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CN105181912B - A method for detecting the freshness of rice during storage - Google Patents

A method for detecting the freshness of rice during storage Download PDF

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CN105181912B
CN105181912B CN201510370444.9A CN201510370444A CN105181912B CN 105181912 B CN105181912 B CN 105181912B CN 201510370444 A CN201510370444 A CN 201510370444A CN 105181912 B CN105181912 B CN 105181912B
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rice
freshness
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gas
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CN105181912A (en
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林颢
管彬彬
金鸿娟
宋奔腾
赵杰文
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Cofco Engineering Yingchun Intelligent Equipment Hunan Co ltd
Cofco Yingchun Agricultural And Animal Husbandry Machinery Shandong Co ltd
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Jiangsu University
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Abstract

本发明涉及一种大米储藏过程中的新鲜度检测方法,属于大米储藏监测技术领域;本发明首先使用带加热装置和特质滤网的气体采集探针采集粮食储藏设备中的挥发性气体,然后利用3CCD相机获取疏水膜上的传感器阵列与大米样本气体反应前后的R、G、B图像,计算机对图像进行处理,最后将其颜色信号值代入线性判别分析模型,计算机输出大米样本的新鲜度;本发明通过大米挥发气味检测其新鲜度,是一种绿色的,快速无损的方法,与传统化学检测方法想比较,本发明较为便捷,无污染,且与人的感官评定有一定的一致性,相比起人工感觉,本发明客观性和重现性较好。本发明对满足消费者对食品质量和安全方面及企业原料充分利用效益最大化有着重要的现实意义。

The invention relates to a freshness detection method during rice storage, which belongs to the technical field of rice storage monitoring; the invention first uses a gas collection probe with a heating device and a special filter to collect volatile gases in grain storage equipment, and then utilizes The 3CCD camera acquires the R, G, and B images before and after the sensor array on the hydrophobic film reacts with the rice sample gas, and the computer processes the image, and finally substitutes the color signal value into the linear discriminant analysis model, and the computer outputs the freshness of the rice sample; The invention detects the freshness of rice by its volatile odor, which is a green, fast and non-destructive method. Compared with traditional chemical detection methods, the present invention is more convenient, non-polluting, and has a certain consistency with human sensory evaluation. Compared with artificial sensation, the present invention has better objectivity and reproducibility. The invention has important practical significance for satisfying consumers' requirements on food quality and safety and maximizing the benefits of fully utilizing raw materials of enterprises.

Description

一种大米储藏过程中的新鲜度检测方法A method for detecting the freshness of rice during storage

技术领域technical field

本发明涉及一种大米储藏过程中的新鲜度检测方法,属于大米储藏过程中的监测技术领域。The invention relates to a method for detecting freshness during rice storage, and belongs to the technical field of monitoring during rice storage.

背景技术Background technique

大米是我国人民的主食之一。稻谷垄谷后,大米由于失去稻壳的保护,胚乳直接与空气接触经过,大米中的淀粉、脂肪和蛋白质等会发生各种变化,使大米失去原有的色、香、味,营养成分和食用品质下降,甚至产生有毒有害物质。此外,大米的新鲜度也会对其附加产品的质量有所影响。譬如用陈化的大米酿造出的啤酒中的糖基化合物的含量增加,导致啤酒的老化等。Rice is one of the staple foods of our people. After the rice is ridged, the rice loses the protection of the rice husk, and the endosperm directly contacts with the air, and the starch, fat and protein in the rice will undergo various changes, making the rice lose its original color, aroma, taste, nutrients and nutrients. The food quality is reduced, and even toxic and harmful substances are produced. In addition, the freshness of rice will also affect the quality of its additional products. For example, the content of glycosyl compounds in beer brewed from aged rice increases, leading to the aging of beer.

