Foaming type eutectic solvent based on natural sweetening agent and application of solubilizing characteristic of foaming type eutectic solvent

Abstract

The invention provides a foaming type eutectic solvent prepared by using a natural sweetening agent as a raw material and application of the foaming type eutectic solvent as a solubilizer. Stevioside and mogroside are two natural sweeteners with extremely wide application, and not only have high sweetness, but also have a series of biological activities; the natural eutecticevaporate solvent can be formed under the heating condition by combining the two hydrogen bond acceptors with hydrogen bond donors including sorbitol, xylitol, glycerol and 1, 3-butanediol. The product can generate abundant foams and has obvious surfactant performance. In the subsequent application, the squalene is used as a solubilizer for improving the solubility of the hydrophobic component squalene in water, and the application of the squalene in the industries of food, health care, cosmetics and the like is greatly limited due to poor water solubility of the squalene. Results prove that the solubilization rate of the natural eutectic solvent to squalene can reach several times to dozens of times. The green solvent is friendly, safe and easy to prepare, and has good application potential in multiple fields.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of fine chemicals, and particularly relates to a foaming-type deep eutectic solvent prepared by using a natural sweetener as a raw material and application of the deep eutectic solvent as a solubilizer. BACKGROUND

[0002] As a new green solvent, deep eutectic solvent (DES) is a new multi-purpose solvent formed by combining a hydrogen bond donor (HBD) and a hydrogen bond acceptor (HBA) in a certain proportion, and exists in a liquid state at room temperature. Due to its unique physicochemical properties and flexible structure composition, DES has shown great application potential and development prospects in many fields. Natural deep eutectic solvent (NADES) is a new type of deep eutectic solvent composed of natural substances with good biocompatibility as hydrogen bond donors and acceptors, such as choline, amino acids and sugars. NADES has the advantages of low cost, easy preparation and friendliness to human body and environment, and has attracted attention from researchers in many fields. Because of its better biocompatibility than ordinary deep eutectic solvents, it is safer to use, and is particularly suitable for use in the fields of food, medicine and daily chemicals.

[0003] Mogroside is a light yellow solid natural extract derived from Fructus Momordicae, which has a unique fragrance of Fructus Momordicae. It is a sweetener with a sweetness of about 240 times that of sucrose, and a melting point of about 197-201°C. Unlike the first and second generation sweeteners, mogroside has neither high heat nor safety problems, and has stable properties and good taste. From the chemical composition, the natural extract is composed of a class of glycosides with cucurbitane triterpenoid mogrol as the aglycone, which is the main source of Fructus Momordicae sweetness. Mogroside is widely used at present. In 2002, the U.S. Food and Drug Administration approved mogroside as a food additive, which can partially or completely replace sucrose; a variety of table desserts, candies, beverages have added mogroside as a sweetener, and many well-known food companies such as Nestle, Starbucks, Coca-Cola, and Wanglaoji have added the extract to their products; at the same time, it can also be used as a natural green feed additive and a traditional Chinese medicine decoction partner. In addition to the characteristic of high sweetness, mogroside also has a series of health care effects; such as reducing blood sugar, anti-inflammatory, asthma relieving, etc. Overall, as a safe and non-toxic natural sweetener, mogroside has obvious advantages over traditional sweeteners.

[0004] Steviol glycosides, like mogrosides, is a natural sweetener, known as the "world's third sugar source" after sugarcane and sugar beet, widely used in food, beverage, pharmaceutical, daily chemical industry, etc. Steviol glycosides are a mixture of diterpene glycosides extracted from the leaves of the herbaceous plant Stevia Rebaudia. It is widely used in food, such as often instead of sucrose added to beverages, beer, wine and other drinks, in addition, it can be added in tea to enhance the sweetness of the latter, also can be used in preserved fruits, both to reduce its heat, and because of the stable physicochemical properties of steviol glycosides to extend the shelf life of preserved fruits. In addition to the basic characteristics of high sweetness, low heat value, steviol glycosides also have many functional activities, such as lowering blood pressure, reducing blood sugar, preventing dental caries, anti-tumor, antibacterial, immune regulation, and antidiarrheal.

