Preparation method and application of s-bathin

Abstract

The application discloses a preparation method and application of S-bolose and belongs to the technical field of S-bolose synthesis; the preparation steps of the S-bolose comprise the following steps: S1, under light-proof conditions, a catalyst ① subjected to inactivation treatment is introduced to react with xylose and acetylacetone as raw materials to obtain 1-C-(beta-D-pyranosyl xylose) acetone; S2, 1-C-(beta-D-pyranosyl xylose) acetone and acetonitrile are mixed to prepare a reaction mother liquor; S3, under nitrogen protection, triethanolamine, nicotinamide nucleotide coenzyme and the catalyst ① are mixed in a Tris buffer solution, and then the reaction mother liquor is added under light-proof conditions to react to obtain the S-bolose; the S-bolose prepared by the application has high yield.

Description

Technical Field

[0001] This invention relates to the field of S-Bosonic synthesis technology, specifically to a method for preparing and applying S-Bosonic. Background Technology

[0002] Pro-Xylane is a xylose derivative developed by L'Oréal with significant cosmetic and anti-wrinkle effects. Its chemical nature is hydroxypropyltetrahydropyranotriol. As a C-glycoside with broad biological activity, Pro-Xylane can improve skin firmness and achieve anti-wrinkle and anti-aging effects by promoting the synthesis of intercellular mucopolysaccharides, rebuilding cell structure, and enhancing the connection between the dermis and epidermis.

[0003] WO02 / 051828A1 first disclosed the synthetic route of Bosein, which uses D-xylose as a raw material and sodium bicarbonate as a base to produce β-acetone xyloside through condensation, cyclization, and cleavage reactions in an aqueous phase. The target product is then obtained by reducing the ketone carbonyl group in methanol using sodium borohydride. However, this traditional process has significant technical drawbacks: First, the reaction system lacks an effective extraction step, requiring electroosmosis or ion exchange column removal of residual salts, increasing process complexity. Second, the boric acid generated during sodium borohydride reduction readily forms stable complexes with the polyhydroxy structures in the product, making impurities difficult to remove. Most importantly, this method has poor stereoselectivity; when the S / R configuration ratio at the 7-position is close to 1:1, the product is an oily mixture that cannot be purified by crystallization, and commercially available aqueous solutions often contain approximately 5% unknown impurities. Even when the S / R configuration ratio is greater than 9:1, although high-purity S-type products can be obtained through crystallization, the impurities remaining in the mother liquor are extremely similar to the physicochemical properties of the target product, making purification extremely difficult. This results in the inability to effectively recover and utilize the S-type and all R-type products in the mother liquor, severely restricting the overall yield.

[0004] To address these issues, L'Oréal subsequently improved the process, replacing sodium bicarbonate with sodium hydroxide to reduce the formation of α-isomer impurities, and using an isopropanol / acetic acid system in conjunction with sodium borohydride for reduction, increasing the S / R configuration ratio to over 9:1. However, this improved approach still relies on sodium borohydride, and the problems of residual boric acid complexes and their difficulty in removal persist. Furthermore, existing preparation methods often require purification using column chromatography, which not only increases solvent consumption and wastewater treatment costs but also makes it difficult to meet the demands of large-scale industrial production.

[0005] Therefore, there is an urgent need to develop a method for preparing S-Bosonic to solve the above problems. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing S-Bosonic and its application, so as to solve the technical problems mentioned in the background art.

[0007] The technical solution to achieve the objective of this invention is: In a first aspect, the present invention provides a method for preparing S-Bosonic, comprising the following steps: S1. Under light-protected conditions, xylose and acetylacetone were used as raw materials, and an inactivated catalyst ① was introduced to react and 1-C-(β-D-pyranoxysyl)acetone was obtained. S2. Prepare a reaction mother liquor by mixing 1-C-(β-D-xylanosyl)acetone and acetonitrile; S3. Under nitrogen protection, triethanolamine and oxidized nicotinamide adenine dinucleotide (NAD) were added to Tris buffer solution. + The catalyst ① is mixed, and then the mother liquor is added under light-protected conditions to react and obtain S-Bosein.

