线状纳米金修饰碳纤维超微电极检测芦荟大黄素

该文建立了芦荟大黄素(AE)的电化学检测方法。通过柠檬酸三钠还原氯金酸制备线状纳米金,采用一步恒电位沉积方法将线状纳米金沉积在碳纤维超微电极(CFME)表面,考察了电极修饰前后对AE的电催化性能,得到最佳修饰时间为12 min。结果表明,线状纳米金修饰碳纤维电极(LGN/CFME)的氧化峰电流与AE浓度在2.0×10-6~1.0×10-4 mol/L范围内呈良好线性关系,线性方程为Ip(nA)=0.318 1C(μmol/L)+25.01,r2=0.965 3,检出限(S/N=3)为6.19×10-7 mol/L,说明此方法可用于芦荟汁中AE的定量检测。     

Determination of melamine in milk powder based on the fluorescence enhancement of Au nanoparticles

We have developed a new analytical method to detect melamine (MA) in milk powder based on the fluorescence enhancement of Au nanoparticles (AuNPs). AuNPs with the average diameter of ～16 nm can emit stable fluorescence at 370 nm when the excitation wavelength was selected at 252 nm. The AuNPs could assemble with melamine to form larger aggregates (AuNPs-MA) through electrostatic interaction and coordinating interaction in acidic conditions, which led to the significant enhancement of the fluorescence intensity. Under the optimized conditions, the enhancement of the fluorescence intensity exhibited a good linear dependence on melamine concentration in the range from 8.0 × 10(-10) to 8.0 × 10(-8) M, and the detection limit is 6.1 × 10(-10) M (3σ). This proposed method showed high precision and accuracy when applied to the real sample analyses. In conclusion, a simple, rapid, accurate and sensitive method to detect melamine has been suggested.     

纳米金放大计时库仑法的PML/RARα融合基因检测

应用恒电位在金基底表面电化学沉积纳米金,通过Au—S键将巯基修饰DNA探针固定在纳米金表面,与互补靶序列杂交,构建计时库仑电化学DNA传感器,并检测急性早幼粒细胞白血病(APL)PML/RARα融合基因.采用扫描电子显微术(SEM)与电化学交流阻抗技术(EIS)观察纳米金和表征DNA传感器的构筑过程.以氯化六氨合钌([Ru(NH3)6]Cl3,RuHex)作电化学杂交指示剂,由计时库仑法检测人工合成APL的PML/RARα融合基因.结果表明,纳米金能放大RuHex检测信号,杂交前后电量差值(ΔQ)与靶标链DNA浓度的对数(lgC)值在1.0×10-13～1.0×10-9mol.L-1范围内呈线性关系,检出下限3.7×10-14mol.L-1(S/N=3).该法操作简便、特异性好,有望用于实际样品的检测.     

镍纳米粒子-离子液体修饰碳糊电极的制备及其对多巴胺的测定

制备了镍纳米粒子-离子液体修饰电极,在0.1 mol/L磷酸缓冲溶液(pH 6.0)中研究了多巴胺(DA)在修饰电极上的电化学行为.与裸电极相比,DA在该修饰电极上的氧化还原电位明显降低,氧化还原反应的峰电流明显增大,DA的峰电流与其浓度在2.0×10~(-8) ～1.0×10~(-4) mol/L范围内呈良好的线性关系,检出限为6.5×10~(-9) mol/L.该修饰电极对抗坏血酸具有明显的抗干扰能力.     

基于多边形金纳米颗粒的非标记型可卡因适体传感器的研制

实验合成了多边形金纳米颗粒,通过壳聚糖(CHIT)将合成的多边形金纳米颗粒固定在玻碳电极表面,然后通过自组装技术将带巯基的捕获DNA探针固定在修饰有多边形金纳米颗粒的电极表面,利用杂交反应使可卡因适体与DNA捕获探针结合,制成非标记型可卡因适体传感器。以六氨合钌作为电化学指示剂,通过测量传感器与目标物可卡因结合前后电流变化情况对可卡因进行测定。考察了缓冲溶液的pH、可卡因培育时间、扫描速度等对测定的影响。结果表明,在pH为7.40时该传感器的检测范围为1.0×10-10～1.0×10-3 mol/L,检测限为3.0×10-11 mol/L。该传感器制作简单,响应好,抗干扰能力强。     

纳米金/石墨烯修饰电极的制备及其对多巴胺的测定

利用电化学还原方法制备纳米金/石墨烯修饰玻碳电极,研究了多巴胺(DA)在该修饰电极上的电化学行为,建立了电化学测定多巴胺的新方法。结果表明,在磷酸盐缓冲溶液中,此修饰电极对多巴胺的电化学响应具有很好的催化作用。利用差示脉冲伏安技术对多巴胺的电化学氧化进行定量分析,多巴胺的氧化峰电流与其浓度在1.0×10-7～1.0×10-5mol/L范围内呈良好的线性关系,检测限低至4.0×10-8mol/L。该修饰电极适于多巴胺的分析检测。     

