A NHDC / pyruvic acid binary liquid supramolecular self-assembly system and preparation method thereof

Abstract

The invention discloses a NHDC / pyruvic acid binary liquid supramolecular self-assembly system and a preparation method thereof, and belongs to the field of supramolecular technology. The method for preparing the neomethyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system of the invention comprises: mixing pyruvic acid and neomethyl hesperidin dihydrochalcone to prepare the neomethyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system. The method of the invention significantly improves the water solubility, antioxidant property and antibacterial property of the neomethyl hesperidin dihydrochalcone.

Description

Technical Field

[0001] The invention relates to an NHDC / pyruvic acid binary liquid supramolecular self-assembly system and a preparation method thereof, belonging to the technical field of supramolecular technology. Background Art

[0002] Neomethyl hesperidin dihydrochalcone (NHDC) is a flavonoid derivative obtained by hydrogenating neomethyl hesperidin extracted from the multi-leafed thorn bean plant. In order to improve the solubility of neomethyl hesperidin dihydrochalcone, the existing technology mainly attempts to solve the solubility problem of neomethyl hesperidin dihydrochalcone through a series of methods such as encapsulation treatment and chemical modification of neomethyl hesperidin dihydrochalcone. However, these methods are too complicated and use some organic solvents. The solubility of the obtained neomethyl hesperidin dihydrochalcone is improved, but the stability is poor and it cannot be directly used as a raw material.

[0003] Specifically:

[0004] Patent CN 109730294 A discloses a method for increasing the water solubility of neomethyl hesperidin dihydrochalcone by using encapsulation technology through the use of dextran-soy protein isolate coupling grafting, but the preparation process is relatively complicated and requires a special reaction device, and the solubility is 4 g / L.

[0005] Patent CN 109730295 A discloses a process for preparing neomethyl hesperidin dihydrochalcone embedding material using special granulation equipment. The water solubility of neomethyl hesperidin dihydrochalcone is improved to a certain extent, but the equipment cost is increased additionally, and the solubility is 4 g / L.

[0006] Patent CN 109836513 A discloses a newly prepared octenylsuccinic acid α-hydroxypropyl-β-cyclodextrin ester, which is used for encapsulation with neomethyl hesperidin dihydrochalcone, thereby increasing the water solubility of neomethyl hesperidin dihydrochalcone. However, the preparation of octenylsuccinic acid α-hydroxypropyl-β-cyclodextrin ester causes additional costs, and a large amount of organic solvents are used in the preparation process, which has poor environmental benefits and a solubility of 2.52 g / L.

[0007] Patent CN 110156852 A discloses a chemical method to improve the solubility of neomethyl hesperidin dihydrochalcone by glycosylation. Although the solubility of neomethyl hesperidin dihydrochalcone is increased to a certain extent, the process flow adopts an enzyme-catalyzed method for synthesizing derivatives, which is relatively complicated and has a solubility of 562.7 g / L.

[0008] In view of the important applications and practical value of neomethyl hesperidin dihydrochalcone, a simpler and greener processing technology is needed to more effectively solve the problem of poor water solubility and instability of neomethyl hesperidin dihydrochalcone.

[0009] Pyruvate is the ionic form of β-hydroxybutyric acid and is one of the important intermediates of ketone body metabolism in the body. It plays an important role in energy metabolism and ketone body production. Its main functions include ketone body energy supply, glycogen metabolism, fat metabolism regulation, and ketoacidosis regulation. Pyruvate has a certain antioxidant effect, which can reduce the generation of free radicals and oxidative damage, protect cells from oxidative stress, and is an intermediate of the three major nutrients in the human body.

[0010] Supramolecular compounds are complex and organized chemical systems formed by non-covalent bonds between host molecules and several guest molecules. From a chemical point of view, the molecules that make up the supramolecular system have not changed, so they can still maintain their original efficacy, but the solubility, bioavailability, stability and other aspects of the original single components in the supramolecular system will be greatly improved, that is, the various molecules in the supramolecular system interact with each other to form a synergistic effect.

