Method for simultaneously detecting 24 main spices in cosmetics

Abstract

The invention relates to the technical field of chemical instrument analysis, in particular to a method for simultaneously detecting 24 main spices in cosmetics, which comprises the following steps: preparing an acetonitrile extracting solution of a sample to be detected as a test solution; according to the steps, a blank matrix solution is prepared from a blank sample; calculating the concentration of the high-concentration series standard solution mixed with the 24 spices according to the required matrix standard curve point concentration, and preparing the high-concentration series standard solution mixed with the 24 spices; preparing a series of matrix standard solutions with the number corresponding to that of the standard curve points, wherein each matrix standard solution is prepared by mixing a large-volume blank matrix solution and a small-volume high-concentration standard solution; and carrying out on-machine analysis by adopting chromatography-mass spectrometry. According to the method, a large-volume blank matrix solution and a small-volume high-concentration standard solution are adopted to prepare a matrix standard solution with required value concentration, after the preparation is completed, the small volume can be ignored during final concentration calculation, the sensitivity is high, the precision is high, and the linear fitting degree is high.

Description

Technical Field

[0001] The invention relates to the technical field of chemical instrument analysis, and in particular to a method for simultaneously detecting 24 main spices in cosmetics. Background Art

[0002] At present, according to various previous documents, the detection of 24 kinds of flavors in cosmetics mainly uses gas chromatography-tandem single-rod mass spectrometry and gas chromatography-tandem triple quadrupole mass spectrometry. The inventors found in many experiments that the properties and polarities of the 24 flavor compounds vary greatly, and many of them are more susceptible to matrix effects. When preparing solvent standard curves, some compounds tend to tail, and the recovery rate of some compounds is too high due to the influence of matrix effects. Summary of the invention

[0003] The purpose of the present invention is to provide a method for simultaneously detecting 24 main flavors in cosmetics, using a matrix standard curve to correct the influence of the matrix effect, with accurate results and simple operation.

[0004] The solution adopted by the present invention to achieve the purpose is: a method for simultaneously detecting 24 main spices in cosmetics, characterized in that it includes the following steps:

[0005] (1) preparing an acetonitrile extract of the sample to be tested as the test solution;

[0006] (2) According to the steps of (1), a blank matrix solution is prepared using a blank sample;

[0007] (3) calculating the concentration of a high-concentration series standard solution of 24 kinds of mixed spices according to the required matrix standard curve point concentration, and preparing a high-concentration series standard solution of 24 kinds of mixed spices;

[0008] (4) preparing a series of matrix standard solutions corresponding to the number of calibration curve points, each of the matrix standard solutions being prepared by mixing a large volume of blank matrix solution and a small volume of high-concentration standard solution;

[0009] (5) Chromatography-mass spectrometry was used for on-machine analysis.

[0010] Preferably, the specific operation in step (1) is: weighing a certain amount of the sample to be tested, adding a saturated sodium chloride aqueous solution for vortex dispersion, then adding acetonitrile for ultrasonic extraction, and filtering the extract after removing water to obtain the test solution.

[0011] Preferably, in step (3), the concentration of the high concentration series standard solution is calculated according to the required matrix curve point concentration, and the calculation formula is as follows:

[0012] C=(ρ×V1) / V2

[0013] ρ: concentration of the matrix standard solution to be prepared, ug / mL;

[0014] V1: volume of blank matrix solution, mL;

[0015] V2: Volume of high concentration series standard solution, mL.

[0016] Preferably, V1 is 0.5 mL and V2 is 0.01 mL.

[0017] Preferably, in step (3), the concentrations of the high-concentration series standard solutions of the 24 spices mixed are 5 ng / mL, 10 ng / mL, 25 ng / mL, 50 ng / mL, 100 ng / mL, 250 ng / mL, 500 ng / mL, and 1000 ng / mL, respectively.