Fluorescence quenching method for the determination of catechol with gold nanoparticles and tyrosinase hybrid system

<正>The determination method of catechol by fluorescence quenching was developed.The assay was based on the combination of the unique property of gold nanoparticles with tyrosinase enzymatic reaction.In the presence of tyrosinase,the fluorescence of gold nanoparticles was quenched by catechol which can be employed to detect catechol.Under the optimal conditions,a linear range 5.0×10~(-7)-1.0×10~(-3) mol L~(-1) and a detection limit 1.0×10~(-7) mol L~(-1) of catechol were obtained.o-Quinone intermediate produced from the enzymatic catalyzed oxidation of catechol was considered to play the main role in the fluorescence quenching.     

碳纳米管负载纳米金-石墨烯量子点修饰电极电化学检测过氧化氢

采用过氧化氢刻蚀法制备石墨烯量子点(GQDs),再采用原位化学还原法制备金纳米粒子-石墨烯量子点纳米复合物(Au NPs-GQDs),最后以聚二甲基二烯丙基氯化铵(PDDA)为交联剂将上述纳米复合物组装于多壁碳纳米管表面,制得金纳米粒子-石墨烯量子点-PDDA-多壁碳纳米管复合材料(Au NPs-GQDsPDDA-MWCNTs)。通过荧光光谱法、紫外-可见吸收光谱法和透射电子显微镜对上述复合材料进行表征。采用滴涂法制得该复合材料修饰的玻碳电极,研究了过氧化氢在该电极上的电化学行为。结果表明:在石墨烯量子点、金纳米粒子和多壁碳纳米管三者的协同作用下,该电极对过氧化氢的电氧化表现出强的催化活性。在优化条件下,安培法检测H_2O_2的线性范围为2.0×10~(-8)~1.5×10~(-3)mol/L,检出限(3sb)为8.0×10~(-9)mol/L,灵敏度为61.6μA/(mmol·L~(-1))。     

Used gold nano-particles as an on/off switch for response of a potentiometric sensor to Al(III) or Cu(II) metal ions

The potentiometric response of a carbon paste electrode modified with silica sol-gel and mercaptosuccinic acid (MSA) in the presence and absence of gold nano-particles was studied. The results showed that the electrode with gold nano-particles was responded to Al(3+) ions as a hard metal ion. On the other hand, the electrode without gold nano-particles was responded to copper ions as a soft metal ion. The electrodes without and with gold nano-particles exhibits a Nernstian slope of 29.1 and 19.2 mV decade(-1) for copper and aluminum ions over a wide concentration range of 4.3×10(-7)-1.0×10(-2) and 4.5×10(-7)-1.6×10(-3) mol L(-1), respectively. The detection limits of electrodes were 4.0×10(-7) and 1.6×10(-7) mol L(-1) for copper and aluminum ions, respectively.     

Comparative electrochemical study of new self-assembled monolayers of 2-{[(Z)-1-(3-furyl)methylidene]amino}-1-benzenethiol and 2-{[(2-sulfanylphenyl)imino]methyl}phenol for determination of dopamine in the presence of high concentration of ascorbic acid and uric acid

The comparative electrochemical behavior of self-assembled monolayers of two Schiff's bases, 2-{[(Z)-1-(3-furyl)methylidene]amino}-1-benzenethiol (FMAB) and 2-{[(2-sulfanylphenyl)imino]methyl}phenol (SIMP) on a bare gold electrode (Au FMAB SAM-modified electrode and Au SIMP SAM-modified electrode, respectively), was investigated by means of cyclic voltammetry and electrochemical impedance spectroscopy in a 0.1 mol L(-1) KCl solution that contains 5.0 × 10(-3) mol L(-1) [Fe(CN)(6)](3-/4-). The results revealed that the modified electrodes showed an electrocatalytic activity toward the anodic oxidation of dopamine by a marked enhancement in the current response and lower overpotential (60 and 90 mV for the Au FMAB and Au SIMP SAM-modified electrodes, respectively) in phosphate buffer solution at pH 6.0. The Au SIMP SAM-modified electrode was applied successfully to the determination of dopamine in the presence of a high concentration of ascorbic acid. Selective detection was realized in total elimination of ascorbic acid response-a method different from the ones based on the potential separations. The detection limit of dopamine was 5.0 × 10(-8) mol L(-1) in a linear range from 1.0 × 10(-6) to 1.2 × 10(-4) mol L(-1) in the presence of 1.0 × 10(-3) mol L(-1) ascorbic acid. The interference studies also showed that the Au SIMP SAM-modified electrode exhibited good selectivity in the presence of a large excess of uric acid and could be employed for the determination of dopamine in pharmaceutical formulations, plasma samples and human urine with adequate selectivity and precision.     

