Method for detecting moss aldehyde in perfume

Abstract

The invention provides a method for detecting moss aldehyde in perfume. The method comprises the following steps: sampling; adding a first volume of the internal standard solution and a second volume of ethyl acetate into the to-be-detected sample, uniformly mixing, and carrying out ice-bath ultrasonic treatment for specified time to obtain an extraction solution; diluting and filtering the extracting solution to obtain a loading test solution; placing the loading test solution in gas chromatography-tandem mass spectrometry for qualitative and quantitative detection and analysis. According to the substance structure composition of the moss aldehyde, an ethyl acetate ultrasonic-assisted extraction method is adopted to carry out corresponding pretreatment on the moss aldehyde, an internal standard method is adopted to carry out analysis and determination through gas chromatography-tandem mass spectrometry (GC-MS / MS), specific identification is realized through characteristic ion pairs of the moss aldehyde, qualitative and quantitative analysis is carried out, and conditions and parameters of the method are optimized. The method has the characteristics of high-efficiency separation, stable base line and the like, has good repeatability and reproducibility, is accurate in quantification, simple and convenient to operate and high in speed, uses easily available equipment, and has high generalizability.

Description

Technical Field

[0001] This application relates to the field of chemical detection technology, and in particular to a method for detecting moss aldehyde in perfumes. Background Technology

[0002] In the cosmetics industry, fragrances are typically added to mask the odor of chemical ingredients, making them pleasant and comforting. This is especially true for perfumes, where fragrances not only enrich the scent but also determine the perfume's characteristics, longevity, complexity, and overall quality.

[0003] However, fragrances are also among the most common ingredients causing cosmetic allergies, often resulting in acute or chronic contact dermatitis. Furthermore, some natural plant fragrances can trigger allergic reactions, leading to skin inflammation, rashes, or dryness. Allergenic fragrances like oakmoss and tree moss are strictly restricted internationally, especially in the EU. However, these fragrances can mimic natural scents such as "earthy soil after rain" or "forest," so the European Commission, in the 7th amendment to the Cosmetic Regulations (Council Directive 76 / 768 / EEC), proposed maximum limits for 26 allergens in cosmetics. These limits require that their content (mass fraction) in leave-on cosmetics not exceed 0.001%, and in non-leave-on cosmetics not exceed 0.01%, and must be listed in the ingredient list.

[0004] On July 9, 2014, the European Union announced that it would officially ban three perfume ingredients starting in 2015 due to their potential to cause allergies. One of these ingredients is natural fragrance oakmoss, and one of the core components of natural fragrance oakmoss is moss aldehyde.

[0005] Currently, relevant testing reports include: determination of 24 allergens in cosmetics, content analysis of linalool and camphor in aromatic oils, component analysis of camphor tree essential oil, analysis of tobacco fragrances and flavors, determination of linalool content in honeysuckle, etc., but there are no reports on the detection and analysis methods of mossaldehyde in perfumes. Summary of the Invention

[0006] In view of the aforementioned problems, this application is made to provide a method for detecting moss aldehyde in perfumes that overcomes or at least partially solves the aforementioned problems.

[0007] A method for detecting moss aldehyde in perfumes, comprising the following steps:

[0008] sampling;

[0009] Add the first volume of internal standard solution and the second volume of ethyl acetate to the sample to be tested, mix well, and then sonicate in an ice bath for a specified time to obtain the extract.

[0010] The extract was diluted and filtered to obtain a test solution for use on the instrument;

[0011] The test solution was subjected to qualitative and quantitative detection and analysis by gas chromatography-tandem mass spectrometry.

[0012] The mass spectrometry parameters of the gas chromatography-tandem mass spectrometry include:

[0013] Scanning method: SRM scan;

[0014] Moss black aldehyde: parent ion: 152 m / z; daughter ions: 151 m / z, 77 m / z; collision voltage: 8 eV, 20 eV;

[0015] Internal standard solution: parent ion: 312 m / z; daughter ions: 152 m / z, 310 m / z; collision voltage 20 eV, 2 eV.

[0016] Furthermore, the chromatographic parameters of the gas chromatography-tandem mass spectrometry include:

[0017] Column: Agilent VF-17ms, 30m × 0.25mm, particle size 0.25μm.

