CN103308620A - Method for rapidly measuring p-hydroxy-benzoate ester in cosmetics - Google Patents
Method for rapidly measuring p-hydroxy-benzoate ester in cosmeticsDownload PDFInfo
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Abstract
Translated fromChineseDescription
Translated fromChinese技术领域technical field
本发明涉及一种化妆品中成分组分的测定方法，尤其是一种化妆品中防腐剂对羟基苯甲酸酯的快速测定方法。 The invention relates to a method for determining components in cosmetics, in particular to a method for rapidly determining preservative parabens in cosmetics. the
背景技术Background technique
对羟基苯甲酸酯，即尼泊金酯，是目前化妆品中较为常用的防腐剂，其分析方法主要为色谱类方法，包括薄层层析法、气相色谱法、高效液相色谱（HPLC）和毛细管电泳法等。气相色谱法在用于测定含有羟基和羧基等极性物质时，一般需经过甲基硅烷化、衍生化后再用气相色谱定性，定量，因此，在防腐剂检测中受到一定限制；薄层色谱法能进行多种组分的定性，不需要特殊仪器设备，易推广；高效液相色谱法是当前使用最广泛的方法，具有操作简便、灵敏度高等优点。但是采用色谱方法的主要限制是需要分离时间，例如HPLC一个样本的分离时间接近15-20分钟，大批量样本的分析效率低，操作强度大。对于大批量样本的分析操作，流动相等试剂损耗大，分析成本高。 Parabens, that is, parabens, are commonly used preservatives in cosmetics, and their analysis methods are mainly chromatographic methods, including thin-layer chromatography, gas chromatography, and high-performance liquid chromatography (HPLC). and capillary electrophoresis, etc. When gas chromatography is used to determine polar substances such as hydroxyl and carboxyl, it generally needs to undergo methyl silylation and derivatization before using gas chromatography for qualitative and quantitative analysis. Therefore, it is limited in the detection of preservatives; thin-layer chromatography The method can carry out the qualitative analysis of various components, does not require special equipment, and is easy to popularize; high performance liquid chromatography is the most widely used method at present, and has the advantages of simple operation and high sensitivity. However, the main limitation of using chromatographic methods is the separation time. For example, the separation time of a sample in HPLC is close to 15-20 minutes. The analysis efficiency of large batches of samples is low and the operation intensity is high. For the analysis operation of a large number of samples, the loss of flow equal reagents is large, and the analysis cost is high. the
发明内容Contents of the invention
本发明要解决的技术问题是：提供一种化妆品中对羟基苯甲酸酯的快速测定方法，以解决现有技术存在的分析效率低、操作强度大以及分析成本高的不足之处。 The technical problem to be solved by the present invention is to provide a rapid determination method for parabens in cosmetics, so as to solve the shortcomings of low analysis efficiency, high operation intensity and high analysis cost in the prior art. the
解决上述技术问题的技术构思：采集已知的待测组分的多波长色谱数据，记录待测组分的出峰时间；采集含有待测组分的多组分混合样本的多波长色谱数据；扣除混合样本色谱数据中与待测组分具有相同保留时间的数据；合并多个样本的扣除待测组分的色谱数据，得到不含被组分的本底数据库，计算主成分数目；用奇异值分解结合主成分数目对本底数据库降维，即可得到数据量较小的本底数据库。运用空间夹角判据计算多组分混合样本中待测物质的含量，从而实现多组分混合体系中待测组分的定量。 The technical idea to solve the above technical problems: collect the known multi-wavelength chromatographic data of the components to be measured, and record the peak time of the components to be measured; collect the multi-wavelength chromatographic data of the multi-component mixed samples containing the components to be measured; Deduct the data that has the same retention time as the component to be tested in the chromatographic data of the mixed sample; combine the chromatographic data of multiple samples that deduct the component to be tested to obtain a background database that does not contain the component, and calculate the number of principal components; Value decomposition combined with the number of principal components reduces the dimensionality of the background database, and a background database with a small amount of data can be obtained. The content of the analyte in the multi-component mixed sample is calculated by using the spatial angle criterion, so as to realize the quantification of the analyte in the multi-component mixed system. the
