CN114315676B - Method for converting lutein ester from all-trans configuration into cis-isomer - Google Patents
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Abstract
The invention discloses a method for converting lutein ester from all-trans configuration into cis-isomer, belonging to the field of chemical modification. The method for converting the lutein ester from an all-trans configuration to a cis isomer comprises the following steps: dispersing lutein ester in a solvent containing a sulfur-containing flavor compound, and reacting to obtain the lutein ester with high cis-lutein ester content; or adding a metal salt solution into a solvent containing lutein ester to react; after the reaction is finished, collecting organic phases in a layered mode, and filtering to obtain the lutein ester with high cis-lutein ester content. The method can quickly and efficiently prepare the lutein ester with high cis-form ratio, has high conversion efficiency and strong product stability, and the prepared product has the cis-form lutein ester accounting for more than 30 percent, thereby providing an efficient and economic method for preparing the lutein ester product with high physiological activity and high bioavailability.
Description
Technical Field
The invention relates to a method for converting lutein ester from all-trans configuration to cis-isomer, belonging to the field of chemical modification.
Background
Natural Lutein ester (Lutein ester) is an important carotenoid fatty acid ester. It is widely existed in marigold, pumpkin, cabbage, alfalfa and other plants, and is obtained by esterifying lutein with 1 fatty acid or 2 fatty acids. The xanthophyll has effects of protecting eyesight, preventing skin ultraviolet burn, and preventing senile macular degeneration (AMD). Natural lutein exists in marigold flowers (30-40%) mainly in the form of lutein ester. The lutein ester can be decomposed into lutein in vivo or in vitro and absorbed by human body, and further shows the same physiological function as lutein. Because the lutein ester is widely and easily obtained, most of eye-protecting health foods for protecting eyesight, preventing blue light and the like sold in the market adopt the lutein ester as a main raw material; in 2008, lutein esters derived from marigold flowers were also listed as new food raw materials (new resource food).
Researches find that the lutein ester existing in nature is mostly in an all-trans (all-E-) straight-chain structure, and can be decomposed into all-trans lutein and fatty acid in the digestion process to be absorbed by human bodies. However, studies have shown that lutein in the cis configuration (Z-) has higher solvent solubility and bioavailability (absorption rate); the antioxidant activity of the cis-lutein is superior to that of the all-trans-lutein. The lutein ester is an oil-soluble substance, so that the absorptivity of the lutein ester in a human body is low, the bioavailability of the lutein ester is low, and if the lutein ester can be preferentially converted into a cis-isomer by an isomerization method, the physiological activity and the bioavailability of the lutein ester and related products thereof can be greatly improved.
The search has shown that the method for improving the bioavailability of lutein esters mainly focuses on the microencapsulated form (CN102920763B), i.e. the apparent water solubility of lutein esters is improved by means of auxiliary agents. Furthermore, a search for an isomerization process of lutein shows that the current publications CN106977439A and CN106582605A describe an isomerization process of converting lutein into zeaxanthin using a metal salt catalyst or a photocatalyst, respectively, and zeaxanthin is a stereoisomer of lutein, is not lutein, and is different from cis-lutein in structure and function.
Therefore, the method for improving the bioavailability of the lutein ester only focuses on the embedding of external additives, no method for improving the physiological activity and the bioavailability of the lutein ester through modification exists, and the effect and implementation difficulty of the method for modifying free lutein in the lutein ester are not clear.
Disclosure of Invention
[ problem ] to
At present, no report on a method for converting all-trans lutein ester into cis lutein ester with high bioavailability is found. Therefore, in order to meet the market and consumer demands, there is an urgent need for a method capable of converting lutein ester from all-trans configuration to cis-isomer to obtain lutein ester product with high physiological activity and high bioavailability.
[ solution ]
In order to solve the problems, the invention can efficiently catalyze the isomerization of the lutein structure in the lutein ester through the application of the sulfur-containing flavor compound and the metal salt catalyst, so that the lutein ester is converted into a cis-isomer from an all-trans configuration, the solvent solubility and the bioavailability of the lutein ester are improved, and the application of the lutein ester in the food industry is expanded.
A first object of the present invention is to provide a process for converting a lutein ester from all-trans configuration to cis isomer comprising the steps of:
dispersing lutein ester in a solvent containing a sulfur-containing flavor compound, and reacting to obtain the lutein ester with high cis-lutein ester content;
or
Adding a metal salt solution into a solvent containing lutein ester for reaction; after the reaction is finished, collecting organic phases in a layering way, and filtering to obtain the lutein ester with high cis-lutein ester content.
In one embodiment of the invention, the reaction scheme of the process is:
wherein R ═ fatty acid or H; r ═ fatty acid.
