CN110294683A - A kind of glycine betaine phenolic acid ion salt and the preparation method and application thereof technical field - Google Patents

A kind of glycine betaine phenolic acid ion salt and the preparation method and application thereof technical field Download PDF

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CN110294683A
CN110294683A CN201910420492.2A CN201910420492A CN110294683A CN 110294683 A CN110294683 A CN 110294683A CN 201910420492 A CN201910420492 A CN 201910420492A CN 110294683 A CN110294683 A CN 110294683A
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glycine betaine
phenolic acid
ion salt
acid ion
preparation
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张嘉恒
王振元
臧俊浩
王滨燊
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Shenzhen Xuanjia Biotechnology Co Ltd
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Shenzhen Xuanjia Biotechnology Co Ltd
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Abstract

The present invention discloses a kind of glycine betaine phenolic acid ion salt and the preparation method and application thereof, wherein, the preparation method of the glycine betaine phenolic acid ion salt is comprising steps of at a predetermined temperature, phenolic acid and glycine betaine are added in organic solvent, obtain glycine betaine phenolic acid ion salt solution, crystallization operation is carried out to the glycine betaine phenolic acid ion salt solution, obtains glycine betaine phenolic acid ion salt.Glycine betaine phenolic acid ion salt produced by the present invention has effects that phenolic acid and glycine betaine and bioactivity, and its water-soluble two order of magnitude higher than monomer phenolic acid simultaneously, can effectively improve the trap of phenolic acid monomer and enhance its application effect.

Description

A kind of glycine betaine phenolic acid ion salt and the preparation method and application thereof technical field
The present invention relates to medicine, compound field used for cosmetic more particularly to a kind of glycine betaine phenolic acid ion salt and its systems Preparation Method and application.
Background technique
Glycine betaine is also known as trimethylaminyl ethlyl lactone or betanidin, is a kind of quaternary amine type alkaloid, is widespread in nature. Intermediate product of the glycine betaine as animal metabolism is excellent methyl donor and Osmolyte regulator, in the metabolism of nutriment It plays a very important role.Studies have shown that glycine betaine has the effects that osmotic adjustment, antitumor, help to maintain liver, the heart The health of blood vessel, enteron aisle and kidney possesses excellent bioactivity and pharmacological activity.But in view of the pharmacological activity of glycine betaine itself It is not very strong and lower bioavailability, it is often necessary to be used in combination with other active components and can be only achieved expected effect Fruit, to limit its application range.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of glycine betaine phenolic acid ion salt and its systems Preparation Method and application, it is intended to by glycine betaine and natural phenolic acid at salt split, solve existing glycine betaine monomer in application process In there are problems that pharmacological activity is not strong, bioavailability is low etc..
Technical scheme is as follows:
A kind of preparation method of glycine betaine phenolic acid ion salt, wherein the following steps are included:
At a predetermined temperature, phenolic acid and glycine betaine are added in organic solvent, obtain glycine betaine phenolic acid ion salt solution;
Crystallization operation is carried out to the glycine betaine phenolic acid ion salt solution, obtains glycine betaine phenolic acid ion salt.
The preparation method of the glycine betaine phenolic acid ion salt, wherein the step at a predetermined temperature, by phenolic acid and beet Alkali is added in organic solvent, is obtained glycine betaine phenolic acid ion salt solution, is specifically included:
In atmosphere of inert gases, phenolic acid is mixed in organic solvent at a predetermined temperature with glycine betaine, reacts the predetermined time, Obtain glycine betaine phenolic acid ion salt solution.
The preparation method of the glycine betaine phenolic acid ion salt, wherein the step is molten to the glycine betaine phenolic acid ion salt Liquid carries out crystallization operation, obtains glycine betaine phenolic acid ion salt, specifically includes:
Under vacuum conditions, be concentrated simultaneously freezing and crystallizing to the glycine betaine phenolic acid ion salt solution, obtain glycine betaine phenolic acid Ion salt.
The preparation method of the glycine betaine phenolic acid ion salt, wherein mole that the phenolic acid and the glycine betaine mix Than for 1:1.2-1.8.
The preparation method of the glycine betaine phenolic acid ion salt, wherein the predetermined temperature is 30-100 DEG C.
