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CN111795943A - A method for non-destructive detection of exogenous sucrose in tea based on near-infrared spectroscopy - Google Patents

A method for non-destructive detection of exogenous sucrose in tea based on near-infrared spectroscopy Download PDF

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CN111795943A
CN111795943A CN202010549143.3A CN202010549143A CN111795943A CN 111795943 A CN111795943 A CN 111795943A CN 202010549143 A CN202010549143 A CN 202010549143A CN 111795943 A CN111795943 A CN 111795943A
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sucrose
black tea
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tea
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董春旺
杨崇山
安霆
杨艳芹
滑金杰
刘中原
江用文
袁海波
王近近
李佳
邓余良
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Tea Research Institute Chinese Academy of Agricultural Sciences
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    • G01MEASURING; TESTING
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    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
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Abstract

本发明涉及茶叶品质检测技术领域,尤其涉及基于近红外光谱技术无损检测茶叶中外源掺杂蔗糖的方法,所述方法是将含不同外源蔗糖量的红茶样本进行近红外光谱扫描,对扫描获取的原始光谱数据进行标准正态变量变换算法处理,以及采用连续投影算法进行变量筛选,随后进行主成分分析,以最优主成分建立检测模型,将待检测的红茶样本的近红外光谱数据输入检测模型中,实现红茶中外源掺杂蔗糖的判别和含量检测。本发明旨在解决加糖红茶人工辨别困难和理化检测费时费力等问题,实现对加糖红茶的无损、快速、准确识别和糖量的定量检测,为红茶中外源蔗糖的定性和定量检测提供了理论方法和科学依据。The invention relates to the technical field of tea quality detection, in particular to a method for nondestructively detecting exogenous sucrose doped in tea based on near-infrared spectroscopy technology. The original spectral data is processed by the standard normal variable transformation algorithm, and the continuous projection algorithm is used for variable screening, and then the principal component analysis is performed to establish a detection model with the optimal principal component, and the near-infrared spectral data of the black tea sample to be detected is input into the detection. In the model, the discrimination and content detection of exogenous sucrose in black tea are realized. The invention aims to solve the problems of difficulty in manual identification of sugar-sweetened black tea and time-consuming and labor-intensive physical and chemical detection, realizes nondestructive, rapid and accurate identification and quantitative detection of sugar content of sugar-sweetened black tea, and provides a theoretical method for qualitative and quantitative detection of exogenous sucrose in black tea and scientific basis.

Description

基于近红外光谱技术无损检测茶叶中外源掺杂蔗糖的方法A method for non-destructive detection of exogenous sucrose in tea based on near-infrared spectroscopy

技术领域technical field

本发明涉及茶叶品质检测技术领域,尤其涉及基于近红外光谱技术无损检测茶叶中外源掺杂蔗糖的方法。The invention relates to the technical field of tea quality detection, in particular to a method for nondestructively detecting exogenous doped sucrose in tea based on near-infrared spectroscopy technology.

背景技术Background technique

近年来,由于消费者对红茶的喜爱,我国红茶产业继续保持稳步增长的态势,红茶产量也逐步增加,据国家统计局数据显示,2018年红茶产量达到23.33万吨,较2008年增长了251.9%。随着红茶产业的兴起,红茶的种类日趋繁多,高端红茶也逐渐走向人们的视野,销量逐年增加。目前市场上有少部分高档红茶却名不副实,原因是一些不法商贩在红茶加工中加入外源蔗糖,以期达到高档红茶的效果,红茶加工中所添加的蔗糖可在香气、色泽等方面影响对成茶的感官品质评判,使得消费者很难辨别,严重影响了红茶市场的秩序,危害了茶农利益;另外,由于蔗糖具有易吸潮、易变质和易滋生细菌等特点,对红茶质量安全有较大的影响。In recent years, due to consumers' love for black tea, my country's black tea industry has continued to maintain a steady growth trend, and the output of black tea has also gradually increased. According to the data of the National Bureau of Statistics, the output of black tea in 2018 reached 233,300 tons, an increase of 251.9% over 2008. . With the rise of the black tea industry, there are more and more types of black tea, and high-end black tea is gradually moving into people's field of vision, and the sales volume is increasing year by year. At present, there are a small number of high-grade black teas on the market, but the name is not true. The reason is that some unscrupulous traders add exogenous sucrose in the processing of black tea, in order to achieve the effect of high-grade black tea. The sensory quality evaluation of sucrose makes it difficult for consumers to distinguish, which seriously affects the order of the black tea market and harms the interests of tea farmers; in addition, because sucrose is easy to absorb moisture, easy to deteriorate, and easy to breed bacteria, it has a great impact on the quality and safety of black tea. Impact.

目前,国内外检测红茶中外源蔗糖含量的方法主要使用化学试剂,例如公开号为CN107589081A,专利名称为“一种茶叶中外源掺杂蔗糖的抗干扰快速检测方法”的中国发明专利,利用交联聚乙烯吡咯烷酮-活性炭组合吸附剂,去除茶样提取液中基质成分对间苯二酚显色反应和检测的干扰,实现了对茶叶加工过程外加蔗糖的定性及定量快速测定。上述方法虽然精度较高,但是需要借助相关仪器,具备一定的科研素养,需要对茶叶进行提取或冲泡,费时、费力,经济成本也较高,对于消费者和茶商来说不适合广泛的推广。因此,研究一种针对红茶中外源蔗糖的无损快速方法显得尤为重要。At present, the methods for detecting the content of exogenous sucrose in black tea at home and abroad mainly use chemical reagents. The polyvinylpyrrolidone-activated carbon combined adsorbent removes the interference of the matrix components in the tea-like extract on the color reaction and detection of resorcinol, and realizes the qualitative and quantitative rapid determination of sucrose added during tea processing. Although the above method has high precision, it requires the help of relevant instruments and certain scientific research literacy, and it is necessary to extract or brew tea leaves, which is time-consuming, laborious, and has high economic costs. It is not suitable for consumers and tea traders. promotion. Therefore, it is particularly important to develop a non-destructive and rapid method for exogenous sucrose in black tea.

