Amperometric hydrogen peroxide biosensor based on immobilization of DNA-Cu(II) in DNA/chitosan polyion complex membrane

DNA/chitosan polyion complex membrane was used as a support for immobilization of electrocatalytic species-copper ions, which specifically bound to dsDNA and catalyzed the hydrogen peroxide reduction. The polyion complex membrane consisted with DNA-Cu(II) complex and chitosan was prepared on a glassy carbon electrode (GCE). Electrochemical measurements of the DNA-Cu(II)/chitosan membrane-modified GCE revealed that the copper ion embedded in the DNA/chitosan layer exhibited good electrochemical behaviors. The DNA-Cu(II)/chitosan/GC electrode showed an excellent electrocatalytic activity for the H₂O₂ reduction. Even in the presence of dissolved oxygen, the sensor exhibited highly sensitive and rapid (response time, about 6 s) response to H₂O₂. The steady-state cathodic current responses of the sensor obtained at ?0.2 V versus Ag/AgCl in air-saturated 100 mmol/L phosphate buffer (pH 5.0) increased linearly up to 10 mmol/L with the detection limit of 3 μmol/L. Effects of applied potential and buffer pH upon the response currents of the sensor were investigated for an optimum analytical performance. Ascorbic acid and glucose almost have no interference to measurement of H₂O₂. In addition, the sensor exhibited good reproducibility.     

Electrocatalytic reduction of ortho nitrobenzaldehyde using modified aluminum electrode and its determination

A simple, cost effective and rapid electrochemical method has been developed for the determination of micro level ortho nitrobenzaldehyde（ONB） based on outstanding properties of modified aluminum electrode tin nanorods/anodic aluminum oxide/aluminum（SnNR/AAO/Al） for the first time. The SnNR/AAO/Al electrode was fabricated by a second step anodization, followed by electrodeposition and its electrochemical behavior was investigated in detail. The cyclic voltammetry results indicated that the SnNR/AAO/Al electrode exhibited efficient electrocatalytic activity toward reduction of ONB in the acidic solution. It provides an appreciable improvement of reduction peak for ONB at-0.721 V.Furthermore, various kinetic parameters such as transfer electron number, transfer proton number and standard heterogeneous rate constant were calculated from the scan rates.The electrocatalytic behavior was further exploited as a sensitive detection scheme for the ONB determination by differential pulse voltammetry. Under the optimized conditions, the concentration range and detection limit are 0.1-100 μmol/L and 0.05 μmol/L, respectively,for ONB. The analytical performance of this modified sensor has been evaluated for detection of real sample such as river water and recovery of ONB was achieved all-out up to102.3% under standard addition method.     

壳聚糖衍生物修饰电极测定水中NO_2~-的研究

利用水杨醛对壳聚糖进行改性,合成壳聚糖席夫碱类衍生物(S-CTS),将其滴涂在玻碳电极表面成膜。用循环伏安法研究了该修饰电极对NO2-的电催化作用。实验结果表明,以0.1mol/LpH4.0的B-R缓冲溶液为底液,还原峰电流与NO2-浓度在1.8×10-1～70mg/L范围内呈良好的线性关系,相关系数为0.9915,检出下限达4.6×10-3mg/L。用于水样测定,结果满意。     

应用胆碱酯酶生物传感器分析测定有机磷及重金属等潜在环境污染物

采用硝化纤维素为载体的固定化丁酰胆碱酯酶膜与银基汞膜电极耦合制得安培胆碱酯酶生物传感器。以该传感器为工作电极,饱和甘汞电极为参比电极组成双电极系统,用示波极谱仪接收电流信号,分析测定了有机磷(包括农用杀虫剂)和重金属等两类酶抑制剂,在较宽的浓度范围内示波峰电流值与抑制剂浓度的对数值之间具有良好的线性关系,最低检出下限可达到2．0×10－6mg／L．上述酶传感系统可用于毒性评价和环境监测等领域。      

BiVO4/rGO涂膜电极光电催化测定水样中的COD

准确、及时且环境友好地检测水体的化学需氧量(COD)已成为环境监测领域的重要研究课题。采用溶液燃烧法和旋转涂膜法制备了一种可见光响应型BiVO₄/rGO涂膜电极用于COD测定,并考察了该电极用于COD检测的光电化学性能。利用X-射线衍射(XRD)、扫描电子显微镜(SEM)、比表面积分析(BET)探究复合电极结构,表明基底完全被BiVO₄/rGO覆盖。采用循环伏安法(CV)、光电流-时间法(I-t)测试其光电性能,确定最佳制备条件为：煅烧温度为500℃、掺杂rGO为5 mL、涂膜厚度为4层。通过考察其测试参数得出,在工作电压为1.0 V、支持电解质为0.1 mol/L Na₂SO₄、光照强度为400μW/cm²、pH为6～8可得到稳定可靠的测试结果。利用BiVO₄/rGO涂膜电极测定有机物溶液COD的测定范围为12.18～719.8 mg/L,转移净电荷量(Q_net)和理论COD间呈良好的线性关系。用于实际水样COD测定时,在60 s内...     