目前我国大米新鲜度的检测方法有TBA值测定法、酸碱指示剂法、酶活性法等。如GB/T15684-1995中利用测定大米中的脂肪酸来检验大米的新鲜度,然而,该方法步骤复杂,准确度较差。发明专利“快速检验大米新鲜度的检测管”(201220263903.5)公开了一种快速检验大米新鲜度的检测管,但其结果通过与标准色卡比较,结果准确度较差,且不可量化。论文“几种检测大米新鲜度的方法比较”介绍了酶活性法测量大米的新鲜度,但该方法步骤复杂,准确度较差,不能快速准确的检测出大米的新鲜度;论文“稻米新鲜度快速检测技术研究”中介绍了日本SATAKE公司的大米测鲜仪,但其进口设备价格昂贵,且样本需要预处理,步骤繁琐,且精度不高。At present, the detection methods of rice freshness in my country include TBA value determination method, acid-base indicator method, enzyme activity method and so on. As in GB/T15684-1995, the freshness of rice is tested by measuring fatty acids in rice, however, the method has complicated steps and poor accuracy. The invention patent "Detection Tube for Quickly Checking Freshness of Rice" (201220263903.5) discloses a test tube for quickly checking the freshness of rice, but the result is poor in accuracy and cannot be quantified when compared with the standard color card. The paper "Comparison of several methods for detecting the freshness of rice" introduces the enzyme activity method to measure the freshness of rice, but the method has complicated steps and poor accuracy, and cannot detect the freshness of rice quickly and accurately; the paper "Rice freshness "Research on Rapid Detection Technology" introduced the rice freshness measuring instrument of SATAKE company in Japan, but the imported equipment is expensive, and the samples need to be pretreated, the steps are cumbersome, and the accuracy is not high.

因此,寻找一种简便、稳定、可量化的大米新鲜度的表征和检测方法,对监控和检测大米品质,满足消费者对食品质量和安全方面及企业原料充分利用效益最大化有着重要的现实意义。色敏传感器技术是近年来出现的一种气体表征的新方法,利用色敏传感器与待测气体反应前后的颜色差值,对待测气体进行定性和定量分析,近年来,色敏传感器技术在食品及农产品检测领域得到了相关应用,如专利“一种基于嗅觉可视化检测鱼新鲜度的方法及装置”(申请号:201010262347.50)公开了一种嗅觉可视化检测鱼新鲜度的方法和装置,但该装置比较笨重,其图像获取装置是扫描仪,难以满足实时监测的要求。色敏传感器技术在农产品气味的检测方面有其独特的优势,但在大米储藏过程中的新鲜度检测还未见报道。Therefore, finding a simple, stable, and quantifiable characterization and detection method for rice freshness has important practical significance for monitoring and testing rice quality, satisfying consumers' concerns about food quality and safety, and maximizing the full utilization of raw materials for enterprises. . Color-sensitive sensor technology is a new method of gas characterization that has emerged in recent years. It uses the color difference before and after the reaction between the color-sensitive sensor and the gas to be measured to conduct qualitative and quantitative analysis of the gas to be measured. In recent years, color-sensitive sensor technology has been used in food and the field of agricultural product detection have been related applications, such as the patent "a method and device for detecting fish freshness based on olfactory visualization" (application number: 201010262347.50) discloses a method and device for olfactory visual detection of fish freshness, but the device It is relatively heavy, and its image acquisition device is a scanner, which is difficult to meet the requirements of real-time monitoring. Color-sensitive sensor technology has its unique advantages in the detection of agricultural product odor, but the freshness detection in the process of rice storage has not been reported.

发明内容Contents of the invention

本发明的目的在于克服现有大米储藏过程中新鲜度检测方法的不足,提出一种基于新型色敏传感器技术的大米储藏过程的新鲜度检测方法,通过无线传感器阵列自动、实时监测整个大米储藏过程中新鲜度的变化情况。The purpose of the present invention is to overcome the deficiency of the freshness detection method in the existing rice storage process, propose a kind of freshness detection method of the rice storage process based on novel color-sensitive sensor technology, monitor the whole rice storage process automatically and in real time through the wireless sensor array Changes in freshness.

本发明采用的技术解决方案如下:The technical solution adopted in the present invention is as follows:

本发明提供一种大米储藏过程中的新鲜度检测装置,包括计算机、信息采集系统、真空泵、加热模块、带有特质滤网的气体采集探针和大米储藏设备。The invention provides a freshness detection device during rice storage, which includes a computer, an information collection system, a vacuum pump, a heating module, a gas collection probe with a special filter screen and rice storage equipment.

