Method for reducing volatile odor of sulfydryl-containing cosmetic raw material, cosmetic raw material and application

By combining ginseng saponin with thiol-containing cosmetic raw materials and using covalent or non-covalent bonds to form a complex, the problem of odor suppression in cosmetics is solved and the user experience is significantly improved.

CN119139155AActive Publication Date: 2024-12-17INCIPIRIT TECH (GUANGZHOU) CO LTD +1
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Patent Information

Application Number
CN202411671561.4
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2024-11-21
Publication Date
2024-12-17
Estimated Expiration
2044-11-21

AI Technical Summary

Technical Problem

The prior art is difficult to effectively inhibit the volatile odor of thiolated materials in cosmetics and affect user experience.

Method used

Complexes are formed by combining ginseng saponins with thiol-containing cosmetic raw materials such as ergothione and glutathione, using covalent or non-covalent bonds (such as hydrogen bonds, hydrophobic action, ionic bonds and van der Waals forces) Combination is carried out to inhibit the production of odor.

Benefits of technology

Almost completely suppresses the odor of cosmetic raw materials, improves the user comfort of cosmetics, and effectively inhibits the generation of odors under light conditions.

✦ Generated by Eureka AI based on patent content.

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Abstract

The invention belongs to the field of daily chemicals, and discloses a method for reducing volatile odor of a sulfydryl-containing cosmetic raw material, and ginsenoside and the sulfydryl-containing cosmetic raw material are combined to form a compound so as to reduce the volatile odor of the cosmetic raw material. According to the method, ginsenoside and cosmetic raw materials are combined to form a compound, and the compound can effectively reduce smell volatilization of the cosmetic raw materials. Meanwhile, the invention further discloses a cosmetic raw material and application.
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Description

Technical Field

[0001] The invention relates to the field of daily chemicals, and in particular to a method for reducing the volatile odor of a cosmetic raw material containing a mercapto group, the cosmetic raw material and its use. Background Art

[0002] Ergothioneine (EGT) is a rare natural amino acid with excellent antioxidant properties and is widely used in cosmetics as a free radical scavenger and metal ion chelator. Despite the benefits of EGT, it has an unpleasant odor that affects the user experience. Glutathione (GSH), known for its antioxidant properties and ability to inhibit tyrosinase activity, is widely used in skin care products for its anti-aging and whitening effects. However, both ingredients produce unpleasant odors due to the presence of thiol (-SH) groups, which reduces user comfort.

[0003] In order to suppress this unpleasant odor, those skilled in the art solve it by the following method: Prior art 1: A patent application with publication number CN117752539A, the subject of which is a composition for inhibiting the degradation and odor of ergothioneine and its application, which adopts a compound of licorice extract, cyclodextrin and ergothioneine, and mainly improves the photostability through licorice extract, thereby reducing the odor.

[0004] Prior art 2: A patent application with publication number CN116531270A, the subject of which is a composition containing ergothioneine and a silicone elastomer active substance and its application, which adopts a silicone elastomer active substance and ergothioneine compound, and mainly stabilizes ergothioneine by the silicone elastomer active substance, thereby reducing the trimethylamine odor produced by ergothioneine under conditions of high temperature, light and normal temperature.

[0005] Prior art 3: A patent application with publication number CN115363980A, the subject of which is a composition containing ergothioneine and persimmon fruit extract and its application, which adopts a compound of persimmon (DIOSPYROS KAKI) fruit extract and ergothioneine, and mainly uses persimmon (DIOSPYROS KAKI) fruit extract to reduce the odor produced by ergothioneine under light, high temperature and normal temperature conditions.

[0006] Prior art 4: Patent application with publication number CN108135964B, with the subject matter being glutathione preparation and method of use, which uses a compound of crystalline ascorbic acid and glutathione, and which does not provide a thiol odor to humans. It does not disclose the reason for not emitting a thiol odor.

[0007] Among the above-mentioned compounds, licorice extract, persimmon (DIOSPYROS KAKI) fruit extract, and ascorbic acid all have clear antioxidant functions. We believe that the main mechanism of inhibiting the odor of related cosmetic raw materials lies in the antioxidant properties to inhibit the decomposition of cosmetic raw materials.

[0008] The technical problem solved in this case is how to suppress the odor of cosmetic raw materials based on a new method. Summary of the invention

[0009] The object of the present invention is to provide a method for reducing the volatile odor of thiol-containing cosmetic raw materials. The method combines ginsenosides with the cosmetic raw materials to form a complex, and the complex can effectively reduce the volatile odor of the cosmetic raw materials.

[0010] At the same time, the invention also discloses a cosmetic raw material, application and cosmetic.

[0011] To achieve the above objectives, this application discloses: A method for reducing the volatile odor of a cosmetic raw material containing a thiol group comprises combining ginsenoside and the cosmetic raw material containing a thiol group to form a complex so as to reduce the volatile odor of the cosmetic raw material.

[0012] Compared with the prior art, which mostly suppresses odor based on its antioxidant properties or inhibits the decomposition of cosmetic raw materials under conditions such as light, the present invention verifies through experiments that ginsenosides and cosmetic raw materials can almost completely suppress the generation of volatile gases even when they are immediately combined, indicating that the ginsenosides of the present invention suppress the generation of odor of cosmetic raw materials based on the form of covalent bonds or non-covalent bonds between the two, and not mainly through antioxidant properties. Under light conditions, the technical solution of the present invention can also effectively suppress the generation of odor.

[0013] In summary, the technical solution of the present invention is superior to the traditional method of suppressing odor generation.

[0014] In the above method, the ginsenoside and the thiol-containing cosmetic raw material are combined by covalent or non-covalent bonding; The non-covalent bond is based on one or more of hydrogen bonds, hydrophobic interactions, ionic bonds and van der Waals forces.

[0015] Through experimental verification, through the changes in mechanical parameters such as enthalpy change, entropy change and Gibbs free energy, it is preliminarily determined that the binding process of ginsenosides and thiol-containing cosmetic raw materials is endothermic and hydrophobic forces play an important role in the binding process. The experimental verification of the present invention cannot rule out the existence of hydrogen bonds and van der Waals forces between the two. The experimental verification process of the present invention proves that the entire binding process is spontaneous.

[0016] In the above method, the ginsenoside is a combination of one or more of protopanaxadiol saponins and protopanaxatriol saponins. In a further preferred embodiment of the present invention, the ginsenoside is ginsenoside Rb1, ginsenoside Rb2, ginsenoside Rc; ginsenoside Rd; ginsenoside Re; ginsenoside Rg1; ginsenoside Rg2; ginsenoside Rg3; ginsenoside Rh1; ginsenoside Rh2; ginsenoside CK; ginsenoside Rk3; ginsenoside Rh4.

[0017] Further preferably, the optional protopanaxadiol type saponins are: ginsenosides Rg3, Rh2, and Rg5; The optional protopanaxatriol saponins are: ginsenosides Rk3, Rh4, Rh1, and Rg2.

[0018] In further experimental verification of the present invention, it is confirmed that thioneine forms a complex with five saponins of ginsenosides Rb1, Rb2, Re, Rg1 and Rg2, thereby covering up the bad smell of thioneine. The binding constant is detected by liquid chromatography-mass spectrometry, and the result shows that the binding constant of thioneine and ginsenoside Rb1 is large, indicating that ginsenoside Rb1 in EGT and GS is more likely to form a stable complex.