[0018] Furthermore, the chromatographic column temperature is: 100℃ for 1 min, then increased to 200℃ at 10℃ / min, then increased to 260℃ at 30℃ / min, and held for 2 min.

[0019] Furthermore, the chromatographic parameters also include:

[0020] Carrier gas: Helium, purity ≥99.999%, flow rate: 1.0 mL / min;

[0021] Inlet temperature: 260℃;

[0022] Injection volume: 1 μL;

[0023] Injection mode: split injection, split ratio is 5.

[0024] Furthermore, the mass spectrometry parameters also include:

[0025] Electron impact source: 70 eV;

[0026] Transmission line temperature: 250℃;

[0027] Ion source temperature: 230℃;

[0028] Solvent delay: 3 min.

[0029] Furthermore, the sampling step includes:

[0030] Weigh 0.25g-0.5g of the sample to be tested into a stoppered colorimetric tube.

[0031] Furthermore, the first volume is 0.1 mL, and the second volume is 8 mL.

[0032] Furthermore, the internal standard solution is 1000 μg / mL 4,4-Dibromobipheny.

[0033] Furthermore, the specified time is 15 minutes.

[0034] Further, the step of diluting and filtering the extract to obtain the test solution includes:

[0035] The extract was diluted to 10 mL with ethyl acetate;

[0036] Take the supernatant and add 2g of anhydrous sodium sulfate for dehydration;

[0037] The solution was filtered using a 0.45 μm filter membrane to obtain the test solution for use.

[0038] This application has the following advantages:

[0039] In an embodiment of this application, a method for detecting moss aldehyde in a perfume includes the following steps: sampling; adding a first volume of internal standard solution and a second volume of ethyl acetate to the sample to be tested, mixing well, and then sonicating in an ice bath for a specified time to obtain an extract; diluting and filtering the extract to obtain a test solution; and placing the test solution in gas chromatography-tandem mass spectrometry for qualitative and quantitative detection and analysis; wherein the mass spectrometry parameters of the gas chromatography-tandem mass spectrometry include: scanning mode: SRM scan; moss aldehyde: parent ion: 152 m / z; daughter ions: 151 m / z, 77 m / z; collision voltage: 8 eV, 20 eV; internal standard solution: parent ion: 312 m / z; daughter ions: 152 m / z, 310 m / z; collision voltage: 20 eV, 2 eV. Based on the material structure and composition of moss black aldehyde, this application employs ethyl acetate ultrasonic-assisted extraction for pretreatment, uses the internal standard method, and analyzes and determines it by gas chromatography-tandem mass spectrometry (GC-MS / MS). Specific identification is achieved through characteristic ion pairs of moss black aldehyde for qualitative and quantitative analysis. The optimized method conditions and parameters enable efficient separation, baseline stability, good repeatability and reproducibility, accurate quantification, simple operation, high speed, and readily available equipment, making it highly scalable. Attached Figure Description

[0040] To more clearly illustrate the technical solution of this application, the drawings used in the description of this application will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0041] Figure 1 This is a flowchart illustrating the steps of a method for detecting moss aldehyde in perfume provided in an embodiment of this application;

[0042] Figure 2 This is a schematic diagram of the standard curve of mossine in perfume provided in the embodiments of this application;

[0043] Figure 3 This is a chromatogram of the standard curve concentration point of mossinaldehyde provided in the embodiments of this application, which is 100 ng / mL.

[0044] Figure 4 The standard curve chromatogram of moss aldehyde provided in this application embodiment has a concentration point of 200 ng / mL;

[0045] Figure 5 The standard curve chromatogram of moss aldehyde provided in this application embodiment has a concentration point of 500 ng / mL;

[0046] Figure 6 The standard curve chromatogram of mossinaldehyde provided in this application embodiment has a concentration point of 1000 ng / mL;

[0047] Figure 7 The standard curve chromatogram of moss aldehyde provided in this application embodiment has a concentration point of 2000 ng / mL;

[0048] Figure 8 This is a chromatogram of the characteristic ion pairs (152 / 151) and (152 / 77) in the perfume sample provided in the embodiments of this application;

[0049] Figure 9 This is a chromatogram of the characteristic ion pairs (152 / 151) and (152 / 77) in the spiked perfume sample provided in the embodiments of this application. Detailed Implementation

[0050] To make the objectives, features, and advantages of this application more apparent and understandable, the application will be further described in detail below with reference to the accompanying drawings and specific embodiments. Obviously, the described embodiments are only some, not all, of the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without inventive effort are within the scope of protection of this application.