其中信息采集系统包括3CCD相机、LED光源、反应室和传感器阵列,其中所述3CCD相机固定于信息采集系统上端,与计算机相连接,3CCD相机是用来获取反应前、后传感器的红(R)、绿(G)、蓝(B)三个分量的图像;其中计算机是用来实时处理采集到的大米储藏过程中的挥发性气体信息,信息采集系统是用来采集大米挥发性气体信息传输入计算机;The information collection system includes a 3CCD camera, LED light source, reaction chamber and sensor array, wherein the 3CCD camera is fixed on the upper end of the information collection system and connected to the computer. The 3CCD camera is used to obtain the red (R) of the sensor before and after the reaction. , green (G), and blue (B) images; the computer is used to process the collected volatile gas information during rice storage in real time, and the information collection system is used to collect rice volatile gas information and transmit it to the computer;

所述LED光源固定于信息采集系统内部两侧,用于给3CCD相机摄像头的采集提供良好的光源保证,提高采集图像的质量,以便后期传送到计算机进行实时处理;The LED light source is fixed on both sides inside the information collection system, which is used to provide a good light source guarantee for the collection of the 3CCD camera head, improve the quality of the collected image, and transmit it to the computer for real-time processing in the later stage;

所述信息采集系统底部设置有反应室,反应室内排布传感器阵列;反应室是大米储藏过程中的挥发性气体与相应色敏传感器进行充分反应的器皿,传感器阵列是先通过微量点样形成的4×3的阵列;A reaction chamber is arranged at the bottom of the information collection system, and a sensor array is arranged in the reaction chamber; the reaction chamber is a container for fully reacting the volatile gas in the rice storage process with the corresponding color-sensitive sensor, and the sensor array is first formed by micro-spotting 4×3 array;

所述真空泵与带有特质滤网的气体采集探针相连接,气体采集探针进样口装有滤网,下端装有加热模块,气体采集探针将采集到的大米储藏过程中的挥发性气体通过真空泵泵入反应室;带有特质滤网的气体采集探针直接置于大米储藏设备中;带有特制滤网的气体采集探针的作用是用来防止大米中的杂质堵塞装置,而只提取储藏过程的大米挥发性气体。The vacuum pump is connected with a gas collection probe with a special filter screen, the gas collection probe inlet is equipped with a filter screen, and the lower end is equipped with a heating module, and the gas collection probe will collect the volatility of the rice during storage The gas is pumped into the reaction chamber through a vacuum pump; the gas collection probe with a special filter is directly placed in the rice storage equipment; the function of the gas collection probe with a special filter is to prevent impurities in the rice from clogging the device, and Only volatile gases from rice during storage are extracted.

加热模块置于大米储藏设备中,可以是任意用来加热的装置,用于检测样本的加热,促进气体挥发。The heating module is placed in the rice storage equipment, which can be any device used for heating, and is used to detect the heating of the sample and promote the volatilization of gas.

本发明的另一目的在于提供一种大米储藏过程中新鲜度的检测方法,包括如下步骤:Another object of the present invention is to provide a method for detecting the freshness of rice during storage, comprising the steps of:

(1)首先通过气相色谱-质谱(GC-MS)确定不同新鲜度大米的特征挥发性气体,其中八(乙二醇)一(十二烷基)醚、苯甲醛及己醛含量在大米储藏过程中变化明显(八(乙二醇)一(十二烷基)醚在大米储藏六个月后,含量急剧减少;苯甲醛在新鲜大米中不存在,随着大米储藏时间增加,含量逐渐增加,己醛在大米的储藏过程中,含量先增加后减少);然后筛选对这些气体敏感的色敏材料:3种卟啉类化合物和1种pH指示剂;其中,3种卟啉类化合物为原卟啉二甲酯、八乙基卟啉、四苯基苯并三元卟啉,将卟啉类化合物分别溶于二氯甲烷溶剂中,浓度范围为1 -2mg/mL,在该浓度下,卟啉溶液的颜色适中,较均匀的分散在介质衬底上,易与大米挥发气体反应; pH 指示剂尼罗红,溶于乙醇中,浓度均为1 -2mg/mL,在该浓度下,卟啉溶液的颜色适中,较均匀的分散在介质衬底上,易与大米挥发气体反应。通过微量点样毛细管将4种色敏材料逐个印染在聚偏二氟乙烯(PVDF)膜上,制得4种色敏传感器,这4种色敏传感器构成色敏材料传感器阵列;(1) Firstly, the characteristic volatile gases of rice with different freshness were determined by gas chromatography-mass spectrometry (GC-MS). The change is obvious in the process (octa(ethylene glycol)-(dodecyl) ether is stored in rice for six months, the content decreases sharply; benzaldehyde does not exist in fresh rice, and as the storage time of rice increases, the content gradually increases , the content of hexanal increases first and then decreases during the storage of rice); then screen the color-sensitive materials sensitive to these gases: 3 porphyrin compounds and 1 pH indicator; among them, the 3 porphyrin compounds are Protoporphyrin dimethyl ester, octaethylporphyrin, tetraphenylbenzo ternary porphyrin, the porphyrin compounds are respectively dissolved in dichloromethane solvent, the concentration range is 1-2mg/mL, at this concentration , the color of the porphyrin solution is moderate, and it is more evenly dispersed on the medium substrate, and it is easy to react with the volatile gas of rice; the pH indicator Nile red is soluble in ethanol, and the concentration is 1-2mg/mL. , the color of the porphyrin solution is moderate, and it is more evenly dispersed on the medium substrate, and it is easy to react with the volatile gas of rice. Four kinds of color-sensitive materials were printed and dyed on the polyvinylidene fluoride (PVDF) film one by one through micro-spotting capillary tubes to make four kinds of color-sensitive sensors, and these four kinds of color-sensitive sensors constituted a color-sensitive material sensor array;