[0011] However, there is no research using supramolecular technology to significantly improve the solubility of neomethylhesperidin dihydrochalcone. Summary of the invention

[0012] In view of the above problems, the present invention provides a new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system and a preparation method thereof, which improves the water solubility, antibacterial and antioxidant properties of the new methyl hesperidin dihydrochalcone.

[0013] The first object of the present invention is to provide a method for preparing a new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system, the method comprising:

[0014] The pyruvic acid and neomethyl hesperidin dihydrochalcone are mixed to prepare the neomethyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system.

[0015] In one embodiment, the molar ratio of pyruvic acid to neomethyl hesperidin dihydrochalcone is 0.1-1:0.01;

[0016] Optionally, the molar ratio of pyruvic acid to neomethyl hesperidin dihydrochalcone is 0.1-0.5:0.01.

[0017] In one embodiment, the mixing is to stir pyruvic acid and neomethyl hesperidin dihydrochalcone in air or inert gas at 15-70° C. for more than 2 hours at a stirring speed of 300-500 rpm;

[0018] Optionally, stirring at 25-60°C for 2h.

[0019] In one embodiment, the pH of the new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system is 2.5-4.5.

[0020] In one embodiment, the mass fraction of neo-methyl hesperidin dihydrochalcone in the neo-methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system is 12% to 41%.

[0021] In one embodiment, the neomethyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system is mixed with water to prepare a neomethyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system aqueous solution; wherein the mass fraction of the neomethyl hesperidin dihydrochalcone in the aqueous solution is 0.1% to 30%;

[0022] Optionally, the mass fraction is 0.1%~25%.

[0023] In one embodiment, when the mass fraction of neomethyl hesperidin dihydrochalcone in the aqueous solution is 0.1% to 30%, the stability is good and no precipitation occurs.

[0024] The second object of the present invention is to provide a new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system prepared by any of the above methods.

[0025] In one embodiment, in the neomethyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system, pyruvic acid can effectively adjust the pH value of the system, and at the same time play a synergistic role with neomethyl hesperidin dihydrochalcone, so that the system has good antibacterial, moisturizing, antioxidant, soothing, repairing and other multiple effects.

[0026] In one embodiment, in the described new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system, the water solubility of the new methyl hesperidin dihydrochalcone is changed by forming intermolecular hydrogen bonds. The process flow is green, simple, and has no environmental pollution problems, and is suitable for large-scale preparation.

[0027] In one embodiment, the novel methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system can be directly applied to the fields of cosmetics, medicine, food, etc. without the need for additional post-processing such as separation and purification.

[0028] In one embodiment, the new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system prepared by the present invention can be directly diluted with water, and the maximum dilution to 50 times can still maintain the stability of the system without solid precipitation, which is conducive to formulation application.

[0029] The third object of the present invention is to provide the application of any of the above methods or the above new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system in the fields of cosmetics, medicine or food.

[0030] In one embodiment, the application in the food field includes preparing general food and special food.

[0031] In one embodiment, common foods include, but are not limited to, beverages, baked goods, food additives or fermented foods.

[0032] In one embodiment, specialty foods include, but are not limited to, health products, functional foods, or dietary supplements.

[0033] In one embodiment, the application in the pharmaceutical field includes but is not limited to the preparation of liver protection drugs, blood sugar lowering drugs, blood lipid lowering drugs, anti-inflammatory drugs or antioxidant drugs, and intestinal flora regulating drugs.

[0034] In one embodiment, the application in the field of cosmetics includes preparing non-functional cosmetics, functional cosmetics or fragrances.

[0035] In one embodiment, the effects of the functional cosmetics include but are not limited to whitening, soothing, moisturizing and anti-oxidation, anti-aging, anti-inflammatory, and anti-free radicals.

[0036] The fourth object of the present invention is to provide a product, which contains the above-mentioned new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system;

[0037] Optionally, the product includes but is not limited to cosmetics, medicines or foods.

[0038] The fifth object of the present invention is to provide a method for simultaneously improving the solubility, antioxidant and antibacterial properties of neomethyl hesperidin dihydrochalcone, the method comprising: mixing pyruvic acid and neomethyl hesperidin dihydrochalcone at a molar ratio of 0.1-1:0.01, stirring at 25-50° C. for 2-6 hours in air or inert gas, and cooling to room temperature to prepare a neomethyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system with improved solubility, antioxidant and antibacterial properties.

