Modified hydroxytyrosol, cosmetic, method of preparation and use

Abstract

The application discloses a modified hydroxytyrosol, cosmetics, a preparation method and application. The preparation method of the modified hydroxytyrosol comprises the following steps: mixing hydroxytyrosol, lipase and fatty acid ester to react in the presence of an acidic solvent, centrifuging the reaction product to separate layers, and collecting the components of the middle layer to prepare the modified hydroxytyrosol. In the preparation method of the modified hydroxytyrosol, the lipase and the fatty acid ester are subjected to enzyme cutting reaction, the active hydroxyl in the product obtained through the enzyme cutting reaction is subjected to dehydration reaction with the hydroxytyrosol, the ester group molecular is grafted into the hydroxytyrosol, and the modified hydroxytyrosol product with the ester group is prepared. The obtained modified hydroxytyrosol has high fat solubility and antioxidant performance.

Description

Technical Field

[0001] This application belongs to the field of cosmetic formulation technology, and relates to modified hydroxytyrosol, cosmetics, preparation methods and applications. Background Technology

[0002] Hydroxytyrosol is a naturally occurring phenolic compound with antioxidant properties. It can scavenge free radicals and protect skin cells from oxidative stress damage, and is widely used in cosmetic formulation development. However, current hydroxytyrosol formulations show relatively poor antioxidant performance. Furthermore, due to its three hydroxyl groups, it is highly hydrophilic and suffers from poor lipid solubility during application. Summary of the Invention

[0003] Therefore, it is necessary to provide a modified hydroxytyrosol, cosmetics, preparation method and application to improve the antioxidant properties and lipid solubility of hydroxytyrosol.

[0004] In some embodiments, a method for preparing modified hydroxytyrosol is provided, comprising the following steps: mixing hydroxytyrosol, lipase and fatty acid ester in the presence of an acidic solvent and reacting them; centrifuging the reaction product to separate it into layers; collecting the middle layer component; and preparing the modified hydroxytyrosol.

[0005] In some embodiments, in the provided method for preparing modified hydroxytyrosol, the fatty acid ester has 4 to 20 carbon atoms.

[0006] In some embodiments, in the provided method for preparing modified hydroxytyrosol, the fatty acid ester includes one or both of caprylic / capric triglyceride and isopropyl myristate.

[0007] In some embodiments, the provided method for preparing modified hydroxytyrosol satisfies one or both of the following conditions:

[0008] (1) The mass ratio of the hydroxytyrosol to the fatty acid ester is 1:(1~2).

[0009] (2) The mass ratio of the hydroxytyrosol to the lipase is 1:(0.5~2).

[0010] In some embodiments, the provided method for preparing modified hydroxytyrosol satisfies one or more of the following conditions:

[0011] (1) The fatty acid ester has 8 to 18 carbon atoms;

[0012] (2) The mass-to-volume ratio of the hydroxytyrosol to the solvent is 1 g: (8~15) mL;

[0013] (3) The pH value of the solvent is 6~6.8;

[0014] (4) The solvent is water;

[0015] (5) The reaction temperature is 40℃~50℃, and the reaction time is 4h~8h;

[0016] (6) In the step of centrifuging the reaction product into layers, centrifuge at 5000 rpm to 8000 rpm for 5 min to 8 min.

[0017] In some embodiments, a modified hydroxytyrosol is provided, which is prepared by the aforementioned preparation method.

[0018] In some embodiments, the modified hydroxytyrosol is provided for use in the preparation of products with free radical scavenging capabilities;

[0019] The products include at least cosmetics.

[0020] In some embodiments, a cosmetic product is provided that contains the modified hydroxytyrosol.

[0021] In some embodiments, the cosmetic comprises 0.1% to 1% of the modified hydroxytyrosol, 5% to 30% of the moisturizer, 4% to 16% of the emulsifier, 0.1% to 5% of the skin conditioning agent, 0.5% to 5% of the thickener, 0.01% to 2% of the preservative and 50% to 80% of the solvent.