In one embodiment of the invention, the source of lutein ester comprises one or more of marigold, corn and pumpkin, and the structure of lutein ester comprises lutein monoester and lutein diester; wherein the lutein monoester is one or more of lutein laurate, palmitate, myristate, oleate, linolenate, linoleate and stearate; the lutein diester is one or more of lutein lauric acid-myristate, dimyristate, myristic acid-palmitate, dipalmitate, palmitic acid-stearate and distearate.
In one embodiment of the present invention, the sulfur-containing flavor compound comprises one or more of diallyl disulfide (DADS), dimethyl trithio (DMTS), and Sulforaphane (Sulforaphane).
In one embodiment of the present invention, the solvent comprises one of vegetable oil, organic solvent and ionic liquid; the vegetable oil comprises one or more of soybean oil, peanut oil, rose seed oil and peony seed oil; the organic solvent comprises one or more of n-hexane, dichloromethane, acetone, cyclohexane, petroleum ether, methanol and ethanol; the ionic liquid comprises one or more of pyrrole hydrochloride, trimethylamine hydrochloride and triethylamine hydrochloride.
In one embodiment of the invention, the sulfur-containing flavor compound is added in an amount of 0.1 to 10mg/g lutein ester.
In one embodiment of the present invention, the concentration of the lutein ester in the solvent is 0.01-0.1 mg/mL.
In one embodiment of the present invention, the reaction is carried out at 30-80 ℃ for 0.5-4 h.
In one embodiment of the present invention, the metal salt includes one or more of copper sulfate, copper chloride, copper acetate, cuprous iodide, cuprous chloride, aluminum sulfate, ferric chloride, ferrous sulfate, and ferric sulfate; the metal salt solution is a metal salt water solution, and the concentration is 1-4 mg/mL.
In one embodiment of the present invention, the volume ratio of the solvent containing lutein ester and the metal salt solution is 4: 0.01 to 1.
In one embodiment of the invention, the layering is performed by adding dichloromethane and water to allow the mixture after the reaction to layer.
In one embodiment of the present invention, the high cis-lutein ester-content lutein ester comprises 13 cis-lutein ester, 9 cis-lutein ester, 15 cis-lutein ester, 5 cis-lutein ester, and the like.
The second purpose of the invention is to obtain the lutein ester with high cis-lutein ester content by the method of the invention.
The third purpose of the invention is the application of the lutein ester with high cis-lutein ester content in the preparation of foods, medicines and health-care products.
[ advantageous effects ]
The method can quickly and efficiently prepare the lutein ester with high cis-form ratio, has high conversion efficiency and strong product stability, and the prepared product has the cis-form lutein ester accounting for more than 30 percent, thereby providing an efficient and economic method for preparing the lutein ester product with high physiological activity and high bioavailability.
Drawings
FIG. 1 is a liquid phase diagram of a saponified lutein ester having a high cis-lutein ester content as in example 1.
FIG. 2 is a liquid phase diagram of a saponified lutein ester of high cis-lutein ester content of example 2.
FIG. 3 is a liquid phase diagram of a saponified lutein ester of high cis-lutein ester content of example 3.
FIG. 4 is a liquid phase diagram of the reaction product of comparative example 1 after saponification.
FIG. 5 is a liquid phase diagram of the reaction product in comparative example 2.
FIG. 6 is a liquid phase diagram of the reaction product in comparative example 3.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
The test method comprises the following steps:
testing of liquid phase diagram:
(1) saponification of lutein ester: dissolving a to-be-detected substance in dichloromethane (0.01mg/mL), adding 15% by mass of KOH methanol solution (1:1, v/v), and saponifying for 12h at 25 ℃ under the condition of nitrogen filling and stirring;
washing the saponified solution with water (1:3, v/v) for layering treatment for 3 times;
collecting organic layer, adding anhydrous sodium sulfate, drying, and passing through 0.22 μm membrane for liquid phase detection;
(2) the analysis conditions of the liquid phase of the cis-trans isomers of the lutein are as follows:
luteal isomers were analyzed by Agilent HPLC 1260 series detection with Diode Array Detector (DAD). Separation was performed using a Kinetex XB-C18 column (100 mm. times.4.6 mm,2.6 μm); the flow rate was maintained at 0.7mL/min for a total run time of 25 min. The injection volume was 10 μ L, and the binary mobile phase consisted of phase a: 0.1% formic acid (v/v) and phase B: 95% methanol with 5% acetonitrile (v/v). The solvent gradient was set as: 0-1.0 min, 60% -90% of phase B; 1.0-15.0 min, 90% -100% of phase B; 15.0-19.0 min, 100% phase B; 19.0-20.5 min, 100% -60% of phase B; 20.5-25.0 min, 60% of phase B. The DAD scanning range is 220-700 nm. A peak was detected at 450 nm.