The preparation method of the glycine betaine phenolic acid ion salt, wherein the phenolic acid is vanillic acid, syringic acid, gallic acid Any one of with gentianic acid.
The preparation method of the glycine betaine phenolic acid ion salt, wherein the organic solvent is acetonitrile, methanol, ethyl alcohol and second One of glycol is a variety of.
The preparation method of the glycine betaine phenolic acid ion salt, wherein the predetermined time is 12-24h.
A kind of glycine betaine phenolic acid ion salt, wherein the glycine betaine phenolic acid ion salt uses glycine betaine phenolic acid described above The preparation method of ion salt is prepared.
A kind of application of glycine betaine phenolic acid ion salt, wherein the glycine betaine phenolic acid ion salt is used as cosmetics Formula material, nutritional supplement raw material or medicine material.
The utility model has the advantages that the present invention is that cationic presoma passes through ionization using phenolic acid as anion presoma with glycine betaine Salt-forming reaction synthesizing betaine phenolic acid ion salt realizes isolating and purifying for product by condensing crystallizing after reaction.The present invention Glycine betaine phenolic acid ion salt obtained has the effect that first, compared with monomer phenolic acid, after at salt split, glycine betaine phenol The irritation of acid ion salt is substantially reduced, while significantly improving dissolubility, to substantially increase trap, enhances application Effect;Second, the main body of glycine betaine and phenolic acid monomer has been fully retained in the glycine betaine phenolic acid ion salt of generation after at salt split Molecular skeleton and functional group, thus have bioactivity and effect there are two types of substance simultaneously, and for anti-inflammatory, antitumor etc. two kinds For substance has effects that simultaneously, at will have significant reinforcing effect after salt.
Detailed description of the invention
Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of glycine betaine phenolic acid ion salt of the present invention.
Fig. 2 is glycine betaine gallate nucleus magnetic hydrogen spectrum figure.
Fig. 3 is glycine betaine syringic acid salt nuclear-magnetism hydrogen spectrogram.
Fig. 4 is glycine betaine vanillate nucleus magnetic hydrogen spectrum figure.
Fig. 5 is glycine betaine gentisate nucleus magnetic hydrogen spectrum figure.
Specific embodiment
The present invention provides a kind of glycine betaine phenolic acid ion salt and the preparation method and application thereof, for make the purpose of the present invention, Technical solution and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that described herein Specific examples are only used to explain the present invention, is not intended to limit the present invention.
Referring to Fig. 1, Fig. 1 provides a kind of stream of the preparation method preferred embodiment of glycine betaine phenolic acid ion salt for the present invention Cheng Tu, as shown, it includes the following steps:
Phenolic acid and glycine betaine are added in organic solvent, obtain glycine betaine phenolic acid ion salt solution by S10, at a predetermined temperature;
S20, crystallization operation is carried out to the glycine betaine phenolic acid ion salt solution, obtains glycine betaine phenolic acid ion salt.
Specifically, glycine betaine phenolate provided by the present invention is cationic presoma with glycine betaine, is yin with phenolic acid Ion presoma is realized by condensing crystallizing after reaction by being ionized into reactant salt synthesizing betaine phenolic acid ion salt Product isolates and purifies, and has obtained glycine betaine phenolic acid ion salt, and the preparation method is made using usual vehicle simple and easy to get For reaction medium, instrument and reaction condition are also easily achieved, and synthesis step is succinct, convenient post-treatment, and products obtained therefrom is pure Degree is high, high income, can meet general Study requirement.
In above-mentioned preparation method provided by the present invention, the phenolic acid is widely present in plant as Secondary metabolites It is that the very wide element of the first species is distributed in human diet in object cell.Natural phenolic acid have multiple biological activities, human body and other In animal body, remove free radical, in addition to anti-oxidant, antitumor, bacteria resistance function except having, also have and inhibit fat, improve mood and Promote the functions such as human body intestinal canal health.However, the water solubility of most natural phenolic acids is very poor, and the bioactivity phase of phenolic acid monomer To weaker, to limit its application effect and application range.Using natural phenolic acid as anion presoma pair in the present invention After glycine betaine carries out Ionization Modification, available one kind it is pure natural there are excellent performances such as anti-oxidant, anti-inflammatory, antitumor The water solubility of glycine betaine phenolic acid ion salt, the glycine betaine phenolic acid ion salt increases significantly compared with monomer phenolic acid, thus Trap is substantially increased, application effect is enhanced.