(2)3CCD相机获取反应前传感器阵列的初始R、G、B图像传输给计算机,计算机进行图像处理获得初始颜色信息;(2) The 3CCD camera acquires the initial R, G, and B images of the sensor array before the reaction and transmits them to the computer, and the computer performs image processing to obtain the initial color information;

(3)不同阶段大米挥发性气体的采集:气体采集探针置于大米样本中,开启加热模块和真空泵,抽取大米储藏过程中的挥发性气体进入反应室与传感器阵列的色敏材料反应; 3CCD相机获取反应后传感器阵列的R、G、B图像传输给计算机,计算机进行图像处理,通过图像高斯滤波去噪、阈值分割、形态学处理、特征区域提取(以色敏材料重心为圆点,15个像素为半径的圆)等获得反应前后图像中各色敏材料的R、G、B灰度的平均值,得到不同新鲜度大米挥发性气体的特征矩阵;(3) Collection of rice volatile gas at different stages: the gas collection probe is placed in the rice sample, the heating module and vacuum pump are turned on, and the volatile gas during rice storage is extracted into the reaction chamber to react with the color-sensitive material of the sensor array; 3CCD The R, G, and B images of the sensor array after the camera captures the reaction are transmitted to the computer, and the computer performs image processing, denoising through image Gaussian filtering, threshold segmentation, morphological processing, and feature region extraction (with the center of gravity of the color-sensitive material as the dot, 15 pixels as the radius of the circle) etc. to obtain the average value of the R, G, and B gray levels of each color-sensitive material in the image before and after the reaction, and obtain the characteristic matrix of the volatile gases of rice with different freshness;

(4)利用色敏材料传感器阵列与样本挥发性气体反应,提取相关信息,输入已建好新鲜度线性判别模型,即可实现对待测样本新鲜度的检测;其中新鲜度线性判别模型的建立,具体操作是将数据进行主成分分析,最后选取前7个主成分构建线性判别分析模型来判别大米的新鲜度。(4) Use the color-sensitive material sensor array to react with the volatile gas of the sample, extract relevant information, and input the established freshness linear discriminant model to realize the detection of the freshness of the sample to be tested; the establishment of the freshness linear discriminant model, The specific operation is to conduct principal component analysis on the data, and finally select the first seven principal components to construct a linear discriminant analysis model to determine the freshness of rice.

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

1.本发明操作快速简便,是一种绿色的,快速无损的大米新鲜度检测方法,检测一个样本只需要几分钟即可,可用于陈化大米的品质检测,也可用于大米储藏过程中陈化过程监控;1. The invention is quick and easy to operate, and is a green, fast and non-destructive rice freshness detection method. It only takes a few minutes to detect a sample, and can be used for the quality detection of aged rice, and can also be used for the aging process of rice storage. monitor;

2. 与传统化学和生物检测方法相比较,本发明较为便捷,无污染,无需预处理,由于是由多个色敏传感器组成的矩阵,与人的感官评定有一定的一致性,更能反映和体现人对食物的评价和喜好;2. Compared with traditional chemical and biological detection methods, the present invention is more convenient, pollution-free, and does not require pretreatment. Since it is a matrix composed of multiple color-sensitive sensors, it has certain consistency with human sensory evaluation and can better reflect and reflect people's evaluation and preferences for food;

3. 相比起人工感官评定,本发明客观性和重现性较好,使得大米的品质可记忆和传承,不易受环境因素和其它主客观因素的干扰。3. Compared with artificial sensory evaluation, the present invention has better objectivity and reproducibility, so that the quality of rice can be memorized and inherited, and it is not easily disturbed by environmental factors and other subjective and objective factors.

