Oil absorption paper for testing skin components of children as well as preparation method and application of oil absorption paper

Abstract

The invention discloses oil-absorbing paper for testing skin components of children as well as a preparation method and application of the oil-absorbing paper, and belongs to the technical field of substance detection. The oil-absorbing paper is prepared from the plant fibers, and the plant fibers are modified by the silicone oil and the modified PHA. When the content of the lipid in the skin of the child is detected, oil absorption paper is firstly used for sampling on the two sides of the nose of the child, and then HPLC-MS is adopted for detecting the lipid components. The oil absorption paper is developed according to the characteristic of less skin grease secretion of children, the oil absorption paper can effectively absorb the grease on the skin surface, then the lipid absorbed in the oil absorption paper is measured, the composition of the skin lipid can be reflected more accurately, and therefore a foundation is laid for determination of components of children cosmetics.

Description

Technical Field

[0001] The invention belongs to the technical field of material detection, and in particular relates to an oil-absorbing paper for testing the components of children's skin, and a preparation method and application thereof. Background Art

[0002] The "Regulations on the Supervision and Administration of Children's Cosmetics" stipulate that the formula design of children's cosmetics should follow the principles of safety first, efficacy necessity, and minimalist formula. It also stipulates that children's cosmetics should evaluate the scientific nature and necessity of the raw materials used in light of the safety, stability, function, and compatibility of the raw materials, combined with the physiological characteristics of children. Prohibited raw materials such as hormones, anti-infective drugs, or other substances that may endanger human health shall not be added.

[0003] Children's skin is thinner than that of adults and they are more sensitive to adverse reactions to external stimuli such as cold, heat, humidity, dryness and sun exposure. However, children's skin has an incomplete structure, incompletely differentiated stratum corneum, poor skin defense barrier, and incompletely developed metabolic function. In addition, the ratio of children's skin surface area to body weight is smaller than that of adults. After harmful substances are absorbed through the skin epidermis and enter the plasma or body fluids, the concentration of harmful substances is higher, causing greater harm.

[0004] The stratum corneum is located in the outermost layer of the epidermis and is composed of about 50 layers of dead flat keratinocytes. It bears the skin barrier function, is the initial site of cosmetics, and is also the main rate-limiting site of cosmetics penetration. Therefore, improving the permeability of the stratum corneum to cosmetics can better promote the skin's absorption of the beneficial components in cosmetics and maintain skin vitality and health. Among them, the lipid components in the stratum corneum have an important influence on the penetration and absorption of cosmetics. Cosmetics act directly on the skin, and analyzing the lipid components and content in the stratum corneum is conducive to preparing cosmetics suitable for skin absorption. In the prior art, lipids in the stratum corneum of the skin are extracted mainly through hospital channels to obtain stratum corneum debris, and then organic solvent extraction and separation, or directly extract lipids on the skin surface with organic solvents, or directly scrape skin secretions to analyze the components of lipids, and then guide the synthesis of cosmetics, which is conducive to the skin's absorption of the beneficial components in cosmetics. However, the disadvantages of these methods are that they often cause physical damage to the stratum corneum of the skin and reduce the skin barrier function. In addition, the extractant used usually contains chloroform, which is a toxic and explosive reagent, and there are safety hazards, and the process of extracting lipid components is relatively complicated and inefficient. Summary of the invention

[0005] In view of the above-mentioned prior art, the present invention provides an oil-absorbing paper for testing the components of children's skin and a preparation method and application thereof, which provide a direction for determining the components of children's cosmetics.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is to provide a method for preparing oil-absorbing paper for testing children's skin components, comprising the following steps: S1: Soak the plant fiber in 3% hydrogen peroxide for 2-5 hours at room temperature; then rinse with water for 3-5 times; then mix the rinsed plant fiber with water and grind into plant fiber slurry; S2: Add silicone oil and modified PHA to the plant fiber slurry and ultrasonically vibrate for 30-45 minutes; S3: the plant fiber pulp treated in S2 is made into paper, and then dried to obtain paper.

[0007] Based on the above technical solution, the present invention can also be improved as follows.

[0008] Furthermore, the plant fiber is flax fiber and / or bamboo fiber, and the concentration of the plant fiber in the plant fiber slurry is 30-50wt%.

[0009] Furthermore, the addition amounts of silicone oil and modified PHA were 1~3% and 0.5~2% of the mass of the plant fiber slurry, respectively.