[0008] Furthermore, the amount of catalyst ① added during the inactivation treatment accounts for 3-4 wt% of the total mass of the raw materials.

[0009] Furthermore, the preparation method of the deactivated catalyst ① is as follows: the catalyst ①, which has been recycled at least once, is shaken in boiling water for at least 20 minutes to obtain the deactivated catalyst ①.

[0010] Furthermore, the catalyst ① used for the inactivation treatment is a catalyst ① that has been recycled at least 5 times.

[0011] Furthermore, 1-C-(β-D-xylanosyl)acetone, tris(hydroxymethyl)aminomethane, triethanolamine, NAD... + The mass ratio of catalyst ① is 1: (1.25~1.27): (7.7~7.9): (0.34~0.36): (0.5~0.55).

[0012] Furthermore, the reaction in step S3 is carried out under light irradiation with a wavelength greater than 420 nm, the reaction temperature is 35~45℃, the reaction pH is 6.5~7.5, and the reaction time is 7~9 h.

[0013] Further, the preparation steps of the catalyst ① are as follows: 0.01 parts by mass of magnetic support are weighed and dispersed in 4-5 parts by mass of Tris buffer solution containing 0.2 mg / mL reductase and pH 7, stirred at 4°C for 2 h, centrifuged, washed, and freeze-dried to obtain the composite enzyme catalyst.

[0014] Furthermore, the preparation steps of the magnetic carrier are as follows: A1. Mix 0.8 parts by weight of magnetic powder with 62.8-64 parts by weight of isopropanol and 3.2 parts by weight of ultrapure water, and ultrasonically disperse for at least 30 minutes. Then, under stirring, add 14.4-16 parts by weight of ammonia water and 4.46-4.8 parts by weight of tetraethyl orthosilicate. React at 40-50°C for 5-7 hours. After the reaction is completed, cool naturally to room temperature, centrifuge, wash 2-4 times with deionized water and anhydrous ethanol, collect with a magnet, and dry to obtain silica-coated magnetic particles. A2. Mix 1.5-1.6 parts by weight of succinic anhydride with 3-3.2 parts by weight of 3-aminopropyltriethoxysilane and 76-96 parts by weight of ethanol, sonicate for at least 30 min, and then react at 25-35℃ for 2-4 h. Finally, add 0.15-0.16 parts by weight of silica-coated magnetic particles, 64-80 parts by weight of ethanol and 12-15 parts by weight of ultrapure water, continue to sonicate for at least 30 min, and react at 25-35 min for 11-13 h. After the reaction is completed, cool naturally to room temperature, centrifuge, wash 2-4 times with deionized water and anhydrous ethanol, collect with a magnet, and dry to obtain carboxylated silica-coated magnetic particles. A3. Dissolve 0.03-0.06 parts by weight of zirconium tetrachloride, 0.03-0.06 parts by weight of 2-aminoterephthalic acid, 0.01-0.02 parts by weight of 5,10,15,20-tetra(4-carboxyphenyl)porphyrin, and 0.5-1 parts by weight of benzoic acid in 3.78-4 parts by weight of N,N-dimethylformamide. After ultrasonic dispersion for at least 20 min, add 0.002-0.004 parts by weight of carboxylated silica to coat the magnetic particles, and continue ultrasonic dispersion for at least 20 min. Under stirring, heat to 120-130℃ and reflux for 4-24 h. Centrifuge, wash 2-4 times with deionized water and anhydrous ethanol, collect with a magnet, and dry to obtain the magnetic carrier.

[0015] Furthermore, the reductase includes Rhodococcus rubrum alcohol dehydrogenase.

[0016] Secondly, the present invention provides an application of S-Pros-Xylane, wherein the S-Pros-Xylane prepared according to the preparation method of the first aspect is applied in the field of cosmetics.