附图说明Description of drawings

图1是粮食储存过程中的新鲜度检测系统示意图。Figure 1 is a schematic diagram of the freshness detection system in the grain storage process.

图2嗅觉可视化软件处理系统示意图。Fig. 2 Schematic diagram of the olfactory visualization software processing system.

图中:1、计算机,2、3CCD相机,3、LED光源,4、反应室,5、传感器阵列,6、真空泵,7、气体采集探针,8、滤网,9、加热模块,10、大米储藏设备。In the figure: 1. computer, 2. 3CCD camera, 3. LED light source, 4. reaction chamber, 5. sensor array, 6. vacuum pump, 7. gas collection probe, 8. filter screen, 9. heating module, 10. Rice storage equipment.

具体实施方式detailed description

以下结合具体实施例和附图,对本发明的技术方案更进一步的阐述。The technical solutions of the present invention will be further described below in conjunction with specific embodiments and accompanying drawings.

实施例1:一种大米储藏过程中的新鲜度检测装置Embodiment 1: A kind of freshness detection device in the rice storage process

如图1所示,本发明提供的一种大米储藏过程中的新鲜度检测装置,包括计算机1、信息采集系统、真空泵6、加热模块9、带有特质滤网8的气体采集探针7和大米储藏设备10。As shown in Fig. 1, a kind of freshness detection device in the rice storage process provided by the present invention comprises computer 1, information collection system, vacuum pump 6, heating module 9, gas collection probe 7 with characteristic filter screen 8 and Rice storage equipment 10 .

其中信息采集系统包括3CCD相机2、LED光源3、反应室4和传感器阵列5,其中所述3CCD相机2固定于信息采集系统上端,与计算机1相连接,3CCD相机2是用来获取反应前、后传感器的红(R)、绿(G)、蓝(B)三个分量的图像;其中计算机1是用来实时处理采集到的大米储藏过程中的挥发性气体信息,信息采集系统是用来采集大米挥发性气体信息传输入计算机1;Wherein the information collection system comprises 3CCD camera 2, LED light source 3, reaction chamber 4 and sensor array 5, wherein said 3CCD camera 2 is fixed on the upper end of the information collection system, is connected with computer 1, and 3CCD camera 2 is used to obtain before reaction, The images of red (R), green (G) and blue (B) components of the rear sensor; among them, the computer 1 is used to process the collected volatile gas information in the rice storage process in real time, and the information collection system is used to Collect rice volatile gas information and transmit it to computer 1;

所述LED光源3固定于信息采集系统内部两侧,用于给3CCD相机2摄像头的采集提供良好的光源保证,提高采集图像的质量,以便后期传送到计算机1进行实时处理;The LED light source 3 is fixed on both sides inside the information collection system, and is used to provide a good light source guarantee for the collection of the 3CCD camera 2 cameras, improve the quality of the collected images, and transmit them to the computer 1 for real-time processing at a later stage;

所述信息采集系统底部设置有反应室4,反应室4内排布传感器阵列5;反应室4是大米储藏过程中的挥发性气体与相应色敏传感器进行充分反应的器皿,传感器阵列5是先通过微量点样形成的4×3的阵列;The bottom of the information collection system is provided with a reaction chamber 4, and a sensor array 5 is arranged in the reaction chamber 4; the reaction chamber 4 is a container for fully reacting the volatile gas in the rice storage process with the corresponding color-sensitive sensor, and the sensor array 5 is first 4×3 array formed by micro spotting;

所述真空泵6与带有特质滤网8的气体采集探针7相连接,气体采集探针进样口装有滤网8,下端装有加热模块9,气体采集探针7将采集到的大米储藏过程中的挥发性气体泵入反应室4;带有特质滤网的气体采集探针7直接置于大米储藏设备10中;带有特制滤网的气体采集探针7的作用是用来防止大米中的杂质堵塞装置,而只提取储藏过程的大米挥发性气体。Described vacuum pump 6 is connected with the gas collection probe 7 that has characteristic filter screen 8, and gas collection probe sampling port is equipped with filter screen 8, and heating module 9 is housed at the lower end, and gas collection probe 7 will collect the rice The volatile gas in the storage process is pumped into the reaction chamber 4; the gas collection probe 7 with a special filter is directly placed in the rice storage device 10; the function of the gas collection probe 7 with a special filter is to prevent Impurities in the rice block the device, and only the volatile gases of the rice during storage are extracted.

