CN104198529A - Method for distinguishing donkey-hide gelatin by utilizing electronic nose technology - Google Patents
Method for distinguishing donkey-hide gelatin by utilizing electronic nose technology Download PDFInfo
- Publication number
- CN104198529A CN104198529A CN201410387156.XA CN201410387156A CN104198529A CN 104198529 A CN104198529 A CN 104198529A CN 201410387156 A CN201410387156 A CN 201410387156A CN 104198529 A CN104198529 A CN 104198529A
- Authority
- CN
- China
- Prior art keywords
- sample
- donkey
- hide gelatin
- data
- electronic nose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 108010010803 Gelatin Proteins 0.000 title claims abstract description 84
- 229920000159 gelatin Polymers 0.000 title claims abstract description 84
- 239000008273 gelatin Substances 0.000 title claims abstract description 84
- 235000019322 gelatine Nutrition 0.000 title claims abstract description 84
- 235000011852 gelatine desserts Nutrition 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000005516 engineering process Methods 0.000 title claims abstract description 20
- 238000000513 principal component analysis Methods 0.000 claims abstract description 26
- 238000012549 training Methods 0.000 claims abstract description 17
- 238000012795 verification Methods 0.000 claims abstract description 12
- 238000012360 testing method Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000004364 calculation method Methods 0.000 claims description 18
- 108010052008 colla corii asini Proteins 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 8
- 238000007781 pre-processing Methods 0.000 claims description 7
- 230000009466 transformation Effects 0.000 claims description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000001228 spectrum Methods 0.000 claims description 4
- 239000002341 toxic gas Substances 0.000 claims description 4
- 238000000844 transformation Methods 0.000 claims description 4
- 238000013461 design Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 238000001134 F-test Methods 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 210000003056 antler Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000002790 cross-validation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013178 mathematical model Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
Landscapes
- Investigating Or Analysing Biological Materials (AREA)
Abstract
本发明公开一种利用电子鼻技术鉴别阿胶的方法,选取特定厂家的阿胶产品作为样本;对样本中每个样品分别检测,将样品粉碎成碎末后称取一定量置于密封样本瓶中,搅动一段时间后将样本瓶中的气体抽出一部分注射入电子鼻气室,电子鼻气室中的传感器阵列采集样品数据;对该样本中的样品数据划分为校正集数据和验证集数据,采用校正集数据建立判别模型,并通过验证集数据对所建立的判别模型进行验证;采集待检测阿胶样品的样品数据,计算待检测阿胶样品的主成分数据与培训集的主成分分析模型的主成分中心的距离,得到待检测阿胶样品的F值,根据设定的方差齐性检验的置信区间,判断其精密度是否有显著性差异,不存在显著性差异的为该特定厂家的阿胶。
The invention discloses a method for identifying donkey-hide gelatin using electronic nose technology. Select donkey-hide gelatin products from specific manufacturers as samples; test each sample in the sample separately, crush the sample into pieces, weigh a certain amount and place it in a sealed sample bottle, and stir After a period of time, a part of the gas in the sample bottle is extracted and injected into the electronic nose air chamber, and the sensor array in the electronic nose air chamber collects sample data; the sample data in the sample is divided into calibration set data and verification set data, and the calibration set data is used to The discriminant model is established from the data, and the established discriminant model is verified through the verification set data; the sample data of the donkey-hide gelatin sample to be detected is collected, and the principal component data of the donkey-hide gelatin sample to be detected is calculated. The principal component center of the principal component analysis model of the training set Distance, to obtain the F value of the donkey-hide gelatin sample to be tested, according to the set confidence interval of the homogeneity of variance test, judge whether there is a significant difference in the precision, and the donkey-hide gelatin of the specific manufacturer does not have a significant difference.
Description
技术领域technical field
本发明涉及阿胶鉴别领域,具体而言,涉及一种利用电子鼻技术鉴别阿胶的方法。The invention relates to the field of identification of donkey-hide gelatin, in particular to a method for identifying donkey-hide gelatin using electronic nose technology.
背景技术Background technique
阿胶,其应用已有3000年历史,历来被誉为“补血圣药”、“滋补国宝”,与人参、鹿茸一起被誉为“中药三宝”。阿胶的原产地是山东“东阿县”。东阿阿胶历来名冠天下,直至今日“东阿阿胶”几乎已经成为阿胶的代名词,同时也演变为对国内最大的阿胶及系列产品生产企业-山东东阿阿胶股份有限公司的简称。Ejiao, which has been used for 3,000 years, has always been known as the "Holy Medicine for Blood" and "National Treasure of Nourishment". Together with ginseng and antler, it is known as the "Three Treasures of Traditional Chinese Medicine". The origin of donkey-hide gelatin is "Dong'e County" in Shandong. Dong'e Ejiao has always been famous all over the world. Until today, "Dong'e Ejiao" has almost become synonymous with Ejiao. At the same time, it has also evolved into the abbreviation of Shandong Dong'e Ejiao Co., Ltd., the largest manufacturer of Ejiao and its series of products in China.