The phenolic acid is widely present in plant cell as Secondary metabolites, is to be distributed in human diet very extensively The element of the first species.Common natural phenolic acid has multiple biological activities, in human body and other animal bodies, removes freely except having Outside base, anti-oxidant, antitumor, bacteria resistance function, also have and inhibit fat, improve mood and promotes the functions such as human body intestinal canal health.
In one or more embodiments, the phenolic acid is syringic acid, gallic acid, vanillic acid, gentianic acid, caffeic acid One of Deng, but not limited to this.
In a kind of specific embodiment, when the phenolic acid is syringic acid, then the syringic acid and glycine betaine are existed It is mixed under predetermined temperature in organic solvent, the syringic acid and glycine betaine is made to be ionized into reactant salt, sweet tea is made Dish alkali cloves acid salt solution.The syringic acid can be from compositae plant knitting wool careless (Artemisia stelleriana, Horseweed Herb), overground part ericad Rhododendron dauricum, leaf korean rhododendron, Ye Baihua cuckoo, Ye little Hua cuckoo, leaf umbelliferae fennel, leaf Lindsaeaceae plant Stenoloma chusana , leaf malvaceae plant Althaea officinalis and leaf Fagaceae gall oak goitre in extract and obtain, syringic acid has stronger antioxygen Change and antibacterial action are the main antibiotic effective ingredient of Artemisia stelleriana, play the role of antibacterium and fungi, the cloves acid monomers are 25 Water solubility under the conditions of DEG C is about 7 mmolL-1, prepared by water-soluble > of glycine betaine cloves hydrochlorate under the conditions of 25 DEG C 1000 mmol·L-1.The glycine betaine cloves hydrochlorate has the bioactivity and function of two kinds of substances of syringic acid and glycine betaine simultaneously Effect, and the trap of syringic acid and glycine betaine is substantially increased, enhance its application effect.
In a kind of specific embodiment, when the phenolic acid is gallic acid, then by the gallic acid and beet Alkali mixes in organic solvent under predetermined temperature, and the gallic acid and glycine betaine is made to be ionized into reactant salt, Glycine betaine gallic acid salting liquid is made.The gallic acid has bacteriostasis to 17 kinds of fungies under 3% concentration, to influenza Virus also has certain inhibiting effect, can treat bacillary dysentery;It has convergence, hemostasis, anti-diarrhea effect, to caused by morpholine plus sodium nitrite Mouse lung adenoma has high inhibition effect.Water solubility of gallic acid under the conditions of 25 DEG C is about 71 mmolL-1, and be made Water-soluble > 1000 mmolL of glycine betaine gallate under the conditions of 25 DEG C-1.The glycine betaine gallate is same When have effects that the bioactivity of two kinds of substances of gallic acid and glycine betaine and, and substantially increase gallic acid and glycine betaine Trap, enhance its application effect.
In one or more embodiments, the organic solvent is one in acetonitrile, methanol, ethyl alcohol and ethylene glycol etc. Kind.It is furthermore preferred that the solvent is methanol, to improve the Crystallization Separation effect of product.
In one or more embodiments, the ratio for being 1:1.2-1.8 according to the molar ratio of phenolic acid and glycine betaine, by institute It states phenolic acid and glycine betaine to mix under predetermined temperature in organic solvent, is ionized into the phenolic acid and glycine betaine Glycine betaine phenolic acid ion salt solution is made in reactant salt.It is furthermore preferred that the molar ratio of the phenolic acid and glycine betaine is 1:1.3-1.6.
In one or more embodiments, phenolic acid and glycine betaine are blended under the conditions of 30-100 DEG C of temperature organic In solvent, after so that the phenolic acid and glycine betaine is ionized into reactant salt 12-24h, glycine betaine phenolic acid ion salt solution is made. Under the reaction temperature, not only there is faster reaction rate, but also the generation of side reaction can be effectively suppressed;Under the reaction time, It can promote fully reacting between phenolic acid and glycine betaine.
In some embodiments, the glycine betaine phenolic acid ion salt solution is concentrated into its volume under vacuum conditions When 1/5 to 1/10, then freezing and crystallizing is carried out, pure glycine betaine phenolic acid ion salt is made.
