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CN102967597A - Olfactory imaging sensing technology based yellow wine storage time identification method and identification system - Google Patents

Olfactory imaging sensing technology based yellow wine storage time identification method and identification system Download PDF

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CN102967597A
CN102967597A CN2012103629815A CN201210362981A CN102967597A CN 102967597 A CN102967597 A CN 102967597A CN 2012103629815 A CN2012103629815 A CN 2012103629815A CN 201210362981 A CN201210362981 A CN 201210362981A CN 102967597 A CN102967597 A CN 102967597A
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rice wine
imaging sensor
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yellow rice
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陈全胜
欧阳琴
赵杰文
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Jiangsu University
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Abstract

本发明公开了一种基于嗅觉成像传感技术的黄酒龄鉴别方法和鉴别系统,具体包括如下步骤:嗅觉成像传感器的制作;通过扫描仪或者CCD摄像头获取反应前嗅觉成像传感器的图像;嗅觉成像传感器与黄酒的挥发物反应;获取反应后嗅觉成像传感器的图像;提取成像传感器阵列中各显色剂的反应前后的颜色特征,计算反应前后的颜色特征变化;结合化学计量学方法对不同酒龄的黄酒进行分类鉴别。本发明克服了传统气味传感器的易受湿度影响的缺点,检测速度快、灵敏度高,结果准确。

Figure 201210362981

The invention discloses a rice wine age identification method and identification system based on olfactory imaging sensing technology, which specifically comprises the following steps: manufacturing an olfactory imaging sensor; acquiring an image of the olfactory imaging sensor before reaction through a scanner or a CCD camera; and using the olfactory imaging sensor React with the volatiles of rice wine; acquire the image of the olfactory imaging sensor after the reaction; extract the color characteristics of each chromogenic agent in the imaging sensor array before and after the reaction, and calculate the color characteristic changes before and after the reaction; Yellow rice wine is classified and identified. The invention overcomes the shortcoming that the traditional odor sensor is easily affected by humidity, and has fast detection speed, high sensitivity and accurate results.

Figure 201210362981

Description

一种基于嗅觉成像传感技术的黄酒酒龄鉴别方法和鉴别系统A method and system for identifying the age of rice wine based on olfactory imaging sensing technology

技术领域 technical field

本发明涉及一种嗅觉成像传感技术用于检测黄酒分类的方法,尤其是嗅觉成像传感器用于黄酒酒龄鉴别的方法。 The invention relates to a method for detecting the classification of yellow rice wine with an olfactory imaging sensor technology, in particular to a method for using an olfactory imaging sensor to identify the age of yellow rice wine.

背景技术 Background technique

黄酒是我国历史上最古老的酒种,是世界三大酿造酒(黄酒、葡萄酒和啤酒)之一。在黄酒酿造过程中,由于原料品种、糖化发酵剂种类、酿造方法、酿造季节、地域(环境)条件等诸多因素的影响,使黄酒种类繁多,其风味物质和香味特征不尽相同。为了评定出黄酒的质量等级和优劣状况,以推向社会,供消费者选择,需要对黄酒品质实行科学的检测和评价。 Yellow rice wine is the oldest kind of wine in the history of our country, and it is one of the three major brewed wines (rice wine, wine and beer) in the world. In the process of rice wine brewing, due to the influence of many factors such as raw material species, saccharification starter, brewing method, brewing season, and regional (environmental) conditions, there are many types of rice wine, and their flavor substances and aroma characteristics are not the same. In order to assess the quality grade and quality of yellow rice wine, and promote it to the society for consumers to choose, it is necessary to carry out scientific testing and evaluation of the quality of yellow rice wine.