[0005] Solubilization refers to the phenomenon that the solubility of organic compounds that are difficult or insoluble in water can be greatly increased when the concentration of surfactants in aqueous solution reaches the critical micelle concentration. The solubilization amount is related to the structural characteristics of surfactants and solubilized substances, temperature, and the addition of organic or inorganic additives. Solubilization plays an important role in drug formulations, emulsion polymerization, micellar oil displacement, cleaning and some physiological processes. Common solubilizers include ethanol, urea, short-chain benzene sulfonate, alkyl phosphate, etc. Many solvents also have certain solubilization effects, such as ethylene glycol ethers, propylene glycol ethers, etc. In addition, commonly used surfactants include polysorbate, polyoxyethylene fatty acid ester, polyglyceryl 10 oleate, and Tween, etc. From the demand for green and friendly, research on natural solubilizers is continuing, and the exploration of foaming eutectic solvents with potential application value in this field is yet to be carried out.

[0006] Squalene, also known as triacontahexaene, is a polyunsaturated hydrocarbon produced in the metabolic process of human body cholesterol synthesis, containing 6 isoprene double bonds, and belongs to terpenoids. Many foods contain squalene, among which the content in shark liver oil is relatively high, and the content in a few plant oils such as olive oil and rice bran oil is also relatively high. Since it was discovered in the early 20th century, squalene has attracted the interest of researchers at home and abroad due to its good biological activity and wide application in food and cosmetics. Squalene has stronger antioxidant capacity than other lipid molecules in the skin, and can help the body surface resist damage caused by ultraviolet radiation and other oxidation reactions; it can be easily emulsified in standard cosmetic formulations (such as creams, ointments, sunscreens), so it can be used as a moisturizing agent in cosmetics (cold cream, skin cleanser, skin cream), emulsion, hair oil, hair cream, lipstick, aromatic oil and powder, etc. In addition, it can also be used as a high-fat agent for high-grade soap. However, the poor water solubility and instability of squalene greatly limit its further application in food, cosmetics and other industries. Although some researchers have prepared squalene into microcapsule form to improve its bioavailability, the water solubility is not ideal, and the effect of using cyclodextrin to solve the above problems needs to be further improved, and the operation is relatively cumbersome. There is an urgent need for green, safe, simple and effective solubilizers. SUMMARY

[0007] The application provides a foaming eutectic solvent prepared from natural sweeteners as raw materials and used as a solubilizer. Steviol glycosides and mogrosides are two natural sweeteners with a wide range of uses, not only high sweetness, but also a series of biological activities; as hydrogen bond acceptors, they are combined with hydrogen bond donors including sorbitol, xylitol, glycerol and 1,3-butanediol to form natural eutectic solvents under heating conditions. The product can produce abundant foam and has obvious surfactant properties. In subsequent applications, it is used as a solubilizer to improve the solubility of hydrophobic component squalene in water, which is greatly limited in the food, health care, cosmetics and other industries due to poor water solubility. The results show that the solubilization rate of the above-mentioned natural eutectic solvent for squalene can reach several times to dozens of times. Such green solvents are friendly, safe and easy to prepare, and have good application potential in many fields.

[0008] Technical scheme: In order to achieve the above purpose, a foaming eutectic solvent based on natural sweeteners and its solubilization characteristics are provided.

[0009] The application of the foaming eutectic solvent based on natural sweeteners and its solubilization characteristics, characterized in that the eutectic solvent takes steviol glycosides or mogrosides as hydrogen bond acceptors, and sorbitol, xylitol, glycerol or 1,3-butanediol as hydrogen bond donors.

[0010] The application of the foaming eutectic solvent based on natural sweeteners and its solubilization characteristics, characterized in that the eutectic solvent takes stevioside or mogroside as a hydrogen bond acceptor and sorbitol, xylitol, glycerol or 1,3-butanediol as a hydrogen bond donor.