Direct fluorescence quantification of chromium(VI) in wastewater with organic nanoparticles sensor.

Under ultrasonic irradiation, organic fluorescence nanoparticles have been prepared by a reprecipitation method. Compared with single organic fluorophores, these nanoparticles are brighter, more stable against photobleaching and more water-soluble. They also have high room-temperature fluorescence quantum yields (approximately 20%) and a long fluorescence lifetime (approximately 0.2 micros). Based on the fluorescence quenching of nanoparticles by chromium(VI), a method for the selective determination of chromium(VI) without the separation of chromium(III) in water was developed. Under the optimal conditions, the linear range of the calibration curve was 7.0 x 10(-6) - 1.0 x 10(-4) mol L(-1). The detection limit was 2.8 x 10(-6) mol L(-1). The method is characterized by a short reaction time, stable fluorescence signals, simplicity and high selectivity. The present assay has been applied to the selective quantification of Cr(VI) in wastewater with satisfactory results.     

纳米金/3-氨丙基-三乙氧基硅烷修饰传感器电化学检测NO-2

将3-氨丙基-三乙氧基硅烷（ATS）修饰在玻碳电极表面,再自组装一层纳米金,制备了一种新型NO2^-的电化学传感器。该修饰电极对NO2^-有较好的催化作用。在pH为3时,NO2^-的氧化峰电流与其浓度在5．0&#215;10^-7～1．0&#215;10^-3mol／L范围内呈良好的线性关系,检出限可达2．0&#215;10^-7mol／L。方法具有较高的灵敏度和较好的重现性。     

以天青Ⅰ为介体的纳米金颗粒增强的葡萄糖传感器

采用层层自组装的方法和异种电荷互相吸引的原理,将Nafion修饰在金电极上固载带正电荷的天青Ⅰ,并利用天青Ⅰ中的氨基固载纳米金,再通过纳米金将酶固定在金电极表面,制成了葡萄糖传感器.采用循环伏安法和交流阻抗法,研究了金电极表面组装各层之后的电化学特征,以及电极对葡萄糖的电化学催化作用. 结果表明,天青Ⅰ不仅可以固定酶和纳米金,而且还可以在酶和电极之间有效地传递电子.在优化的实验条件下,该传感器对葡萄糖响应的线性范围为5.1×10-6 ~4.0×10-3 mol/L,检出限(S/N=3)为1.0 μmol/L.该生物传感器显示出较好的稳定性和抗干扰能力,将其用于人体血清中葡萄糖的测定,结果令人满意.     

Label-free aptamer-based electrochemical impedance biosensor for 17β-estradiol

A novel aptamer-based label-free electrochemical impedance spectroscopy biosensor for 17β-estradiol has been fabricated. The aptamers were firstly immobilized on the gold electrode through Au-S interaction; the aptamer probe was then bound with the addition of 17β-estradiol to form the estradiol/aptamer complex on the electrode surface. This leads to a significantly larger interfacial electron transfer resistance than that without the addition of 17β-estradiol. The change in the resistance had a linear relationship with 17β-estradiol concentration in the range of 1.0 × 10(-8) to 1.0 × 10(-11) mol L(-1), with a detection limit of 2.0 × 10(-12) mol L(-1). The biosensor showed high selectivity to 17β-estradiol and good stability. The designed biosensor has been applied to detect 17β-estradiol in human urine with satisfactory results.     

蔬菜中叶酸的催化氧化荧光法测定

建立了催化氧化荧光法间接测定叶酸的新方法。在pH5.0的HAc-NaAc缓冲溶液中,Co2+催化KIO4氧化叶酸产生强荧光,以262 nm为激发波长,在445 nm处测定叶酸的氧化产物蝶呤-6-羧酸的荧光强度,研究了反应的适宜条件及动力学参数,并探讨了反应机理。在优化实验条件下,叶酸浓度在1.0×10-8~1.0×10-5mol/L范围内与荧光强度呈良好线性关系,回归方程为ΔIF=10.82c(μmol/L)+2.867,相关系数r=0.998 5,方法的检出限为5×10-9mol/L。对5×10-7mol/L叶酸标准溶液进行11次平行测定,相对标准偏差(RSD)为0.1%。该法使用Co2+为催化剂,大大提高了方法的灵敏度。方法用于蔬菜中叶酸的测定,加标回收率为93%~104%,6次测定的相对标准偏差为0.98%~2.1%,结果令人满意。     