检测水中有机磷农药的酶传感器

采用丝网印刷技术制作厚膜型电极,通过交联法将乙酰胆碱酯酶固定在电极上,开发快速检测水中有机磷农药的酶传感器.采用循环伏安法对电极所做的检测结果表明电极彼此间的差异在10%以内,具有较好的一致性.通过在交联剂、酶和底物等方面优化传感器的工作参数,确定了戊二醛、酶和底物的浓度分别为0.2%、0.5 mg/mL和10 mmol/L时,传感器响应最好.在交联固定酶的情况下,根据酶活受到有机磷抑制的原理,采用时间-电流法对特丁硫磷和对硫磷进行了检测.结果表明:这2种有机磷的检测限都可以达到1 ng/mL,线性区间1～10 000ng/mL.在物理吸附固定酶的情况下,采用循环伏安法对特丁硫磷进行了检测.结果表明:采用循环伏安法检测的灵敏度比采用时间-电流法的灵敏度要高.     

谷氨酸分子印迹电化学传感器的研究

谷氨酸在食品、医药、日化等方面用途广泛。但是目前,检测谷氨酸的方法存在种种缺陷而不够理想。因此,一种快速检测谷氨酸的方法很重要。文章以谷氨酸为模板,邻氨基酚为功能单体。铁氰化钾为印迹电极和底液间的探针,利用循环伏安法成功制备了谷氨酸分子印迹聚合物传感器。并优化了其反应条件(pH=5.5,t=20℃,单体:模板=2.2:1,聚合时间25圈,洗脱时间=2 min,洗脱材料:硫酸)。制备的谷氨酸分子印迹电化学传感器的相对标准偏差分别为2.91%～3.39%。线性范围0.5 mmol/L～3.0 mmol/L。对实际样品进行检测,其加标回收率为87%～110%。连续洗脱32次之后电极衰减到30%以上。与其他方法进行比较,该方法有检测灵敏度高,抗干扰能力强等优点,操作简便,为连续检测谷氨酸提供了一种新的方法。     

金/钴氢氧化物膜修饰玻碳电极同时测定邻苯二酚和对苯二酚

文章将纳米金与钴氢氧化物膜的催化作用有效结合,制备了GNPs/CoOOH复合修饰电极,该修饰电极在碱性条件下对邻苯二酚和对苯二酚具有较强的电催化活性。考察了支持电解质酸度及纳米金沉积时间对邻苯二酚和对苯二酚电化学响应的影响,选取0.1 mol/L PBS(pH 10.0)作为支持电解质,纳米金的最佳沉积时间为4 min。在优化的实验条件下,利用差示脉冲伏安法(DPV)对邻苯二酚和对苯二酚进行选择性检测:当两者浓度同时改变时,对苯二酚和邻苯二酚的氧化峰电流与其浓度分别在7~100μmol/L和6~100μmol/L范围内呈良好的线性关系,对应的检出限分别为0.9、0.8μmol/L(S/N=3)。该复合修饰电极具有较好的重现性、稳定性及较强的抗干扰能力。     