目前,阿胶生产厂家众多,由于原料和生产工艺不同,导致产品质量参差不齐,但目前药典标准设置相对较低,无法判定阿胶的真伪优劣和质量等级,特别是一些厂家以次充良,将质量较差的阿胶以著名商标厂家的阿胶的名义出售,破坏市场秩序,给著名商标厂家的名誉造成不良影响的同时,也欺骗和伤害了消费者。在此背景下,急需一种客观、快速、有效的方法对阿胶产品予以鉴定,以使消费者区别名优厂家的阿胶产品与其他生产厂家的阿胶产品。At present, there are many donkey-hide gelatin manufacturers. Due to different raw materials and production processes, the product quality is uneven. However, the current pharmacopoeia standard setting is relatively low, and it is impossible to judge the authenticity and quality level of donkey-hide gelatin. Selling poor-quality donkey-hide gelatin in the name of donkey-hide gelatin produced by well-known trademark manufacturers disrupts market order, adversely affects the reputation of famous trademark manufacturers, and at the same time deceives and hurts consumers. In this context, there is an urgent need for an objective, fast and effective method to identify donkey-hide gelatin products, so that consumers can distinguish donkey-hide gelatin products from well-known manufacturers from other manufacturers' donkey-hide gelatin products.
发明内容Contents of the invention
本发明提供一种利用电子鼻技术鉴别阿胶的方法,用以客观、快速、有效地对阿胶产品予以鉴定,以区别特定厂家的阿胶产品与其他生产厂家的阿胶产品。The invention provides a method for identifying donkey-hide gelatin using electronic nose technology, which is used to identify donkey-hide gelatin products objectively, quickly and effectively, so as to distinguish donkey-hide gelatin products from specific manufacturers from other manufacturers' donkey-hide gelatin products.
为达到上述目的,本发明提供了一种利用电子鼻技术鉴别阿胶的方法,包括以下步骤:In order to achieve the above object, the present invention provides a method for identifying donkey-hide gelatin using electronic nose technology, comprising the following steps:
a)选取特定厂家的阿胶产品作为样本;a) Select donkey-hide gelatin products from specific manufacturers as samples;
b)对所述样本中的每个样品进行检测,检测过程为:b) detecting each sample in the samples, the detection process is:
b1)将样品粉碎过筛后的样品碎末称取0.5-2.0g置于容积为5-20ml的密封样本瓶中,搅动1000s-3000s,将所述样本瓶中的气体取1-5ml用注射针注入电子鼻气室;所述电子鼻气室内设有3个腔室,所述3个腔室设有共18个传感器组成的传感器阵列;b1) Weigh 0.5-2.0g of the sample powder after crushing and sieving the sample, place it in a sealed sample bottle with a volume of 5-20ml, stir for 1000s-3000s, take 1-5ml of the gas in the sample bottle and inject it The needle is injected into the electronic nasal air chamber; the electronic nasal air chamber is provided with 3 chambers, and the 3 chambers are provided with a sensor array composed of a total of 18 sensors;
b2)所述传感器阵列采集所述样本瓶中的样品数据;其中,每个样品的样品数据采集3次,取平均值;所采集的样品数据为样品气味的特征响应谱;b2) The sensor array collects the sample data in the sample bottle; wherein, the sample data of each sample is collected 3 times and averaged; the collected sample data is the characteristic response spectrum of the sample odor;
c)对该样本中的所有样品数据,划分为校正集数据和验证集数据,采用所述校正集数据建立判别模型,并通过所述验证集数据对所建立的判别模型进行验证;c) dividing all sample data in the sample into calibration set data and verification set data, using the calibration set data to establish a discriminant model, and verifying the established discriminant model through the verification set data;
其中采用所述校正集数据建立判别模型的方法是:Wherein the method for establishing a discriminant model using the calibration set data is:
c1)对单个样品的数据进行预处理,提取特征信息并进行下列变换:c1) Preprocessing the data of a single sample, extracting feature information and performing the following transformations:
其中,SNVi是单个样品的电子鼻信号中第i个传感器响应值的标准正态变量;xi为第i个传感器在该单个样品中的响应值;是该单个样品的电子鼻信号中所有传感器响应值的平均值;p为电子鼻气室内的传感器个数;i为自然数,其取值范围为从1到p;Among them, SNV i is the standard normal variable of the i-th sensor response value in the electronic nose signal of a single sample; x i is the response value of the i-th sensor in the single sample; is the average value of all sensor response values in the electronic nose signal of the single sample; p is the number of sensors in the electronic nose air chamber; i is a natural number, and its value ranges from 1 to p;
