Method for analyzing source peculiar smell of 1, 3-butanediol in cosmetics

Abstract

The invention discloses a method for analyzing 1, 3-butanediol source peculiar smell in cosmetics, and aims to solve the problems of high subjectivity, low reproducibility and difficulty in identifying low-concentration peculiar smell components in the prior art for evaluating the peculiar smell of the cosmetics. According to the method, a sample is pretreated through an online solid-phase microextraction technology, and a key peculiar smell factor component spectrum library is established in combination with a gas chromatography-mass spectrometry and sniffing instrument combined technology, so that the scientificity and accuracy of peculiar smell evaluation are improved, and the method can be used for rapidly screening the quality of raw materials and pre-warning the peculiar smell risk of a product at the initial stage of research, development and production.

Description

Technical Field

[0001] The invention belongs to the technical field of cosmetics, and particularly relates to a method for analyzing odor derived from 1,3-butanediol in cosmetics. Background Art

[0002] In the field of cosmetic production technology, 1,3-butanediol has long been used in cosmetic formulas as a moisturizer due to its good water solubility, good skin feel, and moisturizing properties. At the same time, a large number of studies have shown that diols have certain antiseptic capabilities in cosmetics. Manufacturers of cosmetic active ingredients often use 1,3-butanediol as a substitute for preservatives and solvents. Therefore, the cumulative total content of 1,3-butanediol in cosmetic products is relatively high. However, as a fine chemical widely used in the chemical industry, 1,3-butanediol has large differences in production methods and purification processes among its source manufacturers. Although its purity can be controlled at more than 99%, the quality control of the odor of butanediol varies from manufacturer to manufacturer, which will affect the odor of the active ingredient raw material and the overall odor of the cosmetic product. However, to date, there has been no report on the detection method for cosmetic odor caused by butanediol raw materials.

[0003] At present, the evaluation of cosmetic odor is mainly carried out by artificial olfaction. Due to the difference in human perception, the perception threshold and description of the evaluator are easily affected by physiological and environmental factors, making the odor evaluation subjective and unable to form a unified measurement standard. In addition, the faint odor caused by butanediol cannot be directly identified by sensory organs in the early stage of formula product production, but the gradual increase in product odor during long-term storage will affect consumers' sensory experience. However, these odor substances do not exist in the relevant cosmetics testing standards, and conventional testing indicators cannot monitor and trace such odor substances. Therefore, how to make the odor evaluation objective and stable, and to predict its sensory quality in the early stage of product development or production, has become one of the problems plaguing the cosmetics industry.

[0004] In the field of analytical chemistry, the study of volatile components through precision analytical instruments and other means is of great significance for product odor control. Headspace-gas chromatography-mass spectrometry (HS-GC-MS) instruments can separate and identify compounds in complex mixtures, and can be used to analyze and identify various volatile components in chemical products. However, it is impossible to determine the direction of the odor from the perspective of compound identification alone, and the odor components usually have a very low olfactory threshold, and will cause obvious sensory differences when the content is low. The use of conventional headspace pretreatment methods makes it difficult for gas mass spectrometry detection limits to match the results of manual olfaction, making it difficult for cosmetics companies to use instrumental analysis for quality control of cosmetic odors. Summary of the invention

[0005] The purpose of the present invention is to overcome the defects of the prior art, provide a method for analyzing the odor originating from 1,3-butanediol in cosmetics, establish a spectral library of key odor substances originating from 1,3-butanediol, and solve the problems of strong subjectivity, low reproducibility and difficulty in identifying low-concentration odor components in the prior art of cosmetic odor evaluation.