[0017] By adopting the above technical solution, the present invention has the following beneficial effects: (1) In the preparation of S-Bosein of the present invention, xylose and acetylacetone are first reacted with inactivated catalyst ① under light-protected conditions to obtain 1-C-(β-D-pyranoxylosyl)acetone; then 1-C-(β-D-pyranoxylosyl)acetone and acetonitrile are mixed to prepare a reaction mother liquor; finally, under nitrogen protection, triethanolamine, nicotinamide nucleotide coenzyme and catalyst ① are added to Tris buffer solution and mixed, and then the reaction mother liquor is added under light-protected conditions to obtain S-Bosein. The above preparation process can effectively avoid the use of boron reagent, and make the yield and purity of intermediate 1-C-(β-D-pyranoxylosyl)acetone and S-Bosein higher.

[0018] (2) In the preparation of 1-C-(β-D-pyranoxyl)acetone from xylose and acetylacetone, the present invention uses an inactivated catalyst ① instead of a traditional alkaline catalyst. The conversion rate of the obtained 1-C-(β-D-pyranoxyl)acetone is higher than that of the traditional alkaline catalyst. The inactivated catalyst ① is derived from the catalyst ① used for the reduction reaction of Bosein that has been recycled at least once, preferably at least five times. After undergoing multiple reduction cycles, the catalytic efficiency of the catalyst ① will be significantly reduced. After high-temperature inactivation treatment, it is reused in the condensation reaction, which not only reduces the cost of waste catalyst treatment and recycling, but also shows better catalytic performance than the traditional alkaline catalyst, effectively improving the yield of 1-C-(β-D-pyranoxyl)acetone.

[0019] (3) The catalyst ① of the present invention is obtained by loading reductase onto a magnetic support; the magnetic support is obtained by coating magnetic particles with silica and then coating the surface with H2TCPP-UiO-66-NH2 layer after surface carboxylation treatment, which not only endows the magnetic support with magnetic responsiveness for easy recycling, but also gives the magnetic support the characteristics of clear structure and high porosity; the reductase is adsorbed by the magnetic support and is firmly loaded on the magnetic support by electrostatic interaction, so that the catalyst ① exhibits good cycle stability. After being used repeatedly for 5 consecutive times, the catalytic activity of the catalyst ① and the integrity of the material skeleton did not decrease significantly.

[0020] (4) When catalyst ① of the present invention is used as a catalyst to reduce and prepare S-Bosein, the process is carried out under light irradiation. The magnetic support in catalyst ① exerts photocatalytic activity under light irradiation, thereby reducing the coenzyme-oxidized nicotinamide adenine dinucleotide (NAD). + It is reduced to reduced nicotinamide adenine dinucleotide (NADH), and subsequently, the reduced nicotinamide adenine dinucleotide and reductase work synergistically to effectively improve the conversion rate of S-Bosoxine.

[0021] (5) The reductase used in this invention is Rhodococcus rubra alcohol dehydrogenase, which has higher selectivity for reducing and preparing S-configuration bosine. Attached Figure Description

[0022] To make the content of this invention easier to understand, the invention will be further described in detail below with reference to specific embodiments and accompanying drawings, wherein... Figure 1 This is a hydrogen spectrum of S-Bosonic in one embodiment of the present invention. Detailed Implementation

[0023] To better understand the above technical solutions, the following will provide a detailed explanation of the technical solutions in conjunction with the accompanying drawings and specific implementation methods.

[0024] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0025] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.

[0026] The present invention will be further described below with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and should not be used to limit the scope of protection of the present invention.