c2)获取校正集中所有样品经预处理后的数据,采用SIMCA方法对该样本建立一个主成分分析判别模型,先将所述校正集中的样品作为一个训练集,将所述训练集的样品数据矩阵分别进行主成分分析,建立所述训练集的主成分分析判别模型并以留一法对所述主成分分析判别模型进行优化;其中所述样品数据矩阵由p个传感器的响应值的峰值组成;c2) Obtain the preprocessed data of all samples in the calibration set, use the SIMCA method to establish a principal component analysis discriminant model for the sample, first use the samples in the calibration set as a training set, and use the sample data matrix of the training set Carrying out principal component analysis respectively, establishing the principal component analysis discriminant model of the training set and optimizing the principal component analysis discriminant model by leave-one-out method; wherein the sample data matrix is composed of the peak values of the response values of p sensors;
d)根据步骤b的方法采集待检测阿胶样品的样品数据,并按照步骤c1的方法对待检测阿胶样品的样品数据进行预处理,将待检测阿胶样品的样品数据代入所述主成分分析判别模型,得到待检测阿胶样品的主成分数据与所述培训集的主成分分析判别模型的主成分中心的距离,并根据该距离计算待检测阿胶样品的方差齐性检验的F计算值F计算,根据设定的方差齐性检验分类的置信区间,将F计算与设定的显著性水平α处的临界值F临界相比较,判断待检测阿胶样品与所述主成分分析判别模型的精密度是否有显著性差异,若F计算﹤F临界,则待检测阿胶样品与该特定厂家的阿胶样本不存在显著性差异,认定为待检测阿胶样品是该特定厂家的阿胶,若F计 算﹥F临界,则待检测阿胶样品与该特定厂家的阿胶样本存在显著性差异,认定为待检测阿胶样品不是该特定厂家的阿胶。d) collecting the sample data of the donkey-hide gelatin sample to be detected according to the method of step b, and preprocessing the sample data of the donkey-hide gelatin sample to be detected according to the method of step c1, substituting the sample data of the donkey-hide gelatin sample to be detected into the principal component analysis discriminant model, Obtain the principal component data of the donkey-hide gelatin sample to be detected and the distance of the principal component center of the principal component analysis discriminant model of the training set, and calculate the F calculation value F calculation of the variance homogeneity test of the donkey-hide gelatin sample to be detected according to this distance, according to design Determine the confidence interval of the homogeneity of variance test classification, compare the F calculation with the critical value F critical at the set significance level α, and judge whether the precision of the donkey-hide gelatin sample to be detected and the discriminant model of the principal component analysis has significant If F calculation < F critical , there is no significant difference between the donkey-hide gelatin sample to be detected and the donkey-hide gelatin sample of the specific manufacturer, and it is determined that the donkey-hide gelatin sample to be detected is the donkey-hide gelatin of the specific manufacturer. If F calculation > F critical , then If there is a significant difference between the Ejiao sample to be tested and the Ejiao sample from the specific manufacturer, it is determined that the Ejiao sample to be tested is not from the specific manufacturer.
其中,步骤a)中选取的该样本至少具有20个样品。Wherein, the sample selected in step a) has at least 20 samples.
其中,所述传感器阵列包括强氧化能力气体传感器、有毒气体传感器、有机化合物传感器、易燃气体传感器及芳香族化合物传感器。Wherein, the sensor array includes gas sensors with strong oxidizing ability, toxic gas sensors, organic compound sensors, flammable gas sensors and aromatic compound sensors.
其中,所述注射针的温度为80℃-150℃,注射速度为1-5ml/s。Wherein, the temperature of the injection needle is 80°C-150°C, and the injection speed is 1-5ml/s.
其中,所述传感器阵列采集所述样本瓶中的样品数据的采集时间为60-600s。Wherein, the collection time for the sensor array to collect the sample data in the sample bottle is 60-600s.
其中,样品在所述样本瓶中搅动的速度为300-900rpm。Wherein, the stirring speed of the sample in the sample bottle is 300-900rpm.
其中,样品在所述样本瓶中产生气体的温度为50℃-150℃。Wherein, the temperature at which the sample generates gas in the sample bottle is 50°C-150°C.
其中,设定的显著性水平α为0.05。Among them, the set significance level α is 0.05.
与现有技术相比,本发明的有益效果体现在:Compared with the prior art, the beneficial effects of the present invention are reflected in:
本发明提供的利用电子鼻技术鉴别阿胶的方法,通过电子鼻的传感器响应,根据样本的标准正态变量建立判别模型,并利用F检验,客观、准确、快捷,分析过程简便,样品用量少,并可推广到其他领域,具有非常高的实用性。The method for discriminating donkey-hide gelatin using electronic nose technology provided by the present invention, through the sensor response of the electronic nose, establishes a discriminant model according to the standard normal variable of the sample, and utilizes the F test, it is objective, accurate and fast, the analysis process is simple and convenient, and the sample consumption is small , and can be extended to other fields, with very high practicability.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments of the present invention. Those skilled in the art can also obtain other drawings based on these drawings without creative work.