解决上述技术问题的技术方案是： 一种化妆品中对羟基苯甲酸酯的快速测定方法，包括以下步骤： The technical solution for solving the above-mentioned technical problems is: A rapid assay method for parabens in cosmetics, comprising the following steps:
A.待测样本处理：A. Processing of samples to be tested:
将待测化妆品样本用甲醇萃取过滤，制得化妆品滤液； Extract and filter the cosmetic sample to be tested with methanol to obtain the cosmetic filtrate;
B. 本底光谱数据库的建立： B. Establishment of background spectrum database:
B1. 获取化妆品样本的光谱数据：B1. Obtain spectral data of cosmetic samples:
将步骤A制得的化妆品滤液经高效液相色谱分析，采集多个化妆品样本的多波长光谱数据；The cosmetic filtrate prepared in step A is analyzed by high performance liquid chromatography, and multi-wavelength spectral data of multiple cosmetic samples are collected;
B2. 获取待测组分的光谱数据：B2. Obtain the spectral data of the component to be measured:
配制待测组分对羟基苯甲酸酯的甲醇溶液，过滤后经高效液相色谱分析，采集待测组分的多波长光谱数据；Prepare the methanol solution of the paraben ester of the component to be tested, analyze it by high-performance liquid chromatography after filtering, and collect the multi-wavelength spectral data of the component to be tested;
B3. 转化数据格式：B3. Convert data format:
将步骤B1和B2中采集所得的化妆品样本的多波长光谱数据和待测组分的多波长光谱数据由光强数据格式转化成不同时间下多波长下的吸光度值，化妆品样本的光谱数据经数据转化后得到化妆品样本的多波长光谱数据；待测组分的光谱数据经数据转化后得到对羟基苯甲酸酯标准物质的多波长光谱数据；The multi-wavelength spectral data of the cosmetic samples collected in steps B1 and B2 and the multi-wavelength spectral data of the components to be measured are converted from the light intensity data format into absorbance values at multiple wavelengths at different times, and the spectral data of the cosmetic samples are passed through the data After the conversion, the multi-wavelength spectral data of the cosmetic sample is obtained; the spectral data of the components to be tested are converted to obtain the multi-wavelength spectral data of the paraben standard substance;
B4．获取不含待测组分的背景的光谱数据：B4. Obtain spectral data for a background free of analytes:
比对化妆品样本和对羟基苯甲酸酯标准物质的色谱图，从化妆品样本的色谱图中扣除与对羟基苯甲酸酯标准物质具有相同保留时间的光谱数据，其余数据存入本底光谱数据库中；合并多个样本的本底光谱数据库构成本底光谱数据库W；Compare the chromatograms of cosmetic samples and paraben standard substances, deduct the spectral data with the same retention time as the paraben standard substances from the chromatogram of cosmetic samples, and store the remaining data in the background spectrum database Middle; the background spectrum database of multiple samples is combined to form the background spectrum database W;
B5. 本底数据库的降维：B5. Dimensionality reduction of the background database:
将步骤B4中所得的本底光谱数据库W进行奇异值分解，根据体系主成分数目将本底光谱数据库W降到适当的维数，得到本底光谱数据库N；Singular value decomposition is performed on the background spectral database W obtained in step B4, and the background spectral database W is reduced to an appropriate dimension according to the number of principal components of the system to obtain the background spectral database N;
C. 获取对羟基苯甲酸酯的标准光谱数据库v；C. Obtain a standard spectral database v of parabens;
D. 待测化妆品样本光谱测量：D. Spectral measurement of the cosmetic sample to be tested:
采用光纤光谱仪对步骤A处理后制得的化妆品滤液经稀释后进行光谱测量，得到待测化妆品样本光谱数据a；Use a fiber optic spectrometer to measure the spectrum of the cosmetic filtrate obtained after the treatment in step A after dilution, and obtain the spectral data a of the cosmetic sample to be tested;
E. 待测化妆品样本中羟基苯甲酸酯含量测定：E. Determination of paraben content in the cosmetic sample to be tested:
分别将步骤B、C、D所得的本底光谱数据库N、标准光谱数据库v、待测化妆品样本光谱数据a导入计算平台，应用向量-子空间夹角判据算法从待测化妆品样本光谱中扣减对羟基苯甲酸酯的标准光谱，得出待测样本中对羟基苯甲酸酯的实际含量。Import the background spectral database N, standard spectral database v, and cosmetic sample spectral data a obtained in steps B, C, and D into the computing platform, and apply the vector-subspace included angle criterion algorithm to deduct from the spectral data of the cosmetic sample to be tested. Subtract the standard spectrum of parabens to obtain the actual content of parabens in the sample to be tested.
