基于导电聚合物/金属纳米颗粒复合材料味觉传感器系统的黄酒陈酿特性探讨和滋味品质量化机理解析

The taste characteristics of rice wines, which have high correlation with the choice of consumers and economic benefits of producer, were decided by the aging process. The taste quality of rice wine was usually designed by a sensory panel, which was easy disturbed by subjective factors and objective factors, and the sense organ was easy to fatigue in identification..In the recent 10 years, the researches of intelligent gustatory system (electronic tongue) become one of the hot issues, and several laboratories have done lots of work on the development of VE-tongue. Along with the development of research, some problems were apparent gradually. The developed VE-tongues were usually based on blank noble metallic and graphite electrodes, which have low sensitivity to weak electrolyte, such as amino acid, saccharides, alcohol, etc. Those organic substances are always present high relation with gustatory feature of foods, therefore, the taste information of the liquid foods could not be collected completely by the VE-tongue with those blank electrodes. .In this study, the voltammetric electronic tongue was first applied in detecting the aging and taste characteristics of rice wine. The research was focused on the basic research about mechanism of quantification of aging and taste characteristics of rice wines by VE-tongue based on conductive polymer/noble metal nanocomposites modified electrodes. On the basis of the explicit relationship between the content of gustatory substances and taste qualities, to explore the sensitivity of sensor response to gustatory substances on the basis of different conductive polymer/noble metal nanocomposites, and to reveal the characteristics of sensor array’s response to different taste quality of rice wine, cooperation with Weber–Fechner Law, the mathematic correlation between responses obtained by modified sensor array and taste quality of rice wine was confirmed. Data processing has been done to find the optimum pattern recognition to qualified aging and taste characteristics of rice wines by the VE-tongue, and lay scientific basis for the development and application of VE-tongue specialized in the quality detection of rice wine.

黄酒的陈酿特性决定其滋味品质，而滋味品质的好坏直接影响消费者的选择和生产者的经济效益。黄酒的滋味品质通常由专业人员通过感官判定，但该方法易受“客观环境”和“主观心理”的影响。.本课题提出了分析黄酒陈酿特性和滋味品质的新方法，侧重于不同导电聚合物/贵金属纳米颗粒复合材料味觉传感系统的黄酒陈酿特性和滋味品质量化的分析研究。拟在明确黄酒呈味物质含量与滋味品质相关性的基础上，通过分析导电聚合物/贵金属纳米颗粒复合修饰材料的传感机理，研究不同修饰传感器对黄酒呈味物质响应的灵敏特性，探明黄酒不同滋味品质的传感器 响应信号的差异，结合Weber–Fechner Law，揭示黄酒不同的滋味品质影响传感器响应特性的数学规律，确立滋味品质量化模型；在阐明黄酒陈酿中滋味品质变化规律的基础上，通过获取较佳的模式识别方法，实现对黄酒陈酿特性的精确判断，为专用黄酒陈酿特性和滋味品质监测仪器的开发提供理论基础。

黄酒是中国特有的酒种，新酿的黄酒需要自然陈化储藏。因黄酒的质量评价手段较少，导致陈年黄酒造假、乱贴标签现象时常发生，严重侵犯了正规厂商及消费者的权益。黄酒的陈化时间与呈味物质含量存在一定的关系，本课题围针对黄酒在陈化过程中含量变化比较大的多种呈味物质，如酸味（乳酸）、鲜味（谷氨酸）、甜味（葡萄糖），研究和开发相应的灵敏度高、选择性好的纳米复合材料修饰电极。本研究分析了修饰电极溶液中的反应动力学过程，并将三根电极组成阵列，采集1 - 8年不同陈化时间的“女儿红”黄酒中丰富全面的“滋味”信息，主要研究内容、方法和结论如下：.（1）本研究针对乳制备了聚酞菁钴/碳纳米管复合材料修饰电极（CoPPc/MWCNTs/GCE）.CoPPc/MWCNTs复合材料的浓度配置为2 mg/mL且修饰剂用量为 5 μl，pH 4.0，扫速为100 mV/s，富集时间t 为 240 s，检出限为1×10-6 mol/L，参与反应的电子数和质子数均为2，电极的电化学活性面积A = 0.49 cm2，扩散系数D = 9.22×10-5 cm2/s。.（2）本文针对谷氨酸制备了聚中性红/铜纳米复合材料修饰电极（PNR/Cu/GCE），最终在优化pH为4.0，扫速100 mV/s的条件下，检出限为3×10-6 mol/L，参与反应的电子数为2，质子数为4，电极的电化学活性面积A = 0.56 cm2，扩散系数D = 3.72×10-4 cm2/s。.（3）本文制备了聚天门冬氨酸/氧化镍纳米复合材料修饰电极（PASP/NiO/GCE）。在碱性条件下（pH 10.0），扫速为100 mV/s，富集时间t为180 s，检出限为2×10-6 mol/L，参与反应的电子数和质子数均为2，电极的电化学活性面积A = 0.71 cm2，扩散系数D = 1.06×10-4 cm2/s。.（4）将所研制的CoPPc/MWCNTs/GCE、PNR/Cu/GCE和PASP/NiO/GCE组成电极阵列，基于LPP - ELM模型和LLE - SVM模型对黄酒检测的分类准确率均到达100%，且LPP - ELM模型对“女儿红”黄酒原浆的陈化时间具有最佳的回归效果（训练集R2 = 0.9985，RMSE = 0.0892，测试集R2 = 0.9905，RMSE = 0.1733）。

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