[0039] Beneficial effects of the present invention:

[0040] The new methyl hesperidin dihydrochalcone / pyruvic acid system obtained by supramolecular self-assembly of the present invention is in a stable liquid state, can be miscible with a specific proportion of water without precipitation, and effectively improves the water solubility and stability of the new methyl hesperidin dihydrochalcone.

[0041] Specifically:

[0042] (1) The present invention prepares a uniform, transparent and stable neomethyl hesperidin dihydrochalcone / pyruvic acid binary liquid system through supramolecular self-assembly technology. The content of neomethyl hesperidin dihydrochalcone in the system can be as high as 40%, which is much higher than the actual application concentration of neomethyl hesperidin dihydrochalcone, providing sufficient adjustment space for subsequent formulation applications.

[0043] (2) The neo-methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system prepared by the present invention significantly enhances the water solubility of neo-methyl hesperidin dihydrochalcone and is miscible with water. After miscibility, the mass fraction of neo-methyl hesperidin dihydrochalcone can be as high as 30%, and no solid neo-methyl hesperidin dihydrochalcone particles are precipitated.

[0044] (3) The new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system prepared by the present invention is transparent and has low viscosity, can be directly used as a raw material, and can maintain long-term stability.

[0045] (4) The pyruvic acid in the new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system prepared by the present invention can effectively adjust the pH of the system and has a synergistic effect with the new methyl hesperidin dihydrochalcone.

[0046] (5) The preparation method of the new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system adopted in the present invention is green and simple, and the preparation conditions are mild. The obtained system can be directly put into use without post-treatment such as separation and purification.

[0047] In summary, the preparation method of the present invention is green and environmentally friendly, has a simple process, and can significantly improve the water solubility, antibacterial properties and stability of neo-methyl hesperidin dihydrochalcone, which is of great significance for the application of neo-methyl hesperidin dihydrochalcone and can expand its wide application in the fields of cosmetics, food, biomedicine, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 This is the infrared spectrum of the binary liquid supramolecular self-assembly system prepared in Example 1;

[0049] Figure 2 is the DPPH scavenging rate of the binary liquid supramolecular self-assembly system aqueous solution prepared in Example 1;

[0050] Figure 3 is the ABTS removal rate of the aqueous solution of the binary liquid supramolecular self-assembly system prepared in Example 1;

[0051] Figure 4 This is the appearance of the binary liquid supramolecular self-assembly system prepared in Example 1, Example 2, Comparative Example 1, and Comparative Example 2. DETAILED DESCRIPTION

[0052] In order to make the purpose, technical solution and advantages of the present invention clearer and more specific, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0053] The present invention provides a new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system and provides an embodiment of a preparation method. Traditionally, due to the poor water solubility of the new methyl hesperidin dihydrochalcone, the product is unstable and difficult to preserve, thereby reducing the efficacy of the product and affecting its further development and utilization. Therefore, it is necessary to take measures to improve the solubility of the new methyl hesperidin dihydrochalcone and enhance the product stability.

[0054] The present invention utilizes supramolecular self-assembly technology to change the water solubility and stability of neomethyl hesperidin dihydrochalcone by forming intermolecular hydrogen bonds, and can solve these problems well. At the same time, by adjusting the ratio and interaction of neomethyl hesperidin dihydrochalcone and pyruvic acid in the supramolecular self-assembly system, the applicability of neomethyl hesperidin dihydrochalcone can be significantly improved, so that it can be evenly dispersed in water-based skin care products, and the stability and absorbability of the products are increased, thereby improving the texture, stability and efficacy performance of related products, and improving the user experience and product functional effects.

[0055] A method for preparing a new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system in the present invention comprises the following steps:

[0056] A certain amount of pyruvic acid and neomethyl hesperidin dihydrochalcone were weighed and put into a sealed container. After stirring evenly, the system was raised to a specific temperature and stirred at this temperature for a certain time until the system became a uniform and transparent liquid system. The system temperature was lowered to room temperature to obtain the target neomethyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system. The obtained system was miscible with a specific proportion of water, thereby effectively improving the water solubility and stability of neomethyl hesperidin dihydrochalcone.