Fe(Ⅲ)-EDTA作为阴极电子穿梭体的微生物燃料电池持续产电机制

阴极氧还原反应（ORR）是影响微生物燃料电池（microbial fuel cell,MFC）性能的重要因素.采用双室MFC以Fe(Ⅲ)-EDTA为阴极液进行持续产电试验.结果表明,添加Fe(Ⅲ)-EDTA作为阴极液可显著加速氧还原反应速率,降低内阻,提高输出电压与功率.当阴极液中存在20.0 mmol/L的Fe(Ⅲ)-EDTA时,电池内阻仅为300　Ω,比对照降低了900　Ω,其输出电压（1 000　Ω下）与功率密度可维持在200.1 mV、 16.0 mW/m²左右,比不加的对照分别提高73.2%、 70.1%. Fe(Ⅲ)-EDTA氧化再生与持续产电试验表明,Fe(Ⅲ)-EDTA可通过曝气氧化再生、循环利用,即Fe(Ⅲ)-EDTA可作为阴极电子穿梭体加速电子至氧气的传递.Fe(Ⅲ)-EDTA首先接受阴极电子被还原成Fe(Ⅱ)-EDTA,在阴极室充分曝气条件下,Fe(Ⅱ)-EDTA将电子传递给O₂同时被氧化再生成Fe(Ⅲ)-EDTA,从而完成电子从电极传递到氧气的穿梭过程,MFC得以长期稳定运行.进一步优化试验显示,Fe(Ⅲ)-EDTA作为阴极电子穿梭体强化MFC产电的适宜条件为：浓度20.0 mmol/L、pH=5.0左右.在此条件下MFC的最大功率密度达100.9 mW/m².     

Effects of culture conditions on ligninolytic enzymes and protease production by Phanerochaete chrysosporium in air

The production of ligninolytic enzymes and protease by Phanerochaete chrysosporium was investigated under different culture conditions. Different amounts of medium were employed in free and immobilized culture, together with two kinds of medium with different C/N ratios. Little lignin peroxidase （LIP） （〈 2 U/L） was detected in free culture with nitrogen-limited medium （C/N ratio： 56/2.2, in mmol/L）, while manganese peroxidase （MnP） maximum activity was 231 and 240 U/L in 50 and 100 ml medium culture, respectively. Immobilized culture with 50 ml nitrogen-limited medium gave the highest MnP and LiP production with the maximum values of 410 and 721 U/L separately on the day 5; however, flasks containing 100 ml nitrogen-limited medium only produced less MnP with a peak value of 290 U/L. Comparatively, carbon-limited medium （C/N ratio： 28/44, in mmol/L） was adopted in culture but produced little MnP and LiE Medium type had the greatest impact on protease production. Large amount of protease was produced due to glucose limitation. Culture type and medium volume influence protease activity corporately by affecting oxygen supply. The results implied shallow immobilized culture was a possible way to gain high production of ligninolytic enzymes.     

碳纳米管修饰电极对苯二酚3种异构体的研究

文章应用循环伏安法(CV)研究了邻苯二酚(CC)、对苯二酚(HQ)和间苯二酚(RS)在多壁碳纳米管修饰的玻碳电极(MWNTs/GCE)表面的电催化氧化行为,同时对pH、扫描速度、温度等试验条件的影响也进行了研究。结果表明:MWNTs/GCE电极对CC、HQ和RS均表现出较好的电催化和电分离作用;在高浓度HQ和RS存在条件下,CC的氧化峰电流在0.05～7.00mmol/L范围内与浓度呈良好的线性关系,相关系数R²=0.9989;修饰电极实现了对实际废水中苯二酚三种异构体的同时测定。     

菌株Enterobacter sp. L6异化Fe(III)还原及Cr(VI)还原的性质分析

Cr（VI）是一种毒性极强的重金属,利用微生物还原Cr（VI）为Cr（III）是解决Cr（VI）污染的一条有效途径。菌株Enterobacter sp. L6是一株分离自海洋沉积物中的异化铁还原细菌。接种时细胞密度A₆₀₀为（0.25±0.03）,培养12 h,A₆₀₀达到（1.04±0.05）,累积产生Fe（II）浓度为（0.80±0.03）mmol/L;随着培养时间的延长,细胞密度A₆₀₀和累积产生Fe（II）浓度开始下降;培养36 h时,细胞密度A₆₀₀为（0.81±0.04）,累积Fe（II）浓度（0.63±0.01）mmol/L。在厌氧培养过程中,菌株L6细胞生长与异化还原Fe（III）性质存在明显的偶联关系。利用菌株L6的异化铁还原性质还原Cr（VI）的实验结果表明,在Cr（VI）浓度0～24 mg/L范围内,异化铁还原细菌L6都能进行细胞生长并还原Cr（VI）。Cr（VI）浓度为4、8和12 mg/L时,菌株L6对Cr（VI）还原率可达到100%,当Cr（VI）浓度为16 mg/L时,Cr（VI）还原率是参比[未添加Fe（III）]的2.11倍。Cr（VI）浓度为20、24 mg/L时,仍能够还原Cr（VI）。以Fe（III）为电子受体的异化铁还原细菌能明显提高Cr（VI）还原率,这为利用微生物修复Cr（VI）污染提供实验数据支持。     