图1为本发明一实施例的利用电子鼻技术鉴别阿胶的方法流程图;Fig. 1 is the flow chart of the method for identifying donkey-hide gelatin utilizing electronic nose technology in an embodiment of the present invention;
图2为本发明一实施例的利用电子鼻技术鉴别东阿阿胶时的样品数据;Fig. 2 is the sample data when utilizing the electronic nose technology to identify Dong-E-E-Jiao according to an embodiment of the present invention;
图3为本发明一实施例的利用电子鼻技术鉴别东阿阿胶时待检测阿胶样品为伪品阿胶的样品数据;Fig. 3 is the sample data that the donkey-hide gelatin sample to be detected is a counterfeit donkey-hide gelatin when the electronic nose technology is used to identify donkey-hide gelatin according to an embodiment of the present invention;
图4为本发明一实施例的利用电子鼻技术鉴别东阿阿胶时待检测阿胶样品为其他品牌阿胶的样品数据。Fig. 4 is the sample data of donkey-hide gelatin samples to be detected are other brands of donkey-hide gelatin when the electronic nose technology is used to identify donkey-hide gelatin according to an embodiment of the present invention.
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付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 following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
图1为本发明一个实施例的利用电子鼻技术鉴别阿胶的方法流程图。如图1所示,本发明的一种利用电子鼻技术鉴别阿胶的方法,包括以下步骤:Fig. 1 is a flowchart of a method for identifying donkey-hide gelatin using electronic nose technology according to an embodiment of the present invention. As shown in Figure 1, a kind of method utilizing electronic nose technology of the present invention to differentiate donkey-hide gelatin comprises the following steps:
a)选取特定厂家的阿胶产品作为样本;a) Select donkey-hide gelatin products from specific manufacturers as samples;
b)对所述样本中的每个样品进行检测,检测过程为:b) detecting each sample in the samples, the detection process is:
b1)将样品粉碎过筛后的样品碎末称取0.5-2.0g置于容积为5-20ml的密封样本瓶中,搅动1000s-3000s,将所述样本瓶中的气体取1-5ml用注射针注入电子鼻气室;所述电子鼻气室内设有3个腔室,所述3个腔室设有共18个传感器组成的传感器阵列;b1) Weigh 0.5-2.0g of the sample powder after crushing and sieving the sample, place it in a sealed sample bottle with a volume of 5-20ml, stir for 1000s-3000s, take 1-5ml of the gas in the sample bottle and inject it The needle is injected into the electronic nasal air chamber; the electronic nasal air chamber is provided with 3 chambers, and the 3 chambers are provided with a sensor array composed of a total of 18 sensors;
b2)所述传感器阵列采集所述样本瓶中的样品数据;其中,每个样品的样品数据采集3次,取平均值;所采集的样品数据为样品气味的特征响应谱;b2) The sensor array collects the sample data in the sample bottle; wherein, the sample data of each sample is collected 3 times and averaged; the collected sample data is the characteristic response spectrum of the sample odor;
c)对该样本中的所有样品数据,划分为校正集数据和验证集数据,采用所述校正集数据建立判别模型,并通过所述验证集数据对所建立的判别模型进行验证;c) dividing all sample data in the sample into calibration set data and verification set data, using the calibration set data to establish a discriminant model, and verifying the established discriminant model through the verification set data;
其中采用所述校正集数据建立判别模型的方法是:Wherein the method for establishing a discriminant model using the calibration set data is:
c1)对单个样品的数据进行预处理,提取特征信息并进行下列变换:c1) Preprocessing the data of a single sample, extracting feature information and performing the following transformations:
其中,SNVi是单个样品的电子鼻信号中第i个传感器响应值的标准正态变量;xi为第i个传感器在该单个样品中的响应值;是该单个样品的电子鼻信号中所有传感器响应值的平均值;p为电子鼻气室内的传感器个数;i为自然数,其取值范围为从1到p;Among them, SNV i is the standard normal variable of the i-th sensor response value in the electronic nose signal of a single sample; x i is the response value of the i-th sensor in the single sample; is the average value of all sensor response values in the electronic nose signal of the single sample; p is the number of sensors in the electronic nose air chamber; i is a natural number, and its value ranges from 1 to p;
c2)获取校正集中所有样品经预处理后的数据,采用SIMCA方法对该样本建立一个主成分分析判别模型,先将所述校正集中的样品作为一个训练集,将所述训练集的样品数据矩阵分别进行主成分分析,建立所述训练集的主成分分析判别模型并以留一法对所述主成分分析判别模型进行优化;其中所述样品数据矩阵由p个传感器的响应值的峰值组成;c2) Obtain the preprocessed data of all samples in the calibration set, use the SIMCA method to establish a principal component analysis discriminant model for the sample, first use the samples in the calibration set as a training set, and use the sample data matrix of the training set Carrying out principal component analysis respectively, establishing the principal component analysis discriminant model of the training set and optimizing the principal component analysis discriminant model by leave-one-out method; wherein the sample data matrix is composed of the peak values of the response values of p sensors;
