Development and application of vitamin C sensor with synergistic sensitization of gold nanoparticles and multi walled carbon nanotubes
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摘要:目的
开发一种低成本、高响应的维生素C电化学传感器，用于实现果蔬中维生素C含量的快速检测。
方法通过在铅笔芯电极上修饰金纳米颗粒和多壁碳纳米管，构建具有维生素C强催化响应的MWCNTs/Au/PGE电极。通过扫描电镜、X射线光电子能谱、拉曼光谱和循环伏安法表征电极，采用差分脉冲伏安法确定电极的pH适用范围和最优pH条件。采用时间电流法建立标准曲线和方程，以实现快速检测。最后通过加标回收率法检测番茄中维生素C含量。
结果基于MWCNTs/Au/PGE电极的维生素C电化学传感器可在pH 4~8范围内准确地测定维生素C含量，在pH 5时性能最优。快速检测时检测维生素C的质量分数范围为1~500 μg/g，灵敏度达0.244 μA·(μg/g)−1·cm−2。该传感器对葡萄糖、苹果酸和柠檬酸的干扰率均小于1.77%，同一传感器多次测定的相对标准偏差为2.7%。成功检出番茄样品中的维生素C质量分数为69.42 μg/g，加标回收率为109%~113%，相对标准偏差小于2.26%。
结论MWCNTs/Au/PGE电极制备工艺简单，成本低，灵敏度高，测量范围宽，有较强的稳定性和抗干扰性，为实现快速检测果蔬中维生素C提供了新思路。
Abstract:ObjectiveA low-cost and high response electrochemical sensor for vitamin C was developed to realize the rapid detection of vitamin C content in fruits and vegetables.
MethodMWCNTs/Au/PGE electrode with strong catalytic response to vitamin C was constructed by modifying gold nanoparticles and multi walled carbon nanotubes on pencil lead electrode. The electrode was characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and cyclic voltammetry. The application range and optimal condition of the electrode pH were determined by differential pulse voltammetry. The standard curve and equation were established by time-current method to realize rapid detection. Finally, the vitamin C content of tomato was detected by standard addition recovery method.
ResultThe vitamin C electrochemical sensor based on MWCNTs/Au/PGE electrode could accurately determine the vitamin C content in the range of pH 4–8, and its performance was the best when pH was 5. During rapid detection, the detection mass fraction range was 1–500 μg/g, sensitivity up to 0.244 μA·(μg/g)−1·cm−2. The interference rates of the sensor to glucose, malic acid and citric acid were less than 1.77%, and the relative standard deviation (RSD) measured by the same sensor for many times was 2.7%. The vitamin C content of tomato sample was 69.42 μg/g, the recovery was 109%–113%, and the RSD was less than 2.26%.
ConclusionMWCNTs/Au/PGE electrode has the advantages of simple preparation process, low cost, high sensitivity, wide measurement range, strong stability and anti-interference. It provides a new idea for the rapid detection of vitamin C in fruits and vegetables.