[0019] In further experimental verification of the present invention, it was confirmed that glutathione binds to a variety of ginsenosides, and the binding constants were calculated by ultra-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS). The results showed that glutathione had a strong binding effect with ginsenosides Rb1 and Rb2, and the binding constants of the two with GSH could be calculated. They all belonged to the ginsenosides of the ginsenosides group, indicating that compared with the triol group, the molecular structure of the ginsenosides ...

[0020] In the above method, in the composite, the mass ratio of ginsenoside to the thiol-containing cosmetic raw material is 0.1 to 10:1.

[0021] In the above method, the sulfhydryl-containing cosmetic raw material is ergothioneine or glutathione.

[0022] Meanwhile, the present invention also discloses a cosmetic raw material, wherein the cosmetic raw material is powder, and the powder is a composite formed by combining ginsenoside and a thiol-containing cosmetic raw material.

[0023] The preparation method of the above raw materials can refer to the following steps: The ginsenosides are dissolved in 5-10 mL of ethanol according to the mass ratio of the thiol-containing cosmetic raw materials to the ginsenosides, and then the alcohol solution is added to pure water. The thiol-containing compound is dissolved in pure water, and then added to the above-mentioned alcohol solution of ginsenosides, stirred and dispersed at room temperature, and freeze-dried.

[0024] More preferably, the ginsenosides are dissolved in 5-10 mL of ethanol according to the mass ratio of the sulfhydryl-containing compound to the ginsenosides, ultrasonicated for 5-15 minutes to completely dissolve, and then slowly dripped into 10-20 mL of pure water while stirring. The sulfhydryl-containing compound is dissolved in 5-10 mL of pure water, slowly dripped into the above solution while stirring, stirred at room temperature for 1-2 hours, freeze-dried, and sealed and stored at 4°C.

[0025] In the above-mentioned cosmetic raw materials, the ginsenoside and the thiol-containing cosmetic raw materials are combined by covalent bonds or non-covalent bonds; The non-covalent bond is based on one or more of hydrogen bonds, hydrophobic interactions, ionic bonds and van der Waals forces.

[0026] In the above-mentioned cosmetic raw materials, the ginsenosides are one or more combinations of protopanaxadiol saponins and protopanaxatriol saponins.

[0027] In the above-mentioned cosmetic raw materials, the ginsenosides are ginsenoside Rb1, ginsenoside Rb2, ginsenoside Rc, ginsenoside Rd, ginsenoside Re, ginsenoside Rg1, ginsenoside Rg2, ginsenoside Rg3, ginsenoside Rh1, ginsenoside Rh2, ginsenoside CK, ginsenoside Rk3 and ginsenoside Rh4.

[0028] In the above-mentioned cosmetic raw material, in the composite, the mass ratio of ginsenoside to the thiol-containing cosmetic raw material is 0.1 to 10:1.

[0029] In the above-mentioned cosmetic raw materials, the thiol-containing cosmetic raw material is ergothioneine or glutathione or cysteine.

[0030] In addition, the present invention also discloses the use of the cosmetic raw materials mentioned above in preparing cosmetics.

[0031] In the above-mentioned use, the cosmetic is a cosmetic that acts on the skin or a cosmetic that acts on the hair.

[0032] Finally, the present invention also discloses a cosmetic containing the cosmetic raw material as described above.

[0033] This application has at least the following beneficial effects: The present invention uses ginsenosides to form a complex to mask the unpleasant smell of EGT and GSH, and the supramolecular effect of the complex inhibits the release of bad odor. In the study, ultraviolet spectroscopy (UV-2700 spectrophotometer, Shimadzu), fluorescence spectroscopy (RF-6000 spectrophotometer, Shimadzu) and ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry UPLC / QTOF-MS (Xevo G2-XS QTOF, Waters) were used to analyze the spatial conformation, molecular polarity, energy transfer and connection with ginsenoside GS of EGT and GSH in the complex. The results showed that EGT and GSH interacted with GS respectively, and GS quenched the fluorescence of EGT and GSH through a static quenching mechanism. Thermodynamic analysis showed that there were spontaneous reactions and intermolecular forces. UPLC / QTOF-MS detection proved that EGT formed a supramolecular complex with Rb1, Rb2, Re, Rg1 and Rg2 in total ginsenosides, while GSH formed a supramolecular complex with Rb1 and Rb2 in total ginsenosides. The present invention confirmed that the EGT-GS and GTH-GS complexes effectively masked the unpleasant odors of EGT and GTH, providing a promising strategy for masking the unpleasant odors of cosmetics containing glutathione or ergothioneine, and providing a new method for improving the user comfort of skin care products with thiol components. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is the UV-visible absorption spectra of EGT under the influence of GS and different concentrations of GS; Figure 2 It is the fluorescence emission spectrum of EGT under the influence of different concentrations of GS; Figure 3 is the synchronous fluorescence spectra of EGT under the influence of different concentrations of GS (Δλ=15nm); Figure 4 is the synchronous fluorescence spectra of EGT under the influence of different concentrations of GS (Δλ=60nm); Figure 5 It is the resonance light scattering fluorescence spectra of EGT and EGT-GS under the influence of different concentrations of GS; Figure 6 is the 1 / ΔF versus 1 / [Q] plot for the GS-EGT system at different temperatures; Figure 7 It is the Van't Hoff curve of EGT; Figure 8 This is the total ion current of the sample in the negative ion mode when the mass concentration of EGT and GS is 1:1; Fig. 9 It is the mass spectrum and extracted ion chromatogram of EGT in negative ion mode; Fig.10It is the mass spectrum and extracted ion chromatogram of EGT-Rb1 in negative ion mode; Fig.11 This is the mass spectrum and extracted ion chromatogram of EGT-Rb2 in negative ion mode; Fig.12 This is the mass spectrum and extracted ion chromatogram of EGT-Re in negative ion mode; Fig.13 It is the mass spectrum and extracted ion chromatogram of EGT-Rg1 in negative ion mode; Fig.14 This is the mass spectrum and extracted ion chromatogram of EGT-Rg2 in negative ion mode; Fig.15 The GS-Rb1 system 1 / ΔIr versus 1 / C H The linear curve of Fig.16 The GS-Rb2 system 1 / ΔIr versus 1 / C H The linear curve of Fig.17 is the GS-Re system 1 / ΔIr to 1 / C H The linear curve of Fig.18 The GS-Rg1 system 1 / ΔIr versus 1 / C H The linear curve of Fig.19 The EGT-Rg2 system 1 / ΔIr versus 1 / C H The linear curve of Fig. 20 It is the fluorescence spectrum of GSH under the influence of different concentrations of GS; Fig.21 is the resonance light scattering fluorescence spectra of GSH and GSH-GS under the influence of different concentrations of GS; Fig. 22 is the Stern-Volmer plot of GSH at different temperatures; Fig.23 is the Van 't Hoff curve of GSH; Fig.24 This is the total ion current of the sample when the mass concentration of GSH and GS is 1:1 in the negative ion mode; Fig.25 is the mass spectrum (a) and extracted ion chromatogram (b) of GSH in negative ion mode; Fig.26 It is the mass spectra and extracted ion chromatograms of GSH-Rb1 (a1, b1) and GSH-Rb2 (a2, b2) in negative ion mode; Fig. 27 The GS-Rb1 system 1 / ΔIr versus 1 / C H The linear curve of Fig.28 The GS-Rb2 system 1 / ΔIr versus 1 / C H The linear curve. DETAILED DESCRIPTION

[0035] Below in conjunction with embodiments of the present invention, the present invention is clearly and completely described. In the description of the present invention, it should be noted that, in the embodiments, those not indicating specific conditions, are carried out according to the conditions of normal conditions or manufacturer's suggestions. Reagents used or instruments not indicating manufacturers are conventional products that can be obtained by commercial purchase. In the case of not making special instructions, the parts used in the embodiments of the present invention are all parts by weight.