d)根据步骤b的方法采集待检测阿胶样品的样品数据,并按照步骤c1的方法对待检测阿胶样品的样品数据进行预处理,将待检测阿胶样品的样品数据代入所述主成分分析判别模型,得到待检测阿胶样品的主成分数据与所述培训集的主成分分析判别模型的主成分中心的距离,并根据该距离计算待检测阿胶样品的方差齐性检验的F计算值F计算,根据设定的方差齐性检验分类的置信区间,将F计算与设定的显著性水平α处的临界值F临界相比较,判断待检测阿胶样品与所述主成分分析判别模型的精密度是否有显著性差异,若F计算﹤F临界,则待检测阿胶样品与该特定厂家的阿胶样本不存在显著性差异,认定为待检测阿胶样品是该特定厂家的阿胶,若F计 算﹥F临界,则待检测阿胶样品与该特定厂家的阿胶样本存在显著性差异,认定为待检测阿胶样品不是该特定厂家的阿胶。d) collecting the sample data of the donkey-hide gelatin sample to be detected according to the method of step b, and preprocessing the sample data of the donkey-hide gelatin sample to be detected according to the method of step c1, substituting the sample data of the donkey-hide gelatin sample to be detected into the principal component analysis discriminant model, Obtain the principal component data of the donkey-hide gelatin sample to be detected and the distance of the principal component center of the principal component analysis discriminant model of the training set, and calculate the F calculation value F calculation of the variance homogeneity test of the donkey-hide gelatin sample to be detected according to this distance, according to design Determine the confidence interval of the homogeneity of variance test classification, compare the F calculation with the critical value F critical at the set significance level α, and judge whether the precision of the donkey-hide gelatin sample to be detected and the discriminant model of the principal component analysis has significant If F calculation < F critical , there is no significant difference between the donkey-hide gelatin sample to be detected and the donkey-hide gelatin sample of the specific manufacturer, and it is determined that the donkey-hide gelatin sample to be detected is the donkey-hide gelatin of the specific manufacturer. If F calculation > F critical , then If there is a significant difference between the Ejiao sample to be tested and the Ejiao sample from the specific manufacturer, it is determined that the Ejiao sample to be tested is not from the specific manufacturer.
在本发明的一个实施例中,步骤a)中选取的该样本至少具有20个样品。In one embodiment of the present invention, the sample selected in step a) has at least 20 samples.
在本发明的一个实施例中,所述传感器阵列包括强氧化能力气体传感器、有毒气体传感器、有机化合物传感器、易燃气体传感器及芳香族化合物传感器。In one embodiment of the present invention, the sensor array includes a strong oxidizing gas sensor, a toxic gas sensor, an organic compound sensor, a flammable gas sensor and an aromatic compound sensor.
在本发明的一个实施例中,所述注射针的温度为80℃-150℃,注射速度为1-5ml/s。In one embodiment of the present invention, the temperature of the injection needle is 80°C-150°C, and the injection speed is 1-5ml/s.
在本发明的一个实施例中,所述传感器阵列采集所述样本瓶中的样品数据的采集时间为60-600s。In one embodiment of the present invention, the collection time for the sensor array to collect the sample data in the sample bottle is 60-600s.
在本发明的一个实施例中,样品在所述样本瓶中搅动的速度为300-900rpm。In one embodiment of the present invention, the agitation speed of the sample in the sample bottle is 300-900 rpm.
在本发明的一个实施例中,样品在所述样本瓶中产生气体的温度为50℃-150℃。In one embodiment of the present invention, the temperature at which the sample generates gas in the sample bottle is 50°C-150°C.
在本发明的一个实施例中,所述校正集和所述验证集的样品个数比约为2:1。In one embodiment of the present invention, the ratio of the number of samples in the calibration set to the verification set is about 2:1.
在本发明的一个实施例中,设定的显著性水平α为0.05。In one embodiment of the present invention, the set significance level α is 0.05.
以下以鉴别山东东阿阿胶股份有限公司生产的阿胶产品(以下简称东阿阿胶)为例,具体说明本发明的实施过程。Taking the identification of donkey-hide gelatin products (hereinafter referred to as Dong-E-E-Jiao) produced by Shandong Dong-E-E-Jiao Co., Ltd. as an example, the implementation process of the present invention will be specifically described.
选取30个批号为120433的东阿阿胶样品作为样本;Select 30 Dong-E-E-Jiao samples with batch number 120433 as samples;
对所述样本中的每个东阿阿胶样品进行检测,检测过程为:Each Dong'e Ejiao sample in the sample is detected, and the detection process is:
b1)将东阿阿胶样品粉碎后过筛,得到样品碎末,称取样品中的1.0g置于容积为10ml的密封样本瓶中,在90℃的温度下搅动1800s,搅动速度为500rpm。将所述样本瓶中的气体取2.0ml用注射针注入电子鼻气室;注射针的温度为100℃,总体积为5.0ml,注射速度为2.0ml/s。所述电子鼻气室内设有3个腔室,所述3个腔室设有共18个传感器组成的传感器阵列。所述传感器阵列包括强氧化能力气体传感器、有毒气体传感器、有机化合物传感器、易燃气体传感器及芳香族化合物传感器。本实施例中,采用的是法国Alpha MOS公司的FOX4000电子鼻,配有HS100型自动进样器、空气压缩机、空气净化器,可根据需要选择18个传感器中所需的部分传感器,其有效检测的气体请参考表1。b1) Pulverize the donkey-hide gelatin sample and sieve it to obtain the sample powder. Weigh 1.0 g of the sample and place it in a sealed sample bottle with a volume of 10 ml. Stir at a temperature of 90° C. for 1800 s at a stirring speed of 500 rpm. Take 2.0ml of the gas in the sample bottle and inject it into the air chamber of the electronic nose with an injection needle; the temperature of the injection needle is 100°C, the total volume is 5.0ml, and the injection speed is 2.0ml/s. The air chamber of the electronic nose is provided with 3 chambers, and the 3 chambers are provided with a sensor array composed of 18 sensors in total. The sensor array includes gas sensors with strong oxidizing ability, toxic gas sensors, organic compound sensors, flammable gas sensors and aromatic compound sensors. In this embodiment, the FOX4000 electronic nose of Alpha MOS Company in France is used, which is equipped with HS100 automatic sampler, air compressor, and air purifier, and some of the sensors required in the 18 sensors can be selected according to the needs, which are effective Please refer to Table 1 for the detected gases.