[0010] Further, the modified PHA is prepared by the following steps: PHA is dissolved in an organic solvent, and then acrylic acid and benzoyl peroxide are added to the resulting solution under a protective gas atmosphere, and then the temperature is raised to 50-70° C. and the reaction is kept warm for 12-16 hours; then the product is purified and dried to obtain the product.

[0011] Furthermore, the mass ratio of PHA, acrylic acid and benzoyl peroxide is 10:2~5:0.5~2.

[0012] The invention also discloses an oil absorbing paper for testing the components of children's skin, which is prepared by adopting the preparation method of the oil absorbing paper for testing the components of children's skin.

[0013] The present invention also discloses an application of the above-mentioned oil-absorbing paper for testing children's skin components, which is to use the oil-absorbing paper to detect children's skin lipids. The detection method comprises the following steps: (1) Take the oil-absorbing paper of claim 6, wipe both sides of the child's nose 3 to 5 times, then immerse the oil-absorbing paper in n-hexane, remove the oil-absorbing paper after ultrasonic oscillation for 20 minutes, blow dry the n-hexane with nitrogen, add the mobile phase, vortex for 3 minutes, then centrifuge at 10000g for 5 minutes, and then filter through a 0.22 μm filter membrane to obtain a test solution; the mobile phase is a mixture of isopropanol and acetonitrile in a volume ratio of 9:1; (2) The test solution was chromatographically separated by ultra-high performance liquid chromatography and quadrupole time-of-flight mass spectrometry; the chromatographic column used in the ultra-high performance liquid chromatography was Waters ACQUITY UPLC CSH C18, and the mobile phases used included mobile phase A and mobile phase B. Mobile phase A was an acetonitrile solution containing 0.1 wt% formic acid and 10 mmol / L ammonium formate, and the acetonitrile solution was prepared by mixing acetonitrile and purified water in a volume ratio of 3:2; mobile phase B was an isopropanol solution containing 0.1 wt% formic acid and 10 mmol / L ammonium formate, and the isopropanol solution was prepared by mixing isopropanol and acetonitrile in a volume ratio of 9:1; the ionization mode was ESI. + Mode: Gradient elution was performed at a flow rate of 0.3 mL / min, the column temperature was 50°C, and the wavelength range was 210-400 nm. The gradient elution mode is shown in the following table;

[0014] The sample acquisition mode was Fast DDA, in which the primary mass spectrum acquisition range was 100~1200m / z, the secondary mass spectrum acquisition range was 50~1200m / z, and the secondary energy collision energy ramp started from 33.0eV and ended at 44.5eV; the capillary voltage was set to 2.0KV, the sampling cone voltage was 40V, the ion source temperature and the solvent gas temperature were controlled at 140℃ and 450℃ respectively, the sampling cone gas flow rate was 100.0L / Hr, and the desolvation gas flow rate was 800 / 0L / Hr.

[0015] The amount of lipid components added to children's cosmetics is determined based on the content of lipids in the children's skin tested.

[0016] The beneficial effects of the present invention are: 1. Aiming at the characteristic of less oil secretion on children's skin, the present invention develops an oil-absorbing paper. The oil-absorbing paper of the present invention uses plant fibers, especially flax fibers and bamboo fibers as main components. Both of them have excellent oil absorption performance and can effectively absorb oil on the skin surface. Then, the lipids adsorbed in the oil-absorbing paper are measured, which can more accurately reflect the lipid composition of the skin, thereby laying a foundation for determining the components of children's cosmetics.

[0017] 2. When preparing the oil-absorbing paper, the present invention adds silicone oil and modified PHA to the pulp, and uses the two to modify the plant fiber. Among them, the plant fiber modified with silicone oil can maintain its lipophilic properties. At the same time, due to the addition of silicone oil, the prepared oil-absorbing paper has a stronger oil absorption capacity and a faster oil absorption speed. This property enables the prepared oil-absorbing paper to have excellent performance in testing the lipid composition of the skin of children with less oil secretion; moreover, the plant fiber modified with silicone oil has higher stability and durability, so that the prepared oil-absorbing paper is not easy to be damaged during use; at the same time, silicone oil itself has a smooth property. After combining with plant fiber, the oil-absorbing paper can provide better touch and comfort when contacting the skin, which can reduce skin friction and discomfort. PHA (polyhydroxyalkanoate) as a hydrophobic polymer can significantly improve the oil absorption capacity of plant fiber; at the same time, the plant fiber oil-absorbing paper modified with PHA can maintain good oil absorption capacity while avoiding the problem that traditional plant fiber oil-absorbing paper absorbs facial moisture while absorbing oil, thereby avoiding skin damage.