It in some embodiments, further include step after carrying out Freeze crystallization to the glycine betaine phenolic acid ion salt solution It is rapid: separation and vacuum drying are successively filtered to glycine betaine phenolic acid ion salt obtained, wherein drying time 24-48h, Thoroughly to remove the residual solvent in product.
After the present invention carries out Ionization Modification to glycine betaine using natural phenolic acid as anion presoma, the beet of generation Host molecule skeleton and the functional group of glycine betaine and phenolic acid monomer has been fully retained in alkali phenolic acid ion salt, thus simultaneously there are two types of tool The bioactivity and effect of substance, and for two kinds of substances such as anti-inflammatory, antitumor have effects that simultaneously, will have at after salt There is significant reinforcing effect.
Further, the present invention reacts generation with glycine betaine to different types of phenolic acid monomer under the conditions of 25 DEG C of temperature Glycine betaine phenolic acid ion salt and the water solubility datas of various phenolic acid monomers be tested, specifically, the glycine betaine phenol Acid ion salt it is water-soluble shown in the experimental data are shown in the following table:
Water solubility relatively (mmolL-1, 25℃)
Gallic acid Syringic acid Vanillic acid Gentianic acid
Phenolic acid monomer 71 7 10 4
Glycine betaine phenolic acid ion salt > 1000 > 1000 > 1000 > 1000
By comparison, it was found that the water solubility of the glycine betaine phenolic acid ion salt improves two order of magnitude left sides compared with monomer phenolic acid The right side enhances its application effect to substantially increase its trap.
Further, the present invention tests the minimum inhibitory concentration (MIC) of glycine betaine phenolic acid ion salt, specifically, institute The bacteriostatic experiment data for stating glycine betaine phenolic acid ion salt are as shown in the table:
Minimum inhibitory concentration (MIC)
By test result as can be seen that four kinds of glycine betaine phenolic acid ion salts are to candida albicans, Escherichia coli, black song Mould, Pseudomonas aeruginosa, staphylococcus aureus and propionibacterium acnes etc. all have good fungistatic effect, can significantly inhibit thin The growth of bacterium, fungi and mould etc..
Based on above-mentioned preparation method, the present invention also provides a kind of glycine betaine phenolic acid ion salts, wherein using as described above The preparation method of glycine betaine phenolic acid ion salt is prepared.
Further, the present invention also provides a kind of applications of glycine betaine phenolic acid ion salt, wherein by institute of the embodiment of the present invention The glycine betaine phenolic acid ion salt stated is used as the formula material of cosmetics;Alternatively, by glycine betaine phenolic acid described in the embodiment of the present invention Ion salt is used as the medicinal ingredient of the drugs such as antitumor, anticancer.In other words, glycine betaine phenolic acid ion salt described in the present embodiment Anti-inflammatory bactericidal agent, mite killing be can not only be used for except acne agent and moisturizer etc. are used for the formula material of cosmetics, be also used as it is anti-inflammatory, The raw material of the drugs such as antitumor, anticancer.
Below by specific embodiment, the invention will be further described.
Embodiment 1
The preparation method of the present embodiment glycine betaine gallic acid ion salt, comprising the following steps:
Under nitrogen atmosphere, 0.01 mol gallic acid is dissolved in reactor with the methanol of 30 ml, it is molten with the methanol of 20 ml 0.01 mol glycine betaine is solved, and is added dropwise in the reactor dissolved with gallic acid, 60 DEG C is heated to, is ionized into reactant salt 12 hours;
After completion of the reaction, under vacuum conditions concentrate solution to reaction solution 1/10, freezing and crystallizing, and be filtered, washed point From glycine betaine gallic acid ion salt crystalline product is obtained, drying obtain purity in 48 hours in a vacuum drying oven is more than 99% Glycine betaine gallic acid ion salt 2.68g, yield 93.32%.
As shown in Fig. 2, the nucleus magnetic hydrogen spectrum data of glycine betaine gallic acid ion salt are made in the present embodiment are as follows:1H NMR (400 MHz, MeOD) δ 7.06 (s, 2H), 3.84 (s, 2H), 3.26 (s, 9H);Nuclear-magnetism carbon modal data are as follows:13C NMR (101 MHz, MeOD) δ 169.05, 167.46, 145.07, 138.21, 120.71, 108.97, 65.83, 52.48, 52.44, 52.40.The fusing point that glycine betaine gallic acid ion salt is made in the present embodiment is 206-208 DEG C.