[0027] The magnetic powder used is iron(III) oxide powder. The preparation method of iron(III) oxide powder is as follows: 1.01 g of ferric chloride hexahydrate is added to 30 mL of ethylene glycol and stirred until homogeneous. Then, 2.7 g of sodium acetate and 0.75 g of polyethylene glycol are added, and the mixture is sonicated until the sodium acetate is completely dissolved. The solution is then transferred to a 50 mL polytetrafluoroethylene (PTFE) reactor and reacted at 200 °C for 8 h. After the reaction, the mixture is allowed to cool naturally to room temperature, collected by centrifugation, and washed three times with deionized water and anhydrous ethanol. The product is then collected using a magnet and dried in a vacuum oven at 60 °C for 12 h to obtain iron(III) oxide powder with a BET specific surface area of ​​129 m². 2 / g.

[0028] The reductase used was Rhodococcus erythropolis alcohol dehydrogenase, derived from Rhodococcus erythropolis DSM 43297, gene accession number AY161280. [1] Example 1 A method for preparing S-Bosein, comprising the following steps: S1. Under light-protected conditions, 20 mmol xylose, 50 g deionized water, and 156 mg of inactivated catalyst ① were stirred for 10 min to obtain mixture A; 22 mmol acetylacetone was dissolved in 10 mL tetrahydrofuran, and then mixture A was added. The mixture was then heated to 80 °C and reacted for 30 min. After cooling and filtration, the filtrate was collected, washed with ethyl acetate to remove acetylacetone, and the aqueous layer was collected and distilled under reduced pressure to obtain 1-C-(β-D-xylanopyranosyl)acetone. S2. Mix 1-C-(β-D-xylanosyl)acetone and acetonitrile to prepare a 200mM reaction stock solution; S3. Under nitrogen protection, triethanolamine and oxidized nicotinamide adenine dinucleotide (NAD) were added to a 20 mM Tris buffer solution at pH 6.5. + The catalyst ① was mixed, and then the mother liquor was added under light-protected conditions and stirred for 30 min. The mixture was then reacted at 35℃ for 9 h to obtain S-Bosein; 1-C-(β-D-xylanosyl)acetone, tris(hydroxymethyl)aminomethane, triethanolamine, and oxidized nicotinamide adenine dinucleotide (NAD) were present. + The mass ratio of catalyst ① is 1:1.25:7.7:0.34:0.5. After the reaction is completed, catalyst ① is collected with a magnet, washed three times with Tris buffer solution, and directly used in the next cycle reaction.

[0029] The deactivated catalyst ① is prepared as follows: the catalyst ① that has been recycled 5 times is shaken in boiling water for 20 minutes to obtain the deactivated catalyst ①.

[0030] The preparation steps of the catalyst ① are as follows: 0.01 parts by mass of magnetic support are weighed and dispersed in 4 parts by mass of Tris buffer solution containing 0.2 mg / mL reductase and pH 7. The mixture is stirred at 4°C for 2 h, centrifuged, washed and lyophilized to obtain the composite enzyme catalyst.

[0031] The preparation steps of the magnetic carrier are as follows: A1. Mix 0.8 parts by weight of magnetic powder with 62.8 parts by weight of isopropanol and 3.2 parts by weight of ultrapure water, and ultrasonically disperse for 30 min. Then, under stirring, add 14.4 parts by weight of ammonia water and 4.46 parts by weight of tetraethyl orthosilicate. React at 40°C for 7 h. After the reaction is completed, cool naturally to room temperature, centrifuge, wash twice with deionized water and anhydrous ethanol, collect with a magnet, and dry to obtain silica-coated magnetic particles. A2. Mix 1.5 parts by mass of succinic anhydride with 3 parts by mass of 3-aminopropyltriethoxysilane and 76 parts by mass of ethanol, sonicate for 30 min, and then react at 25°C for 2 h. Finally, add 0.15 parts by mass of silica-coated magnetic particles, 64 parts by mass of ethanol and 12 parts by mass of ultrapure water, continue to sonicate for 30 min, and react at 25 min for 13 h. After the reaction is completed, cool naturally to room temperature, centrifuge, wash twice with deionized water and anhydrous ethanol, collect with a magnet, and dry to obtain carboxylated silica-coated magnetic particles. A3. 0.03 parts by mass of zirconium tetrachloride, 0.03 parts by mass of 2-aminoterephthalic acid, 0.01 parts by mass of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin, and 0.5 parts by mass of benzoic acid were dissolved in 3.78 parts by mass of N,N-dimethylformamide. After ultrasonic dispersion for 20 min, 0.002 parts by mass of carboxylated silica-coated magnetic particles were added, and ultrasonic dispersion was continued for another 20 min. Under stirring, the mixture was heated to 120℃ and refluxed for 24 h. After centrifugation, the mixture was washed twice with deionized water and anhydrous ethanol, collected with a magnet, and dried to obtain a magnetic carrier with a specific surface area of ​​154.12 m². 2 / g, with a pore diameter of 3.831nm.