[0018] 3. When preparing the oil-absorbing paper, the plant fiber is first oxidatively modified with hydrogen peroxide. The modified plant fiber can form a more stable combination with silicone oil and modified PHA. In the subsequent oscillation process, silicone oil and PHA will not enter the test liquid, avoiding interference with the test of lipid content.

[0019] 4. The present invention uses HPLC-MS to detect lipid components in children's skin. The detection sensitivity is high and the content of squalene, cholesterol, ceramide AP, ceramide NP, 18:0 (2R-OH) ceramide, etc. in children's skin can be accurately detected, thereby guiding the dosage of lipid components in cosmetics, which is more conducive to the skin's absorption of beneficial components in cosmetics and achieving better cosmetic effects. DETAILED DESCRIPTION

[0020] The specific implementation modes of the present invention are described in detail below with reference to the embodiments.

[0021] Example 1 An oil-absorbing paper for testing the composition of children's skin is prepared by the following steps: S1: Soak the flax fiber in 3% hydrogen peroxide for 3 hours at room temperature; then rinse it with water for 4 times; then mix the rinsed plant fiber with water at a material-liquid ratio of 1g:3mL and grind it into slurry; S2: Add silicone oil and modified PHA to the slurry and ultrasonically vibrate for 30 minutes; the amount of silicone oil and modified PHA added is 2% and 1% of the slurry mass, respectively; the modified PHA is prepared by the following steps: PHA (polyhydroxyalkanoate) was dissolved in dichloromethane, and then acrylic acid and benzoyl peroxide were added to the resulting solution under a nitrogen atmosphere, and then the temperature was raised to 60°C and kept for reaction for 14 hours; then it was extracted with acetone for 24 hours, and then dried at 50°C for 2 hours to obtain the product; the mass ratio of PHA, acrylic acid and benzoyl peroxide was 10:3:1; S3: Pour the slurry treated by S2 into a Buchner funnel with filter paper for filtration, move the formed wet paper sheet into two stacks of filter paper to remove excess free water, then replace the wet filter paper and put it into the press for pressing and drying; the papermaking basis weight is 30g / m 2 ; Get oil-absorbing paper.

[0022] Example 2 An oil-absorbing paper for testing the composition of children's skin is prepared by the following steps: S1: Soak the bamboo fiber in 3% hydrogen peroxide for 2 hours at room temperature; then rinse it with water for 3 times; then mix the rinsed plant fiber with water at a material-liquid ratio of 1g:2mL and grind it into slurry; S2: Add silicone oil and modified PHA to the slurry and ultrasonically vibrate for 45 minutes; the amount of silicone oil and modified PHA added is 1% and 2% of the slurry mass respectively; the modified PHA is prepared by the following steps: PHA (polyhydroxyalkanoate) was dissolved in dichloromethane, and then acrylic acid and benzoyl peroxide were added to the resulting solution under a nitrogen atmosphere, and then the temperature was raised to 50°C and kept for reaction for 16 hours; then it was extracted with acetone for 24 hours, and then dried at 50°C for 2 hours to obtain the product; the mass ratio of PHA, acrylic acid and benzoyl peroxide was 10:2:0.5; S3: Pour the slurry treated by S2 into a Buchner funnel with filter paper for filtration, move the formed wet paper sheet into two stacks of filter paper to remove excess free water, then replace the wet filter paper and put it into the press for pressing and drying; the papermaking basis weight is 30g / m 2 ; Get oil-absorbing paper.

[0023] Example 3 An oil-absorbing paper for testing the composition of children's skin is prepared by the following steps: S1: At room temperature, flax fiber and bamboo fiber were mixed in a mass ratio of 1:1, and the mixture was soaked in 3% hydrogen peroxide for 5 hours; then rinsed with water for 3 times; then the rinsed plant fiber was mixed with water in a material-liquid ratio of 1g:5mL, and ground into slurry; S2: Add silicone oil and modified PHA to the slurry and ultrasonically vibrate for 45 minutes; the amount of silicone oil and modified PHA added is 3% and 0.5% of the slurry mass, respectively; the modified PHA is prepared by the following steps: PHA (polyhydroxyalkanoate) was dissolved in dichloromethane, and then acrylic acid and benzoyl peroxide were added to the resulting solution under a nitrogen atmosphere, and then the temperature was raised to 70°C and kept for reaction for 12 hours; then it was extracted with acetone for 24 hours, and then dried at 50°C for 2 hours to obtain the product; the mass ratio of PHA, acrylic acid and benzoyl peroxide was 10:5:2; S3: Pour the slurry treated by S2 into a Buchner funnel with filter paper for filtration, move the formed wet paper sheet into two stacks of filter paper to remove excess free water, then replace the wet filter paper and put it into the press for pressing and drying; the papermaking basis weight is 30g / m 2 ; Get oil-absorbing paper.