近红外光谱技术作为一种新型的无损检测技术,利用物质中含氢基团对波长范围为780~2526nm之间的近红外光下由于电子的跃迁产生吸收,由于农产品物质成分中含氢基团含量较高,所以近红外光谱在对农产品的检测上取得了较好的效果,近年来在成分含量预测、分类鉴别、腐烂鉴别、实时监测等领域得到了广泛应用,已经逐步发展成熟。近红外光谱技术在茶叶萎凋、发酵等加工领域也进行了相关研究,一些茶企(如小罐茶)也基于近红外检测仪建立了智能化生产线,取得了较好的效果,但在红茶中外源蔗糖定性与定量检测上还未见报道。As a new type of non-destructive testing technology, near-infrared spectroscopy technology uses the hydrogen-containing groups in substances to absorb near-infrared light with a wavelength range of 780-2526 nm due to the transition of electrons. Therefore, NIR spectroscopy has achieved good results in the detection of agricultural products. In recent years, it has been widely used in the fields of component content prediction, classification identification, rot identification, and real-time monitoring, and has gradually developed and matured. Near-infrared spectroscopy technology has also been studied in the processing fields of tea withering and fermentation. Some tea companies (such as small pots of tea) have also established intelligent production lines based on near-infrared detectors, and achieved good results. The qualitative and quantitative detection of source sucrose has not been reported yet.

发明内容SUMMARY OF THE INVENTION

有鉴于此,本发明的目的是提供基于近红外光谱技术无损检测茶叶中外源掺杂蔗糖的方法,旨在解决加糖红茶人工辨别困难和理化检测费时费力等问题,实现对加糖红茶的无损、快速、准确识别和糖量的定量检测,为红茶中外源蔗糖的定性和定量检测提供了理论方法和科学依据。In view of this, the object of the present invention is to provide a method for non-destructively detecting exogenous sucrose in tea based on near-infrared spectroscopy, aiming to solve the problems such as difficulty in manual identification of sugar-sweetened black tea and time-consuming and laborious physical and chemical detection, and realize non-destructive and rapid detection of sugar-sweetened black tea. , Accurate identification and quantitative detection of sugar content provide theoretical methods and scientific basis for the qualitative and quantitative detection of exogenous sucrose in black tea.

本发明通过以下技术手段解决上述技术问题:The present invention solves the above-mentioned technical problems through the following technical means:

基于近红外光谱技术无损检测茶叶中外源掺杂蔗糖的方法,所述方法是将含不同外源蔗糖量的红茶样本进行近红外光谱扫描,对扫描获取的原始光谱数据进行标准正态变量变换算法处理,以及采用连续投影算法进行变量筛选,随后进行主成分分析,以最优主成分建立检测模型,将待检测的红茶样本的近红外光谱数据输入检测模型中,实现红茶中外源掺杂蔗糖的判别和含量检测。A method for non-destructive detection of exogenous sucrose in tea based on near-infrared spectroscopy. The method is to scan black tea samples containing different amounts of exogenous sucrose by near-infrared spectroscopy, and perform a standard normal variable transformation algorithm on the original spectral data obtained by scanning. process, and use continuous projection algorithm to screen variables, then carry out principal component analysis, establish a detection model with the optimal principal component, and input the near-infrared spectral data of the black tea sample to be detected into the detection model, so as to realize the detection of exogenous sucrose in black tea. Discrimination and content detection.

进一步,所述方法包括以下步骤:Further, the method includes the following steps:

S1.制备获取不同含糖量的红茶样本;S1. Prepare and obtain black tea samples with different sugar content;

S2.利用近红外光谱分析仪对红茶样本进行近红外光谱扫描,采集获得红茶样本的原始光谱数据;S2. Use a near-infrared spectrum analyzer to scan the black tea sample by near-infrared spectrum, and collect and obtain the original spectral data of the black tea sample;

S3.采用Kennard-Stone法将原始光谱数据集随机划分为训练集样本和预测集样本;S3. Use the Kennard-Stone method to randomly divide the original spectral data set into training set samples and prediction set samples;

S4.采用标准正态变量变换算法对原始光谱数据进行预处理,随后采用连续投影算法进行变量筛选,获取特征波长;S4. Use the standard normal variable transformation algorithm to preprocess the original spectral data, and then use the continuous projection algorithm to filter variables to obtain characteristic wavelengths;

S5.将预处理后的全波段与特征波长光谱数据分别进行PCA降维分析,随后以PCA处理后的最优主成分作为输入,建立基于全波段光谱的外源掺杂蔗糖的PLS-DA检测模型,以及建立基于特征波长光谱的外源掺杂蔗糖的SPA-PLS-DA检测模型;S5. Perform PCA dimensionality reduction analysis on the preprocessed full-band and characteristic wavelength spectral data respectively, and then use the PCA-processed optimal principal components as input to establish a full-band spectrum-based PLS-DA detection of exogenously doped sucrose model, and the establishment of a SPA-PLS-DA detection model for exogenously doped sucrose based on characteristic wavelength spectra;

S6.在电脑客户端中的matlab软件中分别编程建立PLS-DA检测模型和SPA-PLS-DA检测模型,并将电脑客户端与近红外光谱仪进行通信连接,将近红外光谱仪扫描待检测红茶样本获得的光谱数据输入PLS-DA检测模型和SPA-PLS-DA检测模型中,实现红茶中外源蔗糖含量的判别和含糖量的在线实时检测。S6. Program the PLS-DA detection model and the SPA-PLS-DA detection model in the matlab software in the computer client, respectively, and connect the computer client to the near-infrared spectrometer, and the near-infrared spectrometer scans the black tea sample to be tested to obtain The spectral data is input into the PLS-DA detection model and the SPA-PLS-DA detection model to realize the discrimination of the exogenous sucrose content in black tea and the online real-time detection of the sugar content.