[0018] Preferably, in step (3), the 24 spices include limonene, benzyl alcohol, linalool, methyl 2-octynoate, citronellol, citral, geraniol, cinnamaldehyde, hydroxycitronellol, anise alcohol, cinnamyl alcohol, eugenol, coumarin, isoeugenol, α-isomethyl ionone, butylphenyl methylpropional, amyl cinnamaldehyde, hydroxyhexyl 3-cyclohexenyl carboxaldehyde, amyl cinnamyl alcohol, farnesol, hexyl cinnamaldehyde, benzyl benzoate, benzyl salicylate and benzyl cinnamate.

[0019] Preferably, in step (4), each of the matrix standard solutions is prepared by mixing a blank matrix solution and a high concentration standard solution in a volume ratio greater than or equal to 50:1.

[0020] Preferably, in step (4), the concentrations of the series of matrix standard solutions are: 0.1 ng / mL, 0.2 ng / mL, 0.5 ng / mL, 1.0 ng / mL, 2.0 ng / mL, 5.0 ng / mL, 10 ng / mL, 20 ng / mL, respectively.

[0021] Preferably, in step (5), the chromatographic conditions are: the chromatographic column is a HP-5ms column, 30m×0.25mm×0.25μm; column temperature: 80°C for 5 min, increased to 250°C at 10°C / min, and retained for 6 min; injection volume: 1μL; non-split injection, injection port temperature: 250°C.

[0022] Preferably, in step (5), the mass spectrometry conditions are: EI source, ion source temperature: 230; quadrupole temperature: 150°C; interface temperature: 250°C; and multiple reaction detection is performed.

[0023] The core principle of the method of the present invention is: take a certain volume of blank matrix solution, add a small volume (the volume of the small volume can be ignored when calculating the final concentration) of high-concentration standard solution, so that the concentration of the prepared matrix standard solution is the required value. It specifically includes: preparation of blank matrix solution, calculation of the concentration of high-concentration series standard solution, preparation of high-concentration series standard solution, preparation of series matrix standard solution, and preparation of sample solution for machine. The use of the matrix standard curve prepared by the present invention to detect 24 kinds of fragrances in cosmetics has the advantages of simple preparation (nitrogen blowing step can be omitted), saving experimental consumables and blank base mass, and it has been confirmed that the method of the present invention has the advantages of high sensitivity, high precision and high linear fit.

[0024] The traditional method of preparing the matrix standard curve is to take 1 mL of blank matrix solution, blow it dry with nitrogen, add the standard solution, and then adjust the volume to 1 mL. The method of the present invention does not require nitrogen blowing, which can save time and simplify the preparation of the standard curve.

[0025] The present invention has the following advantages and beneficial effects:

[0026] In the method of the present invention, a large volume of blank matrix solution and a small volume of high concentration standard solution are used to prepare a matrix standard solution of the required concentration, and after the preparation is completed, the volume of the small volume can be ignored when the final concentration is calculated. The matrix standard curve prepared by the present invention is used to detect 24 kinds of fragrances in cosmetics, which has the advantages of simple preparation (the nitrogen blowing step can be omitted), saving experimental consumables and blank base mass, and it is confirmed that the method of the present invention has the advantages of high sensitivity, high precision and high linear fit. DETAILED DESCRIPTION

[0027] For a better understanding of the present invention, the following examples are provided to further illustrate the present invention, but the present invention is not limited to the following examples.

[0028] Example 1

[0029] A method for simultaneously detecting 24 main flavors in cosmetics comprises the following steps:

[0030] (1) Preparation of the test solution: Weigh 0.2 g of the sample into a 10 mL stoppered colorimetric tube, add 1 mL of saturated sodium chloride aqueous solution, vortex to disperse the sample, add 10 mL of acetonitrile and ultrasonically extract for 30 min. Dehydrate the extract with anhydrous sodium sulfate, filter through a 0.22 μm microporous membrane, take 0.5 mL of the filtrate and add 0.01 mL of acetonitrile to obtain the test solution.

[0031] (2) Preparation of blank matrix solution: Weigh 0.2 g of blank sample and treat it in the same way as the sample solution to prepare a blank matrix solution.