[0032] Example 2 A method for preparing S-Bosein, comprising the following steps: S1. Under light-protected conditions, 20 mmol xylose, 50 g deionized water, and 156 mg of inactivated catalyst ① were stirred for 10 min to obtain mixture A; 22 mmol acetylacetone was dissolved in 10 mL tetrahydrofuran, and then mixture A was added. The mixture was then heated to 80 °C and reacted for 30 min. After cooling and filtration, the filtrate was collected, washed with ethyl acetate to remove acetylacetone, and the aqueous layer was collected and distilled under reduced pressure to obtain 1-C-(β-D-xylanopyranosyl)acetone. S2. Mix 1-C-(β-D-xylanosyl)acetone and acetonitrile to prepare a 200mM reaction stock solution; S3. Under nitrogen protection, triethanolamine and oxidized nicotinamide adenine dinucleotide (NAD) were added to a 20 mM Tris buffer solution at pH 7. + The catalyst ① was mixed, and then the mother liquor was added under light-protected conditions and stirred for 30 min. The mixture was then reacted at 40 °C for 8 h to obtain S-Bosein; 1-C-(β-D-xylanosyl)acetone, tris(hydroxymethyl)aminomethane, triethanolamine, and oxidized nicotinamide adenine dinucleotide (NAD) were present. + The mass ratio of catalyst ① was 1:1.26:7.8:0.35:0.52. After the reaction was completed, catalyst ① was collected with a magnet, washed three times with Tris buffer solution, and directly used in the next cycle reaction.

[0033] The deactivated catalyst ① is prepared as follows: the catalyst ① that has been recycled 6 times is shaken in boiling water for 20 minutes to obtain the deactivated catalyst ①.

[0034] The preparation steps of the catalyst ① are as follows: 0.01 parts by mass of magnetic support are weighed and dispersed in 4 parts by mass of Tris buffer solution containing 0.2 mg / mL reductase and pH 7. The mixture is stirred at 4°C for 2 h, centrifuged, washed and lyophilized to obtain the composite enzyme catalyst.

[0035] The preparation steps of the magnetic carrier are as follows: A1. Mix 0.8 parts by weight of magnetic powder with 63.4 parts by weight of isopropanol and 3.2 parts by weight of ultrapure water, and ultrasonically disperse for 30 min. Then, under stirring, add 15.2 parts by weight of ammonia water and 4.46 parts by weight of tetraethyl orthosilicate. React at 45°C for 6 h. After the reaction is completed, cool naturally to room temperature, centrifuge, wash three times with deionized water and anhydrous ethanol, collect with a magnet, and dry to obtain silica-coated magnetic particles. A2. Mix 1.55 parts by weight of succinic anhydride with 3.1 parts by weight of 3-aminopropyltriethoxysilane and 86 parts by weight of ethanol, sonicate for 30 min, and then react at 30°C for 3 h. Finally, add 0.155 parts by weight of silica-coated magnetic particles, 72 parts by weight of ethanol and 13 parts by weight of ultrapure water, continue to sonicate for 30 min, and react at 30 min for 12 h. After the reaction is completed, cool naturally to room temperature, centrifuge, wash three times with deionized water and anhydrous ethanol, collect with a magnet, and dry to obtain carboxylated silica-coated magnetic particles. A3. Dissolve 0.03 parts by weight of zirconium tetrachloride, 0.03 parts by weight of 2-aminoterephthalic acid, 0.01 parts by weight of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin, and 0.5 parts by weight of benzoic acid in 3.78 parts by weight of N,N-dimethylformamide. After ultrasonic dispersion for 20 min, add 0.002 parts by weight of carboxylated silica-coated magnetic particles and continue ultrasonic dispersion for 20 min. Under stirring, heat to 120℃ and reflux for 4 h. Centrifuge, wash three times with deionized water and anhydrous ethanol, collect with a magnet, and dry to obtain a magnetic carrier with a specific surface area of ​​155.56 m². 2 / g, with a pore diameter of 3.820nm.

