阅读说明：本技术 一种α-倒捻子素的纯化方法及含α-倒捻子素的防晒剂 (Purification method of alpha-mangostin and sunscreen containing alpha-mangostin ) 是由 夏颖 于晓霞 古润金 于 2020-05-09 设计创作，主要内容包括：本发明提供了一种α-倒捻子素的纯化方法及含α-倒捻子素的防晒剂,其纯化方法包括如下步骤：将含α-倒捻子素的倒捻子果皮粗提物粉末与甲氧基肉桂酸酯类化合物和无水醇混匀得混悬液,离心取上清液；向上清液中加入水混匀得乳液,离心,下层液即为含α-倒捻子素的甲氧基肉桂酸酯类溶液。该方法通过采用甲氧基肉桂酸酯类化合物和无水醇的混合液作为第一次萃取剂,可充分萃取α-倒捻子素并减少大极性杂质的溶解,提高α-倒捻子素的萃取率和纯度；采用甲氧基肉桂酸酯类、无水乙醇和水的混合液二次萃取,可提高α-倒捻子素的萃取率并降低杂质含量；且纯化得到的含α-倒捻子素的甲氧基肉桂酸酯类溶液可直接用作防晒剂中的原料,无需分离。(The invention provides a purification method of alpha-mangostin and a sunscreen containing the alpha-mangostin, wherein the purification method comprises the following steps: mixing crude extract powder of mangosteen pericarp containing alpha-mangostin with methoxycinnamate compound and anhydrous alcohol to obtain suspension, centrifuging, and collecting supernatant; adding water into the supernatant, mixing uniformly to obtain emulsion, centrifuging, and obtaining subnatant which is methoxy cinnamate solution containing alpha-mangostin. The method adopts the mixed solution of methoxy cinnamic acid ester compounds and anhydrous alcohol as a first extractant, can fully extract the alpha-mangostin and reduce the dissolution of large-polarity impurities, and improves the extraction rate and the purity of the alpha-mangostin; the mixed solution of methoxy cinnamate, absolute ethyl alcohol and water is adopted for secondary extraction, so that the extraction rate of the alpha-mangostin can be improved, and the impurity content can be reduced; and the methoxy cinnamate solution containing the alpha-mangostin obtained by purification can be directly used as a raw material in the sunscreen agent without separation.)

1. A method for purifying alpha-mangostin is characterized by comprising the following steps:

first extraction: uniformly mixing crude extract powder of mangosteen pericarp containing alpha-mangostin with a mixed solution of methoxycinnamate compounds and anhydrous alcohol to obtain a suspension, and centrifuging to obtain a supernatant;

and (3) second extraction: adding water into the supernatant, mixing uniformly to obtain emulsion, centrifuging, and obtaining subnatant which is methoxy cinnamate solution containing alpha-mangostin.

2. The method for purifying alpha-mangostin according to claim 1, further comprising a third extraction step;

and the third extraction is to uniformly mix the lower layer liquid with absolute alcohol and water and centrifuge to obtain the methoxycinnamate solution containing the alpha-mangostin.

3. The method for purifying alpha-mangostin according to claim 1 or 2, wherein the methoxycinnamate compound is ethylhexyl methoxycinnamate and/or isoamyl p-methoxycinnamate;

the anhydrous alcohol is anhydrous ethanol or anhydrous methanol.

4. The method for purifying alpha-mangostin according to any one of claims 1 to 3, wherein the mass ratio of the methoxycinnamate compound to the anhydrous alcohol in the first extraction step is 1: 1.8-2.2.

5. The method for purifying alpha-mangostin according to any one of claims 1 to 4, wherein in the first extraction step, the mass ratio of the crude extract powder of the pericarp of mangostin-containing mangostin to the mixed extract of the methoxycinnamate compound and anhydrous alcohol is 1: 30-35.

6. The method for purifying alpha-mangostin according to any one of claims 1 to 5, wherein the first extraction step further comprises stirring the suspension at 45-55 ℃ and 200-400 rpm for 20-30min before the suspension is centrifuged, and then cooling.

7. The method for purifying alpha-mangostin according to any of claims 1-6, wherein the centrifugation is performed at 3800 and 4600 revolutions per minute for 15-25min in the first extraction step.

8. The method for purifying alpha-mangostin according to any one of claims 1 to 7, wherein water is added in an amount of 15 to 20 wt% of the supernatant in the second extraction step.

9. The method for purifying alpha-mangostin according to any one of claims 1 to 8, wherein the centrifugation in the second extraction step is performed at 5000-.

10. The method for purifying alpha-mangostin according to claim 2, wherein the third extraction step comprises adding anhydrous alcohol at room temperature and stirring for 10-15min, and then adding pure water and stirring for 10-15 min.