[0032] (3) Preparation steps of matrix standard curve:

[0033] A1. Calculate the concentration of high-concentration series standard solution: Calculate the concentration of high-concentration series standard solution according to the required matrix curve point concentration. The calculation formula is as follows:

[0034] C=(ρ×V1) / V2

[0035] ρ: concentration of the matrix standard solution to be prepared, ug / mL;

[0036] V1: volume of matrix solution, mL (0.5 mL in this invention);

[0037] V2: The volume of the high concentration series standard solution, mL (0.01 mL in this invention).

[0038] Use solvent to prepare high concentration series standard solutions: Use acetonitrile to gradually dilute the standard solution to prepare the corresponding series of standard solutions: 5ng / mL, 10ng / mL, 25ng / mL, 50ng / mL, 100ng / mL, 250ng / mL, 500ng / mL, 1000ng / mL of 24 kinds of flavor mixed standard solutions.

[0039] A2. Preparation of series matrix standard solutions: Take the injection vials corresponding to the number of calibration curve points, and add 0.5mL of blank matrix solution to each injection vial with a 1mL pipette. Then add 0.01mL of high concentration series standard solution to obtain series matrix standard solutions with concentrations of 0.1ng / mL, 0.2ng / mL, 0.5ng / mL, 1.0ng / mL, 2.0ng / mL, 5.0ng / mL, 10ng / mL, and 20ng / mL.

[0040] A3. Preparation of sample solution: Take 0.5 mL of the test solution and add 0.01 mL of acetonitrile.

[0041] (4) Perform analysis on the machine according to the following chromatographic and mass spectrometric conditions.

[0042] Chromatographic conditions: the chromatographic column is an HP-5ms column, 30m×0.25mm×0.25μm; column temperature: 80℃ for 5min, increased to 250℃ at 10℃ / min, and retained for 6min; injection volume: 1μL; non-split injection, injection port temperature: 250℃.

[0043] Mass spectrometry conditions: EI source, ion source temperature: 230; quadrupole temperature: 150°C; interface temperature: 250°C; multiple reaction detection.

[0044] The ion pair parameters are shown in the following table:

[0045] Table 1. Reference retention times and ion pair parameters for 24 compounds (fragrances).

[0046]

[0047]

[0048] Table 2. Linearity and correlation coefficients of 24 compounds

[0049]

[0050]

[0051] From the data in Table 2, it can be seen that the correlation coefficients of the calibration curves obtained by the standard series solutions prepared by the method of the present invention are all greater than 0.99 and have good linear shapes, which meet the requirements of the gas chromatography-mass spectrometry for the correlation coefficient of the calibration curve.

[0052] Detection Limit:

[0053] Select cosmetic samples, add 24 kinds of fragrance standard solutions of corresponding concentrations, and obtain the method detection limits as shown in Table 3 below:

[0054] Table 3. Detection limits of 24 spices:

[0055] Recovery rate:

[0056] Select cosmetic samples, add 24 kinds of fragrance standard solutions of corresponding concentrations, and obtain the recovery rate data as shown in Table 4 below:

[0057] Table 4.24 spices spiked recovery table:

[0058]

[0059]

[0060]

[0061] It can be seen from the data in Table 4 that the recovery rate of 24 kinds of fragrances in cosmetics detected by the method of preparing the matrix standard solution of the present invention is 70-120%, which meets the requirements of the detection method.

[0062] Precision:

[0063] For a sample of a certain concentration level (certified standard substances can be used), n parallel samples are measured in the laboratory, and the relative standard deviation (RSD%) in the laboratory should meet the requirements of the method;

[0064] The results of 6 parallel samples are shown in Table 5:

[0065] Table 5 Results of 6 parallel samples

[0066]

[0067]

[0068] From the data in Table 5, it can be seen that the method of the present invention has a high linear fitting degree, which indicates that the method of the present invention has high reliability, high data accuracy, high sensitivity and high precision.

[0069] The above is only a preferred embodiment of the present invention, which certainly cannot be used to limit the scope of rights of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and changes can be made without departing from the principle of the present invention, and these improvements and changes are also regarded as the protection scope of the present invention.