[0036] Example 1

[0037] Preparation of ginsenoside and ergothioneine complex (EGT-GS): The materials were added according to the mass ratio of ergothioneine (1-40 parts) to ginsenoside (1 part). Ginsenoside was dissolved in 5 mL of ethanol, ultrasonicated for 10 minutes to dissolve completely, and then slowly dripped into 10 mL of pure water while stirring. Ergothioneine was dissolved in 5 mL of pure water, slowly dripped into the above solution while stirring, stirred at room temperature for 1-2 hours, freeze-dried, and sealed and stored at 4°C.

[0038] The ginsenosides used in this example are produced by Hezhimei Biotechnology Co., Ltd. HPLC content determination shows that the contents of ginsenoside Rb1, ginsenoside Rb2, ginsenoside Re, ginsenoside Rg1, and ginsenoside Rg2 in total ginsenosides powder are 20.42 mg / g, 39.58 mg / g, 322.32 mg / g, 127.38 mg / g, and 27.01 mg / g, respectively.

[0039] Steady-state UV-visible absorption spectroscopy characterizes the formation of EGT-GS complex: A certain amount of EGT-GS complex powder was accurately weighed, dissolved in 20 mL of pure water, and fully shaken to dissolve and mix to obtain a complex solution with an EGT concentration of 0.05 mg / mL, and the steady-state UV-visible absorption spectrum was detected on a UV-2700 ultraviolet spectrophotometer. The wavelength scanning range was 200 nm-500 nm, the data interval was 0.5 nm, and the ultraviolet spectrum was scanned at 298 K.

[0040] Experimental conclusion: According to the experimental results (see Figure 1) It can be seen that EGT has a maximum absorption peak near 257 nm. As the concentration of GS increases, the absorption value of EGT at 257 nm gradually increases significantly, while GS has no ultraviolet absorption at 257 nm, indicating that GS and EGT interact with each other to form a complex. After adding GS, the maximum absorption wavelength of EGT did not change significantly, and no red shift or blue shift occurred, indicating that the interaction between the two did not cause changes in the structure of EGT.

[0041] Fluorescence emission spectroscopy demonstrated the formation of EGT-GS complex: A certain amount of EGT-GS complex powder was accurately weighed, dissolved in 20 mL of pure water, and fully shaken to dissolve and mix to obtain a complex solution with an EGT concentration of 0.05 mg / mL, and emission spectrum detection was performed on an RF-6000 fluorescence spectrophotometer. The excitation light wavelength was 280 nm, the emission light wavelength range was 300 nm-500 nm, the data interval was 1.0 nm, the scanning speed was 6000 nm / min, the excitation light spectrum width was 5.0 nm, the emission light spectrum width was 5.0 nm, and the fluorescence spectrum was scanned at 298 K.

[0042] Conclusion: The results show that (see Figure 2 ), EGT has a maximum emission peak at 311 nm. As the concentration of GS added to EGT gradually increases, the fluorescence emission intensity of EGT increases regularly, which means that GS has a quenching effect on the fluorescence of EGT. At the same time, it can be seen from the figure that the maximum emission wavelength of EGT has a significant red shift from 311 nm to 313 nm, indicating that GS has changed the conformation of EGT and increased the polarity of the microenvironment where the chromophore in EGT is located.

[0043] Synchronous fluorescence spectroscopy confirmed the formation of EGT-GS complex: A certain amount of EGT-GS complex powder was accurately weighed, dissolved in 20 mL of pure water, and fully shaken to dissolve and mix to obtain a complex solution with an EGT concentration of 0.05 mg / mL, and synchronous fluorescence spectrum detection was performed on an RF-6000 fluorescence spectrophotometer. The excitation wavelength was 280 nm, the emission wavelength ranges of Δλ=15 nm and Δλ=60 nm were 265 nm-500 nm and 220 nm-500 nm, respectively, the data interval was 1.0 nm, the scanning speed was 6000 nm / min, the excitation spectrum width was 5.0 nm, the emission spectrum width was 5.0 nm, and the fluorescence spectrum was scanned at 298 K.

[0044] Conclusion: If Figure 3 , 4As shown in the figure, with the increase of GS concentration, the fluorescence intensity at Δλ=15 nm and Δλ=60 nm gradually increased, and the maximum wavelength of EGT in the synchronous fluorescence spectrum slightly red-shifted, indicating that the polarity of the solvent environment around the chromophore in EGT increased.

[0045] Resonance light scattering spectroscopy characterization of the interaction between GS and EGT: A certain amount of EGT-GS complex powder was accurately weighed, dissolved in 20 mL of pure water, and fully shaken to dissolve and mix to obtain a complex solution with an EGT concentration of 0.05 mg / mL, and resonance light scattering fluorescence spectrum detection was performed on an RF-6000 fluorescence spectrophotometer. The excitation light wavelength was 280 nm, the emission light wavelength range was 280 nm-500 nm, the data interval was 1.0 nm, the scanning speed was 6000 nm / min, the excitation light spectrum width was 5.0 nm, the emission light spectrum width was 5.0 nm, and the fluorescence spectrum scanning was performed at 298 K.

[0046] Conclusion: If Figure 5 As shown in the figure, the maximum RLS scattering peaks of EGT and EGT-GS systems are both located at 290nm, and the RLS intensity of EGT is the lowest. As the concentration of GS increases, the RLS fluorescence intensity of EGT increases significantly, indicating that GS interacts with EGT to form EGT-GS composite particles, which are larger in size than EGT.

[0047] The binding constant between GS and EGT was studied using the fluorescence enhancement theory formula: A certain amount of EGT-GS complex powder was accurately weighed and dissolved in 20 mL of pure water. The powder was fully shaken to dissolve and mix to obtain a complex solution with an EGT concentration of 0.05 mg / mL. Three groups were prepared in parallel and kept in a constant temperature water bath at 310.15 K (37°C), 320.15 K (47°C) and 330.15 K (57°C) for 15 min. The sample solution after the constant temperature water bath was taken for emission spectrum detection on an RF-6000 fluorescence spectrophotometer. The excitation light wavelength was 280 nm, the emission light wavelength range was 300 nm-500 nm, the data interval was 1.0 nm, the scanning speed was 6000 nm / min, the excitation light spectrum width was 5.0 nm, and the emission light spectrum width was 5.0 nm. A quartz cuvette with four sides transparent was used for fluorescence spectrum scanning.

[0048] Fluorescence enhancement formula: (1) ; Where, ΔF=FF 0 , ΔF max =F ∞ -F 0 , while F 0 , F and F ∞The fluorescence intensity of EGT without GS, with a specific concentration of GS, and when the interaction between EGT and GS reaches saturation. K is the binding constant, and [Q] is the concentration of GS added. Plot 1 / ΔF against 1 / [Q], and the ratio of the intercept to the slope is the K value.

[0049] in conclusion: Figure 6 The 1 / ΔF versus 1 / [Q] diagram of the GS-EGT system at different temperatures shows a linear relationship between 1 / ΔF and 1 / [Q]. The linear equations at 310.15K, 320.15K, and 330.15K are y = 1.0081×10 -5 x + 4.3792×10 -5 , y =1.1359×10 -5 x + 5.1615×10 -5 , y =1.1940×10 -5 x + 6.1125×10 -5 The calculation results are shown in Table 1. From the data in the table, we can see that the binding constants K at 310.15 K, 320.15 K, and 330.15 K are A They are 4.3440, 4.5440, and 5.1193 respectively, and the binding constant K A Increases with increasing temperature.