本发明的进一步技术方案是：所述步骤A.待测样本处理的具体步骤如下： The further technical scheme of the present invention is: the specific steps of described step A. sample processing to be tested are as follows:
称取0.5～2.0克待测化妆品样本到具塞试管中，加入甲醇5.0～20.0mL振荡至分散，超声波提取10～15min，转速3500～4500rps，离心5～20min，取上清液过滤，得滤液。Weigh 0.5-2.0 grams of the cosmetic sample to be tested into a stoppered test tube, add 5.0-20.0 mL of methanol and oscillate to disperse, ultrasonically extract for 10-15 minutes at a speed of 3500-4500 rps, centrifuge for 5-20 minutes, take the supernatant and filter to obtain the filtrate .
本发明的进一步技术方案是： 在步骤B5. 本底数据库的降维中，所述的体系主成分数目确定的方法为： The further technical scheme of the present invention is: In step B5. In the dimensionality reduction of the background database, the method for determining the number of principal components of the system is:
在标准化的样本中添加一定强度的白噪声蔽不均匀噪声和非线性因素的干扰，以二阶差分值序列的折点判断独立变量数目，得到体系主成分数目q。Add a certain intensity of white noise to the standardized sample to mask the interference of non-uniform noise and nonlinear factors, judge the number of independent variables by the break point of the second-order difference value sequence, and obtain the number q of the principal components of the system.
本发明的进一步技术方案是：在步骤B5. 本底数据库的降维中，所述的将本底光谱数据库W降到适当的维数的方法如下： The further technical scheme of the present invention is: in step B5. in the dimensionality reduction of background database, the described method that background spectrum database W is reduced to appropriate dimension is as follows:
应用[U，S，V] = svd(W)对本底光谱数据库W进行奇异值分解降维，分解后得到m阶行正交矩阵U、n阶列正交矩阵V和奇异值矩阵S，取U的前q列，为降维后的本底数据库N。Apply [U, S, V] = svd(W) to perform singular value decomposition on the background spectral database W to reduce the dimensionality. After decomposition, the m-order row orthogonal matrix U, the n-order column orthogonal matrix V and the singular value matrix S are obtained. The first q columns of U are the base database N after dimensionality reduction.
本发明的进一步技术方案是：所述的步骤C.对羟基苯甲酸酯的标准光谱数据库v获取的具体内容为： The further technical scheme of the present invention is: the specific content that described step C. the standard spectrum databasev of parabens obtains is:
定量配制系列浓度的对羟基苯甲酸酯-甲醇溶液，分别记录各溶液的浓度和190nm-650nm波长范围光谱，记入标准光谱数据库；选择225nm-350nm波长范围光谱，并按系列对羟基苯甲酸酯均以对羟基苯甲酸含量计，进行多变量最小二乘回归，得到对羟基苯甲酸酯的标准光谱数据库v。Quantitatively prepare paraben-methanol solutions with a series of concentrations, record the concentration of each solution and the spectrum in the 190nm-650nm wavelength range, and record them in the standard spectrum database; select the spectrum in the 225nm-350nm wavelength range, and record the The acid esters were all calculated according to the content of p-hydroxybenzoic acid, and the multivariate least squares regression was performed to obtain the standard spectral databasev of p-hydroxybenzoic acid esters.