蒽醌类有机质介导水铁矿电化学还原的动力学

以水铁矿为实验对象，采用计时电流法研究了"电极-AQS-水铁矿"反应体系中蒽醌介导下的电化学还原动力学过程，阐明了"电极-AQS-水铁矿"三者之间相互作用的动力学特征与机制.结果表明：在超声波的协助下，同市售玻碳电极相比，发生在碳毡电极表面的电化学还原反应的灵敏性得到显著提升，且当体系施加电压为-0.7V时，AQS可以被完全还原.在最佳工作电极和实验条件下，AQS可以作为氧化还原中介体参与水铁矿的电化学还原过程.当AQS浓度从0.005mmol/L升至0.035mmol/L时，单位绝对量水铁矿的还原率从10.4%增至35%.AQS介导水铁矿电化学还原过程中的中间产物AQS_oxi浓度随时间的变化趋势符合由连串反应动力学推导出的函数模型曲线特征：随着时间t的增加，C_AQSoxi在初始某一范围内迅速增长；当时间到达某限度后，C_AQSoxi又出现了不同程度的快速下降，模型拟合的校正决定系数高达0.9990.     

基于针铁矿强化乙酸产甲烷过程的ADM1模型修正与模拟研究

为探究针铁矿对乙酸产甲烷途径的调控作用,利用ADM1模型（厌氧消化1号模型）对添加针铁矿的产甲烷过程进行模拟研究.首先引入氧化还原介质作为新变量,模拟SAO（syntrophic acetate oxidation,互营乙酸氧化）过程中的种间电子转移,进而建立包含DIET（direct interspecies electron transfer,直接种间电子传递）产甲烷过程的ADM1修正模型,最后利用该模型对各产甲烷途径的贡献进行评价.结果表明:①c（乙酸）分别为12和20 mmol/L时,添加40~2 000 mg/L针铁矿明显提高了乙酸体系的产甲烷速率.②修正的ADM1模型能够有效地模拟针铁矿强化乙酸产甲烷过程.③12、20 mmol/L乙酸体系的敏感性参数km_Xst（最大比乙酸氧化速率）校准值分别从1.02、1.46升至1.76、2.03,km_DIET（最大比电子消耗速率）校准值分别从0.78、1.48升至2.44、3.99,表明添加针铁矿提高了互营体系的种间电子传递速率.修正的ADM1模型对各产甲烷途径贡献的计算结果显示,针铁矿对DIET过程的强化作用与其添加量呈正相关,添加2 000 mg/L针铁矿试验组[c（乙酸）为12 mmol/L]中DIET和SAO产甲烷的贡献率相比对照组分别提升了117.99%和130.73%.研究显示,修正的ADM1模型能够有效地模拟针铁矿对乙酸产甲烷过程的强化作用,并且能用于评价各产甲烷途径的贡献.      

纳米TiO_2/Nafion修饰金电极溶出伏安法测量痕量铜

利用纳米二氧化钛(nano-TiO2)的结构特性,采用滴涂法制备了一种nano-TiO2/Nafion修饰金电极,采用差分脉冲溶出伏安法实现了水样中痕量铜的检测。详细研究了Cu2+在nano-TiO2/Nafion修饰金电极上的电化学响应行为,并讨论了nano-TiO2/Nafion膜的厚度、溶液pH值、富集电位、富集时间等对Cu2+溶出峰电流的影响。实验结果表明:在pH=2.0硝酸溶液中,-0.5 V恒电位搅拌富集240 s,静置10 s后阳极化扫描,Cu2+在0.25 V左右出现阳极溶出峰。相比于裸金电极,该峰电流大大提高,表明nano-TiO2对Cu2+的溶出具有一定的增敏作用。在最优化实验条件下,10~900 nmol/L范围内,Cu2+的溶出峰电流与其浓度呈良好的线性关系,检出限可达3.2 nmol/L。该修饰电极具有一定的抗干扰能力,将其应用于国标样品和实际自来水样中Cu2+的检测,结果令人满意。     

Influence of glucose feeding on the ligninolytic enzyme production of the white-rot fungus Phanerochaete chrysosporium