[0050] Table 1 Binding constants of GS and EGT at different temperatures ( K A ) T(K) <![CDATA[K A ]]> <![CDATA[R a ]]> 310.15 4.3440 0.9836 320.15 4.5440 0.9914 330.15 5.1193 0.9948

[0051] a R represents the correlation coefficient The interaction force between EGT and GS in the complex: A certain amount of EGT-GS complex powder was accurately weighed and dissolved in 20 mL of pure water. The powder was fully shaken to dissolve and mix to obtain a complex solution with an EGT concentration of 0.05 mg / mL. Three groups were prepared in parallel and kept in a constant temperature water bath at 310.15 K (37°C), 320.15 K (47°C) and 330.15 K (57°C) for 15 min. The sample solution after the constant temperature water bath was taken for emission spectrum detection on an RF-6000 fluorescence spectrophotometer. The excitation light wavelength was 280 nm, the emission light wavelength range was 300 nm-500 nm, the data interval was 1.0 nm, the scanning speed was 6000 nm / min, the excitation light spectrum width was 5.0 nm, and the emission light spectrum width was 5.0 nm. A quartz cuvette with four sides transparent was used for fluorescence spectrum scanning.

[0052] Calculation formula, Van't Hoff equation (2); in, represents the standard enthalpy change, represents the standard entropy change, R is the molar gas constant, K represents the equilibrium constant, and the binding constant at a specific temperature K A Similarly, T represents temperature (310.15 K, 320.15 K, and 330.15 K).

[0053] Calculation results: Plot the van't Hoff plot with lnK versus 1 / T (e.g. Figure 7 The slope and intercept can be calculated respectively. and , when the temperature changes little within the measurement range, and Can be considered as a constant.

[0054] Gibbs free energy ( ) Calculation formula: (3); Conclusion: Calculated by formula (3). , and The calculation results are listed in Table 2, where (6.9552 kJ∙mol -1 )、 (34.5305 J∙mol -1 ∙K -1 ) are all greater than 0, indicating that the binding process is endothermic and that hydrophobic forces play an important role in the binding process. (-3.7545 kJ∙mol -1 , -4.0998 kJ∙mol -1 and -4.4451 kJ∙mol -1 ) are all negative at 310.15 K, 320.15 K, and 330.15 K, indicating that the reaction process is spontaneous.

[0055] Table 2 Thermodynamic parameters of EGT and GS reactions

[0056] UPLC-QTOF-MS method was used to calculate the binding constant of EGT and GS: The materials were added according to the mass ratio of ergothioneine (1.5-3 parts) to ginsenoside (3 parts). Ginsenoside was dissolved in 5 mL of ethanol, ultrasonicated for 10 minutes to dissolve it completely, and then slowly dripped into 10 mL of pure water while stirring. Ergothioneine was dissolved in 5 mL of pure water, slowly dripped into the above solution while stirring, stirred at room temperature for 1-2 hours, freeze-dried, and sealed and stored at 4°C. A certain amount of EGT-GS complex powder was accurately weighed, dissolved in 1 mL of pure water, and fully oscillated to dissolve and mix to obtain a complex solution with an EGT concentration of 3.0 mg / mL.

[0057] UPLC-QTOF-MS analysis conditions: Ultra-high performance liquid chromatography (Waters ACQUITY UPLC I Class, Waters Corporation, USA) was used to separate the components. The chromatographic column was BEH C18 (2.1 mm×50 mm, 1.7 μm), and the mobile phase consisted of acetonitrile containing 0.1% formic acid (A) and water containing 0.1% formic acid (B). The flow rate was 0.4 mL / min, the injection volume was 2 μL, the pressure range was 0-15 000 psi, and the column temperature was room temperature. The gradient elution program is shown in Table 3. Mass spectrometry detection used an electrospray ionization source (ESI), negative ion mode and MS E Continuum mode. Scanning mass range: 50-2 000 Da, scanning time: 0.5 s, collision energy: 6-20 V.

[0058] Table 3 UPLC gradient elution program Time / min Acetonitrile (A) Water (B) 0 10.0% 90.0% 2 30.0% 70.0% 4 50.0% 50.0% 8 60.0% 40.0% 13 80.0% 20.0% 20 90.0% 10.0% 24 95.0% 5.0% 27 95.0% 5.0% 28 10.0% 90.0% 30 10.0% 90.0%

[0059] UPLC-QTOF-MS identification results: The total ion current of EGT-GS sample is shown in Figure 8 According to the above UPLC / QTOF-MS method and conditions, the chemical components in the complex solution with a mass concentration ratio of EGT to GS of 1:1 were detected, and the total ion current of the test sample was obtained, such as Figure 8 shown.

[0060] UPLC-QTOF-MS was used to collect mass spectrometry data, and the UNIFI database was used to identify the chemical components in the samples. Component screening was performed based on total ion current, mass spectrum, retention time, mass-to-charge ratio, error, response value and other information. Combined with literature data and mass spectrometry fragmentation rules, EGT and 5 chemical components combined with ginsenoside monomers were finally identified from the test samples. The identification results are shown in Table 4.

[0061] Table 4 UPLC-QTOF-MS compound identification results of EGT-GS (1:1) No. Retention time / min Molecular formula Measured value / (Da) Theoretical value / Da Mass deviation / mDa Adduct ion Compound Name Fragment ion m / z 1 3.72 <![CDATA[C 63 H 108 N 3 O 25 S]]> 1319.7572 1319.6809 76.3 <![CDATA[-H 2 O-H + ]]> EGT-Rb1 <![CDATA[1336.7443[M-2H]-,1335.6514[M-3H]-,1365.6885[M-H 2 O+HCOO]-]]> 2 3.90 <![CDATA[C 62 H 106 N 3 O 24 S]]> 1353.7194 1353.6864 33.0 <![CDATA[+HCOO - ]]> EGT-Rb2 <![CDATA[1289.7396[M-H 2 O-H]-]]> 3 4.51 <![CDATA[C 57 H 98 N 3 O 20 S]]> 1221.5829 1221.6441 -61.2 <![CDATA[+HCOO - ]]> EGT-Re <![CDATA[1175.5995[M-H]-,1174.5957[M-2H]-,1173.5922[M-3H]-,1157.5814[M-H 2 O-H]- <!-- 8 -->]]> 4 5.13 <![CDATA[C 51 H 88 N 3 O 16 S]]> 1075.5671 1075.5862 -19.1 <![CDATA[+HCOO - ]]> EGT-Rg1 <![CDATA[1029.6060[M-H]-,1028.6008[M-2H]-,1027.5107[M-3H]-,1011.5363[M-H 2 OH]-,1057.5364[MH 2 O+HCOO]-]]> 5 2.76 <![CDATA[C 51 H 88 N 3 O 15 S]]> 1059.4952 1059.5913 -96.1 <![CDATA[+HCOO - ]]> EGT-Rg2 <![CDATA[1012.5266[M-2H]-,1011.5493[M-3H]-,995.5255[M-H 2 O-H]-]]> 6 0.79 <![CDATA[C 9 H 15 N 3 O 2 S]]> 228.0862 228.0812 5.0 <![CDATA[-H + ]]> EGT 227.0173[M-2H]-

[0062] Extracted ion chromatogram and mass spectrum of main EGT: The chemical composition of EGT was detected by the above-mentioned UPLC-QTOF-MS technology. The detection was carried out in the negative ion mode to obtain the mass spectrum and extracted ion chromatogram of EGT, as shown in FIG. Fig. 9 shown.