Embodiment 2
The preparation method of the present embodiment glycine betaine syringic acid ion salt, comprising the following steps:
Under nitrogen atmosphere, 0.01 mol syringic acid is dissolved in reactor with the methanol of 25 ml, is dissolved with the methanol of 20 ml 0.01 mol glycine betaine, and be added dropwise in the reactor dissolved with gallic acid, 50 DEG C are heated to, reactant salt 16 is ionized into Hour;
After completion of the reaction, under vacuum conditions concentrate solution to reaction solution 1/6, freezing and crystallizing, and be filtered, washed separation Glycine betaine syringic acid ion salt crystalline product is obtained, dries in a vacuum drying oven 48 hours and obtains the sweet tea that purity is more than 99% Dish alkali syringic acid ion salt 2.95g, yield 93.51%.
As shown in figure 3, the nucleus magnetic hydrogen spectrum data of glycine betaine syringic acid ion salt are made in the present embodiment are as follows:1H NMR (400 MHz, MeOD) δ 7.32 (s, 2H), 3.88 (s, 6H), 3.85 (s, 2H), 3.28 (s, 9H);Nuclear-magnetism carbon spectrum Data are as follows:13C NMR (101 MHz, MeOD) δ 168.62, 167.40, 147.46, 140.29, 120.67, 106.91, 65.81, 55.41, 52.47, 52.43, 52.39.The molten of glycine betaine syringic acid ion salt is made in the present embodiment Point is 190-195 DEG C.
Embodiment 3
The preparation method of the present embodiment glycine betaine vanillic acid ion salt, comprising the following steps:
Under nitrogen atmosphere, 0.01 mol vanillic acid is dissolved in reactor with the methanol of 35 ml, is dissolved with the methanol of 20 ml 0.01 mol glycine betaine, and be added dropwise in the reactor dissolved with vanillic acid, 65 DEG C are heated to, it is small to be ionized into reactant salt 16 When;
After completion of the reaction, under vacuum conditions concentrate solution to reaction solution 1/8, freezing and crystallizing, and be filtered, washed separation Glycine betaine vanillic acid ion salt crystalline product is obtained, dries in a vacuum drying oven 48 hours and obtains the sweet tea that purity is more than 99% Dish alkali vanillic acid ion salt 2.66g, yield 93.23%.
As shown in figure 4, the nucleus magnetic hydrogen spectrum data of glycine betaine vanillic acid ion salt are made in the present embodiment are as follows:1H NMR (400 MHz, MeOD) δ 7.55 (dq, J = 3.7, 1.9 Hz, 2H), 6.89 – 6.79 (m, 1H), 3.89 (s, 3H), 3.85 (s, 2H), 3.27 (s, 9H);Nuclear-magnetism carbon modal data are as follows:13C NMR (101 MHz, MeOD) δ 168.70, 167.41, 151.27, 147.29, 123.90, 121.80, 114.50, 112.42, 65.79, 55.03, 52.47, 52.43, 52.39.The fusing point that glycine betaine vanillic acid ion salt is made in the present embodiment is 171-173 DEG C.
Embodiment 4
The preparation method of the present embodiment glycine betaine gentianic acid ion salt, comprising the following steps:
Under nitrogen atmosphere, 0.01 mol gentianic acid is dissolved in reactor with the methanol of 40ml, is dissolved with the methanol of 20 ml 0.01 mol glycine betaine, and be added dropwise in the reactor dissolved with gentianic acid, 70 DEG C are heated to, it is small to be ionized into reactant salt 24 When;
After completion of the reaction, under vacuum conditions concentrate solution to reaction solution 1/10, freezing and crystallizing, and be filtered, washed point From glycine betaine gentisate crystalline product is obtained, dries in a vacuum drying oven 48 hours and obtain the beet that purity is more than 99% Alkali gentisate 2.52g, yield 92.89%.