The present work studied the influence of glucose feeding on the ligninolytic enzyme production of Phanerochaete chrysosporium in a nitrogen-limited (C/N ratio is 56/8.8 mmol/L) medium. Several sets of shaking flask experiments were conducted. The results showed that 2 g/L glucose feeding on the first day of the culture (24 h after the inoculation) simulated both fungal biomass growth and enzyme production. The manganese peroxidase (MnP) activity was 2.5 times greater than that produced in cultures without glucose feeding. Furthermore, the glucose feeding mode in fed-batch culture was also investigated. Compared to cultures with glucose feeding every 48 h, cultures with glucose feeding of 1.5 g/L (final concentration) every 24 h produced more enzymes. The peak and total yield of MnP activity were 2.7 and 3 times greater compared to the contrast culture, respectively, and the enzyme was kept stable for 4 days with an activity of over 200 U/L. Translated from Acta Scientise Circumstantiae, 2007, 27(3): 363–368 [译自: 环境科学学报]     

Carbon dioxide adsorption and cycloaddition reaction of epoxides using chitosan–graphene oxide nanocomposite as a catalyst

One of today's major challenges is to provide green materials for a cleaner environment. We have conducted studies on carbon dioxide(CO2) adsorption and conversion to valuable products by an ecofriendly approach based in chitosan/graphene oxide(CSGO) nanocomposite film. Rheological behavior indicates that the CSGO has a better solvation property than the pure chitosan. An adsorption capacity of 1.0152 mmol CO_2/g of CSGO nanocomposite at4.6 bar was observed. The catalytic behavior of the CSGO nanocomposite in the presence of tetra-n-butylammonium iodide(n-Bu4 NI) as co-catalyst was evaluated for the cycloaddition of CO_2 to epoxides, to give cyclic carbonates, in the absence of any solvent. These results strongly suggest that the CSGO nanocomposite may open new vistas towards the development of ecofriendly material for catalytic conversion and adsorption of CO_2 on industrial scale.     

微生物还原石墨烯修饰碳毡电极的电化学特征

本文探讨了腐败希瓦氏菌（Shewanellaputrefaciens ATCC 8071）与生物呼吸驱动下自组装3D-br-GO修饰碳毡电极之间相互作用的电化学特性,并且进一步探究了施加+0.1V（vs.Ag/AgCl）电势于生物电极对其相互作用的影响.X射线衍射检测表明GO在微生物呼吸驱动下生成了还原态氧化石墨烯（br-GO）.扫描电镜图像显示GO修饰电极表面有大量的br-GO包裹细菌的复合结构,说明br-GO对微生物具有较好的生物相容性,且由微生物呼吸驱动得到的三维br-GO自组装地修饰到生物电极上增加了其比表面积和细菌负载量.通过生物膜生长过程中的产电监测、循环伏安法测试,结果表明GO的修饰有利于细菌附着于电极形成活性生物膜,促进了微生物与电极之间的电子转移.而施加+0.1V（vs.Ag/AgCl）电势于GO修饰的电极,结果显示电极上仅有少量的细菌负载,没有形成活性生物膜,微生物与电极之间的电子转移行为明显减少,表明施加+0.1V（vs.Ag/AgCl）电势可能对电极上微生物呼吸生长有抑制作用.     

络合吸收脱除NO体系中FeⅢ(EDTA)的生物还原

利用驯化得到的微生物还原Fe^Ⅲ(EDTA)的研究结果表明,葡萄糖比乙醇和甲醇更适合于作为该体系的碳源;由于硝酸盐在反应过程中对Fe^Ⅲ(EDTA)的微生物还原形成抑制,选择铵盐为微生物生长的氮源;反应最适pH值范围为6~7;温度在30℃~40℃范围之间变化,Fe^Ⅲ(EDTA)还原率相差不大,温度大于40℃以后,还原率随温度升高而下降.碳源量和菌体接种量满足还原反应需要即可,过量碳源或菌体接种量对还原率没有明显的促进作用.在实验考察的浓度范围内,FeⅢ(EDTA)的生物还原符合1级反应动力学,最大反应速率γ_max=1.3 mmol·(L·h)^-1,半饱和速率常数k_m=53.5 mmol·L^-1.     

电沉积ZnO膜光电催化降解4-硝基酚研究

用硝酸锌水溶液作电解质,采用阴极电沉积法在玻碳电极上制备了具有光电化学活性的氧化锌(ZnO)薄膜。以ZnO膜电极为工作电极对4-硝基酚进行了光电催化降解处理,系统研究了外加偏压、4-硝基酚浓度、电解液浓度以及pH值对4-硝基酚在ZnO膜电极上的光电催化降解效果的影响。结果表明:在外加偏压为1.0V,电解液浓度为0.1mol/L,溶液为近中性条件(pH为6.3)时对0.05mmol/L的4-硝基酚2小时的降解效率达到了98.8%。