进一步,所述S1步骤中,在红茶加工揉捻工序时加入不同含量的外源蔗糖,不同含糖量的红茶样本分别为:无添加蔗糖、每10kg揉捻叶掺入250g蔗糖、每10kg揉捻叶掺入500g蔗糖和每10kg揉捻叶掺入750g蔗糖的红茶样本。Further, in the step S1, different contents of exogenous sucrose are added during the black tea processing and rolling process. The black tea samples with different sugar contents are: no added sucrose, 250 g of sucrose per 10 kg of kneaded leaves, and 10 kg of kneaded leaves mixed with sucrose. A sample of black tea with 500 g of sucrose and 750 g of sucrose per 10 kg of rolled leaves was added.

进一步,所述S2步骤中,分别称取20±0.5g的不同含糖量的红茶样本,均匀平铺在规格为Φ70mm×10mm石英培养皿中,茶叶顶部与皿体上表面平齐,将石英培养皿置于近红外光谱仪上进行近红外光谱扫描采集。Further, in the step S2, 20±0.5g of black tea samples with different sugar contents were weighed, and were evenly spread in a quartz petri dish with a specification of Φ70mm×10mm, the top of the tea leaves was flush with the upper surface of the dish, and the quartz The petri dish was placed on a near-infrared spectrometer for near-infrared spectral scanning collection.

进一步,所述S2步骤中,近红外光谱仪检测波长范围为900~1700nm,分辨率为4cm-1,每个样本的扫描次数为30次。Further, in the step S2, the detection wavelength range of the near-infrared spectrometer is 900-1700 nm, the resolution is 4 cm -1 , and the number of scans for each sample is 30 times.

进一步,所述S2步骤中,对红茶样本进行近红外光谱扫描时,每次扫描采集完成后,对茶叶进行翻拌处理,以便提高模型精度,更好地反映加糖红茶的整体信息。Further, in the step S2, when near-infrared spectrum scanning is performed on the black tea sample, after each scan and collection is completed, the tea leaves are subjected to a stirring process, so as to improve the model accuracy and better reflect the overall information of the sugar-sweetened black tea.

进一步,所述训练集样本和预测集样本的数据量之比为2:1。Further, the ratio of the data amount of the training set samples to the prediction set samples is 2:1.

进一步,所述S4步骤中,对含糖量敏感的特征波长分别为190nm、206nm、227nm、300nm、481nm、502nm、538nm、573nm、598nm、621nm、627nm、684nm、714nm、732nm、737nm和741nm。Further, in the step S4, the characteristic wavelengths sensitive to the sugar content are respectively 190 nm, 206 nm, 227 nm, 300 nm, 481 nm, 502 nm, 538 nm, 573 nm, 598 nm, 621 nm, 627 nm, 684 nm, 714 nm, 732 nm, 737 nm and 741 nm.

本发明的有益效果:Beneficial effects of the present invention:

(1)本发明明确了不同含糖量红茶样品的平均光谱信息,结果表明未添加蔗糖与添加外源蔗糖的红茶样品的平均光谱存在明显的差距,添加不同含量的外源蔗糖红茶样品平均光谱之间虽差距较小,但在吸收峰300nm、580nm与反射谷200nm、400nm处具有显著区别。(1) The present invention clarifies the average spectral information of black tea samples with different sugar contents, and the results show that there is a significant gap between the average spectra of black tea samples without sucrose and those with exogenous sucrose added, and the average spectra of black tea samples with different contents of exogenous sucrose added. Although the gap between them is small, there are significant differences between the absorption peaks at 300nm and 580nm and the reflection valleys at 200nm and 400nm.

(2)本发明通过SNV法对原始光谱进行预处理,采用SPA提取特征波长,并采用PCA对预处理后的全波段与特征波长数据降维,以全波段和特征波长光谱数据最优主成分作为模型输入量分别建立分析模型,结果表明,SPA变量筛选后,基于特征波长建立的检测模型的精度较高。(2) The present invention preprocesses the original spectrum by the SNV method, uses SPA to extract the characteristic wavelength, and uses PCA to reduce the dimension of the preprocessed full-band and characteristic wavelength data, and uses the optimal principal component of the full-band and characteristic wavelength spectral data The analysis models were established as the model input, and the results showed that the detection model based on the characteristic wavelength was more accurate after the SPA variables were screened.

(3)本发明表明,与基于全波段建立的PLS-DA检测模型相比,特征波长建立的SPA-PLS-DA检测模型所用变量为16个,主成分数为5个,主成分和变量数均得到压缩,并且经主成分分析降低了数据维度,较少的主成分输入能够减少计算负担,加快计算速度,能够达到生产中在线监测的时效性需求。(3) The present invention shows that, compared with the PLS-DA detection model established based on the whole waveband, the SPA-PLS-DA detection model established by the characteristic wavelength uses 16 variables, 5 principal components, and the number of principal components and variables. All of them are compressed, and the data dimension is reduced by principal component analysis. Less principal component input can reduce the computational burden, speed up the calculation speed, and meet the timeliness requirements of online monitoring in production.

(4)本发明使用的的近红外检测技术具有成本低、方便快捷、稳定性强和重复性好等优点,是一种理想的检测红茶中外源蔗糖含量的手段。(4) The near-infrared detection technology used in the present invention has the advantages of low cost, convenience and quickness, strong stability and good repeatability, and is an ideal means for detecting the content of exogenous sucrose in black tea.