[0011] The application of the foaming eutectic solvent based on natural sweeteners and its solubilization characteristics, characterized in that the mass ratio of the hydrogen bond acceptor and the hydrogen bond donor is 1:2. ～ 1:8.

[0012] The application of the foaming eutectic solvent based on natural sweeteners and its solubilization characteristics, characterized in that the mixture of the hydrogen bond acceptor and the hydrogen bond donor is heated at 80 ～ 130℃ for 1-3 hours to obtain the eutectic solvent.

[0013] The application of the foaming eutectic solvent based on natural sweeteners and its solubilization characteristics, characterized in that the eutectic solvent can generate abundant foam, has surface activity and can be used as a solubilizer to improve the solubility of hydrophobic components in water. BRIEF DESCRIPTION OF DRAWINGS

[0014] In order to more fully illustrate the technical solutions of the embodiments of the present application, the required drawings in the examples will be briefly described below. The described drawings are only a part of the embodiments of the present application, and those skilled in the art can obtain other drawings of the embodiments according to these drawings. Among them:

[0015] Figure 1 The eutectic solvent prepared in the present application.

[0016] Figure 2 The eutectic solvent prepared by mogroside and glycerol in the present application and the IR spectra of the two components thereof.

[0017] Figure 3 The eutectic solvent prepared by stevioside and sorbitol in the present application and the IR spectra of the two components thereof.

[0018] Figure 4 The foaming state of the eutectic solvent described in the present application.

[0019] Figure 5 The foaming rate and bubble residual rate of the eutectic solvent described in the present application.

[0020] Figure 6 The solubilization effect comparison of the eutectic solvent described in the present application on dihydrosqualene.

[0021] Figure 7The solubility of squalene in water at different temperatures when the eutectic solvent prepared from steviol glycoside and sorbitol in the present application is present at different mass fractions. DETAILED DESCRIPTION

[0022] The following is a detailed description of the application. Although specific embodiments of the application are shown, it is understood that the application can be practiced in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the application to those skilled in the art.

[0023] Example 1

[0024] Mog-Gly, a eutectic solvent in light yellow and transparent state, was obtained by mixing mogroside and glycerol at a mass ratio of 1:3.5 and heating at 80℃ for 2h.

[0025] Example 2

[0026] Mog-Xyl, a eutectic solvent in colorless and transparent state, was obtained by mixing mogroside and xylitol at a mass ratio of 1:5.5 and heating at 85℃ for 2h.

[0027] Example 3

[0028] Set-Gly, a eutectic solvent in colorless and transparent state, was obtained by mixing steviol glycoside and glycerol at a mass ratio of 1:5.5 and heating at 80℃ for 2h.

[0029] Example 4

[0030] Set-But, a eutectic solvent in colorless and transparent state, was obtained by mixing steviol glycoside and 1,3-butanediol at a mass ratio of 1:3.5 and heating at 80℃ for 2h.

[0031] Example 5

[0032] Set-Sor, a eutectic solvent in light yellow and transparent state, was obtained by mixing steviol glycoside and sorbitol at a mass ratio of 1:4.5 and heating at 130℃ for 2h.

[0033] The five eutectic solvents obtained in Examples 1-5 are shown in Table 1. Figure 1

[0034] The five eutectic solvents obtained in Examples 1-5 were subjected to spectral analysis by means of IR spectrum. Taking the eutectic solvents Mog-Gly and Set-Sor obtained in Examples 1 and 5 as examples, the IR spectra of the two are shown in Figures 1 and 2, respectively. Figure 2 3

[0035] Table 1​​​Figure 2 of mogroside spectrum, 3294 cm -1 is the stretching vibration of O-H bond, which presents as a large and wide peak, 2800-3000 cm -1 is the anti-symmetrical stretching vibration peak of CH3, and the anti-symmetrical and symmetrical stretching vibration peaks of CH2; in the spectrum of glycerol, 3371 cm -1 is the stretching vibration of O-H bond, 2935 cm -1 and 2881 cm -1 are the anti-symmetrical and symmetrical stretching vibration peaks of CH2, respectively, and there is a C-O stretching vibration peak at 1044 cm -1 . In the spectrum of the eutectic solvent Mog-Gly prepared from the two, it is found that the general shape of the spectrum is similar to that of glycerol, because the proportion of glycerol in the two components is large, but a characteristic peak belonging to mogroside at 1150 cm -1 can still be observed, proving the existence of the component; in addition, the O-H bond stretching vibration signal above 3000 cm -1 is increased, and the peak of glycerol at 1044 cm -1 is shifted to 1040 cm -1 , proving that there is obvious hydrogen bond interaction between the two substances.