[0063] Extracted ion chromatogram and mass spectrum of the complex generated by the EGT-GS system: UPLC-QTOF-MS technology was used to detect the chemical components in samples of EGT and GS with different mass concentrations. The detection was carried out in negative ion mode to obtain the mass spectra and extracted ion chromatograms of EGT-Rb1, EGT-Rb2, EGT-Re, EGT-Rg1, and EGT-Rg2, as shown in Figure 2. Figure 10-14 shown.

[0064] Calculation of binding constant: According to the formula derived by Loukas, the calculation is based on the ion count ratio of the guest molecule (EGT) to the complex in the solution (1 / ∆ I r ) and the concentration of the main body (1 / C H ), make a Scatchard-style plot of the linear curve, the ratio of the intercept and slope of the line is the binding constant K st .

[0065] Loukas formula and derivation process: (1) ; (1 / ΔI r 1 / C H Plotting, the ratio of the intercept to the slope is K st ); ; Where: K C is the proportionality constant, K st is the binding constant, C H is the initial concentration of the bulk, C G is the initial concentration of the guest, I HG is the complex ion count, I G is the guest ion count, I r is the ionization efficiency, I 0 is the initial ionization efficiency.

[0066] Calculation of binding constant between EGT and ginsenoside Rb1: The concentration of fixed EGT is 9.7693×10 -3mol / L, and the molar concentration ratios of ginsenoside Rb1 were 1:0.0028, 1:0.0034, 1:0.0045, 1:0.0051, 1:0.0054, 1:0.0057, respectively. The integration intervals were 0.77-0.81min and 3.70-3.74min, and the ion counts were statistically calculated. H Drawing, see Fig.15 , we get the linear equation y =5×10 -5 x +0.6653, R 2 = 0.9642, the calculated binding constant is K st =1.3306×10 4 (mol / L) -1 .

[0067] Calculation of binding constant between EGT and ginsenoside Rb2: The concentration of fixed EGT is 9.7693×10 -3 mol / L, and the molar concentration ratios of ginsenoside Rb2 were 1:0.0056, 1:0.0079, 1:0.0090, 1:0.0101, 1:0.0107, 1:0.0173, respectively. The integration intervals were 0.77-0.81min and 3.88-3.92min, and the ion counts were statistically calculated. r 1 / C H Drawing, see Fig.16 , we get the linear equation y = 0.0025x -13.63, R 2 = 0.9908, the calculated binding constant is K st =5.4520×10 3 (mol / L) -1 .

[0068] Calculation of the binding constant of EGT and ginsenoside Re: The concentration of fixed EGT is 9.7693×10 -3 mol / L, and the molar concentration ratios of ginsenoside Re were 1:0.0523, 1:0.0627, 1:0.0732, 1:0.0837, 1:0.0889, 1:0.0941, 1:0.0993, 1:0.1046, respectively. The integration intervals were 0.77-0.81min and 4.49-4.53min, and the ion counts were statistically calculated. H Drawing, see Fig.17 , we get the linear equation y = 0.0119x + 6.9966, R 2 = 0.9327, the binding constant is calculated to be K st =5.8795×10 2(mol / L) -1 .

[0069] Calculation of binding constant between EGT and ginsenoside Rg1: The concentration of fixed EGT is 9.7693×10 -3 mol / L, and the molar concentration ratios of ginsenoside Rg1 were 1:0.0244, 1:0.0342, 1:0.0391, 1:0.0440, 1:0.0464, 1:0.0489, respectively. The integration intervals were 0.77-0.81min and 5.11-5.15min, and the ion counts were statistically calculated. H Drawing, see Fig.18 , we get the linear equation y = 0.0022x +3.7329, R 2 = 0.9594, the calculated binding constant is K st =1.6968×10 3 (mol / L) -1 .

[0070] Calculation of binding constant between EGT and ginsenoside Rg2: The concentration of fixed EGT is 9.7693×10 -3 mol / L, the molar concentration ratio of EGT-Rg2 was 1:0.0063, 1:0.0074, 1:0.0085, 1:0.0095, 1:0.0100, 1:0.0106, the integration interval was 0.77~0.81min, 2.74~2.78min, and the ion count was statistically calculated. H Drawing, see Fig.19 , we get the linear equation y = 0.0009x -3.3127, R 2 = 0.9808, calculated K st =3.6808×10 3 (mol / L) -1 .

[0071] Summary: This study used a variety of spectral methods to deeply study the interaction between EGT and GS. The results of the steady-state UV-visible absorption spectrum experiment showed that a ground state complex was formed between EGT and GS. The results of the fluorescence emission spectrum showed that the formation of the complex led to the enhancement of EGT fluorescence and was a quenching process. Synchronous fluorescence spectroscopy showed that the polarity of the solvent environment around the chromophore in EGT increased. The results of the RLS resonance light scattering experiment showed that GS interacted with EGT to form a larger complex. Thermodynamic parameters showed that the binding process of GS and EGT was endothermic and hydrophobic forces played an important role in it. Based on the above experimental data, we speculate that GS formed a complex with EGT, thereby causing changes in the spatial conformation and physical properties of EGT. The chemical composition of the complex system was identified by UPLC-QTOF-MS, and it was found that EGT formed a complex with five ginsenosides in GS, namely ginsenosides Rb1, Rb2, Re, Rg1 and Rg2, thereby masking the unpleasant smell of ergothioneine. The binding constant was detected by liquid chromatography-mass spectrometry. The results showed that the binding constant of EGT and ginsenoside Rb1 was larger, indicating that EGT and ginsenoside Rb1 in GS can more easily form a stable complex.

[0072] Example 2 Preparation of Ginsenoside-Glutathione Complex (GSH-GS): Ginsenosides were added in a mass ratio of 1-40 parts of glutathione to 1 part of ginsenosides. Ginsenosides were dissolved in 5 mL of ethanol and ultrasonicated for 10 minutes to dissolve them completely. Then, 10 mL of pure water was slowly added while stirring. Glutathione was dissolved in 5 mL of pure water and slowly added while stirring to the above solution. The mixture was stirred at room temperature for 1-2 hours, freeze-dried, and sealed and stored at 4°C.

[0073] The ginsenosides used in this example are produced by Hezhimei Biotechnology Co., Ltd. and are the same raw material as the ginsenosides used in Example 1. During the detection process, only the relevant data of the binding of Rb1 and Rb2 to GSH were detected.

[0074] Fluorescence emission spectroscopy characterizes the formation of GSH-GS complex: A certain amount of GSH-GS complex powder was accurately weighed, dissolved in 20 mL of pure water, and fully shaken to dissolve and mix to obtain a complex solution with a GSH concentration of 3.0 mg / mL and ginsenoside concentrations of 0, 0.075, 0.375, 0.75, 1.5, and 3.0 mg / mL, and the emission spectrum was detected on an RF-6000 fluorescence spectrophotometer. The excitation wavelength was 240 nm, the emission wavelength range was 260 nm-460 nm, the data interval was 1.0 nm, the scanning speed was 6000 nm / min, the excitation spectrum width was 5.0 nm, and the emission spectrum width was 5.0 nm. The fluorescence spectrum was scanned at 298K.