本发明的再进一步技术方案是：所述的步骤E.待测化妆品样本中羟基苯甲酸酯含量测定的具体步骤如下： The further technical scheme of the present invention is: described step E. The specific steps of the content determination of hydroxybenzoate in the cosmetic sample to be tested are as follows:
(1) 依据定量精度设定扣减步长Δ；(1) Set the deduction step size Δ according to the quantitative accuracy;
(2) 在算式 
所述的yi表示在i波长下对羟基苯甲酸酯的吸光度值，ai、bi是常数，x表示对羟基苯甲酸的浓度，v1表示在浓度为x1时对羟基苯甲酸酯的多波长吸光度值y1，v1为所有的yi值组成的矩阵；Theyi represent the absorbance value of parabens at wavelengthi ,aiand bi are constants,x represents the concentration of p-hydroxybenzoic acid, v1 represents p-hydroxybenzoic acid when the concentration isx1 The multi-wavelength absorbance valuey1 of the acid ester, v1 is a matrix composed of allyi values;
(3) 从待测化妆品样本光谱数据a中扣除v1/Δ，扣除后的变量记为da；把本底光谱数据库N和变量da合并后记为对比空间M，计算对比空间M与v1夹角；(3) Deduct v1 /Δ from the spectral dataa of the cosmetic sample to be tested, and record the deducted variable as da ; combine the background spectral databaseN and the variable da and record it as the comparison space M, and calculate the comparison space M andv1 Angle;
(4) 从待测化妆品样本光谱数据a中逐步扣除v1后，重复步骤（3）；(4) After gradually deductingv1 from the spectral dataa of the cosmetic sample to be tested, repeat step (3);
(5) 当待测化妆品样本中的对羟基苯甲酸酯完全被扣除后，比对空间M和对羟基苯甲酸酯的光谱向量v1的空间夹角值会出现最大值θmax，记录空间夹角最大值θmax出现时对应的扣减步数λ，通过对羟基苯甲酸的浓度x1和扣减步数估算化妆品样本中对羟基苯甲酸酯的含量Y1，计算式为Y1= x1×λ/Δ，得到的Y1即为待测化妆品样品中对羟基苯甲酸酯的含量值。(5) When the paraben in the cosmetic sample to be tested is completely deducted, the maximum value of the angle between the space M and the spectral vector v1 of the paraben will appear at the maximum value θmax , record The number of deduction steps λ corresponding to the maximum value of the included angle θmax appears, and the content of parabens in the cosmetic sample is estimated by the concentrationx1 of p-hydroxybenzoic acid and the number of deduction stepsY1 , and the calculation formula isY1 =x1 ×λ/Δ, the obtainedY1 is the content value of parabens in the cosmetic sample to be tested.
在步骤(5)中，若Y1值与x1值相差较大，则带入一个与Y1相接近的x2重新计算。 In step (5), if the difference between the value ofY1 and the value ofx1 is large, bring in a value ofx2 that is close toY1 to recalculate.
由于采用上述结构，本发明之化妆品中对羟基苯甲酸酯的快速测定方法与现有技术相比，具有以下有益效果： Owing to adopting above-mentioned structure, compared with prior art, the fast assay method of parabens in cosmetics of the present invention has following beneficial effect:
1. 分析效率高、操作强度小：1. High analysis efficiency and low operation intensity:
由于本发明采用紫外多波长直接测定，直接定量对羟基苯甲酸酯，不需要分离时间，而且样本测量及定量计算时间小于10秒，其分析效率较高，操作强度较小，非常适合于同类大批量样本的快速分析测定。Since the present invention adopts ultraviolet multi-wavelength direct measurement and direct quantification of parabens, no separation time is required, and the sample measurement and quantitative calculation time is less than 10 seconds, the analysis efficiency is high, and the operation intensity is small, which is very suitable for similar Rapid analytical determination of large batches of samples.
2. 分析成本低： 2. Low analysis cost:
由于本发明是基于本底光谱集、待测光谱和样本光谱间矩阵向量角标准，通过逐量扣减方式实现定量，可以采用最常见的一阶光谱仪器的输出数据，没有对数据维数提出特别要求，因此，本发明无需特殊仪器设备，而且试剂消耗量显著降低，从而降低了分析成本。Since the present invention is based on the matrix vector angle standard between the background spectrum set, the spectrum to be measured, and the sample spectrum, the quantification is realized through the method of gradual subtraction, and the output data of the most common first-order spectrometer can be used, and no data dimension is proposed. Special requirements, therefore, the present invention does not require special instruments and equipment, and the consumption of reagents is significantly reduced, thereby reducing the analysis cost.
3．无需积累不含被测组分的本底数据库： 3. Eliminates the need to accumulate background databases that do not contain analytes:
由于化妆品种类繁多，原料复杂，建立完整的本底数据库工作量大，从而影响分析精度和方法的适用性。而本发明提出借助高效液相色谱-光谱联用方法，分离测取化妆品样本各个色谱时刻的一维谱后，进行分类，获得不含被测组分的本底数据，结合向量-子空间夹角判据算法实现样本中被测组分的分析。因此，本发明无需积累不含被测组分的本底数据库，不仅减小了工作量，而且也提高了分析精度，扩大了方法的适用性。Due to the wide variety of cosmetics and complex raw materials, the workload of establishing a complete background database is heavy, which affects the accuracy of analysis and the applicability of the method. However, the present invention proposes to use high performance liquid chromatography-spectroscopy method to separate and measure the one-dimensional spectrum of each chromatographic moment of the cosmetic sample, and then classify it to obtain the background data that does not contain the measured components. The angle criterion algorithm realizes the analysis of the measured components in the sample. Therefore, the present invention does not need to accumulate background databases that do not contain measured components, which not only reduces the workload, but also improves the analysis precision and expands the applicability of the method.