加热模块9置于大米储藏设备10中,可以是任意用来加热的装置,用于检测样本的加热,促进气体挥发。The heating module 9 is placed in the rice storage equipment 10, and can be any device used for heating, which is used to detect the heating of the sample and promote the volatilization of gas.

实施例2:一种大米储藏过程中新鲜度的检测方法Embodiment 2: a kind of detection method of freshness in rice storage process

一种大米储藏过程中新鲜度的检测方法,包括如下步骤:A method for detecting the freshness of rice during storage, comprising the steps of:

(1)实施实例的样本均来自同一品种的大米,所有样本按照储藏时间分为四组,分别为1个月、2个月、6个月和12个月。每组有30 个样本,共120 个样本;(1) The samples of the implementation examples are all from the same variety of rice, and all samples are divided into four groups according to the storage time, which are 1 month, 2 months, 6 months and 12 months. Each group has 30 samples, a total of 120 samples;

(2)色敏传感器的制作:对大米新鲜度气味敏感的3种卟啉类化合物和1种pH指示剂配成的溶液通过微量点样毛细管将其印染在聚偏二氟乙烯(PVDF)膜上,制成色敏材料传感器阵列,其中,3种卟啉类化合物:①原卟啉二甲酯,②八乙基卟啉,③四苯基苯并三元卟啉,分别溶于二氯甲烷溶剂中,浓度范围为1 -2mg/mL(经过预先优化);pH 指示剂:尼罗红,溶于乙醇中,浓度范围为1 -2mg/mL(经过预先优化);(2) Production of color-sensitive sensor: A solution made of 3 porphyrin compounds and 1 pH indicator sensitive to the freshness of rice is printed and dyed on a polyvinylidene fluoride (PVDF) film through a micro-spotting capillary. On the above, a sensor array of color-sensitive materials was made, among which, 3 kinds of porphyrin compounds: ① dimethyl protoporphyrin, ② octaethyl porphyrin, ③ tetraphenylbenzo ternary porphyrin, respectively dissolved in dichloro In methane solvent, the concentration range is 1-2mg/mL (pre-optimized); pH indicator: Nile Red, dissolved in ethanol, the concentration range is 1-2mg/mL (pre-optimized);

(3)将传感器阵列5至于反应室4中,3CCD相机2获取反应前传感器阵列R、G、B三个颜色通道的初始图像;(3) Put the sensor array 5 in the reaction chamber 4, and the 3CCD camera 2 acquires the initial images of the three color channels of the sensor array R, G, and B before the reaction;

(4)气体采集探针7置于大米样本中,开启加热模块9和真空泵6,抽取大米储藏过程中的挥发性气体进入反应室4与色敏材料反应;3CCD相机获取反应后传感器阵列的R、G、B图像传输给计算机,计算机1进行图像处理,通过图像高斯滤波去噪、阈值分割、形态学处理、特征区域提取(以色敏材料重心为圆点,15个像素为半径的圆)等获得反应前后图像中各色敏材料的R、G、B灰度的平均值,再对反应前后灰度的平均值相减,得到可视化传感器阵列的响应特征矩阵,再将特征矩阵还原为图像(如图2)。将数据进行主成分分析,提取前7个主成分构建线性判别分析模型来判别大米的新鲜度。(4) The gas collection probe 7 is placed in the rice sample, the heating module 9 and the vacuum pump 6 are turned on, and the volatile gas in the rice storage process is extracted into the reaction chamber 4 to react with the color-sensitive material; the 3CCD camera acquires the R of the sensor array after the reaction , G, and B images are transmitted to the computer, and computer 1 performs image processing, denoising through image Gaussian filtering, threshold segmentation, morphological processing, and feature area extraction (with the center of gravity of the color-sensitive material as a dot and a circle with a radius of 15 pixels) Obtain the average value of the R, G, and B gray levels of each color-sensitive material in the image before and after the reaction, and then subtract the average value of the gray level before and after the reaction to obtain the response characteristic matrix of the visual sensor array, and then restore the characteristic matrix to the image ( Figure 2). The data were subjected to principal component analysis, and the first seven principal components were extracted to construct a linear discriminant analysis model to judge the freshness of rice.