[0036] Example 3 A method for preparing S-Bosein, comprising the following steps: S1. Under light-protected conditions, 20 mmol xylose, 50 g deionized water, and 208 mg of inactivated catalyst ① were stirred for 10 min to obtain mixture A; 22 mmol acetylacetone was dissolved in 10 mL tetrahydrofuran, and then mixture A was added. The mixture was then heated to 120 °C and reacted for 60 min. After cooling and filtration, the filtrate was collected, washed with ethyl acetate to remove acetylacetone, and the aqueous layer was collected and distilled under reduced pressure to obtain 1-C-(β-D-xylanosyl)acetone. S2. Mix 1-C-(β-D-xylanosyl)acetone and acetonitrile to prepare a 200mM reaction stock solution; S3. Under nitrogen protection, triethanolamine and oxidized nicotinamide adenine dinucleotide (NAD) were added to a 20 mM Tris buffer solution at pH 7.5. + The catalyst ① was mixed, and then the mother liquor was added under light-protected conditions and stirred for 30 min. The mixture was then reacted at 45℃ for 7 h to obtain S-Bosein; which contained 1-C-(β-D-xylanopyranosyl)acetone, tris(hydroxymethyl)aminomethane, triethanolamine, and oxidized nicotinamide adenine dinucleotide (NAD). + The mass ratio of catalyst ① was 1:1.27:7.9:0.36:0.55. After the reaction was completed, catalyst ① was collected with a magnet, washed three times with Tris buffer solution, and directly used in the next cycle reaction.

[0037] The deactivated catalyst ① is prepared as follows: the catalyst ① that has been recycled 7 times is shaken in boiling water for 20 minutes to obtain the deactivated catalyst ①.

[0038] The preparation steps of the catalyst ① are as follows: 0.01 parts by mass of magnetic support are weighed and dispersed in 5 parts by mass of Tris buffer solution containing 0.2 mg / mL reductase and pH 7, stirred at 4°C for 2 h, centrifuged, washed and freeze-dried to obtain the composite enzyme catalyst.

[0039] The preparation steps of the magnetic carrier are as follows: A1. Mix 0.8 parts by weight of magnetic powder with 64 parts by weight of isopropanol and 3.2 parts by weight of ultrapure water, and ultrasonically disperse for 30 min. Then, under stirring, add 16 parts by weight of ammonia water and 4.8 parts by weight of tetraethyl orthosilicate, and react at 50°C for 5 h. After the reaction is completed, cool naturally to room temperature, centrifuge, wash 4 times with deionized water and anhydrous ethanol, collect with a magnet, and dry to obtain silica-coated magnetic particles. A2. Mix 1.6 parts by mass of succinic anhydride with 3.2 parts by mass of 3-aminopropyltriethoxysilane and 96 parts by mass of ethanol, sonicate for 30 min, and then react at 35°C for 4 h. Finally, add 0.16 parts by mass of silica-coated magnetic particles, 80 parts by mass of ethanol and 15 parts by mass of ultrapure water, continue to sonicate for 30 min, and react at 35 min for 11 h. After the reaction is completed, cool naturally to room temperature, centrifuge, wash 4 times with deionized water and anhydrous ethanol, collect with a magnet, and dry to obtain carboxylated silica-coated magnetic particles. A3. Dissolve 0.06 parts by mass of zirconium tetrachloride, 0.06 parts by mass of 2-aminoterephthalic acid, 0.02 parts by mass of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin, and 1 part by mass of benzoic acid in 4 parts by mass of N,N-dimethylformamide. After ultrasonic dispersion for 20 min, add 0.004 parts by mass of carboxylated silica-coated magnetic particles and continue ultrasonic dispersion for 20 min. Under stirring, heat to 130℃ and reflux for 24 h. Centrifuge, wash four times with deionized water and anhydrous ethanol, collect with a magnet, and dry to obtain a magnetic carrier with a specific surface area of ​​154.68 m². 2 / g, with a pore diameter of 3.826nm.