4．可降低机时和试剂损耗： 4. Can reduce machine time and reagent loss:
对于同类样品的测定，本发明在进行一次色谱分离后，无需再利用联用仪器累积本底，仅通过光谱测量即可实现定量，从而可降低机时和试剂损耗。For the determination of similar samples, the present invention does not need to use a combined instrument to accumulate the background after a chromatographic separation, and can realize quantification only through spectral measurement, thereby reducing machine time and reagent loss.
5. 稳健性好： 5. Good robustness:
本发明与现有的单波长、双波长及若干个波长方法相比，抗干扰能力强，可辨识复杂程度高，稳健性好。Compared with the existing single-wavelength, double-wavelength and several-wavelength methods, the present invention has strong anti-interference ability, high identification complexity and good robustness.
6. 方法简单： 6. The method is simple:
本发明的分析方法比较简单，无复杂步骤，易于推广应用。The analysis method of the present invention is relatively simple, has no complicated steps, and is easy to popularize and apply.
下面，结合附图和实施例对本发明之化妆品中对羟基苯甲酸酯的快速测定方法的技术特征作进一步的说明。 Below, the technical characteristics of the rapid assay method for parabens in cosmetics of the present invention will be further described in conjunction with the accompanying drawings and examples. the
附图说明Description of drawings
图1：步骤B3中经过数据转化后的化妆品样本二维谱图， Figure 1: The two-dimensional spectrogram of the cosmetic sample after data conversion in step B3,
图1中的横坐标标为时间（单位：min），纵坐标为波长（单位；nm）；竖坐标为吸光度；The abscissa in Figure 1 is time (unit: min), the ordinate is wavelength (unit: nm); the vertical axis is absorbance;
图2：化妆品样本对照品的液相色谱图；Figure 2: Liquid chromatogram of cosmetic sample control substance;
图3：化妆品样本在256nm处的液相色谱图，Figure 3: Liquid chromatogram of a cosmetic sample at 256nm,
图3中的横坐标为时间（单位：min），纵坐标为吸光度；The abscissa in Figure 3 is time (unit: min), and the ordinate is absorbance;
图 4 ：空间夹角值与扣减次数之间的曲线图。Figure 4: Curves between the spatial angle value and the number of subtractions.
具体实施方式Detailed ways
实施例一：Embodiment one:
一种化妆品中对羟基苯甲酸酯的快速测定方法，包括以下步骤：A rapid assay method for parabens in cosmetics, comprising the following steps:
A.待测样本处理：A. Processing of samples to be tested:
将待测化妆品样本用甲醇萃取过滤，其具体操作为：称取1.00克样品到具塞试管中，加入甲醇10.0mL振荡至分散，超声波提取15min；转速4000rps，离心10min，取上清液过滤，得化妆品滤液。Extract and filter the cosmetic sample to be tested with methanol. The specific operation is as follows: weigh 1.00 g of the sample into a stoppered test tube, add 10.0 mL of methanol to oscillate until dispersed, extract by ultrasonic wave for 15 min; rotate at 4000 rps, centrifuge for 10 min, take the supernatant and filter, A cosmetic filtrate was obtained.
B. 本底光谱数据库的建立： B. The establishment of the background spectrum database:
B1. 获取化妆品样本的光谱数据：B1. Obtain spectral data of cosmetic samples:
将步骤A制得的化妆品滤液经高效液相色谱分析，采集多个化妆品样本的多波长光谱数据；The cosmetic filtrate prepared in step A is analyzed by high performance liquid chromatography, and multi-wavelength spectral data of multiple cosmetic samples are collected;
B2. 获取待测组分的光谱数据：B2. Obtain the spectral data of the component to be measured:
配制10mg/L的对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯混合甲醇溶液，过滤后用于高效液相色谱分析，获取被测组分对羟基苯甲酸酯的多波长光谱数据。Prepare a 10mg/L mixed methanol solution of methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, and propyl p-hydroxybenzoate, filter it and use it for high-performance liquid chromatography analysis to obtain the measured component p-hydroxybenzoate multi-wavelength spectral data.