11. The method for purifying alpha-mangostin according to claim 2 or 10, wherein in the third extraction step, the mass ratio of the subnatant to the added absolute alcohol is 1: 1-2; the mass ratio of the added amount of water to the added anhydrous alcohol is 0.25-0.35: 1.

12. The method as claimed in claim 11, wherein the centrifugation is performed at 8000 rotation/min and 15-25min in the third extraction step.

13. The method for purifying alpha-mangostin according to any one of claims 1 to 12, wherein the crude extract powder of pericarp of mangosteen containing alpha-mangostin contains 38 to 42 wt% of alpha-mangostin.

14. An alpha-mangostin-containing sunscreen agent, which is characterized by comprising the alpha-mangostin-containing methoxycinnamate solution purified by the alpha-mangostin purification method according to any one of claims 1 to 13.

Technical Field

The invention relates to the technical field of sunscreen products, and particularly relates to a purification method of alpha-mangostin and a sunscreen agent containing the alpha-mangostin.

Background

With the improvement of the living standard of people and the gradually strengthened understanding of the harm of excessive ultraviolet irradiation, more and more people begin to use the sunscreen cosmetics to prevent the ultraviolet rays from damaging human bodies, and the research and development of the sunscreen cosmetics also become one of the hot spots of the research and development of the cosmetics.

Sunscreens currently used in cosmetics fall into two main categories: one is a physical sun-screening agent, represented by titanium dioxide and zinc oxide, and can reflect and scatter light by virtue of a unique crystal structure, so as to achieve the purpose of shielding ultraviolet rays; one is a chemical sunscreen agent, which absorbs the energy of ultraviolet light through a special molecular structure and converts the energy, and is generally a substance with a conjugated structure of carbonyl and aromatic rings, such as cinnamates, salicylates, benzophenones, and the like. However, physical sunscreens tend to cause pore blockage, are not conducive to skin metabolism, and can cause skin disorders, skin allergies, and other symptoms. The chemical sun-screening agent has poor light stability and is easy to oxidize and deteriorate, so that symptoms such as skin allergy and the like are caused.

In order to overcome the defects, the composite sun-screening agent obtained by compounding the natural plant sun-screening agent and the organic or inorganic sun-screening agent is produced, so that the use amount of the original sun-screening agent can be reduced, the safety to the skin is improved, and the side effect caused by the organic or inorganic sun-screening agent can be reduced or relieved by the active ingredients in the natural plant sun-screening agent; for example, chinese patent document CN108553332A discloses a composite sunscreen agent obtained by compounding an extract of α -mangostin with butyl methoxydibenzoylmethane, octocrylene, and octyl salicylate, which has the effects of increasing SPF value and enhancing UVB prevention, and is safe to use, non-toxic to skin, and non-irritating; however, the α -mangostin extract is extracted from the pericarp of mangosteen (also called "mangosteen") by conventional extraction methods such as ultrasonic extraction, filtration, and reflux extraction, and the pericarp of mangosteen is also rich in various flavones and anthraquinones, which have similar physicochemical properties to α -mangostin, so that the α -mangostin extract extracted by conventional methods contains a large amount of flavone and anthraquinone impurities, and the α -mangostin extract with excessive impurities is not completely dissolved and has too deep color after being added with cosmetics, resulting in low consumer acceptance.

For example, chinese patent document CN102241659A discloses a method for purifying α -mangostin, which comprises the following steps:

1) crushing mangosteen casing, adding 3-10 times of 60-80% ethanol solution for soaking and extracting for 2-3 times, concentrating the extracting solution under reduced pressure, adding a double-water phase solvent system into the concentrated solution for extraction, collecting an organic phase, and concentrating to obtain a concentrated solution;

2) adding water into the concentrated solution for dispersion, adding polyamide resin column for adsorption, performing gradient elution with ethanol solution, detecting with thin layer, collecting fraction, concentrating under reduced pressure, standing for crystallization;

3) filtering out crystals, dissolving the crystals by using a mixed solution, recrystallizing the crystals, and drying the crystals to obtain alpha-mangostin;

the method has multiple steps and complicated operation for purifying the alpha-mangostin, and the purification by using the resin column consumes long time, and the resin needs to be cleaned and regenerated before each use, thereby consuming a large amount of time and solvent and generating a large amount of ethanol, water and impurity waste liquid; and the adsorption of a large amount of impurities in the extract can make the resin difficult to regenerate, and the resin needs to be replaced by new resin; mixed liquor (petroleum ether, ethyl acetate, methanol and water) is used for carrying out repeated recrystallization in the subsequent process, the used organic reagent is harmful to human bodies, is unsafe and not environment-friendly, and the crystallized product needs to be dried, so that a large amount of toxic and harmful volatile organic waste gas can be generated.

