,土壤过氧化氢酶活性于第7d就很快恢复,而脱氢酶活性在13d后得以逐渐恢复.添加稻秆可使土壤酶活性提高,土壤脱氢酶比过氧化氢酶活性变化大.4种除草剂对土壤生态环境影响不大,稻秆还田有利于提高土壤中生化过程的活性,缓冲外来污染物对土壤生态的影响.     

固定化碳酸酐酶在立式反应器催化吸收模拟烟气中CO2的实验研究

利用海藻酸钠包埋和戊二醛交联法固定碳酸酐酶,并在立式反应器进行了固定化酶吸收CO2的特性实验.实验结果表明:固定化酶的酶活力回收率是56.3%;固定化酶显著加快模拟烟气中CO2的吸收;载酶量小时,气体流量是影响吸收CO2效果的主要因素,气体流量增大,载酶量成为主要因素;气体流量增大,载酶量对反应终止p H的影响减小;载酶量增大,气体流量对反应终止p H的影响减小;气体流量增大,CO2吸收效率下降,载酶量提高,CO2吸收效率上升;气体流量为650 m L·min-1和载酶量为1 mg时,固定化酶催化吸收CO2效果显著;固定化酶具有较高的操作稳定性;SEM显示反应后的固定化酶表面出现大量形状不规则的小孔,空隙结构变得发达.     

TiO2/GO复合材料紫外光催化降解水中腐植酸

采用溶胶凝胶法在最优煅烧温度（350℃）下,制备不同石墨烯（GO）负载比例的TiO₂/GO复合光催化材料,通过SEM、XRD、Raman、FT-IR、TGA、BET等技术表征并分析材料的表面形貌、晶相结构、官能团与化学键合等特征,进而探究该复合材料在紫外光下对水中腐植酸（HA）的降解性能和机理。结果表明:随着石墨烯（GO）负载比例的增大,TiO₂/GO复合催化剂粒径变小,比表面积增大,有层次的形貌空隙有效减小了团聚,提升了光生载流子迁移效率;Raman光谱中1350 cm-1和1600 cm-1的2处特征峰验证GO成功负载,且晶型仍以锐钛矿相为主;3%GO负载量的TiO₂/GO光催化性能最优。当TiO₂/3%GO投加量为0.5 g/L,水中HA初始浓度为10 mg/L时,在紫外光下催化反应1 h后降解率达到84.7%,其降解速率常数为0.0313 min-1。     

腐植酸改性生物质电厂灰固定化微生物修复石油烃污染土壤

以生物质电厂灰为载体,用腐植酸对其改性后,负载石油烃降解菌形成固定化菌剂对原油污染土壤进行修复,其中对生物质电厂灰改性的最佳条件以及固定化菌剂对原油污染土壤的修复效果进行了考察。结果表明:生物质电厂灰改性的最佳条件为:电厂灰粒径10~40目,固液比1∶1,改性时间4 h,改性后孔状结构增多且表面粗糙,有利于微生物的附着,固定的微生物数量可达1.5×109 CFU/g。进行60 d的修复后,固定化菌剂对污染土壤中石油烃的降解率达到51.9%,比游离菌提高了25.0%,对长链正构烷烃、芳香烃及胶质的降解率分别提高了9.6%、31.7%和37.5%。固定化生物质电厂灰的应用使石油烃降解菌得到保护和支撑,提高了土壤基础呼吸速率和土壤酶活性,实现了石油烃的高效降解。因此,腐植酸改性生物质电厂灰是一种在石油污染土壤修复方面具有应用潜力的微生物固定化材料。     

固定化工程菌对偶氮染料脱色及强化作用

利用聚亚胺酯大孔泡沫吸附固定基因工程菌Escherichia coli JM109 (pGEX-AZR),研究其对偶氮染料的脱色动力学及生物强化作用.实验表明,固定的E.coli JM109(pGEX-AZR) 对酸性大红GR的脱色动力学符合Andrews方程,动力学常数为μ_max,c、K_c、K_ic分别为49 .2 mg·(g·h)^-1、710 .43 mg·L^-1和681 .62　mg·L^-1,R²为0 .995.将固定的E.coli JM109(pGEX-AZR)按10%的比例投加到厌氧序批式活性污泥反应器中连续运行32 d,含有固定化工程菌的强化体系耐浓度冲击的能力和脱色率均高于对照体系,脱色率可以稳定在90%以上.利用RISA对其微生物群落结构进行分析,E.coli JM109(pGEX-AZR)及降解酸性大红GR的优势菌群可以在污泥体系中稳定存在.     

一种耐酚菌种及其固定化细胞降解含酚废水性能的比较研究

通过对土壤及污水的采样、分离、纯化,得到了一种降解苯酚的菌种,经过一系列驯化实验,使其苯酚耐受能力达915 mg/L。在此基础上,利用正交实验,确定了该菌种固定化细胞制备的最优操作条件。之后,对游离细胞和固定化细胞的降解苯酚过程进行了动力学分析与比较。结果表明,2种类型细胞的降解苯酚过程均符合Monod模型,并且固定化细胞的降解效果明显高于游离细胞。      

固定化优势菌种降解2,6-二叔丁基酚

 用海藻酸钙包埋固定优势降解菌(Alcaligenes sp.)降解 2,6-二叔丁基酚(2,6-2DTBP).结果表明,菌株经固定化包埋后,降解底物 2,6-DTBP的能力大大提高,在 100.0mg/L 的初始浓度下其降解率在 12d 可达到 86%.与未固定菌株相比,固定化菌株对 pH 值和温度的适应范围更宽,对底物具有更高的降解能力.对固定化菌株的降解反应过程进行动力学分析,该降解反应符合一级动力学特征,其动力学常数为 0.1519,半衰期为 4.56d.扫描电镜观察到菌种在海藻酸钙包埋载体中能良好地生长和繁殖.     