Claims

1. A method for simultaneously detecting 24 main spices in cosmetics, characterized in that: The following steps are involved: (1) preparing an acetonitrile extract of the sample to be tested as the test solution; (2) Prepare a blank matrix solution using a blank sample according to the steps of (1); (3) calculating the concentration of a high-concentration series standard solution of 24 kinds of mixed spices according to the required matrix standard curve point concentration, and preparing a high-concentration series standard solution of 24 kinds of mixed spices; (4) preparing a series of matrix standard solutions corresponding to the number of calibration curve points, each of the matrix standard solutions being prepared by mixing a large volume of blank matrix solution and a small volume of high-concentration standard solution; (5) Chromatography-mass spectrometry was used for on-machine analysis.

2. The method for simultaneously detecting 24 main spices in cosmetics according to claim 1, characterized in that: The specific operation in step (1) is: weigh a certain amount of the sample to be tested, add a saturated sodium chloride aqueous solution for vortex dispersion, then add acetonitrile for ultrasonic extraction, and filter the extract after removing water to obtain the test solution.

3. The method for simultaneously detecting 24 main spices in cosmetics according to claim 1, characterized in that: In step (3), the concentration of the high concentration series standard solution is calculated according to the required matrix curve point concentration, and the calculation formula is as follows: C=(ρ×V1) / V2 ρ: concentration of the matrix standard solution to be prepared, ug / mL; V1: volume of blank matrix solution, mL; V2: Volume of high concentration series standard solution, mL.

4. The method for simultaneously detecting 24 main spices in cosmetics according to claim 3, characterized in that: V1 is 0.5mL and V2 is 0.01mL.

5. The method for simultaneously detecting 24 main spices in cosmetics according to claim 1, characterized in that: In step (3), the concentrations of the high-concentration series standard solutions of the 24 spices mixed are 5 ng / mL, 10 ng / mL, 25 ng / mL, 50 ng / mL, 100 ng / mL, 250 ng / mL, 500 ng / mL, and 1000 ng / mL, respectively.

6. The method for simultaneously detecting 24 main spices in cosmetics according to claim 1, characterized in that: In step (3), the 24 spices include limonene, benzyl alcohol, linalool, methyl 2-octynoate, citronellol, citral, geraniol, cinnamaldehyde, hydroxycitronellol, anise alcohol, cinnamyl alcohol, eugenol, coumarin, isoeugenol, α-isomethyl ionone, butylphenyl methylpropional, amyl cinnamaldehyde, hydroxyhexyl 3-cyclohexenyl carboxaldehyde, amyl cinnamyl alcohol, farnesol, hexyl cinnamaldehyde, benzyl benzoate, benzyl salicylate and benzyl cinnamate.

7. The method for simultaneously detecting 24 main spices in cosmetics according to claim 1, characterized in that: In step (4), each of the matrix standard solutions is prepared by mixing a blank matrix solution and a high concentration standard solution in a volume ratio greater than or equal to 50:

1.

8. The method for simultaneously detecting 24 main spices in cosmetics according to claim 1, characterized in that: In step (4), the concentrations of the series of matrix standard solutions are: 0.1 ng / mL, 0.2 ng / mL, 0.5 ng / mL, 1.0 ng / mL, 2.0 ng / mL, 5.0 ng / mL, 10 ng / mL, and 20 ng / mL, respectively.

9. The method for simultaneously detecting 24 main spices in cosmetics according to claim 1, characterized in that: In the step (5), the chromatographic conditions are as follows: the chromatographic column is a HP-5ms column, 30m×0.25mm×0.25μm; the column temperature is maintained at 80°C for 5 min, increased to 250°C at 10°C / min, and retained for 6 min; the injection volume is 1 μL; non-split injection, the injection port temperature is 250°C.

10. The method for simultaneously detecting 24 main spices in cosmetics according to claim 1, characterized in that: In the step (5), the mass spectrometry conditions are: EI source, ion source temperature: 230; quadrupole temperature: 150°C; interface temperature: 250°C; and multiple reaction detection is performed.

Images