Samples to be tested were stored in a-20 ℃ freezer prior to analysis.
Example 1
A process for converting a lutein ester from an all-trans configuration to a cis isomer comprising the steps of:
adding lutein dipalmitate into peony seed oil containing dimethyl trisulfide, placing the peony seed oil into a sample bottle with a cover, and blowing out air by using nitrogen; heating in 80 deg.C water bath for 1 h; immediately cooling in ice water bath after heating to obtain lutein ester with high cis-lutein ester content; wherein the concentration of lutein dipalmitate in peony seed oil is 0.025mg/mL, and the addition amount of dimethyl trisulfide is 10mg/g lutein ester;
the reaction route is as follows:
wherein R ═ palmitic acid; r ═ palmitic acid.
The resulting lutein ester with high cis-lutein content was saponified and tested, the test results are shown in fig. 1:
as can be seen from fig. 1: after isomerization and saponification of all-trans lutein dipalmitate, two main products are respectively generated, namely: all-trans-lutein with retention time of 12.213min and cis-lutein (13 cis-and 9 cis-lutein) with retention time of 13.862 min. The result shows that in the peony seed oil solvent, the all-trans lutein dipalmitate can be subjected to dimethyl trisulfide catalytic isomerization to obtain cis-lutein ester, the 13 cis-lutein ester and the 9 cis-lutein ester which are high in bioavailability and good in solubility are mainly used, the proportion of the cis-lutein ester is up to 23%, and the proportion of the total cis-lutein ester is up to 27%. The total cis-lutein ester includes 13 cis-lutein ester, 9 cis-lutein ester, 15 cis-lutein ester, 5 cis-lutein ester and other cis-lutein esters.
Example 2
A process for converting a lutein ester from an all-trans configuration to a cis isomer comprising the steps of:
lutein dipalmitate was added to methylene chloride (4mL) containing dimethyl trisulfide, placed in a capped sample bottle, and the air was purged with nitrogen; heating in 70 deg.C water bath for 1 h; immediately cooling in ice water bath after heating to obtain lutein ester with high cis-lutein ester content; wherein the concentration of lutein dipalmitate in dichloromethane is 0.025mg/mL, and the addition amount of dimethyl trithione is 10mg/g lutein ester;
the reaction route is as follows:
wherein R ═ palmitic acid; r ═ palmitic acid.
The resulting lutein ester with high cis-lutein content was saponified and tested, the test results are shown in fig. 2:
as can be seen from fig. 2: after isomerization and saponification of all-trans lutein dipalmitate, two main products are respectively generated, namely: all-trans-lutein with retention time of 12.138min and cis-lutein (13 cis-and 9 cis-lutein) with retention time of 13.788 min. The results show that the all-trans lutein dipalmitate can obtain cis-lutein ester through dimethyl trithione catalytic isomerization, and the 13 cis-lutein ester and the 9 cis-lutein ester which have high bioavailability and good solubility are taken as main components, the proportion of the cis-lutein ester is up to 27.6%, and the proportion of the total cis-lutein ester is up to 32%.
Example 3
A process for converting a lutein ester from an all-trans configuration to a cis isomer comprising the steps of:
to 4mL of acetone solution in which 0.025mg/mL of xanthophyll dipalmitate was dissolved, 0.1mL of an aqueous aluminum chloride solution (1mg/mL) was added, and the mixture was placed in a sample bottle with a cap, and air was purged with nitrogen; heating in 70 deg.C water bath for 1 h; after heating, adding 4mL of dichloromethane and 4mL of water respectively to stratify the mixed solution, and then collecting an organic phase; adding anhydrous sodium sulfate into the organic phase to absorb water, and filtering and storing to obtain lutein ester with high cis-lutein ester content;
the reaction route is as follows:
wherein R ═ palmitic acid; r ═ palmitic acid.
The resulting lutein ester with high cis-lutein content was saponified and tested, the test results are shown in fig. 3:
as can be seen from fig. 3: 12.156min shows all-trans-lutein, and 13.81min shows 13 cis-lutein and 9 cis-lutein. There were also peaks at 17.853 and 18.502min later, presumably lutein ester degradation products. Wherein 13 cis-lutein ester and 9 cis-lutein ester account for 16.2%, and total cis-lutein accounts for 20%.
Comparative example 1
Dimethyl trisulfide in example 1 was omitted, and the reaction product was obtained in accordance with example 1.