Tyrosinase-modified carbon felt-based flow-biosensors: The role of ultra-sonication in shortening the enzyme immobilization time and improving the sensitivity for p-chlorophenol

Tyrosinase (TYR) was covalently immobilized onto amino-functionalized carbon felt surface via glutaraldehyde-coupling under ultrasonic treatment for 10 min. The resulting TYR-immobilized carbon felt was used as a working electrode unit of bioelectrocatalytic flow-through detector for TYR substrates (catechol, p-chlorophenol (p-CP), p-cresol, phenol etc.). Cathodic peak currents based on the electroreduction of enzymatically produced o-quinones were detected at –50 mV vs. Ag/AgCl. Compared with previous work in which TYR was immobilized onto amino-functionalized carbon felt for 16 hr without the ultrasonic treatment, we succeeded in (1) shortening the enzyme immobilization time from 16 hr to 10 min, (2) enhancing the sensitivity of p-CP, and (3) improving the operational stability of p-CP. The ultrasonic treatment during the TYR immobilization step would lead to certain changes in the structure of the immobilized TYR and the morphology of the immobilized TYR-layer on the carbon felt surface.     

己烯雌酚降解菌固定化条件优化及其降解性能

以海藻酸钠为包埋剂,制备了己烯雌酚(DES)降解菌株S(Serratia sp.)的固定化菌剂,通过正交试验确定了菌株S的最佳固定化条件:海藻酸钠质量分数为4%,菌悬液与海藻酸钠重量比为1:2,CaCl₂质量分数为4%,交联时间为6h.菌株S的固定化菌剂比游离菌株更有优势;7d时,固定化菌株S对无机盐培养基中DES的去除率为83.84%,较游离菌株高22.84%.优化了固定化菌株S对溶液中DES的处理条件:固定化菌株S接入量为300g/L,初始底物浓度为20~40mg/L.固定化菌株S对DES浓度为40.01,37.90 ,33.52μg/L 3个排污口污水中DES的去除率分别达90.0%,96.0%,96.7%.利用固定化菌株处理实际污水中DES等雌激素具有应用潜力.     

固定化脱色菌－活性污泥的脱色性能研究

将所筛选的高效脱色菌群,采用聚集－交联法固定在活性污泥上,形民絮状立体网状微观结构。固定化脱色菌－活性污泥的脱色酶活力较未经固定的活性污泥提高７０％左右。经厌氧条件下处理针织厂印染废水,色度平均去降率为７７．３％,ＣＯＤＣｒ平均去除率为６５．１％。     

Enhanced photocatalytic activities of silicon nanowires/graphene oxide nanocomposite: Effect of etching parameters

Homogeneous and vertically aligned silicon nanowires (SiNWs) were successfully fabricated using silver assisted chemical etching technique. The prepared samples were characterized using scanning electron microscopy, transmission electron microscopy and atomic force microscopy. Photocatalytic degradation properties of graphene oxide (GO) modified SiNWs have been investigated. We found that the SiNWs morphology depends on etching time and etchant composition. The SiNWs length could be tuned from 1 to 42 µm, respectively when varying the etching time from 5 to 30 min. The etchant concentration was found to accelerate the etching process; doubling the concentrations increases the length of the SiNWs by a factor of two for fixed etching time. Changes in bundle morphology were also studied as function of etching parameters. The SiNWs diameter was found to be independent of etching time or etchant composition while the size of the SiNWs bundle increases with increasing etching time and etchant concentration. The addition of GO was found to improve significantly the photocatalytic activity of SiNWs. A strong correlation between etching parameters and photocatalysis efficiency has been observed, mainly for SiNWs prepared at optimum etching time and etchant concentrations of 10 min and 4:1:8. A degradation of 92% was obtained which further improved to 96% by addition of hydrogen peroxide. Only degradation efficiency of 16% and 31% has been observed for bare Si and GO/bare Si samples respectively. The obtained results demonstrate that the developed SiNWs/GO composite exhibits excellent photocatalytic performance and could be used as potential platform for the degradation of organic pollutants.     

十溴联苯醚对土壤酶活性及土壤呼吸强度的影响

采用室内模拟试验考察十溴联苯醚对土壤呼吸强度和土壤脲酶活性、磷酸酶活性及过氧化氢酶活性的影响,探讨十溴联苯醚外源化学物质对土壤环境的生态效应.结果表明,在w(十溴联苯醚)为10,100和500 mg/kg的条件下,十溴联苯醚对土壤呼吸强度和土壤脲酶活性有显著的抑制作用,且随处理土壤样品中w(十溴联苯醚)的增加,抑制作用增强. 十溴联苯醚对过氧化氢酶活性的作用表现为先激活后抑制,而土壤磷酸酶活性对十溴联苯醚不敏感.十溴联苯醚对土壤生态系统具有一定的破坏作用.