(5)利用40个独立样本(每个类别有10个样本)对该方法进行验证,结果如表1所示,结果表明该方法对所有样本的综合识别率达到85%,然而,对于储藏6个月和储藏12个月的大米样本的识别率均为100%。表明该方法可以对大米的新鲜度进行智能化鉴别。(5) Using 40 independent samples (10 samples for each category) to verify the method, the results are shown in Table 1. The results show that the comprehensive recognition rate of all samples reached 85%. However, for storage 6 The identification rate of rice samples stored for 12 months and 12 months was 100%. It shows that the method can intelligently identify the freshness of rice.

表1 LDA模型预测大米新鲜度Table 1 LDA model predicts rice freshness

Claims (5)

1.一种大米储藏过程中新鲜度的检测方法,其特征在于,所述方法是利用色敏材料与不同新鲜度的大米气味反应颜色不同来判别大米的新鲜度,所述方法基于一种大米储藏过程中的新鲜度检测装置,所述装置包括计算机(1)、信息采集系统、真空泵(6)、加热模块(9)、带有特质滤网(8)的气体采集探针(7);其中计算机(1)是用来实时处理采集到的大米储藏过程中的挥发性气体信息,信息采集系统是用来采集大米挥发性气体信息传输入计算机(1);所述信息采集系统底部设置有反应室4,反应室4内排布传感器阵列5;1. a detection method of freshness in the rice storage process, it is characterized in that, described method is to utilize color-sensitive material and the rice smell reaction color difference of different freshness to distinguish the freshness of rice, and described method is based on a kind of rice A freshness detection device during storage, the device includes a computer (1), an information collection system, a vacuum pump (6), a heating module (9), and a gas collection probe (7) with a special filter (8); Among them, the computer (1) is used to process the collected volatile gas information in the rice storage process in real time, and the information collection system is used to collect the rice volatile gas information and transmit it to the computer (1); the bottom of the information collection system is provided with A reaction chamber 4, a sensor array 5 is arranged in the reaction chamber 4; 所述真空泵(6)与带有特质滤网(8)的气体采集探针(7)相连接,气体采集探针进样口装有滤网(8),下端装有加热模块(9),加热模块(9)置于大米储藏设备(10)中;The vacuum pump (6) is connected to the gas collection probe (7) with a special filter (8), the inlet of the gas collection probe is equipped with a filter (8), and the lower end is equipped with a heating module (9), The heating module (9) is placed in the rice storage device (10); 所述检测方法主要包括如下步骤:The detection method mainly includes the following steps: (1)首先通过GC-MS确定不同新鲜度大米的特征挥发性气体,然后筛选对这些气体敏感的色敏材料,制成色敏材料传感器阵列;(1) First determine the characteristic volatile gases of rice with different freshness by GC-MS, and then screen the color-sensitive materials sensitive to these gases to make a color-sensitive material sensor array; (2)3CCD相机(2)获取反应前传感器阵列的初始R、G、B图像传输给计算机(1),计算机(1)进行图像处理获得初始颜色信息;(2) The 3CCD camera (2) acquires the initial R, G, and B images of the sensor array before the reaction and transmits them to the computer (1), and the computer (1) performs image processing to obtain the initial color information; (3)采集不同阶段大米挥发性气体,将采集的信息传输给计算机(1)进行图像处理以得到不同新鲜度大米挥发性气体的特征矩阵;(3) Collect rice volatile gases at different stages, and transmit the collected information to the computer (1) Perform image processing to obtain the characteristic matrix of rice volatile gases with different freshness; (4)利用色敏材料传感器阵列(5)与样本挥发性气体反应,提取相关信息,输入已建好新鲜度线性判别模型,即实现对待测样本新鲜度的检测;(4) Use the color-sensitive material sensor array (5) to react with the volatile gas of the sample, extract relevant information, and input the established freshness linear discriminant model to realize the detection of the freshness of the sample to be tested; 步骤(1)中所述的通过GC-MS确定的不同新鲜度大米的特征性挥发性气体为八(乙二醇)一(十二烷基)醚、苯甲醛、己醛;The characteristic volatile gases of rice with different freshness determined by GC-MS described in step (1) are octa(ethylene glycol)-(dodecyl) ether, benzaldehyde, hexanal; 步骤(1)中所述的色敏材料为3种卟啉类化合物和1种pH指示剂;其中,3种卟啉类化合物为原卟啉二甲酯、八乙基卟啉、四苯基苯并三元卟啉,将卟啉类化合物分别溶于二氯甲烷溶剂中,浓度范围为1 -2mg/mL; pH 指示剂为尼罗红,溶于乙醇中,浓度均为1 -2mg/mL,通过微量点样毛细管将每一个色敏材料逐个印染在聚偏二氟乙烯(PVDF)膜上,制成色敏材料传感器阵列。