[0057] In the present invention, the molar ratio of raw materials n (neomethyl hesperidin dihydrochalcone): n (pyruvic acid) is preferably 0.01:0.1~1, more preferably 0.01:0.1~0.8, and most preferably 0.01:0.1~0.5; specifically, in an embodiment of the present invention, it can be 0.01:0.1, 0.01:0.3 or 0.01:0.5.

[0058] In the present invention, the heating atmosphere is an inert atmosphere or natural air, preferably helium, nitrogen, argon, carbon dioxide or natural air; specifically, in an embodiment of the present invention, the heating atmosphere is natural air or nitrogen.

[0059] In the present invention, the heating temperature is preferably 20-120°C, more preferably 20-100°C, and most preferably 25-50°C; specifically, in the embodiments of the present invention, it may be 25°C, 30°C or 50°C.

[0060] In the present invention, the heating time is preferably 1 to 24 h, more preferably 2 to 12 h, and most preferably 2 to 6 h; specifically, in an embodiment of the present invention, it can be 2 h, 4 h or 6 h.

[0061] In the present invention, the pH of the binary liquid supramolecular self-assembly system is 2.5-4.5, and in the embodiments of the present invention, it can be 2.12, 2.87 or 3.56.

[0062] In the present invention, the mass fraction of neomethyl hesperidin dihydrochalcone in the binary liquid supramolecular self-assembly system can reach 40%, and in the embodiments of the present invention, it can be 12%, 19% or 41%.

[0063] In the present invention, the binary liquid supramolecular combination can be dissolved in water in a specific proportion, and can keep the mass fraction of neomethyl hesperidin dihydrochalcone in the aqueous solution at 0.1% to 30% without precipitation; specifically, in the embodiments of the present invention, it can be 0.1%, 15% or 30%.

[0064] Specifically, the normal temperature of the present invention refers to 25°C.

[0065] In order to further illustrate the present invention, a novel methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system and a preparation method thereof provided by the present invention are described in detail below in conjunction with examples.

[0066] Detection method:

[0067] Fourier transform infrared spectroscopy test parameters are:

[0068] Machine specifications: Nicolet iS5, Machine manufacturer: Thermo Fisher Scientific, USA, Experimental parameters: Scanning range: 450~4000 cm -1 , with a resolution of 4 cm -1 .

[0069] High and low temperature cycle test:

[0070] The new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular combination was frozen at -5°C and then placed at 40°C to dissolve. This was one cycle and then repeated. It was observed that the state after each dissolution could maintain a stable and uniform liquid state without solid precipitation. The example is the data of 15 cycles.

[0071] Example 1

[0072] 1. A method for preparing a new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system, the steps are as follows:

[0073] 0.1 mol (8.8 g) of pyruvic acid and 0.01 mol (6.12 g) of neomethyl hesperidin dihydrochalcone were placed in a sealed container and stirred at 400 rpm for 2 h at room temperature to obtain a binary liquid supramolecular self-assembly system. The mass fraction of neomethyl hesperidin dihydrochalcone in the system was 41%, and the pH of the system was 3.56 when tested by a pH meter.

[0074] The binary liquid supramolecular self-assembly system is miscible with water in a specific proportion so that the mass fraction of neomethyl hesperidin dihydrochalcone in the aqueous solution is 30%, that is, the solubility is 428.6 mg / g, and the system can maintain a stable and uniform liquid state, thereby obtaining an aqueous solution of the binary liquid supramolecular self-assembly system.

[0075] The binary liquid supramolecular self-assembly system and the binary liquid supramolecular self-assembly system aqueous solution were subjected to high and low temperature cycle tests (cycled and stored at -5°C and 40°C for 15 times), and finally both systems were able to maintain a stable and uniform liquid state without solid precipitation.

[0076] The prepared uniform, transparent and stable binary liquid supramolecular self-assembly system was placed at room temperature for 24 h and then sampled and characterized by infrared spectrometer.