[0051] Reference Figure 1 The flowchart illustrates the steps of a method for detecting moss aldehyde in perfume according to an embodiment of this application.

[0052] The detection method includes:

[0053] S110, Sampling;

[0054] S120. Add the first volume of internal standard solution and the second volume of ethyl acetate to the sample to be tested, mix well, and then sonicate in an ice bath for a specified time to obtain the extract.

[0055] S130. The extract is diluted and filtered to obtain a test solution for use on the instrument.

[0056] S140. Place the test solution into gas chromatography-tandem mass spectrometry for qualitative and quantitative detection and analysis.

[0057] The mass spectrometry parameters of the gas chromatography-tandem mass spectrometry include:

[0058] Scanning method: SRM scan;

[0059] Moss black aldehyde: parent ion: 152 m / z; daughter ions: 151 m / z, 77 m / z; collision voltage: 8 eV, 20 eV;

[0060] Internal standard solution: parent ion: 312 m / z; daughter ions: 152 m / z, 310 m / z; collision voltage 20 eV, 2 eV.

[0061] In an embodiment of this application, a method for detecting moss aldehyde in a perfume includes the following steps: sampling; adding a first volume of internal standard solution and a second volume of ethyl acetate to the sample to be tested, mixing well, and then sonicating in an ice bath for a specified time to obtain an extract; diluting and filtering the extract to obtain a test solution; and placing the test solution in gas chromatography-tandem mass spectrometry for qualitative and quantitative detection and analysis; wherein the mass spectrometry parameters of the gas chromatography-tandem mass spectrometry include: scanning mode: SRM scan; moss aldehyde: parent ion: 152 m / z; daughter ions: 151 m / z, 77 m / z; collision voltage: 8 eV, 20 eV; internal standard solution: parent ion: 312 m / z; daughter ions: 152 m / z, 310 m / z; collision voltage: 20 eV, 2 eV. Based on the material structure and composition of moss black aldehyde, this application employs ethyl acetate ultrasonic-assisted extraction for pretreatment, uses the internal standard method, and analyzes and determines it by gas chromatography-tandem mass spectrometry (GC-MS / MS). Specific identification is achieved through characteristic ion pairs of moss black aldehyde for qualitative and quantitative analysis. The optimized method conditions and parameters enable efficient separation, baseline stability, good repeatability and reproducibility, accurate quantification, simple operation, high speed, and readily available equipment, making it highly scalable.

[0062] The following will further describe a method for detecting moss aldehyde in a perfume according to an exemplary embodiment.

[0063] As described in step S110, sampling is generally one of the important steps to extract a small amount of target substance from the target object for testing. It is an effective way to obtain various data from the target object without affecting its main properties. The amount of the analyte extracted needs to be sufficient for 3-5 tests. The sampling area selection process for the analyte during sampling should be random.

[0064] As an example, weigh 0.5g of the sample to be tested (0.25g for wax-based samples), accurate to 0.001g, into a 10mL stoppered colorimetric tube. Understandably, waxy perfumes contain a higher concentration of fragrance, so the sample weight can be reduced to avoid contaminating the instrument.

[0065] As described in step S120, a first volume of internal standard solution and a second volume of ethyl acetate are added to the sample to be tested, mixed well, and then sonicated in an ice bath for a specified time to obtain the extract.

[0066] Understandably, the internal standard solution has similar physical properties to the analyte. The purpose of adding the internal standard is to calibrate the data, because the target analyte is volatile and may be lost when the instrument runs the heating program. Adding a substance with similar physical properties as an internal standard for calibration can make the data more accurate.

[0067] Because perfume-like substances have a high water content, ethyl acetate is used as the extraction agent to minimize the extraction of water-soluble impurities, thus achieving a purification effect.