[0022] In some embodiments, the cosmetic comprises 0.1%–1% of the modified hydroxytyrosol, 1%–2% of fatty acid esters, 3%–10% of butylene glycol, 1%–10% of glycerin, 1%–10% of propylene glycol, 2%–8% of polyglycerol-10 dipalmitate, 1%–3% of isononyl isononanoate, 1%–3% of polyglycerol-6 distearate, 0.1%–2% of cetearyl alcohol, 0.1%–5% of allantoin, 0.1%–2% of ammonium acryloyl dimethyl taurate / VP copolymer, 0.2%–2% of sodium polyacrylate, 0.2%–1% of acrylate (ester) / C10-30 alkanol acrylate cross-linked copolymer, 0.01%–2% of p-hydroxyacetophenone, 0.1%–2% of hexanediol, and 50%–78% of water.

[0023] In the aforementioned method for preparing modified hydroxytyrosol, lipase performs an enzymatic cleavage reaction with a fatty acid ester. The active hydroxyl groups in the product obtained from the enzymatic cleavage reaction undergo a dehydration reaction with hydroxytyrosol, causing the ester group molecules to be branched into the hydroxytyrosol, thus preparing a modified hydroxytyrosol product with ester groups. The obtained modified hydroxytyrosol exhibits high lipophilicity and antioxidant properties. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the embodiments and examples of this application, and to more completely understand this application and its beneficial effects, the accompanying drawings used in the description of the embodiments or examples will be briefly introduced below. Obviously, the drawings described below are merely some embodiments of this application. Those skilled in the art can obtain other drawings based on these drawings without any creative effort.

[0025] Figure 1 Infrared spectrum of unmodified hydroxytyrosol;

[0026] Figure 2 The infrared spectrum of the modified hydroxytyrosol in Example 1;

[0027] Figure 3 This is the mass spectrum of the modified hydroxytyrosol in Example 1. Detailed Implementation

[0028] To facilitate understanding of this application, a more complete description will be provided below with reference to the accompanying drawings. Preferred embodiments of this application are shown in the drawings. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of this application.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0030] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings:

[0031] The terms "and / or," "or / and," and "and / or" as used in this application encompass any one of two or more related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected using at least two conjunctions selected from "and / or," "or / and," and "and / or," it should be understood that in this application, the technical solution undoubtedly includes solutions connected by "logical AND," and also undoubtedly includes solutions connected by "logical OR." For example, "A and / or B" includes three parallel solutions: A, B, and "a combination of A and B."

[0032] In this application, the terms "multiple", "various", "multiple times", "multi-dimensional", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0033] The terms “combinations thereof,” “any combination thereof,” and “any combination thereof” as used in this application include all suitable combinations of any two or more of the listed items.

[0034] In this application, the term "suitable" as used in "suitable combination", "suitable method", "any suitable method", etc., refers to the ability to implement the technical solution of this application, solve the technical problem of this application, and achieve the expected technical effect of this application.

[0035] In this application, terms such as "preferred," "better," "more suitable," and "ideal" are merely used to describe implementation methods or embodiments that achieve better results, and should be understood not to limit the scope of protection of this application.

[0036] In this application, terms such as "further," "even more," and "particularly" are used for descriptive purposes and to indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0037] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0038] In this application, the terms "first aspect," "second aspect," "third aspect," and "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," and "fourth," etc., serve only a non-exhaustive enumeration purpose and should be understood not to constitute a closed limitation on quantity.

[0039] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0040] In this application, numerical intervals (i.e., numerical ranges) are involved. Unless otherwise specified, the selected numerical distributions within the aforementioned numerical intervals are considered continuous and include the two endpoints (i.e., the minimum and maximum values) of the numerical range, as well as every value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints. In this document, this is equivalent to directly listing every integer. For example, if t is an integer selected from 1 to 10, it means that t is any integer selected from the group of integers consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Furthermore, when multiple ranges are provided to describe features or characteristics, these ranges can be merged. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all subranges to which they are included.

[0041] Unless otherwise specified, the temperature parameters in this application are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that the constant-temperature treatment allows temperature fluctuations within the precision range of the instrument control, such as ±5℃, ±4℃, ±3℃, ±2℃, or ±1℃.

[0042] In this application, % (w / w) and wt% both represent weight percentage, % (v / v) refers to volume percentage, and % (w / v) refers to mass-volume percentage.

[0043] In this application, "room temperature" generally refers to 5℃~30℃, and more preferably 25±5℃.

[0044] In this application, in order to enrich and effectively improve the chemical and physiological activity of hydroxytyrosol, the hydroxyl groups on hydroxytyrosol are chemically modified and altered.