[0040] Comparative Example 1 The only difference between Comparative Example 1 and Example 2 is that sodium hydroxide is used as the catalyst in step S1.

[0041] Comparative Examples 2-5 The only difference between Comparative Examples 2-5 and Example 2 is that the amount of catalyst ① added in step S1 catalyst inactivation treatment is 1wt%, 2wt%, 5wt%, and 6wt% of the total mass of raw materials, respectively.

[0042] Comparative Example 6 The only difference between Comparative Example 6 and Example 2 is that no light treatment was performed during the reaction in step S3, and the coenzyme used was reduced nicotinamide adenine dinucleotide.

[0043] Comparative Example 7 The only difference between Comparative Example 7 and Example 2 is that step S3 uses a reductase instead of a complex enzyme catalyst, and the coenzyme is reduced nicotinamide adenine dinucleotide.

[0044] Example of effect Table 1 below shows the product results of the preparation methods of Examples 1-3 and Comparative Examples 1-7: Table 1 As shown in Table 1, the 1-C-(β-D-pyranoxylosyl)acetone obtained in Examples 1-3 had a higher yield, a higher conversion rate of S-Bosein, and a higher ee value. The catalyst activity could still be maintained above 85% after 5 cycles; and the catalytic activity decreased sharply after 6 cycles.

[0045] The only difference between Comparative Example 1 and Example 2 is that in step S1, sodium hydroxide was used instead of the deactivated catalyst ①, and the yield of 1-C-(β-D-pyranoxosyl)acetone was lower than that in Example 2.

[0046] The only difference between Comparative Examples 2-5 and Example 2 is that the amount of catalyst ① added in step S1 that has been inactivated accounts for 1 wt%, 2 wt%, 5 wt%, and 6 wt% of the total mass of the raw materials, respectively. The yield of 1-C-(β-D-pyranoxosyl)acetone increases first and then tends to stabilize as the amount of catalyst ① added increases.

[0047] The only difference between Comparative Example 6 and Example 2 is that no light treatment was performed during the reaction in step S3, the coenzyme used was reduced nicotinamide adenine dinucleotide, and the conversion rate of S-Bosine was lower than that in Example 2.

[0048] The only difference between Comparative Example 7 and Example 2 is that step S3 uses a reductase instead of a complex enzyme catalyst, the coenzyme is reduced nicotinamide adenine dinucleotide, and the conversion rate of S-Bosine is lower than that of Example 2.

[0049] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing S-Bosonic, characterized in that the steps include... include: S1. Under light-protected conditions, xylose and acetylacetone were used as raw materials, and an inactivated catalyst ① was introduced to react and 1-C-(β-D-pyranoxysyl)acetone was obtained. S2. Prepare a reaction mother liquor by mixing 1-C-(β-D-xylanosyl)acetone and acetonitrile; S3. Under nitrogen protection, triethanolamine and NAD+ were added to Tris buffer solution. + The catalyst ① is mixed, and then the mother liquor is added under light-protected conditions to react and obtain S-Bosein.

2. The method for preparing S-Bosein according to claim 1, characterized in that, The amount of catalyst ① added during the inactivation treatment accounts for 3-4 wt% of the total mass of the raw materials.