[0077] The infrared spectrum of the binary liquid supramolecular self-assembly system is shown in Figure 1 As shown in the figure, the results show that the binary liquid supramolecular self-assembly system prepared in Example 1 has a -1 The absorption peak in the range corresponds to the absorption peak of hydroxyl (hydrogen bond). Compared with pyruvic acid, the binary liquid supramolecular self-assembly system has a significant peak. Compared with neomethyl hesperidin dihydrochalcone, the peak position moves significantly to a lower wave number. This is due to the interaction of a large number of hydrogen bonds generated in the system. In addition, compared with neomethyl hesperidin dihydrochalcone, at 1636 cm -1 The carbonyl peak shifted to a higher wave number of 1734 cm -1 This is due to the change in the carbonyl electron cloud density caused by the generation of a large number of hydrogen bonds within the system. The above results all confirm that pyruvic acid and neomethyl hesperidin dihydrochalcone form a supramolecular self-assembly system through intermolecular hydrogen bonds.

[0078] 2. Performance testing

[0079] Triple distilled water was added to the binary liquid supramolecular self-assembly system obtained in Example 1 to prepare aqueous solutions of binary liquid supramolecular self-assembly systems with neomethylhesperidin dihydrochalcone concentrations of 0.1 mg / mL, 0.2 mg / mL, 0.4 mg / mL, 0.6 mg / mL, 0.8 mg / mL, and 1 mg / mL, and antioxidant tests were performed, with equal concentrations of neomethylhesperidin dihydrochalcone standard solutions and equal concentrations of pyruvic acid solutions as controls.

[0080] (1) DPPH free radical scavenging method was used to determine the antioxidant activity.

[0081] DPPH free radical has a strong absorption peak in the visible light with a wavelength of 517nm, showing purple color. When the neohesperidin dihydrochalcone free radical combines with the electrons provided by the antioxidant sample, the purple color disappears and turns colorless or light yellow. The absorbance before and after the reaction is measured with a UV-visible spectrophotometer to reflect the color change.

[0082] Weigh 5.0 mg of DPPH, dissolve it in an appropriate amount of anhydrous ethanol, and dissolve it completely by sonication in the dark. Then dilute the volume to 100 mL with anhydrous ethanol to prepare a DPPH solution with a concentration of 50 μg / mL.

[0083] Prepare the solution in a 96-well plate according to Table 1:

[0084] Table 1

[0085]

[0086] After the sample solution is mixed evenly, react at 25°C in the dark for 30 min and measure the absorbance at a wavelength of 517 nm.

[0087] The free radical scavenging rate was calculated according to the following formula:

[0088]

[0089] P is the clearance rate, A a , A b , A c , A d , corresponding to the absorbance value of each well in the table.

[0090] The results are shown in Table 2 and Figure 2 As shown, the results indicate that the DPPH scavenging rate of the binary liquid supramolecular self-assembly system in aqueous solution is better than that of the single components neohesperidin dihydrochalcone and pyruvic acid.

[0091] Table 2 DPPH test results

[0092]

[0093] (2) Antioxidant activity was determined by ABTS free radical scavenging method.

[0094] After ABTS is oxidized, it generates a relatively stable ABTS free radical, which is blue-green and has a maximum absorption peak at 734 nm wavelength of visible light. After the sample reacts with the ABTS free radical, it fades. The absorbance value after the reaction can be measured to compare the free radical scavenging rate. By comparing with the scavenging ability of neohesperidin dihydrochalcone, the relative half-scavenging amount is used to determine the antioxidant capacity A0 value of the sample.

[0095] Prepare 7 mmol / L ABTS aqueous solution and 2.45 mmol / L potassium persulfate aqueous solution. Mix the above solutions in equal volumes, place in a dark environment for 12 h, and dilute 30 times with deionized water to an absorbance value of A 734 nm =0.70±0.02, as the measuring solution (ABTS solution).

[0096] Prepare the solution in a 96-well plate according to Table 3:

[0097] Table 3

[0098]

[0099] After the sample solution is mixed evenly, react at 25°C in the dark for 5 min, and measure the absorbance value at a wavelength of 734 nm.