附图说明Description of drawings

图1是本发明中不同含糖量红茶样本的平均光谱曲线;Fig. 1 is the average spectral curve of different sugar content black tea samples in the present invention;

图2是本发明中采用SPA法对原始光谱数据提取的特征波长的分布情况;Fig. 2 is the distribution situation of the characteristic wavelength that adopts SPA method to the original spectral data extraction in the present invention;

图3是本发明中全波段光谱的前三个PCA主成分的三维载荷图;Fig. 3 is the three-dimensional loading diagram of the first three PCA principal components of full-band spectrum in the present invention;

图4是本发明中特征波长光谱的前三个PCA主成分的三维载荷图;Fig. 4 is the three-dimensional loading diagram of the first three PCA principal components of characteristic wavelength spectrum in the present invention;

图5为基于全波段建立的PLS-DA检测模型预测结果图;Fig. 5 is the prediction result of the PLS-DA detection model established based on the full band;

图6为基于全波段光谱建立的PLS-DA检测模型预测集预测精度图;Fig. 6 is the prediction accuracy chart of the prediction set of the PLS-DA detection model established based on the full-band spectrum;

图7为基于全波段建立的PLS-DA检测模型预测柱形图;Fig. 7 is the prediction bar chart of the PLS-DA detection model established based on the full band;

图8为基于全波段建立的PLS-DA检测模型预测散点图;Fig. 8 is the prediction scatter diagram of the PLS-DA detection model established based on the full band;

图9为基于特征波长建立的SPA-PLS-DA检测模型预测结果图;Fig. 9 is the prediction result graph of the SPA-PLS-DA detection model established based on the characteristic wavelength;

图10为基于特征波长建立的SPA-PLS-DA检测模型预测集预测精度图;Fig. 10 is the prediction accuracy chart of the prediction set of the SPA-PLS-DA detection model established based on the characteristic wavelength;

图11为基于特征波长建立的SPA-PLS-DA检测模型的预测柱形图;Fig. 11 is the prediction bar chart of the SPA-PLS-DA detection model established based on characteristic wavelength;

图12为基于特征波长建立的SPA-PLS-DA检测模型预测散点图。Figure 12 is a scatter plot of prediction of the SPA-PLS-DA detection model established based on characteristic wavelengths.

具体实施方式Detailed ways

下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

本发明的基于近红外光谱技术无损检测茶叶中外源掺杂蔗糖的方法,采集制备的不同含糖量的红茶样本,提取样本的平均光谱信息,随后进行SNV法预处理和PCA分析,以不同主成分数建立PLS-DA与SPA-PLS-DA模型,能够用来定性和定量分析红茶中掺杂的外源蔗糖情况。该方法包括以下步骤:The method for non-destructively detecting exogenous sucrose in tea based on near-infrared spectroscopy of the present invention collects prepared black tea samples with different sugar contents, extracts the average spectral information of the samples, and then performs SNV method pretreatment and PCA analysis, and uses different main The PLS-DA and SPA-PLS-DA models were established based on the number of components, which could be used to qualitatively and quantitatively analyze the exogenous sucrose doped in black tea. The method includes the following steps:

S1.制备获取不同含糖量的红茶样本;S1. Prepare and obtain black tea samples with different sugar content;

S2.利用近红外光谱分析仪对红茶样本进行近红外光谱扫描,采集获得红茶样本的原始光谱数据;S2. Use a near-infrared spectrum analyzer to scan the black tea sample by near-infrared spectrum, and collect and obtain the original spectral data of the black tea sample;

S3.采用Kennard-Stone法将原始光谱数据集随机划分为训练集样本和预测集样本;S3. Use the Kennard-Stone method to randomly divide the original spectral data set into training set samples and prediction set samples;

S4.采用标准正态变量变换算法对原始光谱数据进行预处理,随后采用连续投影算法进行变量筛选,获取特征波长;S4. Use the standard normal variable transformation algorithm to preprocess the original spectral data, and then use the continuous projection algorithm to filter variables to obtain characteristic wavelengths;

S5.将预处理后的全波段与特征波长光谱数据分别进行PCA降维分析,随后以PCA处理后的最优主成分作为输入,建立基于全波段光谱的外源掺杂蔗糖的PLS-DA检测模型,以及建立基于特征波长光谱的外源掺杂蔗糖的SPA-PLS-DA检测模型;S5. Perform PCA dimensionality reduction analysis on the preprocessed full-band and characteristic wavelength spectral data respectively, and then use the PCA-processed optimal principal components as input to establish a full-band spectrum-based PLS-DA detection of exogenously doped sucrose model, and the establishment of a SPA-PLS-DA detection model for exogenously doped sucrose based on characteristic wavelength spectra;

S6.在电脑客户端中的matlab软件中分别编程建立PLS-DA检测模型和SPA-PLS-DA检测模型,并将电脑客户端与近红外光谱仪进行通信连接,将近红外光谱仪扫描待检测红茶样本获得的光谱数据输入PLS-DA检测模型和SPA-PLS-DA检测模型中,实现红茶中外源蔗糖含量的判别和含糖量的在线实时检测。S6. Program the PLS-DA detection model and the SPA-PLS-DA detection model in the matlab software in the computer client, respectively, and connect the computer client to the near-infrared spectrometer, and the near-infrared spectrometer scans the black tea sample to be tested to obtain The spectral data is input into the PLS-DA detection model and the SPA-PLS-DA detection model to realize the discrimination of the exogenous sucrose content in black tea and the online real-time detection of the sugar content.

具体如下:details as follows:

本实施例的方法需要用到近红外光谱仪、电脑客户端、数据线、规格为Φ70mm×10mm石英培养皿和matlab软件等,近红外光谱仪有数据接口,通过数据线或者硬盘可以将近红外光谱仪扫描获得的数据导入电脑客户端中。近红外光谱仪使用之前先对仪器进行自检,以确保仪器在正常工作状态,自检内容包括能量测试、X轴频率校正和Y轴重复性测试等,均按照常规操作进行自检。The method of this embodiment requires the use of a near-infrared spectrometer, a computer client, a data cable, a quartz petri dish with a size of Φ70mm×10mm, and matlab software. The data is imported into the computer client. Before using the near-infrared spectrometer, perform a self-check on the instrument to ensure that the instrument is in normal working condition. The self-check content includes energy test, X-axis frequency correction and Y-axis repeatability test, etc., all of which are carried out according to routine operations.