黄酒的品质评定的内容主要是理化指标检测和人工感观品评。理化指标的检测一般都采用化学方法,虽然化学方法客观可信,但具有步骤繁琐、检测时间长、检测费用高等缺点,不能对黄酒的品质指标进行实时、在线检测。感官品评容易受到专家的经验、性别、年龄、精神状态、身体状况甚至地域环境等因素的影响,从而影响感官品评结果的准确性和稳定性。 The quality evaluation of rice wine mainly includes physical and chemical index detection and artificial sensory evaluation. The detection of physical and chemical indicators generally adopts chemical methods. Although chemical methods are objective and reliable, they have the disadvantages of cumbersome steps, long detection time, and high detection costs. They cannot perform real-time and online detection of rice wine quality indicators. Sensory evaluation is easily affected by factors such as experts' experience, gender, age, mental state, physical condition and even regional environment, which will affect the accuracy and stability of sensory evaluation results.

黄酒的气味特征是黄酒品质评判的一个重要因素。近年来,电子鼻技术作为一种快速、无损、客观的检测方法,逐步应用于黄酒品质检测的研究。但电子鼻技术多局限于利用金属氧化物传感器(MOS)检测黄酒,M0S传感器易受到环境温湿度的影响。而嗅觉成像传感器可以克服传统金属氧化物传感器的缺点,灵敏度高,不易受到湿度的影响,可以应用于黄酒等液态食品的检测。 The odor characteristic of yellow rice wine is an important factor in judging the quality of yellow rice wine. In recent years, electronic nose technology, as a rapid, non-destructive and objective detection method, has been gradually applied to the research of rice wine quality detection. However, electronic nose technology is mostly limited to the use of metal oxide sensors (MOS) to detect rice wine, and MOS sensors are easily affected by ambient temperature and humidity. The olfactory imaging sensor can overcome the shortcomings of traditional metal oxide sensors, has high sensitivity and is not easily affected by humidity, and can be applied to the detection of liquid foods such as rice wine.

发明内容 Contents of the invention

本发明的目的是为了克服传统气味传感器易受湿度影响的缺点,提供一种快速、灵敏、简便的嗅觉成像传感器对黄酒酒龄进行鉴别的方法。  The purpose of the present invention is to overcome the shortcoming that the traditional smell sensor is easily affected by humidity, and provide a method for identifying the age of yellow rice wine with a fast, sensitive and simple olfactory imaging sensor. the

本发明是基于嗅觉成像传感技术的黄酒酒龄检测方法,具体实施步骤如下: The present invention is a method for detecting the age of rice wine based on olfactory imaging sensing technology, and the specific implementation steps are as follows:

(1)    选择9种卟啉类化合物,如①2,3,7,8,12,13,17,18-八乙基-21H,23H-卟吩锰(III)氯化物;②5,10,15,20-四苯基-21H,23H-卟吩氯化锰(III);③5,10,15,20-四苯基-21H,23H-卟吩;④5,10,15,20-四苯基-21H,23H-卟吩铜(II);⑤5,10,15,20-四苯基-21H,23H-卟吩氯化铁(III);⑥5,10,15,20-四(4-甲氧苯基)-21H,23H-卟吩氯化铁(III);⑦5,10,15,20-四苯基-21H,23H-卟吩锌;⑧5,10,15,20-四(4-甲氧苯基)-21H,23H-卟吩钴(II);⑨5,10,15,20-四(五氟苯基)-21H,23H-卟啉氯化铁(III);以及6种pH指示剂,如①百里香酚蓝,②溴百里酚蓝,③溴甲酚绿,④甲酚红,⑤溴甲酚紫,⑥中性红。将它们溶于氯仿或者乙醇等有机溶剂中,配制成1-2mg/mL的均匀溶液。 (1) Select 9 porphyrin compounds, such as ①2,3,7,8,12,13,17,18-octaethyl-21 H ,23 H -porphin manganese(III) chloride; ②5,10 ,15,20-tetraphenyl-21 H ,23 H -porphine manganese(III) chloride; ③5,10,15,20-tetraphenyl-21 H ,23 H -porphine; ④5,10,15 ,20-tetraphenyl-21 H ,23 H -porphine copper(II); ⑤5,10,15,20-tetraphenyl-21 H ,23 H -porphine iron(III) chloride; ⑥5,10 ,15,20-tetrakis(4-methoxyphenyl)-21 H ,23 H -porphine iron(III) chloride; ⑦5,10,15,20-tetraphenyl-21 H ,23 H -porphine Zinc; ⑧5,10,15,20-tetrakis(4-methoxyphenyl)-21 H ,23 H -porphine cobalt(II); ⑨5,10,15,20-tetrakis(pentafluorophenyl)-21 H ,23 H -porphyrin iron(III) chloride; and 6 pH indicators, such as ①thymol blue, ②bromothymol blue, ③bromocresol green, ④cresol red, ⑤bromocresol purple , ⑥ neutral red. Dissolve them in organic solvents such as chloroform or ethanol, and prepare a uniform solution of 1-2 mg/mL.