[0075] Experimental conclusion: Fig. 20 The effect of GS on the fluorescence emission spectrum of GSH (excitation wavelength is 240nm) is shown. As shown in the figure, GSH has a maximum emission peak near 264nm. As the concentration of GS added increases, the intensity of the fluorescence emission peak of GSH gradually decreases, indicating that GS has a quenching effect on the fluorescence of GSH. At the same time, it can be seen from the figure that the maximum emission wavelength of GSH has a slight blue shift from 264 nm to 263 nm, indicating that GS may have changed the conformation of GSH and reduced the polarity of the microenvironment where the chromophore in GSH is located, proving that the GSH-GS complex has been formed. In this process, the conformation of GSH and the microenvironment where the chromophore is located have changed.

[0076] RLS resonance light scattering spectroscopy characterizes the formation of GSH-GS complex: A certain amount of GSH-GS complex powder was accurately weighed, dissolved in 20 mL of pure water, and fully shaken to dissolve and mix to obtain a complex solution with a GSH concentration of 3.0 mg / mL and ginsenoside concentrations of 0, 0.075, 0.375, 0.75, 1.5, and 3.0 mg / mL, and resonance light scattering spectrophotometry was performed on an RF-6000 fluorescence spectrophotometer. The excitation wavelength was 240 nm, the emission wavelength range was 240 nm-500 nm, the data interval was 1.0 nm, the scanning speed was 6000 nm / min, the excitation spectrum width was 5.0 nm, and the emission spectrum width was 5.0 nm. Fluorescence spectrum scanning was performed at 298K.

[0077] Conclusion: The results show that (see Fig.21 ),like Fig.21 As shown in the figure, the maximum RLS scattering peaks of GSH and GSH-GS system are both located at 253nm, and the RLS intensity of GSH is the lowest. As the concentration of GS increases, the RLS fluorescence intensity of GSH gradually increases, indicating that GS interacts with GSH to form GSH-GS complex particles, which are larger in size than GSH.

[0078] Effect of GSH-GS complex formation on GSH fluorescence quenching: A certain amount of GSH-GS complex powder was accurately weighed and dissolved in 20 mL of pure water. The powder was fully shaken to dissolve and mix to obtain a complex solution with a GSH concentration of 3.0 mg / mL and a ginsenoside concentration of 0, 0.075, 0.3, 0.375, 0.45, 0.60, 0.75, 0.9, 1.2, 1.5, and 3.0 mg / mL. Three groups were prepared in parallel and kept in a constant temperature water bath at 27°C (300.15K), 37°C (310.15K), and 47°C (320.15K) for 15 min. The sample solution after the constant temperature water bath was taken for emission spectrum detection on an RF-6000 fluorescence spectrophotometer. The excitation wavelength was 240 nm, the emission wavelength range was 260 nm-460 nm, the data interval was 1.0 nm, the scanning speed was 6000 nm / min, the excitation spectrum width was 5.0 nm, and the emission spectrum width was 5.0 nm.

[0079] The fluorescence quenching data of GSH at three different temperatures, 300.15 K, 310.15 K and 320.15 K, were investigated and calculated using the Stern-Volmer formula.

[0080] Stern-Volmer formula: , F 0 represents the maximum fluorescence intensity of GSH, F represents the maximum fluorescence intensity of GSH under the action of GS, [Q] represents the concentration of quencher, K SV represents the quenching constant, K q represents the quenching rate constant, represents the average fluorescence lifetime of GSH, which is approximately equal to 10 -8 Second.

[0081] in conclusion: Fig. 22 is the Stern-Volmer plot of GSH. It can be seen from the figure that there is a linear relationship between F0 / F and [Q]. The calculation results are shown in Table 5. From the data in the table, it can be seen that K SV The value increases with the increase of temperature. Therefore, we believe that the mechanism of GS quenching GSH fluorescence is dynamic quenching.

[0082] Table 5 Quenching constant (Ksv) and quenching rate constant (Kq) of GSH at different temperatures

[0083] a R represents the correlation coefficient The interaction force between GSH and GS in the complex; Calculation formula, Van't Hoff equation: (2) in, represents the standard enthalpy change, represents the standard entropy change, R is the molar gas constant, K represents the equilibrium constant, and the binding constant at a specific temperature K A Similarly, T represents temperature (310.15 K, 320.15 K, and 330.15 K).

[0084] Calculation results: Plot the van't Hoff plot with lnK versus 1 / T (e.g. Fig.23 The slope and intercept can be calculated respectively. and , when the temperature changes little within the measurement range, and Can be considered as a constant.

[0085] Gibbs free energy ( ) Calculation formula: (3) Conclusion: According to the above formula, at different temperatures , and The calculation results are listed in Table 6. From the table, we can conclude that The values ​​are -5.57, -5.86 and -6.15 kJ∙mol at 300.15 K, 310.15 K and 320.15 K, respectively. -1 , the results showed that the reaction between GS and GSH was spontaneous, 3.19 kJ∙mol -1 >0, 29.17 J∙mol -1 K -1 >0, indicating that the reaction is endothermic and hydrophobic force plays an important role in the binding process of GS and GSH.

[0086] Table 6 Thermodynamic parameters of the reaction between GSH and GS

[0087] UPLC-QTOF-MS method was used to calculate the binding constant of GSH and GS: According to the mass ratio of glutathione (1-40 parts) to ginsenoside (1 part), ginsenoside was dissolved in 5 mL of ethanol, ultrasonicated for 10 minutes to dissolve completely, and then slowly dripped into 10 mL of pure water while stirring. Glutathione was dissolved in 5 mL of pure water, slowly dripped into the above solution while stirring, stirred at room temperature for 1-2 hours, freeze-dried, and sealed and stored at 4°C. A certain amount of GSH-GS complex powder was accurately weighed, dissolved in 1 mL of pure water, and fully shaken to dissolve and mix to obtain a complex solution with a GSH concentration of 3.0 mg / mL and ginsenoside concentrations of 0.075, 0.3, 0.375, 0.75, 1.5, and 3.0 mg / mL.

[0088] UPLC-QTOF-MS analysis conditions: Ultra-high performance liquid chromatography (Waters ACQUITY UPLC I Class, Waters Corporation, USA) was used to separate the components. The chromatographic column was BEH C18 (2.1 mm×50 mm, 1.7 μm), and the mobile phase was composed of acetonitrile containing 0.1% formic acid (A) and water containing 0.1% formic acid (B). The flow rate was 0.4 mL / min, the injection volume was 2 μL, the pressure range was 0-15 000 psi, and the column temperature was room temperature. The gradient elution program is shown in Table 7. Mass spectrometry detection used an electrospray ionization source (ESI), negative ion mode and MS E Continuum mode. Scanning mass range: 50-2 000 Da, scanning time: 0.5 s, collision energy: 6-20 V.

[0089] Table 7 UPLC gradient elution program Time / minTime Acetonitrile Water(B)Waters 0 10.0% 90.0% 2 30.0% 70.0% 4 50.0% 50.0% 8 60.0% 40.0% 13 80.0% 20.0% 20 90.0% 10.0% 24 95.0% 5.0% 27 95.0% 5.0% 28 10.0% 90.0% 30 10.0% 90.0%

[0090] UPLC-QTOF-MS identification results.

[0091] The total ion current of GSH-GS sample is shown in Fig.24 According to the above UPLC / QTOF-MS method and conditions, the chemical components in the complex solution with a mass concentration ratio of GSH to GS of 1:1 were detected to obtain the total ion current of the test sample, such as Fig.24 shown.