[0024] Comparative Example 1 Compared with Example 1, when preparing the oil-absorbing paper for testing the components of children's skin, silicone oil was not added to the slurry, and the remaining operations were the same as in Example 1.

[0025] Comparative Example 2 Compared with Example 1, when preparing the oil absorbing paper for testing the components of children's skin, no modified PHA was added to the slurry, and the remaining operations were the same as in Example 1.

[0026] Comparative Example 3 Compared with Example 1, the oil-absorbing paper for testing the components of children's skin was replaced with commercially available oil-absorbing paper, and the remaining operations were the same as in Example 1.

[0027] Experimental example The performance of the oil absorbing papers for testing the components of children's skin obtained in Examples 1 to 3 is similar, and Example 1 is taken as an example to illustrate its oil absorption performance.

[0028] 400 healthy children aged 0-3 years old from the same region were selected as subjects (living in the region for at least 2 consecutive years), 200 males and 200 females, and then divided into 4 groups, each group including 50 males and 50 females, and the oil absorbing paper for testing the skin components of children in Example 1 and Comparative Examples 1-3 was used to absorb the oil on the children's facial skin, and then the oil composition of the children's skin was measured as follows: (1) Take a 2 cm × 2 cm oil-absorbing paper and wipe both sides of the child's nose 4 times. Then immerse the oil-absorbing paper in 5 mL of n-hexane and ultrasonically oscillate at a frequency of 25 kHz for 20 min. Then remove the oil-absorbing paper and blow dry the n-hexane with nitrogen. Then add 250 μL of mobile phase, vortex for 3 min, and then centrifuge at 10000g for 5 min. Then filter through a 0.22 μm filter membrane to obtain the test solution. The mobile phase used is a mixture of isopropanol and acetonitrile in a volume ratio of 9:1. (2) The test solution was chromatographically separated by ultra-high performance liquid chromatography and quadrupole time-of-flight mass spectrometer; the chromatographic column used in the ultra-high performance liquid chromatography was Waters ACQUITY UPLC CSH C18, and the mobile phases used included mobile phase A and mobile phase B, wherein the mobile phase A was an acetonitrile solution containing 0.1 wt % formic acid and 10 mmol / L ammonium formate, and the acetonitrile solution was prepared by mixing acetonitrile and purified water in a volume ratio of 3:2; the mobile phase B was an isopropanol solution containing 0.1 wt % formic acid and 10 mmol / L ammonium formate, and the isopropanol solution was prepared by mixing isopropanol and acetonitrile in a volume ratio of 9:1; the ionization mode was ESI. + Mode: Gradient elution was performed at a flow rate of 0.3 mL / min, the column temperature was 50°C, and the wavelength range was 210-400 nm. The gradient elution mode is shown in the following table;

[0029] The sample acquisition mode is Fast DDA, where the primary mass spectrum acquisition range is 100~1200m / z, the secondary mass spectrum acquisition range is 50~1200m / z, and the secondary energy collision energy slope starts from 33.0eV and ends at 44.5eV; the capillary voltage is set to 2.0KV, the sampling cone voltage is 40V, the ion source temperature and the solvent gas temperature are controlled at 140℃ and 450℃ respectively, the sampling cone gas flow rate is 100.0L / Hr, and the desolvation gas flow rate is 800 / 0L / Hr. The main detection objects are squalene, cholesterol, ceramide AP, ceramide NP, and 18:0 (2R-OH) ceramide, and the detection results are shown in Table 1.

[0030] Table 1 Lipid content test results

[0031] As can be seen from Table 1, when the oil-absorbing paper for testing children's skin components in this application is used for the experiment, the measured skin lipid content is the highest and is closest to the actual lipid content of children's skin. This is because the oil-absorbing paper in this application can effectively absorb the oil of the skin, making the test results more accurate and pointing out the direction for the development of children's cosmetics.