1.获取不同含糖量的红茶样本1. Obtain samples of black tea with different sugar content

采摘茶叶嫩度为一芽一叶,品种为福鼎大白,将采摘后的茶叶及时进行自然摊放,自然萎凋时加入不同含量的外源蔗糖,为了保证建立的模型具有较高的泛化性,自然萎凋时外源蔗糖的加入量分别为无添加(标签1),每10kg萎凋叶掺入250g蔗糖(标签2),每10kg萎凋叶掺入500g蔗糖(标签3),每10kg萎凋叶掺入750g蔗糖(标签4)。根据水分测定仪结果(测量三次取平均值),当萎凋叶水分为60%时,采用40型揉捻机进行揉捻,揉捻方式为:空揉15min→轻揉10min→重揉5min→轻揉5min→重揉5min→轻揉5min,总计45min,随后在人工气候箱内,于发酵温度30℃、相对湿度≥90%的条件下发酵4h,获得待检测红茶样本。The tenderness of the picked tea leaves is one bud and one leaf, and the variety is Fuding Dabai. The picked tea leaves are spread out naturally in time, and different contents of exogenous sucrose are added during natural withering, in order to ensure that the established model has a high generalization. , the amount of exogenous sucrose added during natural withering is respectively no addition (label 1), 250g sucrose (label 2) per 10kg wither leaves, 500g sucrose (label 3) per 10kg wither leaves, and 10kg per 10kg wither leaves. Add 750 g of sucrose (label 4). According to the results of the moisture analyzer (the average value of three measurements), when the moisture content of the withered leaves is 60%, the 40-type kneading machine is used for kneading. Heavy kneading for 5 min → light kneading for 5 min, totaling 45 min, and then fermenting for 4 h in an artificial climate box at a fermentation temperature of 30 °C and a relative humidity of ≥90% to obtain a black tea sample to be tested.

2.对红茶样本进行近红外光谱扫描,利用计算机上的光谱采集软件获得红茶样本的原始光谱数据2. Scan the black tea samples by near-infrared spectroscopy, and use the spectral acquisition software on the computer to obtain the original spectral data of the black tea samples

进行近红外光谱数据的采集时,分别称取20±0.5g的不同含糖量的红茶样本,均匀平铺在规格为Φ70mm×10mm石英培养皿中,茶叶顶部与皿体上表面平齐,将石英培养皿置于近红外光谱仪上进行近红外光谱扫描采集,所用近红外光谱仪检测波长范围为900~1700nm,分辨率为4cm-1,以空气为参比,每个样本采集30次光谱,共获得120条原始光谱数据,对照对应的标签保存,采集完成后将全部数据导出。由于近红外光谱仪采集样本光谱时多为定点监测,无法获取样本整体区域的光谱信息,为了使建立的模型拥有较好的鲁棒性和泛化性,提高模型精度,更好地反应加糖红茶的整体信息,所以在每次采集完成后,下一次采集之前,对茶叶作翻动处理,避免采集样本时由于采集区域相同而导致获取的光谱信息完全重合现象的发生。采集完样本光谱数据后,将原始光谱数据导入电脑客户端,使用matlab软件提取不同含糖量红茶样本的平均光谱,如图1所示,由于红茶中掺杂外源蔗糖量的不同,导致不同样本的平均光谱曲线具有明细的差异,可用于模型的判别。When collecting near-infrared spectral data, 20 ± 0.5 g of black tea samples with different sugar contents were weighed and evenly spread in a quartz petri dish with a size of Φ70 mm × 10 mm. The top of the tea leaves was flush with the upper surface of the dish body. The quartz petri dish was placed on a near-infrared spectrometer for near-infrared spectrum scanning and collection. The near-infrared spectrometer used was in the detection wavelength range of 900 to 1700 nm, with a resolution of 4 cm -1 . Taking air as a reference, each sample was collected 30 times of spectrum, a total of 30 spectra were collected. Obtain 120 original spectral data, save them against the corresponding labels, and export all the data after the acquisition is completed. Since the near-infrared spectrometer collects the sample spectrum mostly for fixed-point monitoring, the spectral information of the entire sample area cannot be obtained. In order to make the established model have better robustness and generalization, improve the model accuracy, and better reflect the sugar-sweetened black tea. Therefore, after each collection is completed and before the next collection, the tea leaves are turned over to avoid the phenomenon of complete overlap of the acquired spectral information due to the same collection area during sample collection. After collecting the sample spectral data, import the original spectral data into the computer client, and use the matlab software to extract the average spectra of black tea samples with different sugar content, as shown in Figure 1, due to the difference in the amount of exogenous sucrose doped in the black tea, resulting in different The average spectral curve of the samples has detailed differences, which can be used for model discrimination.

在采集近红外光谱数据时,为了减少原始光谱中噪声的影响,去除1650nm-1700nm光谱中噪声较大的部分。When collecting near-infrared spectral data, in order to reduce the influence of noise in the original spectrum, the noisy part of the 1650nm-1700nm spectrum is removed.

图1的数据明确了不同含糖量红茶样品的平均光谱信息,结果表明未添加蔗糖与添加外源蔗糖的红茶样品的平均光谱存在明显的差距,添加不同含量的外源蔗糖红茶样品平均光谱之间虽差距较小,但在吸收峰300nm、580nm与反射谷200nm、400nm处具有显著区别。The data in Figure 1 clarifies the average spectral information of black tea samples with different sugar content. The results show that there is a significant difference between the average spectra of black tea samples without sucrose and those with exogenous sucrose. The average spectra of black tea samples with different amounts of exogenous sucrose Although the difference between them is small, there are significant differences between the absorption peaks at 300nm and 580nm and the reflection valleys at 200nm and 400nm.