[0045] In some embodiments, a method for preparing modified hydroxytyrosol is provided, comprising the following steps: mixing hydroxytyrosol, lipase and fatty acid ester in the presence of an acidic solvent and reacting them; centrifuging the reaction product to separate the layers; collecting the middle layer component; and preparing modified hydroxytyrosol.

[0046] In some embodiments, in the provided method for preparing modified hydroxytyrosol, the number of carbon atoms in the fatty acid ester can be 4 to 20, or it can be 8 to 18. For example, the number of carbon atoms in the fatty acid ester can be 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, or it can be any combination of the two aforementioned values.

[0047] In some embodiments, the fatty acid esters provided in the method for preparing modified hydroxytyrosol include one or both of caprylic / capric triglyceride and isopropyl myristate.

[0048] In some embodiments, in the provided method for preparing modified hydroxytyrosol, the mass ratio of hydroxytyrosol to fatty acid ester is 1:(1~2), for example, the mass ratio of hydroxytyrosol to fatty acid ester is 1:1, 1:1.5, 1:2, etc., or it can be a range of any two of the aforementioned ratios.

[0049] In some embodiments, the mass ratio of hydroxytyrosol to lipase in the provided method for preparing modified hydroxytyrosol is 1:(0.5~2). For example, the mass ratio of hydroxytyrosol to lipase is 1:0.5, 1:1, 1:1.5, 1:2, etc., or it can be any range of the two aforementioned ratios.

[0050] In some implementations, the lipase is derived from Aspergillus niger.

[0051] In some embodiments, in the provided method for preparing modified hydroxytyrosol, the mass-volume ratio of hydroxytyrosol to solvent is 1g:(8~15)mL. For example, the mass-volume ratio of hydroxytyrosol to solvent is 1g:8mL, 1g:9mL, 1g:10mL, 1g:11mL, 1g:12mL, 1g:13mL, 1g:14mL, 1g:15mL, etc., or it can be a range of any two of the aforementioned ratios.

[0052] In some embodiments, the pH value of the solvent in the provided method for preparing modified hydroxytyrosol is 6 to 6.8. For example, the pH value of the solvent can be 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, etc., or it can be a range composed of any two of the aforementioned values.

[0053] In some embodiments, the solvent provided in the preparation method of modified hydroxytyrosol is water.

[0054] In some embodiments, the reaction temperature in the provided method for preparing modified hydroxytyrosol is 40°C to 50°C, and the reaction time is 4h to 8h. For example, the reaction temperature can be 40°C, 45°C, 50°C, etc., or it can be any range of two of the aforementioned values. The reaction time can be 4h, 5h, 6h, 7h, 8h, etc., or it can be any range of two of the aforementioned values.

[0055] In some embodiments, in the method for preparing modified hydroxytyrosol, the reaction product is centrifuged at 5000 rpm to 8000 rpm for 5 to 8 minutes during the centrifugation layering step. For example, the centrifugation speed can be 5000 rpm, 6000 rpm, 7000 rpm, 8000 rpm, etc., or any combination of the aforementioned two values; the centrifugation time can be 5 minutes, 6 minutes, 7 minutes, 8 minutes, etc., or any combination of the aforementioned two values.

[0056] In the provided method for preparing modified hydroxytyrosol, the reaction product is centrifuged and separated into layers, resulting in lipase deposited at the bottom, an aqueous layer containing modified hydroxytyrosol in the middle, and fatty acid esters in the upper layer.

[0057] In some embodiments, a modified hydroxytyrosol is provided, which is prepared by a preparation method.

[0058] In some embodiments, the use of modified hydroxytyrosol in the preparation of products with free radical scavenging capabilities is provided;

[0059] The products include at least cosmetics.

[0060] In some embodiments, a cosmetic product is provided that contains modified hydroxytyrosol.

[0061] In some embodiments, the cosmetic contains 0.1% to 1% modified hydroxytyrosol, 5% to 30% moisturizer, 4% to 16% emulsifier, 0.1% to 5% skin conditioning agent, 0.5% to 5% thickener, 0.01% to 2% preservative and 50% to 80% solvent.