The reaction product obtained was tested and the results are shown in fig. 4:
as can be seen from fig. 4: after heat treatment saponification of all-trans lutein esters, only a small amount of cis-lutein was detected, i.e.: the 13 cis-lutein and 9 cis-lutein with retention time of 13.82min account for 3.5% and are far less than the isomerization rate (27%) of dimethyl trisulfide to lutein ester in peony seed oil. Therefore, dimethyl trisulfide can catalyze the isomerization of lutein ester to synthesize the high cis-form ratio lutein ester product, and the high cis-form content lutein ester product is difficult to obtain only by heating.
Comparative example 2
The lutein dipalmitate in example 2 was adjusted for lutein, otherwise identical to example 2, to give the reaction product.
The reaction product obtained was tested and the results are shown in fig. 5:
as can be seen from fig. 5: after isomerization of all-trans lutein, two main products are generated respectively, namely: all-trans-lutein with retention time at 12.31min and 13 cis-lutein and 9 cis-lutein with retention time at 13.99 min. Wherein the total ratio of 13 cis-lutein and 9 cis-lutein is only 15%, and the total ratio of cis-lutein is only 17%. Much less than the isomerization rate of dimethyl trithione to lutein ester (32%).
Comparative example 3
The reaction product was obtained by replacing lutein dipalmitate from example 3 with lutein, otherwise identical to example 3.
The reaction product obtained was tested and the results are shown in fig. 6:
as can be seen from fig. 6: lutein is degraded when reacting with metal catalysts such as aluminum chloride. The proportion of all-trans-lutein in the reaction product is only 5.5% (peak time 12.32min), the proportion of 13 cis-lutein and 9 cis-lutein is 6.7% (peak time 13.25min), and the rest are degradation products (peak time after 17 min). Therefore, the metallic catalyst aluminum chloride is adopted to isomerize the lutein, the degradation degree of the lutein is far greater than that of the lutein ester, namely the isomerization product of the lutein ester is more stable, and the proportion of the 13 cis-lutein ester to the 9 cis-lutein ester is higher (16.2%).
Claims (3)
1. A process for converting a lutein ester from an all-trans configuration to a cis isomer comprising the steps of:
dispersing lutein ester in a solvent containing a sulfur-containing flavor compound, and reacting to obtain the lutein ester with high cis-lutein ester content;
or
Adding a metal salt solution into a solvent containing lutein ester for reaction; after the reaction is finished, collecting organic phases in a layering way, and filtering to obtain lutein esters with high cis-lutein ester content;
wherein the sulfur-containing flavor compound is dimethyl trisulfide;
the metal salt solution is an aluminum chloride aqueous solution;
the addition amount of the sulfur-containing flavor compound is 0.1-10 mg/g lutein ester;
the concentration of the lutein ester in the solvent is 0.01-0.1 mg/mL;
the reaction is carried out for 0.5-4 h at 30-80 ℃;
the volume ratio of the solvent containing lutein ester to the metal salt solution is 4: 0.01 to 1.
2. The method according to claim 1, wherein the lutein ester is derived from one or more of marigold, corn and pumpkin, and has the structure of lutein monoester and lutein diester; wherein the lutein monoester is one or more of lutein laurate, lutein palmitate, lutein myristate, lutein oleate, lutein linoleate and lutein stearate; the lutein diester is one or more of lutein lauric acid-myristate, lutein dimyristate, lutein myristic acid-palmitate, lutein dipalmitate, lutein palmitic acid-stearate and lutein distearate.
3. The method according to claim 1, wherein the solvent is one of vegetable oil and organic solvent; the vegetable oil is one or more of soybean oil, peanut oil, rose seed oil and peony seed oil; the organic solvent is one or more of n-hexane, dichloromethane, acetone, cyclohexane, petroleum ether, methanol and ethanol.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1872839A (en) * | 2006-05-17 | 2006-12-06 | 浙江医药股份有限公司新昌制药厂 | Method for separating and purifying fatty acid ester of lutein in high content from resin of marigold oil |
| CN104090062A (en) * | 2014-07-30 | 2014-10-08 | 江苏省农业科学院 | Detection method for single-cis and double-cis lutein isomers |
| CN105272895A (en) * | 2014-07-18 | 2016-01-27 | 周子童 | High purity lutein ester composition and preparation process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1872839A (en) * | 2006-05-17 | 2006-12-06 | 浙江医药股份有限公司新昌制药厂 | Method for separating and purifying fatty acid ester of lutein in high content from resin of marigold oil |
| CN105272895A (en) * | 2014-07-18 | 2016-01-27 | 周子童 | High purity lutein ester composition and preparation process |
| CN104090062A (en) * | 2014-07-30 | 2014-10-08 | 江苏省农业科学院 | Detection method for single-cis and double-cis lutein isomers |
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