3.原始光谱数据的预处理3. Preprocessing of raw spectral data

采用Kennard-Stone(K-S)法将120个原始光谱数据集随机划分为训练集样本和预测集样本,用于模型的训练和优化,利用训练集样本校正建立的模型,利用预测集样本验证优化建立的模型,训练集样本和预测集样本的数据量之比为2:1,训练集样本含有80个原始光谱数据,预测集样本含有40个原始光谱数据。为了减少光谱信息中噪声和茶叶表面引起的散射现象对数据准确性的影响,采用标准正态变量变换算法(standard normal Ztransformation,SNV)对原始光谱数据预处理。The Kennard-Stone (K-S) method is used to randomly divide the 120 original spectral data sets into training set samples and prediction set samples, which are used for model training and optimization. The ratio of the data volume of the training set samples to the prediction set samples is 2:1, the training set samples contain 80 original spectral data, and the prediction set samples contain 40 original spectral data. In order to reduce the influence of noise in the spectral information and the scattering phenomenon caused by the tea surface on the accuracy of the data, the standard normal Ztransformation (SNV) algorithm was used to preprocess the original spectral data.

4.变量的筛选和检测模型的建立4. Screening of variables and establishment of detection models

对SNV法预处理后的原始光谱数据采用SPA法进行变量筛选,提取原始数据中对含糖量敏感的特征波长,提取了16个特征波长,即190nm、206nm、227nm、300nm、481nm、502nm、538nm、573nm、598nm、621nm、627nm、684nm、714nm、732nm、737nm和741nm,提取的特征波长的分布情况如图2所示。The original spectral data preprocessed by the SNV method was filtered by the SPA method, and the characteristic wavelengths sensitive to sugar content in the original data were extracted, and 16 characteristic wavelengths were extracted, namely 190nm, 206nm, 227nm, 300nm, 481nm, 502nm, 538nm, 573nm, 598nm, 621nm, 627nm, 684nm, 714nm, 732nm, 737nm and 741nm, the distribution of the extracted characteristic wavelengths is shown in Figure 2.

随后将预处理后的全波段与特征波长光谱数据分别进行PCA降维分析,得到基于全波段光谱数据的前三个PCA主成分的三维载荷图如图3所示,其前三个PCA主分即PC1、PC2、PC3对应的特征值累计贡献率为99.81%,可以表征大部分信息,PC1、PC2、PC3的贡献率分别为81.99%、17.32%、0.50%;基于特征波长光谱数据的前三个PCA主成分的三维载荷图如图4所示,其前三个PCA主分即PC1’、PC2’、PC3’对应的特征值累计贡献率为99.83%,可以表征大部分信息,PC1’、PC2’、PC3’的贡献率分别为87.34%、12.29%、0.20%。从图3和图4可以看出,经SPA提取的特征波长样本散点分布更为集中,但是不同含糖量的样本分布区域也有所差异,部分区域还存在交叉,因此,需要进一步的模型识别。Then, the preprocessed full-band and characteristic wavelength spectral data were subjected to PCA dimensionality reduction analysis, and the three-dimensional loading diagram of the first three PCA principal components based on the full-band spectral data was obtained as shown in Figure 3. The first three PCA principal components That is, the cumulative contribution rate of the eigenvalues corresponding to PC1, PC2, and PC3 is 99.81%, which can represent most of the information. The contribution rates of PC1, PC2, and PC3 are 81.99%, 17.32%, and 0.50%, respectively; The three-dimensional loading diagram of each PCA principal component is shown in Figure 4. The cumulative contribution rate of the eigenvalues corresponding to the first three PCA principal components, namely PC1', PC2', and PC3', is 99.83%, which can represent most of the information. PC1', PC1', PC3' The contribution rates of PC2' and PC3' are 87.34%, 12.29% and 0.20%, respectively. As can be seen from Figure 3 and Figure 4, the characteristic wavelength samples extracted by SPA are more concentrated, but the distribution areas of samples with different sugar content are also different, and some areas still have crossovers. Therefore, further model identification is required. .

偏最小二乘判别分析法(PLS-DA)是一种集主成分分析、典型相关分析和多元回归分析的基本功能为一体多元统计方法,分析过程可以消除众多信息中相互重叠的部分,使得分析数据更加准确可靠。本实施例的偏最小二乘判别分析法在Matlab软件中编程,利用提取出近红外光谱的主成分数据,对四类不同含糖量的红茶样本进行分类判别。Partial least squares discriminant analysis (PLS-DA) is a multivariate statistical method that integrates the basic functions of principal component analysis, canonical correlation analysis and multiple regression analysis. Data is more accurate and reliable. The partial least squares discriminant analysis method in this embodiment is programmed in Matlab software, and uses the principal component data extracted from the near-infrared spectrum to classify and discriminate four types of black tea samples with different sugar contents.