步骤B1、B2中高效液相色谱条件为： The high performance liquid chromatography condition in step B1, B2 is:
色谱柱：Pgrandsil-STC C18色谱柱（4.6mm×150mm）；Chromatographic column: Pgrandsil-STC C18 chromatographic column (4.6mm×150mm);
梯度洗脱，流动相：Gradient elution, mobile phase:
0～25min，乙腈：0.02mol/L乙酸铵水溶液=20:80～50:50（V /V） 0～25min, acetonitrile: 0.02mol/L ammonium acetate aqueous solution=20:80～50:50 (V /V)
25～35min，乙腈：水=5:95～15:85（V /V）；25～35min, acetonitrile: water=5:95～15:85 (V/V);
35～55min，乙腈：异丙醇=50:50～80:20（V /V）；35～55min, acetonitrile:isopropanol=50:50～80:20 (V/V);
55～65min，乙腈：水=5:95～15:85（V /V）55～65min, acetonitrile: water=5:95～15:85 (V/V)
流速1mL/min；进样量：20μL；柱温：20℃；紫外检测波长：190～380nm。Flow rate: 1mL/min; injection volume: 20μL; column temperature: 20°C; UV detection wavelength: 190-380nm.
B3. 转化数据格式： B3. Convert data format:
将步骤B1和B2中采集所得的化妆品样本的多波长光谱数据和待测组分的多波长光谱数据由光强数据格式转化成不同时间下多波长下的吸光度值，转化后的数据的每一行代表一个波长下的色谱数据，每一列代表一个时刻下洗脱出来物质的光谱数据（参见图1）。B1步骤中的化妆品样本的光谱数据经数据转化后得到化妆品样本的光谱数据；B2步骤中的待测组分的光谱数据经数据转化后得到对羟基苯甲酸酯标准物质的光谱数据；Convert the multi-wavelength spectral data of the cosmetic samples collected in steps B1 and B2 and the multi-wavelength spectral data of the components to be measured from the light intensity data format into absorbance values at multiple wavelengths at different times, and each row of the converted data Represents the chromatographic data at one wavelength, and each column represents the spectral data of the eluted substance at one moment (see Figure 1). The spectral data of the cosmetic sample in the B1 step is converted to obtain the spectral data of the cosmetic sample; the spectral data of the component to be measured in the B2 step is converted to obtain the spectral data of the paraben standard substance after data conversion;
B4．获取不含待测组分的背景的光谱数据：B4. Obtain spectral data for a background free of analytes:
确定被测组分、被测组分与本底组分完全分离的液相色谱条件。在此条件下对样本进行分析，得到待测的化妆品样本和对照品样本的液相色谱图。图2为对照品的液相色谱图。其中三种酯的出峰时间分别为甲酯3.9～4.8min、乙酯6.0～7.3min、丙酯12.0～13.5min。图3为其中一种化妆品样本的液相色谱图。经分析对比，图3中A为甲酯、B为乙酯、C为丙酯，其他的色谱峰为化妆品样本中相对于对羟基苯甲酸酯的本底物质。从化妆品样本的色谱图中扣除与对羟基苯甲酸酯标准物质具有相同保留时间的光谱数据，其余数据存入本底光谱数据库中；合并多个化妆品样本的本底光谱数据库构成本底光谱数据库W；Determine the liquid chromatographic conditions for the complete separation of the measured components and the measured components from the background components. Analyze the sample under these conditions to obtain the liquid chromatograms of the cosmetic sample to be tested and the reference sample. Fig. 2 is the liquid chromatogram of reference substance. The peak eluting times of the three esters are respectively 3.9-4.8 min for methyl ester, 6.0-7.3 min for ethyl ester and 12.0-13.5 min for propyl ester. Figure 3 is a liquid chromatogram of one of the cosmetic samples. After analysis and comparison, in Figure 3, A is methyl ester, B is ethyl ester, and C is propyl ester. The other chromatographic peaks are background substances in cosmetic samples relative to parabens. The spectral data with the same retention time as the paraben standard substance is deducted from the chromatogram of the cosmetic sample, and the remaining data are stored in the background spectrum database; the background spectrum database of multiple cosmetic samples is combined to form the background spectrum database W;
B5. 本底数据库的降维：B5. Dimensionality reduction of the background database:
步骤B4得到的数据库W数据量大，会导致计算量很大。将步骤B4中所得的本底光谱数据库W进行奇异值分解，根据体系主成分数目将本底光谱数据库W降到适当的维数，得到本底光谱数据库N；The database W obtained in step B4 has a large amount of data, which will lead to a large amount of calculation. Singular value decomposition is performed on the background spectral database W obtained in step B4, and the background spectral database W is reduced to an appropriate dimension according to the number of principal components of the system to obtain the background spectral database N;
所述的体系主成分数目确定的方法为：The method for determining the number of principal components of the system is:
在标准化的样本中添加一定强度的白噪声蔽不均匀噪声和非线性因素的干扰，以二阶差分值序列的折点判断独立变量数目，得到体系主成分数目q。Add a certain intensity of white noise to the standardized sample to mask the interference of non-uniform noise and nonlinear factors, judge the number of independent variables by the break point of the second-order difference value sequence, and obtain the number q of the principal components of the system.