As shown in figure 5, the nucleus magnetic hydrogen spectrum data of glycine betaine gentisate are made in the present embodiment are as follows:1H NMR (400 MHz, MeOD) δ 7.26 (d, J=3.1 Hz, 1H), 6.94 (dd, J=8.9, 3.1 Hz, 1H), 6.76 (d, J = 8.9 Hz, 1H), 3.90 (s, 2H), 3.28 (s, 9H).The present embodiment be made glycine betaine gentisate fusing point be 198-203℃。
In conclusion a kind of glycine betaine phenolic acid ion salt provided by the invention and the preparation method and application thereof.The present invention with Glycine betaine is cationic presoma, using phenolic acid as anion presoma, by be ionized into reactant salt synthesizing betaine phenolic acid from Alite realizes isolating and purifying for product by condensing crystallizing after reaction.The glycine betaine phenolic acid ion salt is natural ion Salt, antioxidant activity is higher than or is equivalent to vitamin C, water-soluble two numbers magnitude higher than monomer phenolic acid, and has simultaneously There are the effect of phenolic acid and glycine betaine and bioactivity.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention Protect range.

Claims (10)

1. a kind of preparation method of glycine betaine phenolic acid ion salt, which comprises the following steps:
At a predetermined temperature, phenolic acid and glycine betaine are added in organic solvent, obtain glycine betaine phenolic acid ion salt solution;
Crystallization operation is carried out to the glycine betaine phenolic acid ion salt solution, obtains glycine betaine phenolic acid ion salt.
2. the preparation method of glycine betaine phenolic acid ion salt according to claim 1, which is characterized in that the step is in predetermined temperature Under degree, phenolic acid and glycine betaine are added in organic solvent, glycine betaine phenolic acid ion salt solution is obtained, specifically includes:
In atmosphere of inert gases, phenolic acid is mixed in organic solvent at a predetermined temperature with glycine betaine, reacts the predetermined time, Obtain glycine betaine phenolic acid ion salt solution.
3. the preparation method of glycine betaine phenolic acid ion salt according to claim 1, which is characterized in that the step is to the sweet tea Dish alkali phenolic acid ion salt solution carries out crystallization operation, obtains glycine betaine phenolic acid ion salt, specifically includes:
Under vacuum conditions, be concentrated simultaneously freezing and crystallizing to the glycine betaine phenolic acid ion salt solution, obtain glycine betaine phenolic acid Ion salt.
4. the preparation method of glycine betaine phenolic acid ion salt according to claim 1, which is characterized in that the phenolic acid and the sweet tea The molar ratio that dish alkali mixes is 1:1.2-1.8.
5. the preparation method of glycine betaine phenolic acid ion salt according to claim 1, which is characterized in that the predetermined temperature is 30-100℃。
6. the preparation method of glycine betaine phenolic acid ion salt according to claim 1, which is characterized in that the phenolic acid is vanilla Any one of acid, syringic acid, gallic acid and gentianic acid.
7. the preparation method of glycine betaine phenolic acid ion salt according to claim 1, which is characterized in that the organic solvent is second One of nitrile, methanol, ethyl alcohol and ethylene glycol are a variety of.
8. the preparation method of glycine betaine phenolic acid ion salt according to claim 2, which is characterized in that the predetermined time is 12-24h。
9. a kind of glycine betaine phenolic acid ion salt, which is characterized in that the glycine betaine phenolic acid ion salt is any using claim 1-8 The preparation method of the glycine betaine phenolic acid ion salt is prepared.
10. a kind of application of glycine betaine phenolic acid ion salt, which is characterized in that by glycine betaine phenolic acid ion as claimed in claim 9 Salt is used as formula material, nutritional supplement raw material or the medicine material of cosmetics.
CN201910420492.2A 2019-05-20 2019-05-20 A kind of glycine betaine phenolic acid ion salt and the preparation method and application thereof technical field Pending CN110294683A (en)

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Publication number Priority date Publication date Assignee Title
CN112250588A (en) * 2020-11-06 2021-01-22 哈尔滨工业大学(深圳) L-carnitine ionic liquid and preparation method and application thereof
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WO2023274401A1 (en) * 2021-07-02 2023-01-05 深圳市萱嘉生物科技有限公司 Betaine salicylic acid eutectic, preparation method therefor, and application thereof
CN116284814A (en) * 2023-01-17 2023-06-23 杭州三式化妆品有限公司 Supermolecule tranexamic acid glycolate ion salt and preparation method and application thereof

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