[0062] In some embodiments, the cosmetic comprises 0.1%–1% modified hydroxytyrosol, 1%–2% fatty acid esters, 3%–10% butylene glycol, 1%–10% glycerin, 1%–10% propylene glycol, 2%–8% polyglycerol-10 dipalmitate, 1%–3% isononyl isononanoate, 1%–3% polyglycerol-6 distearate, 0.1%–2% cetearyl alcohol, 0.1%–5% allantoin, 0.1%–2% ammonium acryloyl dimethyl taurate / VP copolymer, 0.2%–2% sodium polyacrylate, 0.2%–1% acrylate (ester) / C10-30 alkanol acrylate cross-linked copolymer, 0.01%–2% p-hydroxyacetophenone, 0.1%–2% hexanediol, and 50%–78% water.

[0063] In this application, fatty acid esters that can be successfully modified with hydroxytyrosol were obtained through screening. The modified hydroxytyrosol prepared using the method provided in this application exhibits high fat solubility and antioxidant properties.

[0064] The following are specific embodiments. They are intended to provide further detailed explanation of this application to help those skilled in the art and researchers to better understand it. The technical conditions and other details do not constitute any limitation on this application. Any modifications made within the scope of the claims of this application are protected by the claims of this application.

[0065] Unless otherwise stated, all raw materials and reagents used in the following examples are commercially available or can be prepared by known methods. Experimental methods not specifying particular conditions in the examples were performed under conventional conditions, such as those described in literature, books, or methods recommended by the manufacturer.

[0066] The lipase was purchased from Xiasheng Bioenzyme, FDY-2261.

[0067] Example 1

[0068] This embodiment provides a modified hydroxytyrosol, prepared using caprylic / capric triglyceride (a fatty acid ester). The preparation method is as follows:

[0069] (1) Add 0.5 g of hydroxytyrosol (HT) and 0.5 g of lipase to 10 ml of water to form solution A;

[0070] (2) Add 1 gram of caprylic / capric triglyceride to solution A to form solution B;

[0071] (3) Use acetic acid to adjust the pH of solution B to 6.5, forming solution C;

[0072] (4) The enzymatic hydrolysis reaction was carried out under magnetic stirring at 45℃ for 5 hours;

[0073] (5) Centrifuge the sample at 6000 rpm for 8 min to allow the enzyme preparation to deposit at the bottom, the water layer containing hydroxytyrosol in the middle, and the caprylic / capric triglyceride in the upper layer.

[0074] (6) A hydroxytyrosol sample from the middle water layer was obtained and freeze-dried to obtain an oily hydroxytyrosol modified product.

[0075] Example 2

[0076] This embodiment provides a modified hydroxytyrosol, prepared using isopropyl myristate (a fatty acid ester). The preparation method is as follows:

[0077] (1) Add 0.5 g of hydroxytyrosol (HT) and 0.5 g of lipase to 10 ml of water to form solution A;

[0078] (2) Add 1 gram of isopropyl myristate to solution A to form solution B;

[0079] (3) Use acetic acid to adjust the pH of solution B to 6.5, forming solution C;

[0080] (4) The enzymatic hydrolysis reaction was carried out under magnetic stirring at 45℃ for 5 hours;

[0081] (5) Centrifuge the sample at 6000 rpm for 8 min;

[0082] (6) A hydroxytyrosol sample from the middle water layer was obtained and freeze-dried to obtain a hydroxytyrosol modified product.

[0083] Example 3

[0084] This embodiment provides a modified hydroxytyrosol.

[0085] The preparation method of modified hydroxytyrosol is similar to that in Example 1, except that in step (1), 0.5 g of hydroxytyrosol (HT) and 1 g of lipase are added to 10 ml of water to form solution A.

[0086] Example 4

[0087] This embodiment provides a modified hydroxytyrosol.

[0088] The preparation method of modified hydroxytyrosol is similar to that in Example 1, except that in step (2), 0.5 g of caprylic / capric triglyceride is added to solution A to form solution B.

[0089] Example 5

[0090] This embodiment provides a modified hydroxytyrosol.

[0091] The preparation method of modified hydroxytyrosol is similar to that in Example 1, except that in step (4), the enzymatic hydrolysis reaction is carried out by magnetic stirring at 45°C for 4 hours.

[0092] Example 6

[0093] This embodiment provides a modified hydroxytyrosol.

[0094] The preparation method of modified hydroxytyrosol is similar to that in Example 1, except that in step (4), the enzymatic hydrolysis reaction is carried out by magnetic stirring at 45°C for 8 hours.