Disclosure of Invention

Therefore, the technical problem to be solved by the invention is to overcome the defects of low extraction efficiency, multiple steps, long extraction time, multiple materials consumption, large solvent usage amount, insecurity and environmental pollution of the alpha-mangostin in the prior art, thereby providing a method for purifying the alpha-mangostin and a sunscreen agent containing the alpha-mangostin.

The invention aims to solve another technical problem of overcoming the defects that alpha-mangostin obtained by extraction in the prior art has high impurity content, cannot be completely dissolved and has too deep color after being added into cosmetics, thereby providing a method for purifying alpha-mangostin and a sunscreen agent containing the alpha-mangostin and being convenient to be added into the cosmetics.

Therefore, the invention provides the following technical scheme:

a method for purifying alpha-mangostin comprises the following steps:

first extraction: uniformly mixing crude extract powder of mangosteen pericarp containing alpha-mangostin with methoxycinnamate compounds and anhydrous alcohol to obtain suspension, and centrifuging to obtain supernatant;

and (3) second extraction: adding water into the supernatant, mixing uniformly to obtain emulsion, centrifuging, and obtaining subnatant which is methoxy cinnamate solution containing alpha-mangostin.

Further, the purification method of the alpha-mangostin further comprises a third extraction step;

and the third extraction is to uniformly mix the lower layer liquid with absolute alcohol and water and centrifuge to obtain the methoxycinnamate solution containing the alpha-mangostin.

Further, the methoxy cinnamic acid ester compounds are ethylhexyl methoxycinnamate (OMC for short) and/or isoamyl p-methoxycinnamate;

the anhydrous alcohol is anhydrous ethanol or anhydrous methanol.

Further, in the first extraction step, the mass ratio of the methoxy cinnamic acid ester compound to the anhydrous alcohol is 1: 1.8-2.2.

Further, in the first extraction step, the mass ratio of the alpha-mangostin-containing mangostin pericarp crude extract powder to the mixed extract of the methoxycinnamate compounds and anhydrous alcohol is 1: 30-35.

Further, the first extraction step comprises stirring the suspension at 45-55 deg.C and 200-400 rpm for 20-30min before centrifuging the suspension, and cooling.

Further, in the first extraction step, the rotation speed of centrifugation is 3800-.

Further, in the second extraction step, water is added in an amount of 15 to 20 wt% of the supernatant.

Further, in the second extraction step, the rotation speed of the centrifugation is 5000-.

Further, in the third extraction step, anhydrous alcohol is added at room temperature and stirred for 10-15min, and then pure water is added and stirring is continued for 10-15 min.

Further, in the third extraction step, the mass ratio of the lower layer liquid to the added anhydrous alcohol is 1: 1-2;

the mass ratio of the added amount of water to the added anhydrous alcohol is 0.25-0.35: 1.

Further, in the third extraction step, the rotation speed of centrifugation is 5000-.

Furthermore, the content of alpha-mangostin in crude extract powder of the mangosteen pericarp containing alpha-mangostin is 38-42 wt%.

The invention also provides a sunscreen agent containing alpha-mangostin, which comprises the methoxycinnamate solution containing alpha-mangostin purified by the alpha-mangostin purification method.

The content of alpha-mangostin in crude extract powder of the peridium of mangosteen containing alpha-mangostin is not limited to 38-42 wt%, and if the content is not in the limited range, the proportions of methoxycinnamate and absolute alcohol, and methoxycinnamate, absolute alcohol and water can be properly adjusted, and a methoxycinnamate solution containing high-purity alpha-mangostin can still be obtained.

The technical scheme of the invention has the following advantages:

1. according to the purification method of alpha-mangostin, the inventor finds that the dissolution of high-polarity impurities can be effectively reduced by adopting the mixed solution of the methoxycinnamate compound and the anhydrous alcohol as the extractant for the first extraction and utilizing the characteristic of small polarity of the extractant on the premise of fully extracting the alpha-mangostin, so that the high-polarity impurities can be removed through centrifugal separation, and the extraction rate and the purity of the alpha-mangostin are improved; moreover, because the methoxycinnamate compounds are oily substances and are viscous, the viscosity of the methoxycinnamate compounds can be greatly reduced by mixing anhydrous alcohol with the methoxycinnamate compounds, and the extraction efficiency of the alpha-mangostin is improved;