[0036] Similar to the above spectrum analysis results, in the spectrum of stevioside attached Figure 3 , 3401 cm -1 is the stretching vibration of O-H bond, which presents as a wide peak, 1638 cm -1 is the stretching vibration of C=C; in the spectrum of sorbitol, 3358 cm -1 is the stretching vibration of O-H bond, 2931 cm -1 is the anti-symmetrical stretching vibration peak of CH2, and there is a H-O bending vibration peak at 1419 cm -1 . For the eutectic solvent Set-Sor prepared, its spectrum also collects the characteristic signals of the two components; 1638 cm -1 can observe the characteristic peak of C=C stretching vibration belonging to stevioside; 1419 cm -1 can observe the characteristic peak of H-O bending vibration belonging to sorbitol; in addition, the O-H bond stretching vibration signal above 3000 cm -1 is also widened, and the peak of stevioside at 1074 cm -1 is shifted to 1080 cm -1 , proving that hydrogen bond interaction occurs between the two components.

[0037] The five eutectic solvents obtained in Examples 1-5 can produce abundant foam after mixing with water and shaking, indicating that they have surface activity, as shown in the following figure. Figure 4

[0038] According to the literature method (Jiequan Jie. Synthesis and performance research of new starch-based surfactants [D]. Guangxi University for Nationalities, 2023), the five eutectic solvents obtained in Examples 1-5 were more detailedly evaluated for foam performance, including foaming performance and foam stability. In the specific operation, the eutectic solvent was configured into a 10% mass fraction aqueous solution, mechanically stirred at a speed of 700 r / min for 3 min, then immediately poured into a glass tube with an inner diameter of 2 cm and a height of 36 cm, the height of the foam was recorded, and then placed for 5, 10, 20, 40, 60, 90, 120, 150, 180 s, and the height of the foam was recorded again; the same sample was tested in parallel for 5 times, and the average value was taken. For similar surfactants, the better the foaming performance, the stronger the surface activity, and the longer the defoaming time. The results are shown in the following figure. Figure 5 As can be seen from the figure, the foaming ability of ste-gly, ste-sor and ste-but is good, and the foaming ability of the remaining two eutectic solvents is poor; in terms of defoaming time, ste-sor has the longest defoaming time and the most stable foam, followed by ste-gly.

[0039] The safety of the five eutectic solvents obtained in Examples 1-5 was evaluated using zebrafish as a model animal. According to the current national standard GB / T 31270.12-2014 "Chemical pesticides environmental safety evaluation test guidelines Part 12: Fish acute toxicity test", the 96h LC 50 The acute toxicity of chemicals to zebrafish is divided into: extremely toxic (96h-LC 50 ≤0.10 mg / L), highly toxic (0.10 mg / L < 96h-LC 50 ≤1.00 mg / L), moderately toxic (1.00 mg / L < 96h-LC 50 ≤10.00 mg / L) and low toxicity (96h-LC 50 >10.00 mg / L). The results showed that under the limit experimental conditions of a concentration of 100 mg / L, no zebrafish died within 96h in the experimental groups involving the five eutectic solvents, and the survival state of the zebrafish was as active as the blank group, so the 96h-LC 50 of the five eutectic solvents was greater than the limit experimental concentration with a reliability of 99.9%; according to the toxicity classification standard, they all belong to low toxicity substances.