Determination of catecholamine in human serum by a fluorescent quenching method based on a water-soluble fluorescent conjugated polymer-enzyme hybrid system

In this paper, a sensitive water-soluble fluorescent conjugated polymer biosensor for catecholamine (dopamine DA, adrenaline AD and norepinephrine NE) was developed. In the presence of horse radish peroxidase (HRP) and H(2)O(2), catecholamine could be oxidized and the oxidation product of catecholamine could quench the photoluminescence (PL) intensity of poly(2,5-bis(3-sulfonatopropoxy)-1,4-phenylethynylenealt-1,4-poly(phenylene ethynylene)) (PPESO(3)). The quenching PL intensity of PPESO(3) (I(0)/I) was proportional to the concentration of DA, AD and NE in the concentration ranges of 5.0 × 10(-7) to 1.4 × 10(-4), 5.0 × 10(-6) to 5.0 × 10(-4), and 5.0 × 10(-6) to 5.0 × 10(-4) mol L(-1), respectively. The detection limit for DA, AD and NE was 1.4 × 10(-7) mol L(-1), 1.0 × 10(-6) and 1.0 × 10(-6) mol L(-1), respectively. The PPESO(3)-enzyme hybrid system based on the fluorescence quenching method was successfully applied for the determination of catecholamine in human serum samples with good accuracy and satisfactory recovery. The results were in good agreement with those provided by the HPLC-MS method.     

空心纳米金在甲醛气体传感器中的应用研究

通过牺牲模板法合成了具有空心结构的纳米金催化剂,并进行了TEM、 SEM和XRD等物理表征.把该催化剂作为工作电极的活性物质,以1 mol/L KOH为电解质,组装了电流型甲醛气体传感器.在甲醛气体浓度为0～2.23×10-6 mol/L范围内对传感器进行了性能测试,传感器响应信号y(A)与气体浓度x(mol/L)线性回归方程为y=16.63x+4.063×10-7, r=0.9989.该传感器灵敏度高于同载量实心金纳米催化剂组装的传感器70%左右,达到了降低贵金属用量的目的.因其具有较快的响应时间、 良好的重现性和良好的线性关系等优点,可用于适当浓度范围内的甲醛气体检测.     

毛细管电泳电化学法检测过氧化氢

以金微盘电极和离子液体修饰单壁碳纳米管糊微盘电极分别作为毛细管电泳电化学检测器,试验了两种电极对过氧化氢的响应情况,将金微盘电极与毛细管电泳联用,对过氧化氢进行了定性和定量检测.探讨了分离电压、缓冲溶液pH值和工作电位等条件对H2O2检测的影响.实验结果表明,峰电流与H2O2浓度在1.0×10-6～1.0×10-5mo...     

荧光素-曙红Y能量转移荧光猝灭法测定微量白蛋白研究

在λex/λem=405/547 nm,于缓冲溶液和表面活性剂存在的情况下,荧光素和曙红Y能够发生有效能量转移,而牛血清白蛋白(BSA)的加入使得曙红Y荧光猝灭,该体系可用于微量蛋白质的测定。系统探讨了荧光素-曙红Y能量转移体系发生荧光猝灭的条件,最佳条件为:2.0 mL pH=3.8的B-R缓冲溶液,0.4 mL 0.05%曲拉通X-100,1.5 mL 1.0×10-4mol/L的荧光素水溶液,2.0 mL 1.0×10-4mol/L的曙红Y水溶液,最佳实验时间为溶液配制完成静置15 min后60 min内,最佳加入顺序为pH=3.8缓冲溶液+荧光素+曙红Y+曲拉通+蛋白质标准溶液或样品。在优化的实验条件下,蛋白质含量在0～2.0μg/mL范围内与荧光猝灭强度呈良好的线性关系。检出限为6.6 ng/mL;测定样品的相对标准偏差(RSD)在±5%以内;样品加标回收率为90.4%～95.3%。该法可用于人血清、牛奶中蛋白质含量的测定。     

Eu~(3+)荧光探针构建及对牛奶中盐酸四环素残留的测定

本文构建了Eu~(3+)-苯甲酸(BA)-邻菲啰啉(Phen)三元配合物体系荧光探针,建立了一种检测牛奶中盐酸四环素残留的新方法。对三元配合物体系进行优化,确定Eu~(3+)、BA、Phen的最佳浓度配比为1∶1.5∶2,最佳检测时间为20min。该方法检测盐酸四环素的线性范围为1.0×10~(-6)~5.0×10~(-5) mol/L,检测限为1.8×10~(-7) mol/L。利用该荧光探针对处理后的牛奶进行加标回收实验,其回收率范围为99.5%~108%,平均回收率为103.8%。实验证明该方法科学可行,对盐酸四环素具有较高的选择性。