表1 FOX4000电子鼻中的传感器阵列及其敏感气体Table 1 Sensor array and its sensitive gas in FOX4000 electronic nose
本实施例中18个传感器全部选择,传感器阵列采集所述样本瓶中的样品数据;其中,每个样品的样品数据采集3次,每次的采集时间为120s,取平均值;所采集的样品数据为东阿阿胶样品气味的特征响应谱。本实施例中采集的东阿阿胶样品数据如图2所示。In this embodiment, all 18 sensors are selected, and the sensor array collects the sample data in the sample bottle; wherein, the sample data of each sample is collected 3 times, and each collection time is 120s, and the average value is taken; the collected samples The data is the characteristic response spectrum of the odor of Dong-E-E-Jiao samples. The sample data of Dong-E-E-Jiao collected in this example are shown in Figure 2.
对该样本中的30个样品的样品数据,划分为校正集数据和验证集数据,并将18个传感器的响应峰值作为样品数据矩阵。其中,校正集数据包括20个东阿阿胶样品数据,验证集数据包括10个东阿阿胶样品数据。采用所述校正集数据建立判别模型,并通过所述验证集数据对所建立的判别模型进行验证。The sample data of 30 samples in this sample are divided into calibration set data and verification set data, and the response peak values of 18 sensors are used as a sample data matrix. Among them, the calibration set data includes 20 Dong-E-E-Jiao sample data, and the verification set data includes 10 Dong-E-E-Jiao sample data. A discriminant model is established by using the calibration set data, and the established discriminant model is verified by the verification set data.
其中采用所述校正集数据建立判别模型的方法是:Wherein the method for establishing a discriminant model using the calibration set data is:
对单个样品的数据进行预处理,提取特征信息并进行下列变换:Preprocess the data of a single sample, extract feature information and perform the following transformations:
其中,SNVi是单个样品的电子鼻信号中第i个传感器数据的标准正态变量;xi为第i个传感器在该样品中的响应值;是该单个样品信号所有传感器响应值的平均值;18为电子鼻气室内的传感器个数;i为自然数,其取值范围为从1到18;Among them, SNV i is the standard normal variable of the i-th sensor data in the electronic nose signal of a single sample; x i is the response value of the i-th sensor in this sample; is the average value of all sensor response values of the single sample signal; 18 is the number of sensors in the electronic nose air chamber; i is a natural number, and its value range is from 1 to 18;
获取校正集中所有样品经预处理后的数据,采用SIMCA方法对该样本建立一个PCA判别分析模型,先将所述校正集中的样品作为一个训练集,将每个所述训练集的样品数据矩阵分别进行主成分分析,建立每个所述训练集的主成分分析数学模型;采用校正集样本对模型进行优化,优化内容包括信号选择、主成分数、预处理方法。优化时以留一法交叉验证的结果作为判据,即每次从校正集样品中剔除一个样品,而采用其他样品进行建模,用所建模型对剔除样品进行预测,判断其是否为东阿阿胶,这样校正集所有样品都会被预测一次,以总的误判率作为判据,优选建模参数。本实施例中,最终确定,选用17根传感器上的信号进行建模,主成分数为6。设定F检验的置信区间为95%(即为1-α,α=0.05)。Obtain the preprocessed data of all samples in the calibration set, and use the SIMCA method to establish a PCA discriminant analysis model for the sample. First, the samples in the calibration set are used as a training set, and the sample data matrix of each training set is respectively Perform principal component analysis, and establish a principal component analysis mathematical model of each training set; optimize the model by using calibration set samples, and the optimization content includes signal selection, principal component numbers, and preprocessing methods. When optimizing, the result of the leave-one-out method cross-validation is used as the criterion, that is, one sample is removed from the calibration set each time, and other samples are used for modeling, and the model is used to predict the removed sample to determine whether it is Dong-A Ejiao, in this way, all samples in the calibration set will be predicted once, and the total misjudgment rate is used as the criterion to optimize the modeling parameters. In this embodiment, it is finally determined that the signals on 17 sensors are selected for modeling, and the number of principal components is 6. The confidence interval of the F-test is set to 95% (that is, 1-α, α=0.05).