The color-sensitive material described in step (1) is three kinds of porphyrin compounds and one pH indicator; wherein, the three kinds of porphyrin compounds are protoporphyrin dimethyl ester, octaethylporphyrin, tetraphenyl Benzoternary porphyrin, the porphyrin compounds are dissolved in dichloromethane solvent, the concentration range is 1-2mg/mL; the pH indicator is Nile red, dissolved in ethanol, the concentration is 1-2mg/mL mL, each color-sensitive material is printed and dyed on the polyvinylidene fluoride (PVDF) film one by one through a micro-spotting capillary to make a color-sensitive material sensor array. 2.根据权利要求1所述的一种大米储藏过程中新鲜度的检测方法,其特征在于,步骤(3)中所述不同阶段大米挥发性气体的采集具体操作如下:2. A method for detecting the freshness of rice during storage according to claim 1, characterized in that the specific operations of collecting volatile gases from rice at different stages in step (3) are as follows: 气体采集探针(7)置于大米样本中,开启加热模块(9)和真空泵(6),抽取大米储藏过程中的挥发性气体进入反应室(4)与传感器阵列(5)的色敏材料反应; 3CCD相机(2)获取反应后将传感器阵列(5)的R、G、B图像传输给计算机(1),计算机(1)进行图像处理。The gas collection probe (7) is placed in the rice sample, the heating module (9) and the vacuum pump (6) are turned on, and the volatile gas during the rice storage process is extracted into the reaction chamber (4) and the color-sensitive material of the sensor array (5) Response; 3CCD camera (2) transmits the R, G, B images of the sensor array (5) to the computer (1) after acquiring the reaction, and the computer (1) performs image processing. 3.根据权利要求1所述的一种大米储藏过程中新鲜度的检测方法,其特征在于,步骤(2)或(3)中所述的计算机进行图像处理的具体方法为:3. The method for detecting the freshness of a kind of rice during storage according to claim 1, characterized in that, the specific method for performing image processing by the computer described in step (2) or (3) is: 将采集到的图像信息通过高斯滤波去噪、阈值分割、形态学处理、特征区域提取,以色敏材料重心为圆点,15个像素为半径的圆,获得反应前后图像中各色敏材料的R、G、B灰度的平均值,得到不同新鲜度大米挥发性气体的特征矩阵。The collected image information is denoised by Gaussian filtering, threshold segmentation, morphological processing, and feature region extraction. The center of gravity of the color-sensitive material is used as a dot and the radius of 15 pixels is a circle to obtain the R of each color-sensitive material in the image before and after the reaction. , G, and B gray values to obtain the characteristic matrix of volatile gases in rice with different freshness. 4.根据权利要求2所述的一种大米储藏过程中新鲜度的检测方法,其特征在于,其中所述气体采集探针(7)下端装有加热模块(9),用于检测样本的加热,促进气体挥发,气体采集探针(7)进样口装有滤网(8),用于防止大米中的杂质堵塞装置,而只提取储藏过程的大米挥发性气体。4. The method for detecting the freshness of rice during storage according to claim 2, wherein a heating module (9) is installed at the lower end of the gas collection probe (7) for detecting the heating of the sample , to promote gas volatilization, the inlet of the gas collection probe (7) is equipped with a filter screen (8), which is used to prevent the impurity in the rice from clogging the device, and only extracts the volatile gas of the rice during storage. 5.根据权利要求2所述的一种大米储藏过程中新鲜度的检测方法,其特征在于,其中步骤(4)中所述新鲜度线性判别模型的建立,具体操作是将数据进行主成分分析,最后选取前7个主成分构建线性判别分析模型来判别大米的新鲜度。5. The method for detecting the freshness of rice during storage according to claim 2, wherein the establishment of the freshness linear discriminant model in step (4) is performed by performing principal component analysis on the data , and finally select the first 7 principal components to build a linear discriminant analysis model to judge the freshness of rice.
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