[0092] UPLC-QTOF-MS was used to collect mass spectrometry data, and the UNIFI database was used to identify the chemical components in the samples. The components were screened based on the total ion current, mass spectrum, retention time, mass-to-charge ratio, error, response value and other information. Combined with the literature and mass spectrometry fragmentation rules, GSH and two chemical components combined with ginsenoside monomers were finally identified from the test samples. The identification results are shown in Table 8; Table 8 UPLC-QTOF-MS compound identification results of GSH-GS (1:1) No. Retention time / min Molecular formula Measured value / (Da) Theoretical value / Da Mass deviation / mDa Adduct ion Compound Name Fragment ion m / z 1 3.70 <![CDATA[C 64 H 109 N 3 O 29 S]]> 1460.7935 1460.6849 108.6 <![CDATA[+HCOO - ]]> Rb1-GSH <![CDATA[1414.7780[M-H]-,1413.7306[M-2H]-,1442.8076[M-H 2 O+HCOO]-,1396.6729[MH 2 OH]-]]> 2 0.84 <![CDATA[C 63 H 107 N 3 O 28 S]]> 1430.8298 1430.6744 155.4 <![CDATA[+HCOO - ]]> Rb2-GSH 1384.3475[MH]-, 1383.8523[M-2H]-, 1382.8545[M-3H]- 3 0.84 <![CDATA[C 10 H 17 N 3 O 6 S]]> 306.0798 306.0765 3.0 <![CDATA[-H + ]]> GSH <![CDATA[177.0400[M-C 5 H 9 NO 4 +H 2 O-H]-]]>

[0093] Extracted ion chromatogram and mass spectrum of main GSH: The chemical composition of GSH was detected by the UPLC-QTOF-MS technique described above. The detection was performed in negative ion mode to obtain the mass spectrum and extracted ion chromatogram of GSH, as shown in FIG. Fig.25 shown.

[0094] Extracted ion chromatogram and mass spectrum of the complex generated by the GSH-GS system: UPLC-QTOF-MS technology was used to detect the chemical components in samples of GSH and GS with different mass concentrations. The detection was carried out in negative ion mode to obtain the mass spectra and extracted ion chromatograms of GSH-Rb1 and GSH-Rb2, as shown in Figure 2. Fig.26 shown.

[0095] Calculation of binding constant: According to the formula derived by Loukas, the calculation is based on the ion count ratio of the guest molecule (GSH) to the complex in the solution (1 / ∆ I r ) and the concentration of the main body (1 / C H ), make a Scatchard-style plot of the linear curve, the ratio of the intercept and slope of the line is the binding constant K st .

[0096] Loukas formula and derivation process: (3); (1 / ΔI r 1 / C H Plotting, the ratio of the intercept to the slope is K st ); ;

[0097] Where: K C is the proportionality constant, K st is the binding constant, C H is the initial concentration of the bulk, C G is the initial concentration of the guest, I HG is the complex ion count, I G is the guest ion count, I r is the ionization efficiency, I 0 is the initial ionization efficiency.

[0098] Calculation of the binding constant between GSH and ginsenoside Rb1: The fixed GSH concentration is 9.7693×10 -3 mol / L, the molar concentration ratio of GSH-Rb1 was 1:0.0006, 1:0.0007, 1:0.0014, 1:0.0028, 1:0.0057, the integration interval was 0.82~0.86min, 3.69~3.73min, and the ion count was statistically calculated. H Drawing, see Fig. 27 , we get the linear equation y = 0.0878x - 1613.8, R 2 = 0.9188, calculated K st =1.8380×10 4 (mol / L) -1 .

[0099] Calculation of the binding constant between GSH and ginsenoside Rb2: The fixed GSH concentration is 9.7693×10 -3 mol / L, the molar concentration ratio of GSH-Rb2 was 1:0.0003, 1:0.0011, 1:0.0014, 1:0.0028, 1:0.0056, 1:0.0113, the integration interval was 0.82~0.86min, 0.82~0.86min, and the ion count was statistically calculated. H Drawing, see Fig.28 , we get the linear equation y = 0.001x + 1191.7, R 2 = 0.9248, calculated K st =1.1917×10 6 (mol / L) -1 .

[0100] Summary: In this example, the formation of GSH-GS complex was characterized by multiple spectral methods. The results of RLS resonance light scattering experiments showed that GS interacted with GSH to form a larger complex. The results of fluorescence emission spectroscopy showed that the formation of the complex led to the quenching of GSH fluorescence, and it was a dynamic quenching process. Thermodynamic parameters (∆H, ∆S, ∆G) showed that hydrophobic force was the main force maintaining the GS-GSH complex system, and the occurrence of this binding reaction was an entropy increase process. Based on the above experimental data, it was shown that GS formed a complex with GSH, which led to changes in the spatial conformation and physical properties of GSH. Through UPLC-QTOF-MS detection, it was found that GSH combined with various ginsenosides in GS. The results showed that GSH had a strong binding effect with Rb1 and Rb2, and the binding constants of the two with GSH were calculated. They all belonged to the ginsenosides of the ginsenosides group, indicating that the molecular structure of the ginsenosides of the ginsenosides group was more conducive to forming a complex with GSH than the triol group, thereby covering up the bad smell of GSH.

[0101] Example 3 Odor elimination experiment under different lighting conditions: Light is an important factor that promotes the generation of odor of thiol-containing cosmetic raw materials. In order to further verify the odor suppression of cosmetic raw materials under different light conditions by the solution of the present invention, the following experiment was conducted to further verify the effect of the present invention.

[0102] 3.1 Verification of the odor elimination effect of VC on ergothioneine: Experimental method: ergothioneine was added to water to prepare a 0.3% concentrated solution, and different amounts of VC were added. Under different lighting conditions, the changes in odor were observed. The specific scheme and experimental results are shown in Table 9. Table 9 Experimental results

[0103] 3.2 Verification of the odor elimination effect of VC on glutathione: Experimental method: Glutathione was added to water to prepare a 0.3% concentrated solution, and different amounts of VC were added. Under different lighting conditions, the changes in odor were observed. For specific schemes and experimental results, please refer to Table 10; Table 10 Experimental results

[0104] 3.3 Verification of the odor elimination effect of ginsenosides on ergothioneine: Experimental method: Add ergothioneine to water to prepare a 0.3% concentrated solution, add different amounts of ginsenosides, and observe the changes in odor under different lighting conditions. For specific plans and experimental results, refer to Table 11; Table 11 Experimental results

[0105] 3.4 Verification of the odor elimination effect of ginsenosides on glutathione: Experimental method: Glutathione was added to water to prepare a 0.3% concentrated solution, and different amounts of ginsenosides were added. Under different lighting conditions, the changes in odor were observed. For specific schemes and experimental results, please refer to Table 12; Table 12 Experimental results

[0106] 3.5 Verification of the odor elimination effect of ginsenosides on ammonium thioglycolate: Experimental method: Add ammonium thioglycolate into water to prepare a 0.3% concentrated solution, add different amounts of ginsenosides, and observe the changes in odor under different lighting conditions. For specific plans and experimental results, refer to Table 13; Table 13 Experimental results

[0107] 3.6 Verification of the odor elimination effect of ginsenosides on cysteine: Experimental method: add cysteine ​​to water to prepare a 0.3% concentrated solution, add different amounts of ginsenosides, and observe the changes in odor under different lighting conditions. For specific schemes and experimental results, refer to Table 14; Table 14 Experimental results

[0108] It should be noted that the ginsenosides used in Example 3 of the present invention are the ginsenosides shown in Example 1: From the above Tables 9 to 14, it can be seen that: 1. VC has a certain effect on improving the odor of ergothioneine; VC has no obvious effect on improving the characteristic odor of glutathione; 2. Ginsenosides have a certain effect on improving the odor of ergothioneine, glutathione, and cysteine, but the effect on ammonium thioglycolate is not obvious. The reason is that the odor of ammonium thioglycolate itself is particularly strong, and the addition of ginsenosides in the above proportion does not significantly change its characteristic odor; 3. Judging from the odor-inhibiting effect of VC and ginsenosides on glutathione, ginsenosides are more effective. When the dosage of ginsenosides reaches 0.3% or above, it can effectively inhibit the characteristic odor.