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图 1 电极表面纳米结构形貌和成分表征
a：Au/PGE电极电镜图；b：MWCNTs/Au/PGE电极电镜图；c、d：MWCNTs/Au/PGE电极电镜图和能谱分析；e：PGE、Au/PGE、MWCNTs/Au/PGE电极拉曼光谱分析；f：MWCNTs/Au/PGE电极XPS分析；g、h：Au 4f和C 1s的精细图谱分析
Figure 1. Nanostructure morphology and composition characterization of electrode surface
a: Electron microscope of Au/PGE electrode; b: Electron microscope of MWCNTs/Au/PGE electrode; c, d: Electron microscope and energy spectrum analysis of MWCNTs/Au/PGE electrode; e: Raman spectrum analysis of PGE, Au/PGE and MWCNTs/Au/PGE electrodes; f: XPS analysis of MWCNTs/Au/PGE electrode; g, h: Fine atlas of Au 4f and C 1s
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图 2 MWCNTs/Au/PGE的电化学性能
a：不同修饰的电极在含0.1 mol/L KCl的5.0 mmol/L Fe(CN)63-/4-溶液的循环伏安图；b：不同修饰的电极在50 μg/g的维生素C标准液中的差分脉冲伏安图；c：MWCNTs/Au/PGE在50 μg/g的维生素C标准液中不同扫描速率的循环伏安图；d：MWCNTs/Au/PGE的峰值电流(Ip)与扫描速率(v)平方根的线性拟合图；图中电位以饱和Ag/AgCl电极为参考
Figure 2. Electrochemical performance of MWCNTs/Au/PGE
a: Cyclic voltammetry images of different modified electrodes in 5.0 mmol/L Fe(CN)63-/4-solution containing 0.1 mol/L KCl; b: Differential pulse voltammetry images of different modified electrodes in 50 μg/g vitamin C standard solution; c: Cyclic voltammetry images of MWCNTs/Au/PGE at different scanning rates in 50 μg/g vitamin C standard solution; d: Linear relationship between different peak currents (Ip) of MWCNTs/Au/PGE and square root of scanning rate (v); The potential in the figure is based on the saturated Ag/AgCl electrode
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图 3 MWCNTs/Au/PGE在不同pH的维生素C (VC)含量梯度中的差分脉冲伏安法曲线
a~e的插图为对应pH条件下峰电流(I)与维生素C质量分数的线性关系；f：在180 μg/g维生素C溶液中不同pH条件下的峰电流变化，插图分别为pH和峰电流、pH和峰电位(V)的关系；图中电位以饱和Ag/AgCl电极为参考
Figure 3. Differential pulse voltammetry curves of MWCNTs/Au/PGE in the content gradients of vitamin C (VC) at different pH
Illustration of figure a−e: Linear relationship between peak current and vitamin C mass fraction at corresponding pH; f: Peak current variation diagram of different pH in 180 μg/g vitamin C solution, Illustration: pH and peak current diagram, relationship between pH and peak potential; The potential in the figure is based on saturated Ag/AgCl electrode
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图 4 MWCNTs/Au/PGE时间电流曲线和线性关系
a：MWCNTs/Au/PGE电极随维生素C质量分数变化时间电流曲线；b：电流均值随维生素C质量分数的变化趋势
Figure 4. Time current curve and linear relationship of MWCNTs/Au/PGE
a: Time current curve of MWCNTs/Au/PGE electrode with vitamin C content; b: Variation trend of average current with vitamin C content
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图 6 10倍稀释的鲜榨番茄汁中维生素C含量的测定过程
a：番茄鲜榨；b：番茄鲜榨后过滤；c：电极封装模具；d：电化学测试过滤稀释10倍后的番茄汁
Figure 6. Determination of vitamin C content in 10-fold diluted fresh tomato juice
a: Fresh pressed tomato juice; b: Filtered fresh pressed tomato juice; c: Electrode packaging mold; d: Electrochemical test of the filtered tomato juice diluted 10 times
表 1 加标回收率法电化学检测番茄汁维生素C含量
Table 1 Electrochemical determination of vitamin C content in tomato juice by standard addition recovery method
n=3 加标量/
(μg·g−1)
Spiked
mass fraction检测量/
(μg·g−1)
Detection
mass fraction回收率/
%
Recovery相对标准
偏差/%
Relative
standard
deviation0 6.14 2.26 5 11.64 109.95 1.68 10 17.04 109.03 0.81 20 28.77 113.16 2.00 
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表 2 不同方法检测番茄汁中维生素C含量
Table 2 Vitamin C content in tomato juice detected by different methods
n=3 检测方法
Test method线性方程1)
Linear equation决定系数
Determination coefficient
(R2)w(维生素C)/(μg·g−1)
vitamin C
content相对标准偏差/%
Relative standard
deviation钼蓝比色法
Molybdenum blue colorimetryy = 0.682 7x–0.013 1 0.996 6 76.91 7.63 电化学法
Electrochemical methody = 0.049 7x + 0.054 7 0.998 0 69.42 6.50 1) 钼蓝比色法线性方程中，y为光密度，x为维生素C质量浓度；电化学法线性方程中，y为电流，x为维生素C质量分数
1) In the linear equation of molybdenum blue colorimetry, y is the absorbance and x is the vitamin C content; In the linear equation of electrochemical method, y is the current value, x is the vitamin C content
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