为比较基于全波段与特征波长光谱建立的红茶中外源蔗糖含量分析模型预测效果,以PCA处理后的最优主成分作为输入,基于全波段和特征波长光谱分别建立外源掺杂蔗糖的检测模型。即基于全波段光谱最优主成分作为模型输入量,建立PLS-DA检测模型,图5为基于全波段建立的PLS-DA检测模型预测结果图,图6为基于全波段光谱建立的PLS-DA检测模型预测集预测精度图,图7为基于全波段建立的PLS-DA检测模型预测柱形图,图8为基于全波段建立的PLS-DA检测模型预测散点图;基于16个特征波长光谱最优主成分作为模型输入量,建立SPA-PLS-DA检测模型,图9为基于特征波长建立的SPA-PLS-DA检测模型预测结果图,图10为基于特征波长建立的SPA-PLS-DA检测模型预测集预测精度图,图11为基于特征波长建立的SPA-PLS-DA检测模型的预测柱形图,图12为基于特征波长建立的SPA-PLS-DA检测模型预测散点图。检测模型对加糖红茶样品的具体分类情况如表1所示。In order to compare the prediction effect of the analysis model for exogenous sucrose content in black tea established based on full-band and characteristic wavelength spectra, the optimal principal components after PCA treatment were used as input, and the detection models of exogenous sucrose content were established based on full-band and characteristic wavelength spectra, respectively. . That is, based on the optimal principal component of the full-band spectrum as the model input, the PLS-DA detection model is established. Figure 5 is the prediction result of the PLS-DA detection model established based on the full-band spectrum, and Figure 6 is the PLS-DA established based on the full-band spectrum. The prediction accuracy chart of the detection model prediction set, Figure 7 is the prediction bar chart of the PLS-DA detection model established based on the full band, and Figure 8 is the prediction scatter plot of the PLS-DA detection model established based on the full band; based on 16 characteristic wavelength spectra The optimal principal component is used as the model input to establish the SPA-PLS-DA detection model. Figure 9 is the prediction result of the SPA-PLS-DA detection model established based on the characteristic wavelength, and Figure 10 is the SPA-PLS-DA established based on the characteristic wavelength. The prediction accuracy of the detection model prediction set, Figure 11 is the prediction bar chart of the SPA-PLS-DA detection model established based on the characteristic wavelength, and Figure 12 is the prediction scatter diagram of the SPA-PLS-DA detection model established based on the characteristic wavelength. The specific classification of sugar-sweetened black tea samples by the detection model is shown in Table 1.

Figure BDA0002541872020000071
Figure BDA0002541872020000071

表1:基于全波段与特征波长建立的PLS-DA、SPA-PLS-DA模型判别结果Table 1: Discrimination results of PLS-DA and SPA-PLS-DA models based on full-band and characteristic wavelengths

基于全波段光谱数据建立的PLS-DA判别模型对训练集和预测集的识别精度为95%和87.5%,其中样品识别正确率为100%,对未添加蔗糖中3个样品未识别,每10kg萎凋叶掺入250g蔗糖的样品中2个未识别;基于特征波长光谱数据建立的SPA-PLS-DA判别模型对训练集和预测集的识别精度为96.25%和95%,其中样品识别正确率为100%,对每10kg萎凋叶掺入250g蔗糖的样品中2个未识别。The recognition accuracy of the PLS-DA discriminant model based on the full-band spectral data for the training set and the prediction set is 95% and 87.5%, of which the correct rate of sample recognition is 100%, and 3 samples without added sucrose are not recognized, each 10kg Two samples of withered leaves mixed with 250g sucrose were not identified; the recognition accuracy of the SPA-PLS-DA discriminant model based on the characteristic wavelength spectral data for the training set and the prediction set was 96.25% and 95%, and the sample identification accuracy was 96.25% and 95%. 100%, 2 were not identified in samples spiked with 250 g of sucrose per 10 kg of withered leaves.

图5和图9的数据结果表明,当主成分数为6,lv数为5时,基于全波段建立的PLS-DA模型性能最佳,对应的训练集和预测集的识别率为95%和87.5%。当主成分数为5,lv数为5时,基于特征波长建立的SPA-PLS-DA模型性能最佳,对应的训练集和预测集的识别率为96.25%和95%。基于全波段建立的PLS-DA模型性能不及基于特征波长建立的SPA-PLS-DA模型性能,光谱数据经SPA变量筛选后,剔除了光谱数据中97.9%的冗余信息,所用主成分数由6个降为5个,并且主成分分析可以降低数据维度,较少的主成分输入能够减少计算负担,加快了模型的计算速度,故SPA-PLS-DA模型更适合生产中在线监测的时效性需求,可以实现加糖红茶的外源蔗糖含量无损检测和快速判别。The data results in Figure 5 and Figure 9 show that when the number of principal components is 6 and the number of lv is 5, the performance of the PLS-DA model based on the full band is the best, and the recognition rate of the corresponding training set and prediction set is 95% and 87.5%. %. When the number of principal components is 5 and the number of lv is 5, the performance of the SPA-PLS-DA model based on the characteristic wavelength is the best, and the recognition rates of the corresponding training set and prediction set are 96.25% and 95%. The performance of the PLS-DA model based on the whole waveband is not as good as that of the SPA-PLS-DA model based on the characteristic wavelength. After the spectral data is screened by the SPA variable, 97.9% of the redundant information in the spectral data is eliminated, and the number of principal components used is 6 The number is reduced to 5, and the principal component analysis can reduce the data dimension. Fewer principal component inputs can reduce the computational burden and speed up the calculation speed of the model. Therefore, the SPA-PLS-DA model is more suitable for the timeliness requirements of online monitoring in production. , which can realize non-destructive detection and rapid identification of exogenous sucrose content in sugar-sweetened black tea.

另外,基于全波段光谱数据建立的PLS-DA检测模型得到的相关系数Rc为0.9925,Rp为0.9955,基于特征波长光谱数据建立的SPA-PLS-DA检测模型得到的相关系数Rc为0.9937,Rp为0.9956,经SPA提取特征波长后,剔除了97.9%的冗余信息,并且训练集相关系数和预测集相关系数均得到提高。In addition, the correlation coefficient Rc obtained by the PLS-DA detection model established based on the full-band spectral data is 0.9925, Rp is 0.9955, and the correlation coefficient Rc obtained by the SPA-PLS-DA detection model established based on the characteristic wavelength spectral data is 0.9937, and Rp is 0.9956, 97.9% redundant information is removed after the feature wavelength is extracted by SPA, and both the training set correlation coefficient and the prediction set correlation coefficient are improved.