[0095] Example 7

[0096] This embodiment provides a modified hydroxytyrosol.

[0097] The preparation method of modified hydroxytyrosol is similar to that in Example 1, except that in step (1), 0.5 g of hydroxytyrosol (HT) and 0.1 g of lipase are added to 10 ml of water to form solution A.

[0098] Comparative Example 1

[0099] This comparative example provides a modified hydroxytyrosol, prepared using squalane. The preparation method is as follows:

[0100] (1) Add 0.5 g of hydroxytyrosol (HT) and 0.5 g of lipase to 10 ml of water to form solution A;

[0101] (2) Add 1 gram of squalane to solution A to form solution B;

[0102] (3) Use acetic acid to adjust the pH of solution B to 6.5, forming solution C;

[0103] (4) The enzymatic hydrolysis reaction was carried out under magnetic stirring at 45℃ for 5 hours;

[0104] (5) The sample was centrifuged at 6000 rpm for 8 min to allow the enzyme preparation to settle at the bottom, the water layer containing hydroxytyrosol to be in the middle, and the squalane to be in the upper layer.

[0105] (6) A hydroxytyrosol sample from the middle water layer was obtained and freeze-dried to obtain an oily hydroxytyrosol modified product.

[0106] Comparative Example 2

[0107] This comparative example provides a modified hydroxytyrosol, prepared using jojoba oil. The preparation method is as follows:

[0108] (1) Add 0.5 g of hydroxytyrosol (HT) and 0.5 g of lipase to 10 ml of water to form solution A;

[0109] (2) Add 1 gram of jojoba oil to solution A to form solution B;

[0110] (3) Use acetic acid to adjust the pH of solution B to 6.5, forming solution C;

[0111] (4) The enzymatic hydrolysis reaction was carried out under magnetic stirring at 45℃ for 5 hours;

[0112] (5) The sample was centrifuged at 6000 rpm for 8 min to allow the enzyme preparation to settle at the bottom, the water layer containing hydroxytyrosol to be in the middle, and the jojoba oil to be in the upper layer.

[0113] (6) A hydroxytyrosol sample from the middle water layer was obtained and freeze-dried to obtain an oily hydroxytyrosol modified product.

[0114] Comparative Example 3

[0115] This comparative example provides a modified hydroxytyrosol, prepared using dimethyl silicone oil. The preparation method is as follows:

[0116] (1) Add 0.5 g of hydroxytyrosol (HT) and 0.5 g of lipase to 10 ml of water to form solution A;

[0117] (2) Add 1 gram of dimethyl silicone oil to solution A to form solution B;

[0118] (3) Use acetic acid to adjust the pH of solution B to 6.5, forming solution C;

[0119] (4) The enzymatic hydrolysis reaction was carried out under magnetic stirring at 45℃ for 5 hours;

[0120] (5) The sample was centrifuged at 6000 rpm for 8 min to allow the enzyme preparation to deposit at the bottom, the water layer containing hydroxytyrosol in the middle, and the dimethyl silicone oil in the upper layer.

[0121] (6) A hydroxytyrosol sample from the middle water layer was obtained and freeze-dried. The dried sample was in a solid state and was not a normal oily hydroxytyrosol modified product. The sample preparation failed.

[0122] Performance testing

[0123] I. Infrared Spectroscopy Detection

[0124] Infrared spectroscopy was performed on both the unmodified hydroxytyrosol and the prepared modified hydroxytyrosol, and the results are as follows: Figure 1 and Figure 2 As shown. Figure 1 The infrared spectrum of unmodified hydroxytyrosol. Figure 2 The infrared spectrum of the modified hydroxytyrosol obtained in Example 1 is shown.

[0125] contrast Figure 1 and Figure 2 The stretching vibration frequency of the OH group of hydroxytyrosol is 3375 cm⁻¹. -1 The stretching vibration frequency of the modified hydroxytyrosol (OH) is 3380 cm⁻¹. -1 The modified sample showed a significant red shift in peak value compared to the unmodified raw material. Specifically, the unmodified hydroxytyrosol peaked at 1045 cm⁻¹. -1 Only a weak expression was observed, but after modification, it reached 1044cm. -1 There is a distinct peak at [cm]. The COC symmetric stretching vibration in the ester group is typically between 1050 and 1250 cm⁻¹. -1 Within the range, 1045cm -1These peaks may be characteristic of esters or ethers; the infrared spectrum suggests that the grafting modification of hydroxytyrosol with caprylic / capric triglycerides was successfully achieved.