[0100] The free radical scavenging rate was calculated according to the following formula:

[0101]

[0102] P is the clearance rate, A a , A b , A c , A d , corresponding to the absorbance value of each well in the table.

[0103] The results are shown in Table 4 and Figure 3 As shown, the results indicate that the ABTS removal rate of the binary liquid supramolecular self-assembly system in aqueous solution is better than that of the single components neohesperidin dihydrochalcone and pyruvic acid.

[0104] Table 4 ABTS test results

[0105]

[0106] The above results show that the aqueous solution of the binary liquid supramolecular self-assembly system exhibits excellent antioxidant capacity. Compared with the neohesperidin dihydrochalcone standard and pyruvic acid, the antioxidant capacity of the sample is improved, reflecting the supramolecular synergistic effect.

[0107] (3) Antibacterial properties

[0108] Triple distilled water was added to the binary liquid supramolecular self-assembly system obtained in Example 1 to prepare aqueous solutions of binary liquid supramolecular self-assembly systems with different neomethyl hesperidin dihydrochalcone concentrations. Antibacterial tests were performed, with triple distilled water as a control.

[0109] Inoculate the overnight resuscitated streptococcal culture into 5 mL THB liquid medium at a 1% v / v inoculation volume and incubate in a 37°C, 5% CO2 incubator for 24 hours. 9 CFU / mL, take it out for later use.

[0110] Under sterile conditions in a biosafety cabinet, aqueous solutions of binary liquid supramolecular self-assembly systems of different concentrations were added to a sterile 96-well culture plate. The drug solution was added to wells 1 to 9, 100 μL per well, and 100 μL of triple-distilled water was added to well 10 as a control.

[0111] The culture inoculum bacterial solution was diluted tenfold with culture medium and added to the corresponding 96-well culture plate at 100 μL / well after dilution. After sealing, it was placed in an incubator at 37°C and 5% CO2 for 24 hours to observe the antibacterial effect of the aqueous solution of the binary liquid supramolecular self-assembly system.

[0112] After the drug and bacteria are incubated for 24 hours, 100 μL of each well is applied to the THB plate and incubated in an incubator at 37°C and 5% CO2 for 24 hours. The lowest drug concentration that achieves complete sterile growth is defined as the MIC. The test is meaningful only when bacteria in the positive control well (i.e., without drug) grow significantly.

[0113] The minimum complete inhibitory concentration plate experiment confirmed that the binary liquid supramolecular self-assembly system had a significant inhibitory effect on Streptococcus mutans, Streptococcus suis serotype 2, and group A Streptococcus. The results are shown in Table 5. The minimum inhibitory concentration of the binary liquid supramolecular self-assembly system was at the mg / mL level. That is, the binary liquid supramolecular self-assembly system has good efficacy in antibacterial performance.

[0114] Table 5 Antibacterial effect

[0115]

[0116] Example 2

[0117] A method for preparing a new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system, comprising the following steps:

[0118] 0.3 mol (26.4 g) of pyruvic acid and 0.01 mol (6.12 g) of neomethyl hesperidin dihydrochalcone were placed in a sealed container, and the container was slowly heated in a natural air atmosphere. After the temperature reached 30°C, it was continuously heated and stirred for 4 h. The container was cooled to room temperature to obtain a binary liquid supramolecular self-assembly system. The mass fraction of neomethyl hesperidin dihydrochalcone in the system was 19%, and the pH of the system was 2.87 when tested by a pH meter.

[0119] The binary liquid supramolecular self-assembly system is miscible with a specific proportion of water, so that the mass fraction of neomethyl hesperidin dihydrochalcone in the aqueous solution is 15%, that is, the solubility is 176.5 mg / g. The system can maintain a stable and uniform liquid state, and an aqueous solution of the binary liquid supramolecular self-assembly system is obtained;

[0120] The binary liquid supramolecular self-assembly system and the binary liquid supramolecular self-assembly system aqueous solution were subjected to high and low temperature cycle tests (cycled and stored at -5°C and 40°C for 15 times), and finally both systems were able to maintain a stable and uniform liquid state without solid precipitation.