[0006] The technical solution to achieve the above purpose is: a method for analyzing the odor of 1,3-butanediol in cosmetics, comprising the following steps:

[0007] Step S1, respectively collecting 1,3-butanediol raw materials of the abnormal odor batches to be tested, performing incubation pretreatment on the abnormal odor active material containing 1,3-butanediol by online solid phase microextraction technology (online-SPME), and after the incubation, the instrument automatically inserts the SPME fiber head into the gas chromatography mass spectrometry (GC-MS) injection port for analysis;

[0008] Step S2, the tail end of the chromatographic column of the gas chromatograph (GC) is connected to an olfactometer (ODP) and a mass spectrometer (MS) through a three-way connection, and odor smelling and non-targeted substance identification are performed simultaneously; according to the appearance time of the chromatographic peak, the olfactory evaluation results of each person are counted, and the average value is calculated to obtain the odor score corresponding to each GC-MS substance, and the corresponding peaks of the volatile substance components with an average odor score greater than or equal to 1 are deconvoluted and identified using the NIST spectral library to obtain key odor factor component substances and establish a corresponding odor component spectral library;

[0009] Step S3, conduct accelerated stability test on cosmetic products containing 1,3-butanediol raw materials or active ingredients containing 1,3-butanediol, take samples for pre-treatment using online-SPME technology, and then automatically perform GC-MS testing. After data processing using the deconvolution method, use the key odor component spectral library for qualitative identification to quickly determine whether the cosmetic product has the risk of odor.

[0010] In the above-mentioned method for analyzing the odor derived from 1,3-butanediol in cosmetics, in step S1, the parameters of the online-SPME technology are: taking 0.1-2 g of the abnormal odor raw material sample in a headspace bottle, the incubation temperature is 60°C, the SPME fiber material is preferably 65μm DVB / PDMS, the equilibrium adsorption time is 20min, and the online analysis time is preferably 10min.

[0011] In the above-mentioned method for analyzing the odor derived from 1,3-butanediol in cosmetics, in step S2, the parameter conditions of GC-MS are: the gas phase capillary column is HP-5ms (30m*250μm*0.25μm), the injection port temperature is 260°C, the split mode is non-split, the column oven starting temperature is 40°C, maintained for 1 min, then heated to 120°C at a heating rate of 5°C / min, maintained for 1 min, and then heated to 280°C at a heating rate of 10°C / min, the carrier gas is helium, the constant flow rate is 1.5mL / min, the mass spectrometry ion source is an electron bombardment ion source, the acquisition mode is full scan, the transmission line temperature is 280°C, the ion source temperature is 230°C, the quadrupole temperature is 150°C, and the mass scan range m / z is 29-500;

[0012] The parameters of the olfactometer are as follows: pipeline temperature is 280°C and the temperature of the olfactometer olfactory port is 150°C.

[0013] In the above-mentioned method for analyzing the odor derived from 1,3-butanediol in cosmetics, in step S2, each person's olfactory evaluation result is divided into 1 to 4 levels from weak to strong.

[0014] In the above-mentioned method for analyzing the odor from 1,3-butanediol in cosmetics, in step S2, the minimum matching factor of the non-targeted substance identification deconvolution method is 75, and the odor component library is shown in Table 1:

[0015] Table 1, odor component library:

[0016] Key odor factor ingredients CAS Number Molecular formula Average odor rating 2-Ethyl-5-methyl-1,3-dioxane 20627-54-7 <![CDATA[C7H 14 O2]]> 4.00 2,4-Dimethyl-1,3-dioxane 766-20-1 <![CDATA[C6H 12 O2]]> 3.75 Unknown alcohol-flavored substance-1 / / 3.75 2-Heptyl-1,3-dioxetane 61732-92-1 <![CDATA[C 12 H 24 O2]]> 2.75 Unknown alcohol-flavored substance-2 / / 2.75 Ethyl isobutyrate 97-62-1 <![CDATA[C6H 12 O2]]> 2.25 2-Phenyl-4-methyl-1,3-dioxane 774-44-7 <![CDATA[C 11 H 14 O2]]> 2.00 2-Heptyl-6-methyl-1,3-dioxane-4-one 99902-24-6 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 22 <h2 style=";text-align:left;direction:ltr"> O3]]><h2 style=";text-align:left;direction:ltr"> 1.50 2-Heptyl-4-methyl-1,3-dioxane 3271-56-5 <![CDATA[C 12 H 24 O2]]> 1.25 4-Methyl-1,3-dioxane 1120-97-4 <![CDATA[C5H 10 O2]]> 1.25