[0126] II. Mass Spectrometry Detection

[0127] The modified hydroxytyrosol obtained was analyzed by mass spectrometry. The mass spectrometry results of the modified hydroxytyrosol obtained in Example 1 are as follows: Figure 3 As shown.

[0128] Based on the molecular formula of caprylic / capric triglyceride, lipase cleaves the caprylic / capric triglyceride at the ester group. The active hydroxyl group in the product undergoes a dehydration reaction with hydroxytyrosol, causing the ester group to branch onto the hydroxytyrosol. Figure 3 The mass spectrum of the modified hydroxytyrosol shown indicates that the m / z of the hydroxytyrosol esterified molecular ion is 437. Since the detection mode is positively charged (M+H), this indicates a molecular mass of 436, which matches the actual relative molecular mass. The molecular formula is C1. 26 H 44 O5. Due to the formation of other hydroxytyrosol esterification molecules during the modification process, and the presence of multiple isomers, substances with other molecular weights are present in the mass spectrum. Overall, the main modified hydroxytyrosol component has the molecular formula C. 26 H 44 O5 successfully synthesized a modified hydroxytyrosol product with an ester group.

[0129] III. DPPH Scavenging Experiment

[0130] Equal volumes of distilled water were added to prepare 0.1 mg / mL samples of unmodified hydroxytyrosol and the samples prepared in the examples. 2 mL of each hydroxytyrosol sample solution was added to 2 mL of DPPH (0.1 mM, methanol-soluble) solution, mixed thoroughly, and incubated in the dark at room temperature for 30 min. The absorbance was measured at 517 nm. Distilled water was used as the blank group, and vitamin C (Vc) was used as the positive control. All samples were measured in triplicate, and the average value was calculated. The scavenging ability is expressed as the scavenging rate, which was calculated using the following formula:

[0131]

[0132] Among them, A 空白 The absorbance of the blank group (2 mL of distilled water was used to replace the sample);

[0133] A 样品 The absorbance of the sample solution;

[0134] A 对照 The absorbance is calculated by replacing DPPH with 2 mL of methanol.

[0135] Table 1

[0136]

[0137] As shown in Table 1, the DPPH free radical scavenging data indicate that, compared with unmodified hydroxytyrosol, modified hydroxytyrosol exhibits varying degrees of change in DPPH free radical scavenging. Among them, the scavenging rate of modified caprylic / capric triglyceride is improved. This is because after grafting ester groups onto the modified hydroxytyrosol, the carbon chain becomes longer and the molecular weight becomes larger, thus enhancing the antioxidant capacity and achieving the purpose of modification to enhance antioxidant properties.

[0138] IV. ABTS Removal Experiment

[0139] Preparation of ABTS free radical stock solution: Mix 10 mL of 7.4 mol / L ABTS solution and 10 mL of 2.6 mmol / L K₂S₂O₈ solution, and oxidize at room temperature in the dark for 12 h to obtain the stock solution. Before use, dilute the ABTS stock solution with PBS (0.2 M, pH=7.4) to achieve an absorbance of 0.7 ± 0.02 at 734 nm. Add an equal volume of distilled water to prepare the unmodified hydroxytyrosol and the sample prepared in the examples to a concentration of 0.1 mg / mL. Take 2 mL of ABTS solution, add 2 mL of sample solutions from different groups, mix, and let stand at room temperature for 6 min. Measure the absorbance at 734 nm. Use ascorbic acid (Vc) as a positive control. Measure all samples in triplicate and calculate the average value. The ABTS scavenging ability is expressed as the scavenging rate, calculated using the following formula:

[0140]

[0141] Among them, A 空白 The absorbance of the blank group (2 mL of distilled water was used to replace the sample);

[0142] A 样品 The absorbance of the sample solution;

[0143] A 对照 2 mL of sample control (2 mM 0.2 M buffer instead of ABTS).