3. The method for preparing S-Bosein according to claim 1, characterized in that, The inactivated catalyst ① is prepared as follows: the catalyst ①, which has been recycled at least once, is shaken in boiling water for at least 20 minutes to obtain the inactivated catalyst ①.

4. The method for preparing S-Bosein according to claim 3, characterized in that, The catalyst ① used for the inactivation treatment is a catalyst ① that has been recycled at least 5 times.

5. The method for preparing S-Bosein according to claim 1, characterized in that, The 1-C-(β-D-xylanosyl)acetone, tris(hydroxymethyl)aminomethane, triethanolamine, and NAD + The mass ratio of catalyst ① is 1: (1.25~1.27): (7.7~7.9): (0.34~0.36): (0.5~0.55).

6. The method for preparing S-Bosein according to claim 1, characterized in that, The reaction in step S3 is carried out under light irradiation with a wavelength greater than 420 nm, at a reaction temperature of 35~45℃, a reaction pH of 6.5~7.5, and a reaction time of 7~9 h.

7. The method for preparing S-Bosein according to claim 1, characterized in that, The preparation steps of the catalyst ① are as follows: 0.01 parts by mass of magnetic support are weighed and dispersed in 4-5 parts by mass of Tris buffer solution containing 0.2 mg / mL reductase and pH 7, stirred at 4°C for 2 h, centrifuged, washed and freeze-dried to obtain the composite enzyme catalyst.

8. The method for preparing S-Bosein according to claim 7, characterized in that, The preparation steps of the magnetic carrier are as follows: A1. Mix 0.8 parts by weight of magnetic powder with 62.8-64 parts by weight of isopropanol and 3.2 parts by weight of ultrapure water, and ultrasonically disperse for at least 30 minutes. Then, under stirring, add 14.4-16 parts by weight of ammonia water and 4.46-4.8 parts by weight of tetraethyl orthosilicate. React at 40-50°C for 5-7 hours. After the reaction is completed, cool naturally to room temperature, centrifuge, wash 2-4 times with deionized water and anhydrous ethanol, collect with a magnet, and dry to obtain silica-coated magnetic particles. A2. Mix 1.5-1.6 parts by weight of succinic anhydride with 3-3.2 parts by weight of 3-aminopropyltriethoxysilane and 76-96 parts by weight of ethanol, sonicate for at least 30 min, and then react at 25-35℃ for 2-4 h. Finally, add 0.15-0.16 parts by weight of silica-coated magnetic particles, 64-80 parts by weight of ethanol and 12-15 parts by weight of ultrapure water, continue to sonicate for at least 30 min, and react at 25-35 min for 11-13 h. After the reaction is completed, cool naturally to room temperature, centrifuge, wash 2-4 times with deionized water and anhydrous ethanol, collect with a magnet, and dry to obtain carboxylated silica-coated magnetic particles. A3. Dissolve 0.03-0.06 parts by weight of zirconium tetrachloride, 0.03-0.06 parts by weight of 2-aminoterephthalic acid, 0.01-0.02 parts by weight of 5,10,15,20-tetra(4-carboxyphenyl)porphyrin, and 0.5-1 parts by weight of benzoic acid in 3.78-4 parts by weight of N,N-dimethylformamide. After ultrasonic dispersion for at least 20 min, add 0.002-0.004 parts by weight of carboxylated silica to coat the magnetic particles, and continue ultrasonic dispersion for at least 20 min. Under stirring, heat to 120-130℃ and reflux for 4-24 h. Centrifuge, wash 2-4 times with deionized water and anhydrous ethanol, collect with a magnet, and dry to obtain the magnetic carrier.

9. The method for preparing S-Bosein according to claim 7, characterized in that, The reductase includes Rhodococcus rubrum alcohol dehydrogenase.

10. An application of S-Bosonic, characterized in that, The S-Bosein prepared by the method according to any one of claims 1 to 9 is used in the cosmetics field.

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