[0017] In the above-mentioned method for analyzing the odor derived from 1,3-butanediol in cosmetics, in step S3, the accelerated stability test conditions are 25°C to 50°C and room temperature illumination; the acceleration time is 3 to 7 days, 1 to 5 g of the accelerated product is taken in a headspace bottle, the incubation temperature is 60°C, the SPME fiber material uses 65μm DVB / PDMS, the equilibrium adsorption time is 20 minutes, the online analysis time is preferably 10 minutes, the GC-MS parameter conditions are the same as in step S2, and the minimum matching factor of the non-targeted substance identification deconvolution method is 75.

[0018] In the above-mentioned method for analyzing the odor derived from 1,3-butanediol in cosmetics, the accelerated stability test conditions are 40°C to 50°C and room temperature illumination.

[0019] The analytical method for the odor from 1,3-butanediol in cosmetics of the present invention pre-treats the sample by online solid phase microextraction technology, and establishes a key odor factor component library by combining the combined technology of gas chromatography-mass spectrometry and olfactometer, which not only improves the scientificity and accuracy of odor evaluation, but also can be used for rapid screening of raw material quality and early warning of product odor risks in the early stages of research and development and production. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The mass spectrum information of the unknown alcohol-flavor substance-1 in the key odor factor component library of Example 1;

[0021] Figure 2 The mass spectrum information of the unknown alcohol-flavor substance-2 in the key odor factor component library of Example 1;

[0022] Figure 3 This is the total ion current diagram of sample B in Example 2 after being placed at 50° C. for the third day;

[0023] Figure 4 This is the total ion current diagram of sample C in Example 2 after being stored at 50°C for 3 days. DETAILED DESCRIPTION

[0024] In order to enable those skilled in the art to better understand the technical solution of the present invention, its specific implementation method is described in detail below with reference to the accompanying drawings.

[0025] Embodiment 1:

[0026] A method for establishing a 1,3-butanediol-derived odor component spectrum library comprises the following steps:

[0027] Step S1, collecting batches of 1,3-butanediol raw materials from 5 manufacturers and 40 different active ingredients containing butanediol from different manufacturers for incubation pretreatment using online solid phase microextraction technology (online-SPME), taking 2 g of each sample in a headspace bottle, weighing 4 parallel samples for each sample, the SPME fiber material is DVB / PDMS (65 μm), and automatically balancing adsorption at an incubation temperature of 60° C. for 20 minutes. After the incubation, the instrument automatically inserts the SPME fiber head into the gas phase mass spectrometry (GC-MS) injection port for online analysis for 10 minutes;

[0028] Step S2, using gas chromatography (GC) to connect the tail end of the chromatographic column to an olfactory identification instrument (ODP) and a mass spectrometer (MS) through a three-way connection at the tail end of the chromatographic column, and simultaneously perform odor sniffing and non-targeted substance identification. According to the spectrum, the GC-MS conditions are optimized, wherein the optimal conditions are: the gas phase capillary column is HP-5ms (30m*250μm*0.25μm); the injection port temperature is 260°C, the split mode is non-split, the column oven starting temperature is 40°C, maintained for 1min, then heated to 120°C at a heating rate of 5°C / min, maintained for 1min, and then heated to 280°C at a heating rate of 10°C / min, the carrier gas is helium, the constant flow rate is 1.5mL / min, the mass spectrometer ion source is an electron bombardment ion source, the acquisition mode is full scan, the transmission line temperature is 280°C, the ion source temperature is 230°C, the quadrupole temperature is 150°C, and the mass scanning range m / z is 29-500. The parameters of ODP are: pipeline temperature 280℃, ODP sniff port temperature 150℃.