根据上述采集样品数据的步骤采集待检测阿胶样品的样品数据,对该样品数据按上面的变换公式进行预处理,将待检测阿胶样品的样品数据代入所述主成分分析判别模型,得到待检测阿胶样品的主成分数据与所述培训集的主成分分析判别模型的主成分中心的距离,并根据该距离计算待检测阿胶样品的方差齐性检验的F计算值F计算,根据设定的方差齐性检验分类的置信区间,将F计算与设定的显著性水平α处的临界值F临界相比较,本实施例中显著性水平α=0.05,若F计算值﹤F临界,则待检测阿胶样品与东阿阿胶样本不存在显著性差异,认定为待检测阿胶样品是东阿阿胶,若F计算值﹥F临界,则待检测阿胶样品与东阿阿胶样本存在显著性差异,认定为待检测样阿胶本不是东阿阿胶。如图3所示,为一伪品阿胶的样品数据;图4为一其他品牌阿胶的样品数据。Collect the sample data of the donkey-hide gelatin sample to be detected according to the above-mentioned steps of collecting sample data, preprocess the sample data according to the above transformation formula, substitute the sample data of the donkey-hide gelatin sample to be detected into the principal component analysis discriminant model, and obtain the donkey-hide gelatin to be detected The principal component data of the sample and the distance of the principal component center of the principal component analysis discriminant model of the training set, and calculate the F calculation value F calculation of the variance homogeneity test of the donkey-hide gelatin sample to be detected according to this distance, according to the variance homogeneity of setting Confidence interval for the classification of sex test , compare the F calculation with the critical value F critical at the set significance level α, the significance level α=0.05 in this embodiment, if the calculated value of F<F critical , then the donkey-hide gelatin to be detected If there is no significant difference between the sample and the Dong-E-E-Jiao sample, it is determined that the E-Jiao sample to be detected is Dong-E-E-Jiao. If the calculated value of F > F is critical , there is a significant difference between the E-Jiao sample to be detected and the Dong-E-E-Jiao sample, and it is determined to be detected Sample donkey-hide gelatin is not Dong'e donkey-hide gelatin. As shown in Figure 3, it is the sample data of a counterfeit donkey-hide gelatin; Figure 4 is the sample data of another brand of donkey-hide gelatin.
本领域普通技术人员可以理解:附图只是一个实施例的示意图,附图中的模块或流程并不一定是实施本发明所必须的。Those skilled in the art can understand that the accompanying drawing is only a schematic diagram of an embodiment, and the modules or processes in the accompanying drawing are not necessarily necessary for implementing the present invention.
本领域普通技术人员可以理解:实施例中的装置中的模块可以按照实施例描述分布于实施例的装置中,也可以进行相应变化位于不同于本实施例的一个或多个装置中。上述实施例的模块可以合并为一个模块,也可以进一步拆分成多个子模块。Those of ordinary skill in the art can understand that: the modules in the device in the embodiment may be distributed in the device in the embodiment according to the description in the embodiment, or may be changed and located in one or more devices different from the embodiment. The modules in the above embodiments can be combined into one module, and can also be further split into multiple sub-modules.
最后应说明的是:以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明实施例技术方案的精神和范围。Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: it can still be Modifications are made to the technical solutions described in the foregoing embodiments, or equivalent replacements are made to some of the technical features; these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410387156.XA CN104198529A (en) | 2014-08-07 | 2014-08-07 | Method for distinguishing donkey-hide gelatin by utilizing electronic nose technology |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410387156.XA CN104198529A (en) | 2014-08-07 | 2014-08-07 | Method for distinguishing donkey-hide gelatin by utilizing electronic nose technology |
Publications (1)
Publication Number | Publication Date |
---|---|
CN104198529A true CN104198529A (en) | 2014-12-10 |
Family
ID=52083854
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410387156.XA Pending CN104198529A (en) | 2014-08-07 | 2014-08-07 | Method for distinguishing donkey-hide gelatin by utilizing electronic nose technology |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104198529A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105044161A (en) * | 2015-07-03 | 2015-11-11 | 宁波大学 | Method for discriminating furacilin and furazolidone in Tegillarca granosa by using electron nose |
CN105136899A (en) * | 2015-09-11 | 2015-12-09 | 东阿阿胶股份有限公司 | Method of identifying donkey-hide gelatins produced by different manufacturers in different regions |
CN105223316A (en) * | 2015-10-15 | 2016-01-06 | 上海应用技术学院 | A kind of method of quick discriminating donkey-hide gelatin quality |
CN106645606A (en) * | 2016-12-28 | 2017-05-10 | 东阿阿胶股份有限公司 | Evaluation method of sensory quality of ass-hide glue |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102645502A (en) * | 2012-04-23 | 2012-08-22 | 上海应用技术学院 | Method for detecting age of yellow rice wine by using high-speed gas chromatography type electronic nose fingerprint analysis system |
CN102749370A (en) * | 2012-07-19 | 2012-10-24 | 浙江大学 | Nondestructive rapid detection method of quality index of shell agricultural products |
CN103018177A (en) * | 2012-12-06 | 2013-04-03 | 江苏易谱恒科技有限公司 | Spectrogram abnormal sample point detection method based on random sampling agree set |
