表面增强拉曼光谱结合化学计量学快速检测黄酒中的组胺
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(1.河北农业大学食品科技学院 河北保定 071000;2.中粮营养健康研究院 营养健康与食品安全北京市重点实验室 北京 102209)

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研究生教育质量提升-在读研究生创新项目(2022/1009209);国家自然科学基金项目(32001732)


Rapid Determination of Histamine in Huangjiu by Surface-enhanced Raman Spectroscopy Combined with Chemometrics
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(1.College of Food Science and Technology, Hebei Agricultural University, Baoding 071000, Hebei;2.Nutrition and Health Research Institute, COFCO Corporation, Beijing Key Laboratory of Nutrition and Health and Food Safety, Beijing 102209)

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    摘要:

    组胺是一种生物胺,由组氨酸脱羧产生,是黄酒发酵的副产物之一,其含量超标会对人体健康有重大影响。本研究将表面增强拉曼光谱(SERS)技术与化学计量学方法相结合,快速检测黄酒中的组胺。以制备的银纳米粒子(Ag NPs)为增强剂,NaCl溶液为聚集剂来获取组胺的SERS光谱。首先利用组胺水溶液对NaCl溶液浓度、组胺与NaCl和Ag NPs的混合比例、三者混合时间等反应条件进行优化。然后基于最优条件对比C18固相萃取柱和PXC强阳离子交换反相固相萃取柱对黄酒的净化效果,对黄酒中的组胺进行分析。结果表明:当NaCl溶液浓度为0.5 mol/L,组胺水溶液∶Ag NPs∶NaCl溶液(体积比)=2∶1∶3,混合时间为15 s时,组胺1 002 cm-1特征峰处增强效果最好,在该条件下组胺水溶液的检出限为1 mg/L。PXC强阳离子交换反相固相萃取柱为黄酒前处理方法,黄酒中组胺的检出限为2 mg/L。建立了组胺含量的多元线性回归分析和偏最小二乘回归(PLSR)预测模型,并对比竞争性自适应重加权抽样(CARS)、主成分分析(PCA)、连续投影算法(SPA)对组胺特征信息提取的有效性,其中利用CARS筛选出的51个变量建立的PLSR模型校正集和验证集均获得较高的决定系数Rc2=0.9777,Rv2=0.9604,以及较低的均方根误差RMSEC=0.0712 mg/L,RMSEV=0.1405 mg/L。结论:SERS技术和化学计量学结合的方法可用于黄酒中组胺的快速检测。

    Abstract:

    Histamine is a kind of biogenic amine, which is produced by decarboxylation of histamine acid. It is one of the by-products of Huangjiu fermentation and is closely related to human health. In this study, surface-enhanced Raman spectroscopy (SERS) and chemometrics were combined to detect histamine in Huangjiu quickly. SERS spectra of histamine were obtained by using silver nanoparticles (Ag NPs) as SERS substrate and NaCl solution as aggregating agent. Firstly, the SERS reaction conditions were optimized by using the concentration of histamine aqueous solution to NaCl solution, the mixing volume ratio of histamine to NaCl and Ag NPs, and the mixing time of the three. Then, based on the optimal conditions, the purification effects of C18 solid-phase extraction column and PXC strong cation exchange reversed-phase solid-phase extraction column on Huangjiu were further compared to quantitatively analyze histamine in Huangjiu. The results showed that when NaCl solution concentration 0.5 mol/L, histamine solution∶NaCl solution∶Ag NPs=2∶1∶3, and mixing time 15 s, the enhancement effect at the characteristic peak of histamine at 1 002 cm-1 was the strongest. Under this condition, the detection limit of histamine solution was 1 mg/L. At the same time, under this condition, PXC strong cation exchange reversed-phase solid phase extraction column was determined as the pretreatment method of Huangjiu, and the detection limit of histamine in Huangjiu was 2 mg/L. Finally, multiple linear regression analysis and partial least squares regression (PLSR) prediction models of histamine content are established, and the effectiveness of competitive adaptive weighted sampling (CARS), Principal component analysis (PCA) and Successive projections algorithm (SPA) in screening characteristic variables of original spectrum was compared. Among them, the calibration set and verification set of PLSR model established by using 51 variables screened by CARS have obtained higher determination coefficients Rc2=0.9777, Rv2=0.9604, and lower root mean square error RMSEC=0.0712 mg/L and RMSEV=0.1405 mg/L. The results showed that the rapid quantitative detection of histamine in yellow rice wine could be realized based on SERS technology and chemometrics method, which provided a new idea for the on-site monitoring of histamine in fermented alcoholic beverage.

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苏心悦,锁然,翟晨,马倩云,孙剑锋,王文秀.表面增强拉曼光谱结合化学计量学快速检测黄酒中的组胺[J].中国食品学报,2024,24(12):332-342

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  • 收稿日期:2023-12-08
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  • 在线发布日期: 2025-01-23
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