[0029] Each of the four olfactory experts scored the odor intensity detected at the olfactory port on a 1-4 scale based on the time when the chromatographic peak appeared. After calculating the average value, the volatile substances with an average odor score ≥ 1 were deconvoluted and identified using the NIST spectral library to obtain the key odor factor components and establish the corresponding odor component spectral library. The odor component spectral library is shown in Table 1:

[0030] Table 1, odor component library:

[0031] Key odor factor ingredients CAS Number Molecular formula Average odor rating 2-Ethyl-5-methyl-1,3-dioxane 20627-54-7 <![CDATA[C7H 14 O2]]> 4.00 2,4-Dimethyl-1,3-dioxane 766-20-1 <![CDATA[C6H 12 O2]]> 3.75 Unknown alcohol-flavored substance-1 / / 3.75 2-Heptyl-1,3-dioxetane 61732-92-1 <![CDATA[C 12 H 24 O2]]> 2.75 Unknown alcohol-flavored substance-2 / / 2.75 Ethyl isobutyrate 97-62-1 <![CDATA[C6H 12 O2]]> 2.25 2-Phenyl-4-methyl-1,3-dioxane 774-44-7 <![CDATA[C 11 H 14 O2]]> 2.00 2-Heptyl-6-methyl-1,3-dioxane-4-one 99902-24-6 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 22 <h2 style=";text-align:left;direction:ltr"> O3]]><h2 style=";text-align:left;direction:ltr"> 1.50 2-Heptyl-4-methyl-1,3-dioxane 3271-56-5 <![CDATA[C 12 H 24 O2]]> 1.25 4-Methyl-1,3-dioxane 1120-97-4 <![CDATA[C5H 10 O2]]> 1.25

[0032] The odor component library contains the MS mass spectrum information, CAS number and molecular formula of substances with NIST identification greater than 75 and average odor score ≥1. For substances with average odor score ≥1 but not identified by the NIST library, the MS mass spectrum information can also be retained in the library and named as unknown alcohol substances-1 and 2.

[0033] Through the detection method of the present invention, the key odor components derived from 1,3-butanediol are successfully and quickly identified and screened out, and a material odor score and mass spectrum information library is established. There is no need to perform non-target identification processing on all GC-MS peaks, thereby improving the scientificity and efficiency of sample processing.

[0034] Comparative Example 1: Headspace Gas Chromatography Mass Spectrometry (HS-GC-MS) and Olfactometer (GC-O) Test

[0035] The raw material samples collected in step 1 of Example 1 were tested by headspace gas chromatography-mass spectrometry (HS-GC-MS) and olfactometer (GC-O). 4 g of each sample was taken in a headspace bottle and incubated at 60° C. for 20 min before sampling and analysis. The GC-MS and GC-O parameters were the same as in Example 1. The odor intensity smelled at the olfactory port was scored on a scale of 1 to 4 according to the time when the chromatographic peak appeared. The results showed that for the raw material samples directly sniffed as having an abnormal odor, the olfactory scores of each chromatographic peak were all less than 1, and the key odor factor component spectrum library could not be established.

[0036] Embodiment 2:

[0037] A method for analyzing odor from 1,3-butanediol in cosmetics comprises the following steps: firstly, establishing an odor component library according to Example 1, and then using 1.3-butanediol from three different manufacturers to prepare facial mask essence samples, which are recorded as sample A, sample B and sample C respectively. The products are placed under five conditions of 5°C, 25°C, room temperature light, 40°C and 50°C for accelerated treatment. On the 0th day (the day of sample preparation), the 3rd day, the 5th day and the 7th day, 4g of the accelerated product is taken into a headspace bottle, and the parameters of online-SPME and GC-MS are the same as those in Example 1 for sample injection test, and the deconvolution method is used for non-target data identification, and the minimum matching factor is set to 75. The average value of the total number of substances matched by the odor component library for samples under each accelerated condition is shown in Table 2.