because the crude extract of the alpha-mangostin pericarp is powdery, if the methoxycinnamate compounds are directly used, the alpha-mangostin in the extract powder cannot be efficiently extracted, but if water is added during the first extraction, the alpha-mangostin distributed in a methoxycinnamate system is reduced, so that the extraction rate of the alpha-mangostin is reduced; and water is directly combined with anhydrous alcohol, so that the anhydrous alcohol is separated from the methoxycinnamate, and a water-alcohol mixed solution dissolves a large amount of impurities which cannot be dissolved by the methoxycinnamate-alcohol in the extract powder, thereby influencing the purification effect;

secondly, a mixed solution of methoxy cinnamate, anhydrous alcohol and water is adopted for extraction, the characteristics that methoxy cinnamate compounds and anhydrous alcohol can be mixed in any proportion, water can also be mixed with the anhydrous alcohol in any proportion, but the water and the methoxy cinnamate compounds are mutually incompatible are utilized, after water is added, the water and the alcohol are mixed into one phase, at the moment, the polarity is changed, the mangostin originally dissolved in the alcohol-methoxy cinnamate is redistributed and dissolved in a methoxy cinnamate system, the alcohol-water system dissolves other part of impurities, and after two times of extraction, the extraction rate of the alpha-mangostin is further improved, and the content of the impurities in the methoxy cinnamate system is reduced.

Thirdly, because the methoxycinnamate is a common sunscreen agent, the methoxycinnamate solution containing the alpha-mangostin obtained by purification can be directly used as a raw material in sunscreen cosmetics without separation, and has antibacterial and anti-inflammatory effects; the alcohol-water system can recover alcohol for recycling; moreover, the method has the advantages of simple and rapid purification process, short time consumption, less material consumption, less solvent consumption, safety, environmental protection, no need of special equipment and special reagents, low energy consumption and less production loss, and the purification method is suitable for all the existing extraction processes to extract the crude extract powder of the perillaca of mangostin-containing mangostin.

2. According to the purification method of alpha-mangostin, provided by the invention, a mixed solution consisting of anhydrous alcohol, a methoxycinnamate compound and water is used for extraction for the third time, so that part of impurities in a lower layer solution can be extracted from a methoxycinnamate system to an alcohol-water system, and the impurity content in the methoxycinnamate system is obviously reduced.

3. The purification method of alpha-mangostin provided by the invention can further improve the extraction rate of the alpha-mangostin and reduce the impurity content in a methoxycinnamate system by limiting various parameters.

4. According to the purification method of alpha-mangostin provided by the invention, the addition amount of water in the second extraction step is limited, so that the effect of three-solvent two-phase separation can be improved, the alpha-mangostin is basically transferred to a methoxycinnamate system, and the subsequent recovery of alcohol is facilitated.

5. According to the composite sun-screening agent containing alpha-mangostin, provided by the invention, the composite of the alpha-mangostin and methoxycinnamate is added, so that the sun-screening effect is improved, and the anti-inflammatory and antibacterial effects are achieved; moreover, after the compound of the alpha-mangostin and the methoxy cinnamate is added into cosmetics, the compound can be completely dissolved, has light color and high consumer acceptance.

6. When OMC is selected as the methoxy cinnamate, the absorption of the alpha-mangostin and OMC compound to ultraviolet light at 290-320nm is close to that of pure OMC, the alpha-mangostin and OMC compound are diluted by a dilution method for 4 ten thousand times to test the ultraviolet absorption at 290-320nm, the absolute difference value of the ultraviolet light transmittance of the alpha-mangostin and OMC compound is not more than 1 percent at most, the maximum light transmittance of the compound interval is 3.1 percent, the average value is 1.8 percent, and the alpha-mangostin-containing compound sunscreen agent can effectively protect skin and avoid UVB damage.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is a high performance liquid chromatogram obtained by measuring the content of methoxycinnamate compounds in Experimental example 1 at 311nm of an ethylhexyl methoxycinnamate (OMC) standard of the present invention;

FIG. 2 is a high performance liquid chromatogram obtained by measuring the content of alpha-mangostin in Experimental example 1 at 280nm of an ethylhexyl methoxycinnamate (OMC) standard according to the present invention;

FIG. 3 is a high performance liquid chromatogram obtained by measuring the content of alpha-mangostin in Experimental example 1 at 280nm of a standard sample of alpha-mangostin in the present invention;

FIG. 4 is a high performance liquid chromatogram of a water-ethanol phase raffinate at 280nm according to the method for detecting the content of alpha-mangostin in Experimental example 1 in example 6 of the present invention;

FIG. 5 is a high performance liquid chromatogram obtained by measuring the content of alpha-mangostin in Experimental example 1 at 280nm of OMC phase extract in example 6 of the present invention;

FIG. 6 is a spectrum of UV-VIS absorption of OMC phase extract and pure OMC phase after diluted 4 ten thousand times with absolute ethanol in example 6 of the present invention.

Detailed Description

The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.