-
2014
- 2014-08-07 CN CN201410387156.XA patent/CN104198529A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102645502A (en) * | 2012-04-23 | 2012-08-22 | 上海应用技术学院 | Method for detecting age of yellow rice wine by using high-speed gas chromatography type electronic nose fingerprint analysis system |
CN102749370A (en) * | 2012-07-19 | 2012-10-24 | 浙江大学 | Nondestructive rapid detection method of quality index of shell agricultural products |
CN103018177A (en) * | 2012-12-06 | 2013-04-03 | 江苏易谱恒科技有限公司 | Spectrogram abnormal sample point detection method based on random sampling agree set |
Non-Patent Citations (3)
Title |
---|
刘雪云等: "基于SIMCA模型的纸浆种类近红外光谱鉴别", 《中国造纸》 * |
周显青等: "电子鼻用于粮食储藏的研究进展", 《粮油食品科技》 * |
瞿海滨等: "近红外漫反射光谱法快速无损鉴别阿胶真伪", 《光谱学与光谱分析》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105044161A (en) * | 2015-07-03 | 2015-11-11 | 宁波大学 | Method for discriminating furacilin and furazolidone in Tegillarca granosa by using electron nose |
CN105044161B (en) * | 2015-07-03 | 2017-10-31 | 宁波大学 | Differentiate the method for nitrofurazone and furazolidone in mud blood clam using electronic nose |
CN105136899A (en) * | 2015-09-11 | 2015-12-09 | 东阿阿胶股份有限公司 | Method of identifying donkey-hide gelatins produced by different manufacturers in different regions |
CN105136899B (en) * | 2015-09-11 | 2018-05-29 | 东阿阿胶股份有限公司 | A kind of method for differentiating different manufacturers, different geographical and producing donkey-hide gelatin |
CN105223316A (en) * | 2015-10-15 | 2016-01-06 | 上海应用技术学院 | A kind of method of quick discriminating donkey-hide gelatin quality |
CN106645606A (en) * | 2016-12-28 | 2017-05-10 | 东阿阿胶股份有限公司 | Evaluation method of sensory quality of ass-hide glue |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Kiani et al. | Integration of computer vision and electronic nose as non-destructive systems for saffron adulteration detection | |
CN107894408A (en) | A kind of edible oil based near infrared spectrometer is polynary to mix pseudo- discrimination method | |
CN112539785B (en) | Tobacco grade identification system and method based on multi-dimensional characteristic information | |
CN102087212A (en) | Pueraria lobata starch adulteration identification method based on principal component analysis | |
CN104990892B (en) | The spectrum picture Undamaged determination method for establishing model and seeds idenmtification method of seed | |
CN108319813A (en) | Circulating tumor DNA copies the detection method and device of number variation | |
Wang et al. | Big data driven outlier detection for soybean straw near infrared spectroscopy | |
CN107607598B (en) | Method for identifying authenticity of lycium ruthenicum based on nonlinear chemical fingerprint technology | |
CN104198529A (en) | Method for distinguishing donkey-hide gelatin by utilizing electronic nose technology | |
CN104132968A (en) | Identification method of rice geographical indications and application of identification method of rice geographical indications | |
CN104155359A (en) | Edible vegetable oil authenticity quick screening method based on ionic migration spectrometry | |
CN101620178B (en) | Method for quickly detecting additive chemical component in Chinese patent medicine, health-care food or food based on near-infrared spectrum technique | |
CN102507676A (en) | On-line drift compensation method of electronic nose based on multiple self-organizing neural networks | |
Li et al. | Geographical origin traceability and identification of refined sugar using UPLC-QTof-MS analysis | |
CN104345045A (en) | Chemical pattern recognition and near infrared spectrum-based similar medicinal material identification method | |
CN113406249B (en) | A method for predicting the types of adulterated oils in camellia oil | |
CN110596080A (en) | A method for identifying the origin of golden pomfret based on mineral elements | |
CN104655812A (en) | Method for rapidly identifying trueness and quality of radix notoginseng | |
Wang et al. | Rapid identification and semi-quantification of adulteration in walnut oil by using excitation–emission matrix fluorescence spectroscopy coupled with chemometrics and ensemble learning | |
CN112268899B (en) | Method for rapidly identifying fritillaria medicinal materials | |
Li et al. | Excitation-emission matrix fluorescence spectroscopy combined with chemometrics methods for rapid identification and quantification of adulteration in Atractylodes macrocephala Koidz | |
CN104237370A (en) | A rapid identification method of counterfeit sesame oil added with sesame oil essence | |
CN105158424A (en) | Method for rapidly identifying authenticity and quality of Cordyceps sinensis | |
CN103488868B (en) | A kind of method of the intelligent smell discrimination model for setting up honey quality difference | |
CN112540971B (en) | Full-information online acquisition system and method based on tobacco leaf characteristics |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141210 |