[0038] Table 2, the average value of the total number of substances matched by the odor component library for samples under each accelerated condition:

[0039]

[0040] For facial mask essence samples prepared with 1,3-butanediol from different manufacturers, this method can quickly and accurately identify trace amounts of odorous components and give stable test results. Preferably, it can quickly determine whether relevant odorous substances exist under accelerated conditions of 40°C or 50°C for 3 days, providing a reference for raw material screening and formula shelf life, shortening the cosmetic odor stability inspection cycle, and reducing the product odor stability risk.

[0041] Comparative Example 2: Artificial olfactory sensory evaluation of the odor of cosmetics containing 1,3-butanediol

[0042] Samples A, B and C prepared in Example 2 were placed under five conditions of 5°C, 25°C, room temperature, 40°C and 50°C for accelerated treatment. Four smellers conducted manual olfactory sensory evaluation on the 0th day (the day of sample preparation), the 7th day, the 14th day and the 28th day, respectively. The overall odor intensity was scored on a scale of 0 to 4 (no odor was smelled, 0, and the odor intensity was from weak to strong, with a total of 1 to 4 levels). The results are shown in Table 3:

[0043] Table 3, artificial olfactory sensory evaluation of the odor of cosmetics containing 1,3-butanediol:

[0044]

[0045] From the average sensory evaluation score, it can be seen that for the facial mask essence samples prepared with 1.3-butylene glycol from different manufacturers, sample A, sample B and sample C did not produce obvious odor under various accelerated experimental conditions except 50°C at 0, 7 and 14 days. In the 28-day artificial olfactory scoring, the samples with accelerated conditions of room temperature illumination, 40°C and 50°C were evaluated by artificial olfactory sensory evaluation, and it can be seen that the 1,3-butylene glycol from three different manufacturers produces different degrees of odor in the formula, and the trend of the results is consistent with the results of the odor component library matching in Example 2.

[0046] Embodiment 3:

[0047] A method for analyzing the odor from a purslane extract containing 1,3-butanediol in cosmetics comprises the following steps: first, a spectral library of odor components is established according to Example 1, and then a mask essence sample is prepared using a batch of abnormal odor raw materials of a purslane extract containing 1,3-butanediol, which is recorded as sample D, and the active raw material is replaced with purified water to prepare a mask essence sample with the same formula as a blank control, which is recorded as sample E. The product is placed under five conditions of accelerated treatment at 5°C, 25°C, room temperature light, 40°C and 50°C. The test is conducted on day 0 (the day of sample preparation), day 3, day 5 and day 7, respectively. The parameters and non-target data identification methods of online-SPME and GC-MS are the same as those in Example 1, and the results are shown in Table 4.

[0048] Table 4, analysis results of odor from Purslane extract containing 1,3-butylene glycol in cosmetics:

[0049]

[0050]

[0051] The results show that this method can also be used for odor analysis of cosmetic samples prepared with abnormal odor active ingredients containing 1,3-butanediol, shortening the product odor stability inspection cycle and helping to quickly identify product odor stability risks.

[0052] In summary, the method for analyzing the odor from 1,3-butanediol in cosmetics of the present invention aims to solve the problems of strong subjectivity, low reproducibility and difficulty in smelling low-concentration odor components in the existing technology of cosmetic odor evaluation. This method pre-treats samples by online solid phase microextraction technology and combines the combination of gas chromatography-mass spectrometry and olfactometer to establish a key odor factor component library, which not only improves the scientificity and accuracy of odor evaluation, but also can be used for rapid screening of raw material quality and early warning of product odor risks in the early stages of research and development and production.

[0053] Those skilled in the art should recognize that the above embodiments are only used to illustrate the present invention, and are not intended to limit the present invention. As long as they are within the spirit of the present invention, any changes or modifications to the above embodiments will fall within the scope of the claims of the present invention.

