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基于低场核磁共振技术的大豆霉变等级判别方法

Method for discriminating soybean mildew grades based on low-field nuclear magnetic resonance technology

  • 摘要: 为解决大豆储存过程中霉变检测的技术难题,研究采用低场核磁共振(low-field nuclear magnetic resonance,LF-NMR)技术,对大豆内部水分状态与霉变程度进行快速、无损检测与等级判别。研究选取在温度40 ℃、相对湿度75%条件下储存21 d的大豆样本作为试验对象,分别在第0、7、14、21天进行LF-NMR波谱检测。基于采集的波谱特征参数,构建了支持向量回归(support vector regression,SVR)、随机森林(random forest,RF)和梯度提升机(gradient boosting machines,GBM)3种大豆霉变等级判别模型。研究结果表明:各时间点大豆的弛豫谱中均存在3种水分相态:结合水(0.1 ms≤T21<10 ms)、半结合水(10 ms≤T22<150 ms)、自由水(150 ms≤T231000 ms),对应的信号幅值及水分比例分别为A21A22A23P21P22P23。霉变过程中各相态水分呈规律性变化,自由水比例P23先增高后降低,半结合水比例P22持续升高,这一转化过程是霉变发生的核心特征。相关性分析显示A23P23在表征样品霉变过程中水分状态变化方面具备较高的敏感性与可靠性,被确定为建模的关键输入参数。通过混淆矩阵及性能评估指标对比,发现相较于RF和GBM模型,SVR模型的中位数最低,约为0.07%,箱体整体范围较窄,须的长度最短,在泛化性能和分类准确性方面表现最为优异。学习曲线分析进一步证实,SVR模型在霉变等级分类的可靠性和拟合效果上均表现最优,具有更高的预测精度和更好的稳定性。该研究不仅建立了一套高效、精准的大豆霉变检测技术体系,也为农产品储存管理的智能化发展奠定了理论基础。

     

    Abstract: Soybean mildew has posed a significant threat to the economic viability and food safety in agricultural storage. Mildew detection is also limited to the technical problem during storage. Conventional detection, such as visual inspection, sensory evaluation, and chemical analysis, can often suffer from some challenges, such as time-consuming procedures, subjective judgment errors, and destructive sampling. It is often required for the timely and accurate identification of mildew. Therefore, it is important for the more advanced, efficient, and non-invasive detection. In this study, the Low-Field Nuclear Magnetic Resonance (LF-NMR) was adopted to achieve the rapid, non-destructive detection and grade discrimination of the internal water state and mildew degree of soybeans. Specifically, the soybean samples were stored at a temperature of 40 ℃. While a relative humidity of 75% RH for 21 days was selected for the test objects. These specific environmental parameters were chosen to investigate the mildew development. The mildew was more prone to occur due to the high-risk storage scenarios. Furthermore, the LF-NMR spectroscopy was carried out on the 0th, 7th, 14th, and 21st days. In addition, the LF-NMR instrument was calibrated before each detection, according to the standard samples with the known water content for the high accuracy and reliability of the measurement. The soybean samples were uniformly placed in the cylindrical glass tubes with a diameter of 10 mm, and the tubes were then inserted into the sample holder of the LF-NMR instrument. The parameters were optimized, including the magnetic field strength, radiofrequency pulse sequence, and acquisition time, using preliminary experiments to obtain the high-quality relaxation spectra. According to the spectral characteristic parameters, three discrimination models were obtained to determine the grade of the soybean mildew, namely Support Vector Regression (SVR), Random Forest (RF), and Gradient Boosting Machines (GBM). In the construction of the RF model, the systematic adjustment was performed on the number of decision trees, the number of features for splitting at each node, as well as the minimum number of samples required to split an internal node. The GBM model was fine-tuned to optimize the parameters, such as the learning rate, the number of boosting iterations, and the maximum depth of the trees. The results show that there were three water phases in the relaxation spectra of soybeans at each time point: bound water (0.1 ms < T21 < 10 ms), semi-bound water (10 ms < T22 < 150 ms), and free water (150 ms < T23 < 1000 ms), with the signal amplitudes and water proportions of A21, A22, A23 and P21, P22, P23, respectively. The water content of each phase changed regularly during mildew. At the initial stage of mildew, the metabolic activities of the mold microorganisms triggered the breakdown of the cell walls and membranes in soybeans, thus causing the release of the bound and semi-bound water into the free state. There was an increase in the free water proportion P23. As the mildew progressed, the free water was gradually consumed by the growing mold for its physiological activities, leading to a subsequent decrease in P23. Meanwhile, the continuous rise of the semi-bound water proportion P22 was attributed to the formation of new hydrogen bonds or other interactions between water molecules and the macromolecules in soybeans during mildew. Correlation analysis showed that the A23 and P23 shared high sensitivity and reliability. There were some changes in the water state during mildew of the samples. Thus, some influencing factors were then determined as the key input parameters for modeling. A comparison was made on the confusion matrices and multiple indicators of performance, including the accuracy, precision, recall, F1-score, and area under the receiver operating characteristic curve. It was found that the SVR model performed the best in terms of generalization and classification accuracy, compared with the RF and GBM models. The SVR model was also utilized to accurately classify the different mildew levels, according to the non-linear relationships between the input spectral parameters and mildew grades. The learning curve analysis further confirmed that the SVR model performed the best in terms of reliability and fitting in the classification of the mildew grades. The higher prediction accuracy and better stability were achieved, indicating its strong adaptability to various soybean samples. Efficient and accurate technology was obtained to detect soybean mildew for the intelligent storage of agricultural products. In practical applications, this LF-NMR-based detection can be integrated into the large-scale storage facilities of soybeans, enabling real-time monitoring of mildew status. Early warnings of potential mildew can greatly contribute to taking timely measures, such as ventilation, humidity, or separating contaminated batches, thereby minimizing economic losses. Moreover, the findings can also provide valuable references for similar detection for agricultural products, thereby contributing to food safety and quality control in the agricultural industry.

     

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