5.外源掺杂蔗糖红茶的判别与含糖量的快速检测5. Discrimination of exogenous sucrose-doped black tea and rapid detection of sugar content

将数据线连接到电脑客户端,用于接收在线检测的近红外光谱数据,并在电脑客户端使用matlab软件分别建立PLS-DA检测模型和SPA-PLS-DA检测模型,最后将检测模型通过数据线等传输介质导入到近红外光谱仪中,将近红外光谱仪采集的近红外光谱数据输入检测模型中,在近红外光谱仪的操作界面便可以实现加糖红茶的判别和红茶中外源蔗糖含量的动态在线实时检测,并且检测完成后,仪器自动计算,在操作界面直接显示含糖量结果,实现红茶中外源蔗糖含量的动态在线实时检测。Connect the data cable to the computer client to receive the near-infrared spectral data of online detection, and use the matlab software on the computer client to establish the PLS-DA detection model and the SPA-PLS-DA detection model respectively, and finally pass the detection model through the data. The transmission medium such as line is imported into the near-infrared spectrometer, and the near-infrared spectral data collected by the near-infrared spectrometer is input into the detection model. In the operation interface of the near-infrared spectrometer, the identification of sugar-sweetened black tea and the dynamic online real-time detection of exogenous sucrose content in black tea can be realized. , and after the detection is completed, the instrument automatically calculates and directly displays the results of sugar content on the operation interface, realizing dynamic online real-time detection of exogenous sucrose content in black tea.

以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的宗旨和范围,其均应涵盖在本发明的权利要求范围当中。本发明未详细描述的技术、形状、构造部分均为公知技术。The above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced. Without departing from the spirit and scope of the technical solutions of the present invention, all of them should be included in the scope of the claims of the present invention. The technology, shape, and structural part that are not described in detail in the present invention are all well-known technologies.

Claims (8)

1. The method is characterized in that a black tea sample containing different amounts of exogenous sucrose is subjected to near infrared spectrum scanning, original spectrum data obtained by scanning is subjected to standard normal variable transformation algorithm processing, variable screening is performed by adopting a continuous projection algorithm, then principal component analysis is performed, a detection model is established by using the optimal principal component, near infrared spectrum data of the black tea sample to be detected are input into the detection model, and discrimination and content detection of the exogenous sucrose in the black tea are realized.
2. The method for nondestructive testing of sucrose exogenously doped in tea based on near infrared spectroscopy as claimed in claim 1, wherein said method comprises the steps of:
s1, preparing and obtaining black tea samples with different sugar contents;
s2, performing near infrared spectrum scanning on the black tea sample by using a near infrared spectrum analyzer, and acquiring original spectrum data of the black tea sample;
s3, randomly dividing an original spectrum data set into a training set sample and a prediction set sample by adopting a Kennard-Stone method;
s4, preprocessing original spectral data by adopting a standard normal variable transformation algorithm, and then performing variable screening by adopting a continuous projection algorithm to obtain characteristic wavelengths;
s5, carrying out PCA dimension reduction analysis on the preprocessed full-waveband and characteristic wavelength spectrum data respectively, and then establishing a full-waveband spectrum-based PLS-DA detection model of the exogenous doped sucrose and an SPA-PLS-DA detection model of the exogenous doped sucrose based on the characteristic wavelength spectrum by taking the optimal principal component processed by PCA as input;
s6, respectively programming and establishing a PLS-DA detection model and an SPA-PLS-DA detection model in matlab software in a computer client, and communicating the computer client with a near infrared spectrometer, inputting spectral data obtained by scanning a black tea sample to be detected by the near infrared spectrometer into the PLS-DA detection model and the SPA-PLS-DA detection model, so as to realize the discrimination of the content of the external sucrose in the black tea and the online real-time detection of the content of the sugar.
3. The method for nondestructive testing of sucrose doped in tea leaves based on near infrared spectrum technology as claimed in claim 2, wherein in the step S1, different amounts of exogenous sucrose are added during the kneading process of black tea processing, and the black tea samples with different sugar contents are respectively: black tea samples without added sucrose, with 250g sucrose per 10kg twisted leaf, 500g sucrose per 10kg twisted leaf and 750g sucrose per 10kg twisted leaf.
4. The method for nondestructive detection of sucrose doped in tea leaves based on near infrared spectroscopy as claimed in claim 2, wherein in step S2, 20 ± 0.5g of black tea samples with different sugar contents are respectively weighed and evenly spread in quartz petri dishes with a specification of Φ 70mm × 10mm, the tops of the tea leaves are flush with the upper surface of the dish body, and the quartz petri dishes are placed on a near infrared spectrometer for near infrared spectrum scanning and collection.
5. The nondestructive testing method for the exogenous sucrose-doped tea leaves based on the near infrared spectrum technology of claim 4, wherein in the step S2, the detection wavelength range of the near infrared spectrometer is 900-1700 nm, and the resolution is 4cm-1The number of scans per sample was 30.
6. The method for nondestructive testing of sucrose doped in tea leaves based on near infrared spectrum technology as claimed in claim 5, wherein in step S2, during scanning of black tea sample in near infrared spectrum, after each scanning acquisition is completed, tea leaves are stirred.
7. The method for nondestructive testing of sucrose doped in tea leaves based on near infrared spectrum technology as claimed in claim 2, wherein the ratio of the data volume of the training set sample to the data volume of the prediction set sample is 2: 1.
8. The method for nondestructive detection of sucrose exogenously doped in tea based on near infrared spectroscopy as claimed in claim 2 wherein in said step S4, the characteristic wavelengths sensitive to sugar content are 190nm, 206nm, 227nm, 300nm, 481nm, 502nm, 538nm, 573nm, 598nm, 621nm, 627nm, 684nm, 714nm, 732nm, 737nm and 741nm, respectively.
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