所述的将本底光谱数据库W降到适当的维数的方法如下： The described method of reducing the background spectral database W to an appropriate dimension is as follows:
应用[U，S，V] = svd(W)对本底光谱数据库W进行奇异值分解降维，分解后得到m阶行正交矩阵U、n阶列正交矩阵V和奇异值矩阵S，取U的前q列，为降维后的本底数据库N。Apply [U, S, V] = svd(W) to perform singular value decomposition on the background spectral database W to reduce the dimensionality. After decomposition, the m-order row orthogonal matrix U, the n-order column orthogonal matrix V and the singular value matrix S are obtained. The first q columns of U are the base database N after dimensionality reduction.
C. 获取对羟基苯甲酸酯的标准光谱数据库v： C. Obtain the standard spectral database v of parabens:
分别配制一系列浓度为0.2mg/L-12.0mg/L的对羟基苯甲酸甲、乙、丙酯的甲醇溶液，分别记录各溶液的浓度和190nm-650nm波长范围光谱，记入标准光谱数据库。选择225nm-350nm波长范围光谱，对羟基苯甲酸甲、乙、丙酯按对羟基苯甲酸含量计，经多变量最小二乘回归后得到对羟基苯甲酸酯的标准光谱数据库v。Prepare a series of methanol solutions of methyl, ethyl, and propyl p-hydroxybenzoate with a concentration of 0.2mg/L-12.0mg/L, respectively record the concentration of each solution and the spectrum in the wavelength range of 190nm-650nm, and record them in the standard spectrum database. Select the spectrum in the wavelength range of 225nm-350nm, and the methyl, ethyl, and propyl p-hydroxybenzoates are calculated according to the content of p-hydroxybenzoic acid, and the standard spectral databasev of p-hydroxybenzoic acid esters is obtained after multivariate least squares regression.
D. 待测化妆品样本光谱测量： D. Spectral measurement of the cosmetic sample to be tested:
将步骤A处理后制得的化妆品滤液依照吸光度的线性范围，定量移取滤液，用甲醇稀释定容至5～20mL容量瓶中，采用多波长紫外-可见光纤光谱仪进行光谱测量，得到待测化妆品样本光谱数据a；According to the linear range of absorbance, quantitatively pipette the filtrate from the cosmetic filtrate obtained after the treatment in step A, dilute the filtrate with methanol to a 5-20mL volumetric flask, and use a multi-wavelength ultraviolet-visible optical fiber spectrometer to perform spectrum measurement to obtain the cosmetic to be tested Sample spectral data a;
E. 待测化妆品样本中羟基苯甲酸酯含量测定：E. Determination of paraben content in the cosmetic sample to be tested:
分别将步骤B、C、D所得的本底光谱数据库N、标准光谱数据库v、待测化妆品样本光谱数据a导入计算平台，应用向量-子空间夹角判据算法从待测化妆品样本光谱扣减对羟基苯甲酸酯的标准光谱，得出待测样本中对羟基苯甲酸酯的实际含量。Import the background spectral database N, the standard spectral database v, and the spectral data a of the cosmetic sample to be tested into the computing platform respectively, and apply the vector-subspace included angle criterion algorithm to subtract from the spectrum of the cosmetic sample to be tested The standard spectrum of parabens gives the actual content of parabens in the sample to be tested.