[0144] Table 2

[0145]

[0146] As shown in Table 2, the ABTS free radical scavenging data indicate that, compared with unmodified hydroxytyrosol, modified hydroxytyrosol exhibits varying degrees of change in ABTS free radical scavenging. Among them, the scavenging rate is improved after modification with caprylic / capric triglyceride. This is because after grafting ester groups onto the modified hydroxytyrosol, the carbon chain becomes longer and the molecular weight increases, resulting in enhanced antioxidant capacity. This can reduce the amount of raw materials used and improve efficiency when applied to products.

[0147] V. Comparative Experiment on the Oil Solubility of Modified Hydroxytyrosol

[0148] Weigh 0.01 g of unmodified hydroxytyrosol and the sample from Example 1, respectively, and dissolve them in 10 mL of corn oil. Stir and dissolve at room temperature for 10 min and observe the state of the oil sample; sonicate at room temperature for 10 min and observe the state of the oil sample; heat (50℃) and sonicate for 10 min and observe the state of the oil sample.

[0149] Table 3

[0150]

[0151] As can be seen from the experimental results in Table 3, modified hydroxytyrosol can be completely dissolved in corn oil when heated and ultrasonically treated, while unmodified hydroxytyrosol cannot be dissolved in corn oil by the above methods. This is because the grafting of oil ester groups onto modified hydroxytyrosol enhances its fat solubility and improves the poor oil solubility of hydroxytyrosol itself.

[0152] Application examples

[0153] This application example provides an emulsion containing modified hydroxytyrosol. The preparation process includes the following steps:

[0154] (1) Weigh the following components: 6g of butanediol, 5g of polyglycerol-10 dipalmitate, 3g of glycerol, 1g of isononyl isononanoate, 1g of polyglycerol-6 distearate, 0.5g of cetearyl alcohol, 0.3g of hexanediol, 1g of p-hydroxyacetophenone, 1g of ammonium acryloyl dimethyl taurate / VP copolymer, 0.2g of sodium polyacrylate, 0.2g of allantoin, 1g of acrylic (ester) / C10-30 alkanol acrylate cross-linked copolymer, 3g of propylene glycol, and 75.3g of deionized water;

[0155] (2) Mix the above emulsion raw materials and heat to 80°C, homogenize for 3 min, and cool to room temperature;

[0156] (3) Add 0.5g of modified hydroxytyrosol and 1g of caprylic / capric triglyceride prepared in Example 1, stir evenly to obtain an emulsion.

[0157] The performance test results of the obtained emulsion samples are shown in Table 4 below.

[0158] Table 4 Performance test results of emulsion samples containing modified hydroxytyrosol

[0159]

[0160] As can be seen from the data in Table 4 above, the prepared emulsion sample containing modified hydroxytyrosol has a uniform and stable appearance, and remains stable under both high and low temperature conditions, without any layering or demulsification. The pH value is weakly acidic, which meets the relevant standards of the cosmetics industry.

[0161] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0162] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims, and the specification and drawings can be used to interpret the content of the claims.

Claims

1. A method for preparing a modified hydroxytyrosol, characterized by, The method comprises the following steps: mixing hydroxytyrosol, lipase and fatty acid ester in the presence of an acidic solvent to react, centrifuging the reaction product to separate layers, and collecting the components of the middle layer to obtain the modified hydroxytyrosol. The solvent is water. The pH value of the solvent is 6-6.

8. The fatty acid ester comprises one or both of caprylic capric triglyceride and isopropyl myristate. The lipase is purchased from Xiasheng Biozyme, and the model number is FDY-2261.

2. The method for preparing modified hydroxytyrosol according to claim 1, characterized by, The mass ratio of the hydroxytyrosol to the fatty acid ester is 1:(1-2).

3. The method of preparing modified hydroxytyrosol according to claim 1, characterized in that, The mass ratio of the hydroxytyrosol to the lipase is 1:(0.5-2).

4. The method of preparing modified hydroxytyrosol according to any one of claims 1 to 3, characterized in that, The mass-volume ratio of the hydroxytyrosol to the solvent is 1g:(8-15)mL.

5. The method of producing modified hydroxytyrosol according to any one of claims 1 to 3, characterized in that, The reaction temperature is 40-50°C, and the reaction time is 4-8h.

6. The method of producing modified hydroxytyrosol according to any one of claims 1 to 3, characterized in that, In the step of centrifuging the reaction product to separate layers, centrifugation is performed at 5000-8000rpm for 5-8min.

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