[0121] Example 3

[0122] A method for preparing a new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system, comprising the following steps:

[0123] 0.5 mol (44 g) of pyruvic acid and 0.01 mol (6.12 g) of neomethyl hesperidin dihydrochalcone were placed in a sealed container, and the container was slowly heated in a natural air atmosphere. After the temperature reached 50°C, the container was continuously heated and stirred for 6 h. The container was cooled to room temperature to obtain a binary liquid supramolecular self-assembly system. The mass fraction of neomethyl hesperidin dihydrochalcone in the system was 12%, and the pH of the system was 2.12 when tested by a pH meter.

[0124] The binary liquid supramolecular self-assembly system is miscible with a specific proportion of water, so that the mass fraction of neomethyl hesperidin dihydrochalcone in the aqueous solution is 0.1%, that is, the solubility is 1 mg / g. The system can maintain a stable and uniform liquid state, and an aqueous solution of the binary liquid supramolecular self-assembly system is obtained;

[0125] The binary liquid supramolecular self-assembly system and the binary liquid supramolecular self-assembly system aqueous solution were subjected to high and low temperature cycle tests (cycled and stored at -5°C and 40°C for 15 times), and finally both systems were able to maintain a stable and uniform liquid state without solid precipitation.

[0126] Comparative Example 1

[0127] 0.1 mol of pyruvic acid and 0.01 mol of neomethyl hesperidin dihydrochalcone were placed in a sealed container, and the container was slowly heated in a natural air atmosphere. After the temperature reached 80°C, heating and stirring were continued for 2 h. As time went on, the system became a uniform and transparent liquid state.

[0128] The results are as follows Figure 4 As shown, compared with Example 1, only the heating temperature was increased, but the color of the system became darker, which suggests that a chemical reaction may have occurred during the reaction process.

[0129] Comparative Example 2

[0130] 0.1 mol of pyruvic acid and 0.01 mol of neomethyl hesperidin dihydrochalcone were placed in a sealed container and stirred at 400 rpm for 1 h at room temperature. As time went by, the system became a solid-liquid mixture.

[0131] The results are as follows Figure 4 As shown, compared with Example 1, only by shortening the stirring time, a uniform and stable transparent liquid system cannot be obtained, and the system maintains a solid-liquid mixed state. The system is mixed with water in a specific proportion so that the mass fraction of neomethyl hesperidin dihydrochalcone is 30%, that is, the solubility is 428.6 mg / g, but the system cannot maintain a stable and uniform liquid state, and solid insoluble matter exists.

[0132] Comparative Example 3

[0133] 0.02 mol of neomethyl hesperidin dihydrochalcone and 0.2 mol of pyruvic acid were placed in a sealed container and stirred at 400 rpm at room temperature for 2 hours. As time went by, the system became a solid-liquid mixture.

[0134] Compared with Example 1, only by increasing the feeding amount of neomethyl hesperidin dihydrochalcone, a uniform and stable transparent liquid system cannot be obtained, and the system maintains a solid-liquid mixed state. The system is mixed with water in a specific proportion so that the mass fraction of neomethyl hesperidin dihydrochalcone is 30%, that is, the solubility is 428.6 mg / g, but the system cannot maintain a stable and uniform liquid state, and solid insoluble matter exists.

[0135] Comparative Example 4

[0136] 0.02 mol of neomethyl hesperidin dihydrochalcone and 0.2 mol of lactic acid were placed in a sealed container and stirred at 400 rpm at room temperature for 2 hours. As time went by, the system became a solid-liquid mixture.

[0137] Compared with Example 1, when lactic acid is used instead of pyruvic acid, a uniform and stable transparent liquid system cannot be obtained, and the system maintains a solid-liquid mixed state. The system is mixed with water in a specific proportion so that the mass fraction of neomethyl hesperidin dihydrochalcone is 30%, that is, the solubility is 428.6 mg / g, but the system cannot maintain a stable and uniform liquid state, and solid insoluble matter exists.