该步骤E的具体步骤如下： The concrete steps of this step E are as follows:
(1) 依据定量精度设定扣减步长Δ（本实施例为1000）；(1) Set the deduction step size Δ according to the quantitative accuracy (1000 in this example);
(2) 在算式
所述的yi表示在i波长下对羟基苯甲酸酯的吸光度值，ai、bi是常数，x表示对羟基苯甲酸的浓度，v1表示在浓度为x1时对羟基苯甲酸酯的多波长吸光度值y1，v1为所有的yi值组成的矩阵；Theyi represent the absorbance value of parabens at wavelengthi ,aiand bi are constants,x represents the concentration of p-hydroxybenzoic acid, v1 represents p-hydroxybenzoic acid when the concentration isx1 The multi-wavelength absorbance valuey1 of the acid ester, v1 is a matrix composed of allyi values;
(3) 从待测化妆品样本光谱数据a中扣除v1/Δ（本实施例是扣除Δv1=v1/1000），扣除后的变量记为da；把本底光谱数据库N和变量da合并后记为对比空间M，计算对比空间M与v1夹角；(3) Deduct v1 /Δ from the spectral dataa of the cosmetic sample to be tested (in this example, Δv1=v1 /1000 is deducted), and the variable after deduction is denoted as da ; the background spectral databaseN and the variable da are combined The postscript is the comparison space M, and the angle between the comparison space M andv1 is calculated;
(4) 从待测化妆品样本光谱数据a中逐步扣除v1后，重复步骤（3）；(4) After gradually deductingv1 from the spectral dataa of the cosmetic sample to be tested, repeat step (3);
(5) 当待测化妆品样本中的对羟基苯甲酸酯完全被扣除后比对空间M和对羟基苯甲酸酯的光谱向量v1空间夹角值会出现最大值θmax，记录空间夹角最大值θmax出现时对应的扣减步数λ，（参见图4，出现最大夹角是的扣减步数为976），这时通过对羟基苯甲酸的浓度x1和扣减步数化妆品样本中对羟基苯甲酸酯的含量Y1；计算式为Y1= x1×λ/Δ，得到的Y1即为待测化妆品样品中对羟基苯甲酸酯的含量值。若Y1值与x1值相差较大，则带入一个与Y1相接近的x2重新计算。(5) When the parabens in the cosmetic sample to be tested are completely deducted, the angle between the comparison space M and the spectral vector v1 of the parabens will have a maximum value θmax , and the space clip The number of deduction steps λ corresponding to the appearance of the maximum angle θmax , (see Figure 4, the number of deduction steps when the maximum angle appears is 976), at this time, the concentration of p-hydroxybenzoic acidx1 and the number of deduction steps The contentY1 of paraben in the cosmetic sample; the calculation formula isY1 =x1 ×λ/Δ, and the obtainedY1 is the content value of paraben in the cosmetic sample to be tested. If the value ofY1 is quite different from the value ofx1 , bring in a value ofx2 that is close toY1 to recalculate.
作为本实施例的一种变换，所述的步骤A中各参数还可变换，一般为： As a transformation of the present embodiment, each parameter in the described step A can also be transformed, generally as follows:
待测化妆品为0.5～2.0克，加入的甲醇为5.0～20.0mL，超声波提取10～15min，转速3500～4500rps，离心5～20min。The amount of cosmetics to be tested is 0.5-2.0 grams, the amount of methanol added is 5.0-20.0 mL, ultrasonic extraction is performed for 10-15 minutes, the rotation speed is 3500-4500 rps, and centrifugation is performed for 5-20 minutes.
为了验证本发明测定结构的准确性，选择了六种市售的洗发香波类的样本，通过高效液相色谱-紫外-可见光纤光谱仪联用建立本地数据库后，用本发明之化妆品中对羟基苯甲酸酯的快速测定方法测定化妆品样本中对羟基苯基酸的含量，并和高效液相色谱法结果比较（参见表1）。 In order to verify the accuracy of the present invention's determination structure, six commercially available shampoo samples were selected, and after the local database was established by the high performance liquid chromatography-ultraviolet-visible optical fiber spectrometer, the p-hydroxyl group in the cosmetics of the present invention was used to A rapid method for the determination of parabens was used to determine the content of p-hydroxybenzoic acid in cosmetic samples and compare with the results of HPLC (see Table 1). the
the
表1 两种方法测定样本中对羟基苯甲酸酯的含量Table 1 Two methods to determine the content of parabens in samples
本发明还进行了回收率实验，结果如表2所示。The present invention has also carried out the recovery rate experiment, and the results are shown in Table 2.
表2 回收率实验 Table 2 Recovery experiment
对B1平行六次实验，RSD值为1.045%。Six parallel experiments were performed on B1, and the RSD value was 1.045%.
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| CN103823004A (en)* | 2013-12-18 | 2014-05-28 | 广西科技大学 | Method for quickly measuring pigment and preservative in jelly |
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| CN109765326A (en)* | 2019-01-17 | 2019-05-17 | 广西科技大学 | Rapid detection method of Sudan red in pepper products |
| CN110618230A (en)* | 2019-10-17 | 2019-12-27 | 北京君德同创生物技术股份有限公司 | Method for detecting dodecyl paraben |
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