[0109] In summary, ginsenosides, as an effective odor inhibitor, can be widely used in suppressing the odor of thiol-containing cosmetic raw materials in cosmetics.

[0110] 3.7 Effects of other ginsenosides on the odor suppression of thiol-containing cosmetic raw materials 3.7.1 Verification of the odor elimination effect of ginsenoside A on ergothioneine: Experimental method: Add ergothioneine into water to prepare a 0.3% concentrated solution, add different amounts of ginsenoside A, and observe the changes in odor under different lighting conditions.

[0111] The composition of ginsenoside A is: ginsenosides Rg3, Rh2, and Rg5; Ginsenoside Rg3 50wt%; Ginsenoside Rh2 30wt%; Ginsenoside Rg5 20wt%; For specific schemes and experimental results, please refer to Table 15; Table 15 Experimental results

[0112] Verification of the odor elimination effect of ginsenoside B on ergothioneine: Experimental method: Add ergothioneine into water to prepare a 0.3% concentrated solution, add different amounts of ginsenoside B, and observe the changes in odor under different lighting conditions.

[0113] The composition of ginsenoside B is: ginsenosides Rk3, Rh4, Rh1, Rg2; Ginsenoside Rk3 17wt%; Ginsenoside Rh4 33wt%; Ginsenoside Rh1 33wt%; Ginsenoside Rg2 17wt%; For specific schemes and experimental results, please refer to Table 16; Table 16 Experimental results

[0114] 3.7.2 Verification of the odor elimination effect of ginsenosides on ergothioneine: Verification of the odor elimination effect of ginsenoside A glutathione: Experimental method: Glutathione was added to water to prepare a 0.3% concentrated solution, and different amounts of ginsenoside A were added. Under different lighting conditions, the changes in odor were observed. For specific schemes and experimental results, please refer to Table 17; Table 17 Experimental results

[0115] Verification of the odor elimination effect of ginsenoside B glutathione Experimental method: Glutathione was added to water to prepare a 0.3% concentrated solution, and different amounts of ginsenoside B were added. Under different lighting conditions, the changes in odor were observed. For specific schemes and experimental results, please refer to Table 18; Table 18 Experimental results

[0116] 3.7.2 Verification of the odor elimination effect of ginsenosides on cysteine: Verification of the odor elimination effect of ginsenoside A on cysteine: Experimental method: add cysteine ​​to water to prepare a 0.3% concentrated solution, add different amounts of ginsenoside A, and observe the changes in odor under different lighting conditions. For specific schemes and experimental results, refer to Table 19; Table 19 Experimental results

[0117] Verification of the odor elimination effect of ginsenoside B on cysteine: Experimental method: Cysteine ​​was added to water to prepare a 0.3% concentrated solution, and different amounts of ginsenoside B were added. The changes in odor were observed under different light conditions. For specific schemes and experimental results, please refer to Table 20; Table 20 Experimental results

[0118] Example 4 Application formula The recipe is shown in Table 21; Table 21: Application formula

[0119] Process: 1. Add 1 and 8 to the water phase pot, sprinkle 2 evenly on the liquid surface, wet evenly, start stirring, heat to 85℃, stir evenly and pump into the main emulsification pot; 2. Add the premix of 5, 6, 7, maintain 85℃, stir evenly, then add 2, 3, 9, stir evenly; 3. Cool down to 60℃, add 10% aqueous solution and stir evenly; 4. Add phase C materials and stir evenly; 5. Cool down to 40℃, add phase D materials and stir evenly; 6. Take the material for testing, pH5.5-6.5, qualified material will be discharged.

[0120] Physical and chemical indicators: Appearance: Transparent essence-like liquid; pH: 5.5-6.5; It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that the equivalents falling within the claims be included. All changes in the meaning and scope of the elements are encompassed by the present invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A method for reducing the volatile odor of a thiol-containing cosmetic raw material, characterized in that: Ginsenosides and thiol-containing cosmetic raw materials are combined to form a complex to reduce the volatile odor of the cosmetic raw materials.

2. The method according to claim 1, characterized in that The ginsenoside and the thiol-containing cosmetic raw material are combined by covalent bonds or non-covalent bonds; The non-covalent bond is based on one or more of hydrogen bonds, hydrophobic interactions, ionic bonds and van der Waals forces.

3. The method according to claim 1, characterized in that: The ginsenosides are one or more combinations of protopanaxadiol saponins and protopanaxatriol saponins.

4. The method according to claim 3, characterized in that The ginsenosides are ginsenoside Rb1, ginsenoside Rb2, ginsenoside Rc, ginsenoside Rd, ginsenoside Re, ginsenoside Rg1, ginsenoside Rg2, ginsenoside Rg3, ginsenoside Rh1, ginsenoside Rh2 and ginsenoside CK.

5. The method according to claim 1, characterized in that In the composite, the mass ratio of ginsenoside to the thiol-containing cosmetic raw material is 0.1 to 10:

1.

6. The method according to claim 1, characterized in that The sulfhydryl-containing cosmetic raw material is ergothioneine, glutathione or cysteine.

7. A cosmetic raw material, characterized in that: The cosmetic raw material is powder, and the powder is a composite formed by combining ginsenoside and a thiol-containing cosmetic raw material.

8. The cosmetic raw material according to claim 7, characterized in that: The ginsenoside and the thiol-containing cosmetic raw material are combined by covalent bonds or non-covalent bonds; The non-covalent bond is based on one or more of hydrogen bonds, hydrophobic interactions, ionic bonds and van der Waals forces.

9. The cosmetic raw material according to claim 7, characterized in that: The ginsenosides are one or more combinations of protopanaxadiol saponins and protopanaxatriol saponins.

10. The cosmetic raw material according to claim 7, characterized in that: The ginsenosides are ginsenoside Rb1, ginsenoside Rb2, ginsenoside Rc, ginsenoside Rd, ginsenoside Re, ginsenoside Rg1, ginsenoside Rg2, ginsenoside Rg3, ginsenoside Rh1, ginsenoside Rh2 and ginsenoside CK.

11. The cosmetic raw material according to claim 7, characterized in that: In the composite, the mass ratio of ginsenoside to the thiol-containing cosmetic raw material is 0.1 to 10:

1.

12. The cosmetic raw material according to claim 7, characterized in that: The sulfhydryl-containing cosmetic raw material is ergothioneine, glutathione or cysteine.

13. Use of the cosmetic raw material according to any one of claims 7 to 12 in preparing cosmetics.

14. The use according to claim 13, characterized in that The cosmetics are cosmetics that act on the skin or cosmetics that act on the hair.

15. A cosmetic, characterized in that: Contains the cosmetic raw material according to any one of claims 7 to 12.

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