[0138] Comparative Example 5

[0139] 0.02 mol of glycyrrhizic acid and 0.2 mol of pyruvic acid were placed in a sealed container and stirred at 400 rpm for 2 hours at room temperature. As time went by, the state of the system became a solid-liquid mixture.

[0140] Compared with Example 1, glycyrrhizic acid was used instead of neomethyl hesperidin dihydrochalcone, and a uniform and stable transparent liquid system could not be obtained. The system maintained a solid-liquid mixed state. The system was mixed with water in a specific proportion so that the mass fraction of glycyrrhizic acid was 30%, that is, the solubility was 428.6 mg / g, but the system could not maintain a stable and uniform liquid state, and solid insoluble matter was present.

[0141] Comparative Example 6

[0142] 0.02 mol of glycyrrhetinic acid and 0.2 mol of pyruvic acid were placed in a sealed container and stirred at 400 rpm for 2 hours at room temperature. As time went by, the system became a solid-liquid mixture.

[0143] Compared with Example 1, glycyrrhetinic acid was used instead of neomethyl hesperidin dihydrochalcone, and a uniform and stable transparent liquid system could not be obtained. The system maintained a solid-liquid mixed state. The system was mixed with water in a specific proportion so that the mass fraction of glycyrrhetinic acid was 30%, that is, the solubility was 428.6 mg / g, but the system could not maintain a stable and uniform liquid state, and solid insoluble matter was present.

[0144] Comparative Example 7

[0145] 0.1 mol of cis-3-hexenyl pyruvate and 0.01 mol of neomethyl hesperidin dihydrochalcone were placed in a sealed container and stirred at room temperature for 2 h. As time went on, the system became a uniform and transparent liquid state.

[0146] Compared with Example 1, cis-3-hexenyl pyruvate was used instead of pyruvic acid to obtain a uniform, stable, transparent liquid system, which remained in a liquid state. The system was mixed with water in a specific proportion so that the mass fraction of neomethyl hesperidin dihydrochalcone was 30%, that is, the solubility was 428.6 mg / g, but the system could not maintain a stable, uniform liquid state, and solid insoluble matter was present.

[0147] It can be seen from Comparative Examples 4 to 7 that the binary system prepared by replacing one of pyruvic acid or neomethyl hesperidin dihydrochalcone is unstable and has the problem of poor solubility. It can be seen that neomethyl hesperidin dihydrochalcone cannot form a binary liquid supramolecular self-assembly system with conventional acids, and pyruvic acid cannot form a binary liquid supramolecular self-assembly system with other poorly soluble compounds. The combination of pyruvic acid or neomethyl hesperidin dihydrochalcone has the particularity of the raw materials.

[0148] Although the present invention has been disclosed as above in the form of a preferred embodiment, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the definition of the claims.

Claims

1. A method for preparing a new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system, characterized in that: The method comprises: mixing pyruvic acid and neomethyl hesperidin dihydrochalcone at a molar ratio of 0.1-1:0.01, stirring at 25-50°C for 2-6 hours in air or inert gas, cooling to room temperature, and preparing a neomethyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system.

2. The new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system prepared by the method according to claim 1.

3. Application of the new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system according to claim 2 in the field of preparing cosmetics, preparing medicines or preparing foods.

4. The use according to claim 3, characterized in that: Applications in the field of food preparation include preparation of beverages, baked goods, food additives, and fermented foods.

5. The use according to claim 3, characterized in that: The application in the field of drug preparation includes the preparation of liver protection drugs, blood sugar lowering drugs, blood lipid lowering drugs, anti-inflammatory drugs, antioxidant drugs, and intestinal flora regulating drugs.

6. The use according to claim 3, characterized in that: The application in the cosmetics field includes the preparation of non-functional cosmetics and functional cosmetics.

7. The use according to claim 3, characterized in that: Its application in the cosmetic field is in the preparation of fragrances.

8. A cosmetic, characterized in that: The cosmetic contains the new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system according to claim 2.

9. A drug, characterized in that The medicine contains the new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system according to claim 2.

10. A food, characterized in that The food contains the new methyl hesperidin dihydrochalcone / pyruvic acid binary liquid supramolecular self-assembly system according to claim 2.

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