(2)    用微量取样器取适量上述溶液,固定在反相C2硅胶板上或疏水性PVDF膜上,干燥后得到5×3成像传感器阵列,密闭保存。 (2) Use a micro sampler to take an appropriate amount of the above solution, fix it on a reversed-phase C2 silica gel plate or a hydrophobic PVDF membrane, and dry it to obtain a 5×3 imaging sensor array, which is sealed and stored.

(3)    通过扫描仪或者CCD摄像头获取未与黄酒挥发物反应的成像传感器阵列图像。 (3) Obtain images of the imaging sensor array that have not reacted with rice wine volatiles through a scanner or a CCD camera.

(4)    取适量黄酒样品于密闭容器中,将成像传感器阵列固定在样品的顶空,使成像传感器阵列与黄酒的挥发物相接触,反应一段时间。通过扫描仪或CCD摄像头获取与黄酒挥发物反应后的成像传感器阵列图像。 (4) Take an appropriate amount of yellow rice wine sample in an airtight container, fix the imaging sensor array in the headspace of the sample, make the imaging sensor array contact with the volatile matter of yellow rice wine, and react for a period of time. The image of the imaging sensor array after reacting with the rice wine volatiles is acquired by a scanner or a CCD camera.

(5)    提取成像传感器阵列中各显色剂反应前后的R、G、B颜色特征(R、G、B分别代表红、绿、蓝三个通道的颜色),并计算各显色剂反应前后的颜色特征变化,每个显色剂得到3个特征值,即△R, △G和 △B。为加大传感器可视图像间的对比度,以使人眼看上去更直观、更清晰,将ΔR、ΔG、ΔB的绝对值通过正规化处理映射到0-255之间。将三个5×3差矩阵(ΔR、ΔG、ΔB)绝对值分别生成5×3的R、G、B分量的灰度图像。再将灰度图像叠加,生成可视化差值图像。每个传感器阵列共有15个显色剂,则一个黄酒样品就包含45个成像传感器特征值。 (5) Extract the R, G, and B color features before and after the reaction of each chromogenic agent in the imaging sensor array (R, G, and B represent the colors of the three channels of red, green, and blue, respectively), and calculate the color characteristics of each chromogenic agent before and after the reaction The color characteristic changes, each chromogenic agent gets 3 characteristic values, namely △R, △G and △B. In order to increase the contrast between the visible images of the sensor, so that the human eye looks more intuitive and clearer, the absolute values of ΔR, ΔG, and ΔB are mapped to 0-255 through normalization processing. The absolute values of the three 5×3 difference matrices (ΔR, ΔG, ΔB) are respectively generated into 5×3 grayscale images of R, G, and B components. Then the grayscale images are superimposed to generate a visual difference image. There are 15 chromogens in each sensor array, and a rice wine sample contains 45 imaging sensor feature values.

(6)    将成像传感器阵列的特征值与黄酒的酒龄相关联,通过判别函数分析(DFA)对黄酒的酒龄进行判别。 (6) Correlate the eigenvalues of the imaging sensor array with the age of rice wine, and discriminate the age of rice wine through discriminant function analysis (DFA).