Claims

1. A method for analyzing the odor of 1,3-butanediol in cosmetics, characterized in that: The following steps are involved: Step S1, respectively collecting 1,3-butanediol raw materials of the abnormal odor batches to be tested, performing incubation pretreatment on the abnormal odor active material containing 1,3-butanediol using online-SPME technology, and after the incubation, the instrument automatically inserts the SPME fiber head into the GC-MS injection port for analysis; Step S2, the tail end of the GC chromatographic column is connected to the olfactory analyzer and the mass spectrometer through a three-way connection, and odor smelling and non-targeted substance identification are performed simultaneously; according to the appearance time of the chromatographic peak, the olfactory evaluation results of each person are counted, and the average value is calculated to obtain the odor score corresponding to each GC-MS substance, and the corresponding peaks of the volatile substance components with an average odor score greater than or equal to 1 are deconvoluted and identified using the NIST spectral library to obtain the key odor factor component substances and establish the corresponding odor component spectral library; Step S3, conduct accelerated stability test on cosmetic products containing 1,3-butanediol raw materials or active ingredients containing 1,3-butanediol, take samples for pre-treatment using online-SPME technology, and then automatically perform GC-MS testing. After data processing using the deconvolution method, use the key odor component spectral library for qualitative identification to quickly determine whether the cosmetic product has the risk of odor.

2. The method for analyzing the odor of 1,3-butanediol in cosmetics according to claim 1, characterized in that: In step S1, the parameters of the online-SPME technology are: taking 0.1-2 g of abnormal odor raw material sample into a headspace bottle, the incubation temperature is 60°C, the SPME fiber material is preferably 65 μm DVB / PDMS, the equilibrium adsorption time is 20 min, and the online analysis time is preferably 10 min.

3. The method for analyzing the odor of 1,3-butanediol in cosmetics according to claim 1, characterized in that: In step S2, the parameter conditions of GC-MS are as follows: the gas phase capillary column is HP-5ms (30m*250μm*0.25μm), the injection port temperature is 260°C, the split mode is non-split, the column oven starting temperature is 40°C, maintained for 1 min, then heated to 120°C at a heating rate of 5°C / min, maintained for 1 min, and then heated to 280°C at a heating rate of 10°C / min, the carrier gas is helium, the constant flow rate is 1.5mL / min, the mass spectrometry ion source is an electron bombardment ion source, the acquisition mode is full scan, the transmission line temperature is 280°C, the ion source temperature is 230°C, the quadrupole temperature is 150°C, and the mass scan range m / z is 29-500; The parameters of the olfactometer are as follows: pipeline temperature is 280°C and the temperature of the olfactometer olfactory port is 150°C.

4. The method for analyzing the odor of 1,3-butanediol in cosmetics according to claim 1, characterized in that: In step S2, each person's olfactory evaluation result is divided into 1 to 4 levels from weak to strong.

5. The method for analyzing the odor of 1,3-butanediol in cosmetics according to claim 1, characterized in that: In step S2, the minimum matching factor of the non-targeted substance identification deconvolution method is 75, and the odor component library is shown in Table 1: Table 1, odor component library:

6. The method for analyzing the odor of 1,3-butanediol in cosmetics according to claim 1, characterized in that: In step S3, the accelerated stability test conditions are 25°C to 50°C and room temperature illumination; the acceleration time is 3 to 7 days, 1 to 5 g of the accelerated product is taken in a headspace bottle, the incubation temperature is 60°C, the SPME fiber material uses 65μmDVB / PDMS, the equilibrium adsorption time is 20min, the online analysis time is preferably 10min, the GC-MS parameter conditions are the same as in step S2, and the minimum matching factor of the non-targeted substance identification deconvolution method is 75.

7. The method for analyzing the odor of 1,3-butanediol in cosmetics according to claim 6, characterized in that: The accelerated stability test conditions are 40℃~50℃ and room temperature with light.

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