[0068] In this embodiment, the internal standard solution is 1000 μg / mL 4,4-Dibromobipheny (4,4'-dibromobiphenyl); the first volume is 0.1 mL, the second volume is 8 mL, and the specified time is 15 min.

[0069] As an example, accurately transfer 0.1 mL of 1000 μg / mL 4,4-Dibromo bipheny to 8 mL of ethyl acetate, vortex for 2 min to ensure the sample and extraction solvent are thoroughly mixed, and then perform ultrasonic extraction in an ice bath for 15 min (working frequency 20–43 kHz, 200 W).

[0070] As described in step S130, the extract is diluted and filtered to obtain a test solution for use.

[0071] As an example, the extract was diluted to 10 mL with ethyl acetate and centrifuged at 10,000 r / min for 15 min if necessary (if there was precipitate); the supernatant was dehydrated by adding 2 g of anhydrous sodium sulfate; and filtered through a 0.45 μm filter membrane to obtain the test solution for use.

[0072] Anhydrous sodium sulfate can remove moisture from the sample, allowing for more complete vaporization during instrument injection. When using a VF-17ms column, it is important to avoid allowing aqueous sample solutions to enter the column, thereby extending the column's lifespan.

[0073] As described in step S140, the test solution is placed in gas chromatography-tandem mass spectrometry for qualitative and quantitative detection and analysis.

[0074] The mass spectrometry parameters of the gas chromatography-tandem mass spectrometry include:

[0075] Column: Agilent VF-17ms, 30m × 0.25mm, particle size 0.25μm;

[0076] The column temperature was set at 100℃ for 1 min, then increased to 200℃ at a rate of 10℃ / min, and then increased to 260℃ at a rate of 30℃ / min, and held for 2 min.

[0077] Carrier gas: Helium, purity ≥99.999%, flow rate: 1.0 mL / min;

[0078] Inlet temperature: 260℃;

[0079] Injection volume: 1 μL;

[0080] Injection mode: split injection, split ratio of 5;

[0081] Mass spectrometry parameters include:

[0082] Electron impact source: 70 eV;

[0083] Transmission line temperature: 250℃;

[0084] Ion source temperature: 230℃;

[0085] Solvent delay: 3 min;

[0086] Scanning method: SRM mode;

[0087] Ionization mode, parent ion, daughter ion, declustering voltage, and collision energy are shown in Table 1 below:

[0088]

[0089] Specifically, the steps of placing the test solution in gas chromatography-tandem mass spectrometry for qualitative and quantitative detection and analysis include: establishing a series of standard curve solutions with concentrations of 100 ng / mL, 200 ng / mL, 500 ng / mL, 1000 ng / mL, and 2000 ng / mL, containing the same internal standard; then performing qualitative analysis on the test sample; calculating the content of moss aldehyde in the test sample based on the standard curve and chromatographic data, and performing quantitative analysis.

[0090] like Figure 2 The diagram shows a standard curve for gentamicin in perfume. The linear range of the standard curve is 100-2000 ng / mL. Figures 3-7 These are chromatograms of various concentration points on the standard curve.

[0091] The present invention will be further described in detail below with reference to specific implementation examples, but this does not limit the invention to the scope of the implementation examples.

[0092] Example: Spiked recovery test on perfume samples.

[0093] Weigh 0.5 g of the sample, accurate to 0.001 g, into a 10 mL stoppered colorimetric tube. Accurately transfer 0.1 mL of 1000 μg / mL 4,4-Dibromo biphenyrine solution, and simultaneously add 0.1 mL of 1000 μg / mL target analyte solution. Then add 8 mL of ethyl acetate, vortex for 2 min to ensure thorough mixing of the sample and extraction solvent, and sonicate in an ice bath for 15 min (operating frequency 20–43 kHz, 200 W). Dilute to 10 mL with ethyl acetate, shake well, and centrifuge at 10000 r / min for 15 min if necessary. Add 2 g of anhydrous sodium sulfate to the supernatant for dehydration, filter through a 0.45 μm filter membrane, and use the filtrate as the test solution. Then, perform qualitative and quantitative analysis of the filtrate using gas chromatography-tandem mass spectrometry.