本发明还公开了基于上述方法的黄酒鉴别系统,由反应器、嗅觉成像传感器、扫描仪或者CCD摄像头、以及图像处理分析模块构成; The invention also discloses a rice wine identification system based on the above method, which is composed of a reactor, an olfactory imaging sensor, a scanner or a CCD camera, and an image processing and analysis module;

反应器用于盛放黄酒样品和固定嗅觉成像传感器,黄酒挥发物与嗅觉成像传感器在反应器中进行反应; The reactor is used to hold rice wine samples and fix the olfactory imaging sensor, and the rice wine volatiles react with the olfactory imaging sensor in the reactor;

扫描仪或者CCD摄像头,用于获取反应前、后嗅觉成像传感器的图像信息,并传送至图像处理分析模块; A scanner or a CCD camera is used to obtain the image information of the front and rear olfactory imaging sensors, and transmit it to the image processing and analysis module;

图像处理分析模块,用于接收扫描仪或者CCD摄像头传送的图像信息,提取成像传感器中各显色剂的反应前后的颜色特征,计算反应前后的颜色特征变化;结合化学计量学方法对不同酒龄的黄酒进行分类鉴别。 The image processing and analysis module is used to receive the image information transmitted by the scanner or CCD camera, extract the color features of each chromogenic agent in the imaging sensor before and after the reaction, and calculate the color feature changes before and after the reaction; Classification and identification of yellow rice wine.

所述嗅觉成像传感器是由显色剂构成的阵列。 The olfactory imaging sensor is an array composed of chromogenic agents.

本发明的优点是:1. 嗅觉成像传感器阵列与黄酒的挥发物反应,是在自然环境下,即无须加热或者震动情况下,黄酒的自由挥发物与成像感器阵列反应;2. 嗅觉成像传感器技术可以快速、方便、准确的评判黄酒的酒龄,检测灵敏度高,可以克服传统理化分析及人工感官品评的局限性,以及传统气体传感器易受湿度影响的缺点。本发明为黄酒的质量评判提供了有效、简便的新方法。 The advantages of the present invention are: 1. The reaction between the olfactory imaging sensor array and the volatile matter of rice wine is in a natural environment, that is, without heating or vibration, the free volatile matter of rice wine reacts with the imaging sensor array; 2. The olfactory imaging sensor The technology can quickly, conveniently and accurately judge the wine age of rice wine with high detection sensitivity, which can overcome the limitations of traditional physical and chemical analysis and artificial sensory evaluation, as well as the shortcomings of traditional gas sensors that are easily affected by humidity. The invention provides an effective and convenient new method for evaluating the quality of rice wine.

附图说明 Description of drawings

图1 嗅觉成像技术检测黄酒的实验过程示意图; Figure 1 Schematic diagram of the experimental process of rice wine detection by olfactory imaging technology;

图2判别函数分析处理4个不同年份黄酒的嗅觉成像传感器特征值的得分图。 Figure 2 The score chart of the eigenvalues of the olfactory imaging sensor for four different years of rice wine processed by discriminant function analysis.

具体实施方式 Detailed ways

实施例1: Example 1:

(1)    所测试的黄酒为“旦阳”牌的4个不同年份的黄酒,分别为3年、5年、8年和10年陈黄酒。每种黄酒为15个样本,共60个样本。 (1) The yellow rice wines tested are the "Danyang" brand yellow rice wines of 4 different years, namely 3, 5, 8 and 10 years old rice wines. There are 15 samples of each rice wine, 60 samples in total.