[0032] Although the specific implementation of the present invention is described in detail in conjunction with the embodiments, it should not be understood as limiting the scope of protection of this patent. Within the scope described in the claims, various modifications and variations that can be made by those skilled in the art without creative work still fall within the scope of protection of this patent.

Claims

1. A method for preparing oil-absorbing paper for testing children's skin components, characterized in that: The following steps are involved: S1: Soak the plant fiber in 3% hydrogen peroxide for 2-5 hours at room temperature; then rinse with water for 3-5 times; then mix the rinsed plant fiber with water and grind into plant fiber slurry; S2: Add silicone oil and modified PHA to the plant fiber slurry and ultrasonically vibrate for 30-45 minutes; S3: the plant fiber pulp treated in S2 is made into paper, and then dried to obtain paper.

2. The method for preparing the oil absorbing paper for testing the skin composition of children according to claim 1, characterized in that: The plant fiber is flax fiber and / or bamboo fiber, and the concentration of the plant fiber in the plant fiber slurry is 30-50wt%.

3. The method for preparing the oil-absorbing paper for testing the skin composition of children according to claim 2, characterized in that: The added amounts of the silicone oil and modified PHA are 1-3% and 0.5-2% of the mass of the plant fiber slurry, respectively.

4. The method for preparing the oil-absorbing paper for testing the skin composition of children according to claim 1 or 3, characterized in that: The modified PHA is prepared by the following steps: PHA is dissolved in an organic solvent, and then acrylic acid and benzoyl peroxide are added to the resulting solution under a protective gas atmosphere, and then the temperature is raised to 50-70° C. and the reaction is kept warm for 12-16 hours; then the product is purified and dried to obtain the product.

5. The method for preparing the oil absorbing paper for testing the skin composition of children according to claim 4, characterized in that: The mass ratio of the PHA, acrylic acid and benzoyl peroxide is 10:2-5:0.5-2.

6. An oil-absorbing paper for testing the composition of children's skin, characterized by: The oil-absorbing paper for testing the components of children's skin is prepared by the preparation method of any one of claims 1 to 5.

7. The use of the oil-absorbing paper for testing the composition of children's skin according to claim 6, characterized in that: The oil absorbing paper is used to detect children's skin lipids, and the detection method comprises the following steps: (1) Take the oil-absorbing paper of claim 6, wipe both sides of the child's nose 3 to 5 times, then immerse the oil-absorbing paper in n-hexane, remove the oil-absorbing paper after ultrasonic oscillation for 20 minutes, blow dry the n-hexane with nitrogen, add the mobile phase, vortex for 3 minutes, then centrifuge at 10000g for 5 minutes, and then filter through a 0.22 μm filter membrane to obtain a test solution; the mobile phase is a mixture of isopropanol and acetonitrile in a volume ratio of 9:1; (2) The test solution was chromatographically separated by ultra-high performance liquid chromatography and quadrupole time-of-flight mass spectrometer; the chromatographic column used in the ultra-high performance liquid chromatography was Waters ACQUITY UPLC CSH C18, and the mobile phases used included mobile phase A and mobile phase B, wherein the mobile phase A was an acetonitrile solution containing 0.1 wt % formic acid and 10 mmol / L ammonium formate, and the acetonitrile solution was prepared by mixing acetonitrile and purified water in a volume ratio of 3:2; the mobile phase B was an isopropanol solution containing 0.1 wt % formic acid and 10 mmol / L ammonium formate, and the isopropanol solution was prepared by mixing isopropanol and acetonitrile in a volume ratio of 9:1; the ionization mode was ESI. + Mode: Gradient elution was performed at a flow rate of 0.3 mL / min, the column temperature was 50°C, and the wavelength range was 210-400 nm. The gradient elution mode is shown in the following table; The sample acquisition mode was Fast DDA, in which the primary mass spectrum acquisition range was 100~1200m / z, the secondary mass spectrum acquisition range was 50~1200m / z, and the secondary energy collision energy ramp started from 33.0eV and ended at 44.5eV; the capillary voltage was set to 2.0KV, the sampling cone voltage was 40V, the ion source temperature and the solvent gas temperature were controlled at 140℃ and 450℃ respectively, the sampling cone gas flow rate was 100.0L / Hr, and the desolvation gas flow rate was 800 / 0L / Hr.

8. The use according to claim 7, characterized in that: The amount of lipid components added to children's cosmetics is determined based on the content of lipids in the children's skin tested.

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