[0094] like Figure 8 The chromatograms of the characteristic ion pairs (152 / 151) and (152 / 77) in the perfume sample are shown; Figure 9 The chromatograms show the characteristic ion pairs (152 / 151) and (152 / 77) in the spiked perfume sample. The figure demonstrates that this method achieves efficient separation and baseline stability. Spiked recovery tests on the samples showed a satisfactory recovery rate within the range of 60%–120%. The method exhibits good repeatability and reproducibility, and accurate quantification.

[0095] The detection amplification in this embodiment fills a market gap. The determination of moss aldehyde in perfume using gas chromatography-tandem mass spectrometry (GC-MS / MS) has excellent repeatability and reproducibility. It is simple to operate, fast, and the equipment used is readily available, making it highly scalable.

[0096] Although preferred embodiments of the present application have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments as well as all changes and modifications falling within the scope of the embodiments of the present application.

[0097] Finally, it should be noted that in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or terminal device that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or terminal device. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or terminal device that includes said element.

[0098] The above provides a detailed description of the method for detecting moss aldehyde in perfume provided by this application. Specific examples have been used to illustrate the principle and implementation of this application. The description of the above embodiments is only for the purpose of helping to understand the method and core idea of ​​this application. At the same time, for those skilled in the art, there will be changes in the specific implementation and application scope based on the idea of ​​this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A method for detecting mossaldehyde in perfume, characterized in that, Includes the following steps: sampling; Add the first volume of internal standard solution and the second volume of ethyl acetate to the sample to be tested, mix well, and then sonicate in an ice bath for a specified time to obtain the extract. The extract was diluted and filtered to obtain a test solution for use on the instrument; The test solution was subjected to qualitative and quantitative detection and analysis by gas chromatography-tandem mass spectrometry. The mass spectrometry parameters of the gas chromatography-tandem mass spectrometry include: Scanning method: SRM scan; Moss black aldehyde: parent ion: 152 m / z; daughter ions: 151 m / z, 77 m / z; collision voltage: 8 eV, 20 eV; Internal standard solution: parent ion: 312 m / z; daughter ions: 152 m / z, 310 m / z; collision voltage 20 eV, 2 eV.

2. The method for detecting mossaldehyde in perfume according to claim 1, characterized in that, The chromatographic parameters of the gas chromatography-tandem mass spectrometry include: Column: Agilent VF-17ms, 30m × 0.25mm, particle size 0.25μm.

3. The method for detecting mossaldehyde in perfume according to claim 2, characterized in that, The column temperature was set at 100℃ for 1 min, then increased to 200℃ at a rate of 10℃ / min, and then increased to 260℃ at a rate of 30℃ / min, and held for 2 min.

4. The method for detecting mossaldehyde in perfume according to claim 3, characterized in that, The chromatographic parameters also include: Carrier gas: Helium, purity ≥99.999%, flow rate: 1.0 mL / min; Inlet temperature: 260℃; Injection volume: 1 μL; Injection mode: split injection, split ratio is 5.

5. The method for detecting moss aldehyde in perfume according to claim 4, characterized in that, The mass spectrometry parameters also include: Electron impact source: 70 eV; Transmission line temperature: 250℃; Ion source temperature: 230℃; Solvent delay: 3 min.

6. The method for detecting mossaldehyde in perfume according to claim 1, characterized in that, The sampling steps include: Weigh 0.25g-0.5g of the sample to be tested into a stoppered colorimetric tube.

7. The method for detecting mossaldehyde in perfume according to claim 6, characterized in that, The first volume is 0.1 mL, and the second volume is 8 mL.

8. The method for detecting mossaldehyde in perfume according to claim 7, characterized in that, The internal standard solution was 1000 μg / mL of 4,4-Dibromobipheny.

9. The method for detecting moss aldehyde in perfume according to claim 8, characterized in that, The specified time is 15 minutes.

10. The method for detecting mossaldehyde in perfume according to claim 9, characterized in that, The steps of diluting and filtering the extract to obtain the test solution include: The extract was diluted to 10 mL with ethyl acetate; Take the supernatant and add 2g of anhydrous sodium sulfate for dehydration; The solution was filtered using a 0.45 μm filter membrane to obtain the test solution for use.

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