(2)    选取了9种卟啉类化合物:①2,3,7,8,12,13,17,18-八乙基-21H,23H-卟吩锰(III)氯化物;②5,10,15,20-四苯基-21H,23H-卟吩氯化锰(III);③5,10,15,20-四苯基-21H,23H-卟吩;④5,10,15,20-四苯基-21H,23H-卟吩铜(II);⑤5,10,15,20-四苯基-21H,23H-卟吩氯化铁(III);⑥5,10,15,20-四(4-甲氧苯基)-21H,23H-卟吩氯化铁(III);⑦5,10,15,20-四苯基-21H,23H-卟吩锌;⑧5,10,15,20-四(4-甲氧苯基)-21H,23H-卟吩钴(II);⑨5,10,15,20-四(五氟苯基)-21H,23H-卟啉氯化铁(III);以及6种pH指示剂:①百里香酚蓝,②溴百里酚蓝,③溴甲酚绿,④甲酚红,⑤溴甲酚紫,⑥中性红。将它们分别溶于氯仿或者无水乙醇等有机溶液中,配制成2mg/mL的均匀溶液。 (2) Nine porphyrin compounds were selected: ①2,3,7,8,12,13,17,18-octaethyl-21 H ,23 H -porphin manganese(III) chloride; ②5,10 ,15,20-tetraphenyl-21 H ,23 H -porphine manganese(III) chloride; ③5,10,15,20-tetraphenyl-21 H ,23 H -porphine; ④5,10,15 ,20-tetraphenyl-21 H ,23 H -porphine copper(II); ⑤5,10,15,20-tetraphenyl-21 H ,23 H -porphine iron(III) chloride; ⑥5,10 ,15,20-tetrakis(4-methoxyphenyl)-21 H ,23 H -porphine iron(III) chloride; ⑦5,10,15,20-tetraphenyl-21 H ,23 H -porphine Zinc; ⑧5,10,15,20-tetrakis(4-methoxyphenyl)-21 H ,23 H -porphine cobalt(II); ⑨5,10,15,20-tetrakis(pentafluorophenyl)-21 H ,23 H -porphyrin iron(III) chloride; and 6 pH indicators: ① thymol blue, ② bromothymol blue, ③ bromocresol green, ④ cresol red, ⑤ bromocresol purple, ⑥ neutral red. They were respectively dissolved in organic solutions such as chloroform or absolute ethanol to prepare a uniform solution of 2 mg/mL.

(3)    用微量取样器取适量上述溶液,固定在反相C2硅胶板上,干燥后得到5×3成像传感器阵列,密闭保存。 (3) Use a micro sampler to take an appropriate amount of the above solution, fix it on a reversed-phase C2 silica gel plate, and dry it to obtain a 5×3 imaging sensor array, which is sealed and stored.

(4)    通过扫描仪获取未与黄酒挥发物反应的成像传感器阵列图像。 (4) Obtain images of the imaging sensor array that have not reacted with rice wine volatiles through a scanner.

(5)    取20mL黄酒样品于培养皿中,将成像传感器阵列固定在培养皿的盖子上,即样品的顶空,使成像传感器阵列与黄酒的挥发物相接触,反应16min后,通过扫描仪获取与黄酒挥发物反应之后的成像传感器阵列图像。 (5) Take 20mL rice wine sample in a petri dish, fix the imaging sensor array on the lid of the petri dish, that is, the headspace of the sample, make the imaging sensor array contact with the volatile matter of rice wine, react for 16 minutes, and obtain it through the scanner Imaging sensor array image after reaction with rice wine volatiles.

(6)    提取成像传感器阵列中各显色剂反应前后的R、G、B颜色特征,并计算各显色剂反应前后的颜色特征变化,每个显色剂得到3个特征值,即△R, △G和 △B。每个传感器阵列共有15个显色剂,则一个黄酒样品就包含45(15×3)个成像传感器特征值。 (6) Extract the R, G, and B color features of each chromogenic agent before and after the reaction in the imaging sensor array, and calculate the color feature change of each chromogenic agent before and after the reaction. Each chromogenic agent obtains three eigenvalues, namely △R , △G and △B. There are 15 chromogens in each sensor array, and a rice wine sample contains 45 (15×3) imaging sensor feature values.

(7)    采用判别函数分析(DFA)处理60个黄酒样品的传感器特征值。图2显示了前两个判别函数的得分图,从图中可以看出,LDA可以完全区分4个不同年份的黄酒。说明,嗅觉成像传感器技术结合合适的化学计量学方法可以快速、准确的评判黄酒的酒龄,该方法是可行的。 (7) Using discriminant function analysis (DFA) to process the sensor eigenvalues of 60 rice wine samples. Figure 2 shows the score plots of the first two discriminant functions. It can be seen from the figure that LDA can completely distinguish rice wine from 4 different years. It shows that the combination of olfactory imaging sensor technology and appropriate chemometric method can quickly and accurately judge the wine age of rice wine, and this method is feasible.