[0040] ​The solubilizing ability of the five eutectic solvents obtained in Examples 1-5 was evaluated with squalene as a representative hydrophobic component. First, a quantitative working curve (y = 88.84 + 6.88x, R 2 = 0.993) was established based on the method in the literature (Chen WZ, Jin WH, Zhang YP, et al. High performance liquid chromatography detection method of squalene [J]. Food Research and Development, 2015), where x is the squalene concentration (μg / mL) and y is the liquid chromatography peak area (mAu*s). Then, squalene in oil form was added to the bottom of a centrifuge tube, 5% mass fraction of the eutectic solvent aqueous solution was added, and the homogenizer was stirred at 35000 r / min for 5 min until it was mixed evenly. Finally, the system was allowed to stand until the oil and water phases were re-laminated, and the water phase after separation was determined by high performance liquid chromatography. The solubility of squalene was calculated according to the above quantitative working curve.

[0041] Figure 1 shows the solubilizing effect of the five eutectic solvents obtained in Examples 1-5 on squalene, and the solubility of squalene in water at different temperatures and different mass fractions of the eutectic solvent Set-Sor obtained in Example 5. It can be seen that the solubilizing ability of the eutectic solvent prepared from stevioside is stronger than that of the eutectic solvent prepared from mogroside, and the solubilizing rate is tens of times, while the solubilizing rate of the latter is about 5 times. Among the five eutectic solvents obtained in Examples 1-5, the solubilizing effect of Ste-Sor obtained in Example 5 is the best, and the solubilizing rate of this eutectic solvent is 3301.6%, which significantly improves the solubility of squalene in water. In addition, with the increase of the mass fraction of Ste-Sor, the solubility of squalene shows a linear upward trend, and the higher the temperature, the more the solubility. When the mass fraction of Ste-Sor is low, the effect of temperature is small, while when the mass fraction of Ste-Sor is large enough, the effect of temperature is more obvious. Figure 6 and 7 Figure 1 shows the solubilizing effect of the five eutectic solvents obtained in Examples 1-5 on squalene, and the solubility of squalene in water at different temperatures and different mass fractions of the eutectic solvent Set-Sor obtained in Example 5. It can be seen that the solubilizing ability of the eutectic solvent prepared from stevioside is stronger than that of the eutectic solvent prepared from mogroside, and the solubilizing rate is tens of times, while the solubilizing rate of the latter is about 5 times. Among the five eutectic solvents obtained in Examples 1-5, the solubilizing effect of Ste-Sor obtained in Example 5 is the best, and the solubilizing rate of this eutectic solvent is 3301.6%, which significantly improves the solubility of squalene in water. In addition, with the increase of the mass fraction of Ste-Sor, the solubility of squalene shows a linear upward trend, and the higher the temperature, the more the solubility. When the mass fraction of Ste-Sor is low, the effect of temperature is small, while when the mass fraction of Ste-Sor is large enough, the effect of temperature is more obvious.

Claims

1. Use of a natural sweetener-based foaming eutectic solvent and its solubilizing properties, characterized in that, The eutectic solvent takes natural sweeteners as raw materials, and specifically includes steviol glycosides and mogroside.

2. Use of the natural sweetener-based foaming eutectic solvent and its solubilizing properties according to claim 1, characterized in that, The eutectic solvent takes steviol glycosides or mogroside as a hydrogen bond acceptor, and sorbitol, xylitol, glycerol or 1,3-butanediol as a hydrogen bond donor.

3. Use of the natural sweetener-based foaming deep eutectic solvent and its solubilizing properties according to claim 1, characterized in that, The mass ratio of the above hydrogen bond acceptor and hydrogen bond donor is 1:2 ～ 1:

8.

4. Use of the natural sweetener-based foaming deep eutectic solvent and its solubilizing properties according to claim 1, characterized in that, The mixture of the above hydrogen bond acceptor and hydrogen bond donor is heated at 80 ～ The eutectic solvent is prepared by heating at 130 °C for 1-3 h.

5. Use of the natural sweetener-based foaming deep eutectic solvent of claim 1 and its solubilizing properties, characterized by, The eutectic solvent can generate abundant foam, has surface activity, and can be used as a solubilizer to improve the solubility of hydrophobic components in water.

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