发酵食品中酪胺和色胺的电化学检测方法研究与应用

发布时间：2018-08-17 13:40

【摘要】：本文针对酪胺和色胺建立了4种电化学检测方法,并成功应用于实际样品的检测,主要内容如下:(1)利用循环伏安法在玻碳电极(GCE)表面通过电化学聚合形成聚邻氨基酚膜,对聚合膜进行过氧化处理后得到过氧化聚邻氨基酚修饰电极,对电极的修饰方法和酪胺的测定条件等进行优化。并用扫描电子显微镜和交流阻抗法对该电极进行了表征。最后采用方波伏安法对米醋中酪胺的含量进行测定。结果表明,将GCE置于0.01mol/L邻氨基酚的高氯酸溶液(0.3 mol/L)中,在-0.5~1.5V电位范围内循环伏安扫描14圈,将得到的聚邻氨基酚修饰电极在无水乙醇和超纯水中各超声1 min,然后在0.09mol/L NaOH溶液中于-0.15~1.0V电位范围内循环伏安扫描16圈,得到的修饰电极在测定酪胺时具有灵敏的响应。酪胺的氧化峰电流与其浓度在1.0×10~(-7)~1.0×10~(-5) mol/L和1.0×10~(-5)~2.0×10~(-4) mol/L范围内分别呈良好的线性关系,检出限(S/N=3)为5.4×10~(-8)mol/L。将该修饰电极应用于米醋样品中酪胺的测定,并采用高效液相色谱法(HPLC)进行了方法验证。该修饰电极制作简单、成本低、检测速度快,适用于米醋样品中酪胺含量的测定。(2)利用电流-时间曲线法在GCE表面通过恒电位聚合形成聚吡咯膜,对聚合膜进行过氧化处理后得到过氧化聚吡咯修饰电极,优化了该修饰电极对酪胺的测定参数及评估了该电极的各项性能指标。利用循环伏安法、交流阻抗法和扫描电子显微镜对该修饰电极进行了表征。最后用方波伏安法对酪胺进行测定。结果表明:GCE在含0.01 mol/L吡咯和0.1 mol/L HNO3的磷酸缓冲溶液中,于0.7V电位下聚合300s,然后在0.2 mol/L NaOH溶液中于-0.2~0.8V电位范围内循环伏安扫描10圈,得到的修饰电极在测定酪胺时具有较高的灵敏度。酪胺在该电极上的氧化电流与其浓度在8.0×10~(-8)~3.0×10~(-6) mol/L和3.0×10~(-6)~1.5×10~(-4) mol/L范围内呈线性关系。检出限(S/N=3)为1.6×10~(-8) mol/L。应用该电极对两种白酒样品进行检测,并采用HPLC进行验证测定。该修饰电极制备简单,成本低,且具有良好的重复性、稳定性和选择性,可用于市售白酒中酪胺含量的测定。(3)利用胶体金/粘土(AuCS/Clay)复合物对GCE进行修饰,得到对色胺具有较高电流响应的修饰电极(AuCS/Clay/GCE)。优化了该修饰电极测定色胺的方法和条件,利用扫描电子显微镜对该修饰电极进行了表征,并对修饰电极的选择性和重现性等电化学性能进行评估。然后采用电流-时间曲线法对色胺进行测定。色胺在AuCS/Clay/GCE上的氧化电流与其浓度在4.2×10~(-8)~1.4×10~(-5) mol/L范围内呈良好的线性关系,检出限(S/N=3)为1.8×10~(-8)mol/L。进一步基于丝网印刷电极(PK-SPE),采用方波伏安法对色胺进行测定,得到色胺的氧化电流与其浓度在1.0×10~(-7)~5.0×10~(-5)mol/L范围内呈良好的线性关系,检出限(S/N=3)为3.3×10~(-8) mol/L。最后对米醋等样品中的色胺含量进行测定,并用HPLC进行了方法验证。AuCS/Clay/GCE修饰电极制作简单,测试灵敏度高,但比PK-SPE的检测时间长。用PK-SPE测定时样品用量少(50μL),检测速度快,选择性好,两种方法均可用于市售米醋等样品中色胺含量的测定。
[Abstract]:In this paper, four electrochemical methods for the determination of tyramine and tryptamine were established and successfully applied to the detection of real samples. The main contents are as follows: (1) Poly (o-aminophenol) film was formed on the surface of glassy carbon electrode (GCE) by cyclic voltammetry. The poly (o-aminophenol) modified electrode was prepared by peroxidation of the film. The electrode was characterized by scanning electron microscopy and alternating current impedance spectroscopy. The content of tyramine in rice vinegar was determined by square wave voltammetry. The results showed that GCE was placed in 0.01 mol/L o-aminophenol perchloric acid solution (0.3 mol/L) at - 0.5-1.5 V potential. Cyclic voltammetry was used to scan 14 cycles in the range of - 0.15 V to 1.0 V. The results showed that the modified electrode had a sensitive response to the determination of tyramine. The modified electrode was applied to the determination of tyramine in rice vinegar samples by high performance liquid chromatography (HPLC). The modified electrode was characterized by simple fabrication, low cost, low detection limit (S/N=3) and good linear relationship in the range of 1.0 (-7) ~1.0 (-5) and 1.0 (-5) ~2.0 (-4) mol/L, respectively. (2) Polypyrrole film was formed on the surface of GCE by potentiostatic polymerization using current-time curve method, and the polypyrrole peroxide modified electrode was obtained by peroxidation of the polymer film. The determination parameters of tyramine were optimized and the properties of the electrode were evaluated. The modified electrode was characterized by cyclic voltammetry, alternating current impedance spectroscopy and scanning electron microscopy. Tyramine was determined by square wave voltammetry. The results showed that GCE was polymerized at 0.7V potential in phosphate buffer solution containing 0.01 mol/L pyrrole and 0.1 mol/L HNO3 for 300 seconds, and then in 0.2 mol/L NaOH solution at - 0.2~0.2. The oxidation current of tyramine on the modified electrode is linearly related to its concentration in the range of 8.0 (-8) (-6) mol/L and 3.0 (-6) (-4) mol/L. The detection limit (S/N=3) is 1.6 65507 The modified electrode has the advantages of simple preparation, low cost, good repeatability, stability and selectivity, and can be used for the determination of tyramine content in liquor. (3) GCE was modified by colloidal gold/clay (AuCS/Clay) complex to obtain high electricity for tryptamine. Modified current-responsive electrode (AuCS/Clay/GCE). The method and conditions for the determination of tryptamine were optimized. The modified electrode was characterized by scanning electron microscopy (SEM). The selectivity and reproducibility of the modified electrode were evaluated. Then the current-time curve method was used to determine tryptamine. Clay/GCE has a good linear relationship between oxidation current and its concentration in the range of 4.2 (-8) ~ 1.4 (-5) mol/L. The detection limit (S/N=3) is 1.8 (-8) mol/L. Based on the screen printed electrode (PK-SPE), the oxidation current and its concentration in the range of 1.0 (-7) ~ 5.0 (-5) mol/L were determined by square wave voltammetry. The detection limit (S/N=3) was 3.3 (-8) mol/L. Finally, the content of tryptamine in rice vinegar and other samples was determined and validated by HPLC. The AuCS/Clay/GCE modified electrode was simple to make and had high sensitivity, but the detection time was longer than that of PK-SPE. The two methods can be used for the determination of the content of the color amine in rice vinegar and other samples.
【学位授予单位】：仲恺农业工程学院
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TS207.3;O657.1

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