Claims (5)

1. the yellow rice wine discrimination method in age based on sense of smell imaging sensing technology is to make first the sense of smell imaging sensor; Obtain the image of the front sense of smell imaging sensor of reaction by scanner or CCD camera; Make the volatile matter reaction of sense of smell imaging sensor and yellow rice wine; Obtain the image of the rear sense of smell imaging sensor of reaction by scanner or CCD camera; Be extracted into the color characteristic of the reaction front and back of each developer in the image-position sensor array, the color characteristic that calculates the reaction front and back changes; In conjunction with chemometrics method to the discriminating of classifying of different wine storage time of the yellow rice wine.
2. the yellow rice wine discrimination method in age based on sense of smell imaging sensing technology according to claim 1 is characterized in that concrete steps are as follows:
(1) selection is some for porphyrins and the pH indicator of chromogenic reaction, respectively they is dissolved in the organic solvents such as chloroform or ethanol, is mixed with the homogeneous solution of 1-2mg/mL; Get respectively an amount of mentioned solution with microscale sampler, be separately fixed on the anti-phase C2 silica gel plate or on the hydrophobicity pvdf membrane, obtain the imaging sensor array after the drying, airtight preservation;
(2) obtain not imaging sensor array image with the reaction of yellow rice wine volatile matter by scanner or CCD camera;
(3) get an amount of yellow rice wine sample in closed container, the imaging sensor array is fixed on the top of sample, the imaging sensor array is contacted with the volatile matter of yellow rice wine, obtain and the reacted imaging sensor array image of yellow rice wine volatile matter by scanner or CCD camera after reaction a period of time;
(4) be extracted in the image-position sensor array color characteristic before and after each developer reaction, and the color characteristic that calculates before and after each developer reaction changes, each developer obtains 3 eigenwerts, i.e. △ R, △ G and △ B;
(5) eigenwert with the imaging sensor array was associated with the wine storage time of yellow rice wine, by linear discriminant analysis to differentiating the wine storage time of yellow rice wine.
3. the yellow rice wine discrimination method in age based on sense of smell imaging sensing technology according to claim 2 is characterized in that described porphyrins is: 1. 2,3,7,8,12,13,17, and 18-octaethyl-21 H, 23 H-porphines manganese (III) chloride; 2. 5,10,15,20-tetraphenyl-21 H, 23 H-porphines manganese chloride (III); 3. 5,10,15,20-tetraphenyl-21 H, 23 H-porphines; 4. 5,10,15,20-tetraphenyl-21 H, 23 H-porphines copper (II); 5. 5,10,15,20-tetraphenyl-21 H, 23 H-porphines iron chloride (III); 6. 5,10,15,20-four (4-anisyl)-21 H, 23 H-porphines iron chloride (III); 7. 5,10,15,20-tetraphenyl-21 H, 23 H-porphines zinc; 8. 5,10,15,20-four (4-anisyl)-21 H, 23 H-porphines cobalt (II); 9. 5,10,15,20-four (pentafluorophenyl group)-21 H, 23 H-porphyrin iron chloride (III);
Described pH indicator is 1. thymol blue, 2. bromthymol blue, 3. bromcresol green, 4. cresol red, 5. bromcresol purple, 6. dimethyl diaminophenazine chloride.
4. the yellow rice wine identification system based on the described method of claim 1 is characterized in that, by reactor, sense of smell imaging sensor, scanner or CCD camera and image processing and analyzing module composition;
Reactor is used for holding yellow rice wine sample and fixing sense of smell imaging sensor, and yellow rice wine volatile matter and sense of smell imaging sensor react in reactor;
Scanner or CCD camera are used for obtaining the image information of the forward and backward sense of smell imaging sensor of reaction, and are sent to the image processing and analyzing module;
The image processing and analyzing module is used for the image information that reception scanner or CCD camera transmit, and is extracted into the color characteristic of the reaction front and back of each developer in the image-position sensor, and the color characteristic that calculates the reaction front and back changes; In conjunction with chemometrics method to the discriminating of classifying of different wine storage time of the yellow rice wine.
5. system according to claim 4 is characterized in that described sense of smell imaging sensor is the array that is made of developer.
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