CN115812960A - Preparation method of oil-based high-solubility non-oxygen-containing carotenoid - Google Patents
Preparation method of oil-based high-solubility non-oxygen-containing carotenoid Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing a grease-ethanol-CO 2 Method for preparing oil-based non-oxygen-containing carotenoid rich in high solubility by using ternary system. The method promotes all-trans carotenoid to be converted into cis configuration by regulating and controlling the pressure and temperature of a reaction system so as to be solubilized in the oil, thereby improving the solubility and bioavailability of the non-oxygen-containing carotenoid and simultaneously reducing the thermal degradation loss in the reaction process. The reaction system is a green reaction system and is suitable for industrial production. The process has the characteristics of simplicity, high efficiency, high solubilization, high retention rate and environmental friendliness. The oil-based product rich in the high-solubility non-oxygen-containing carotenoid not only meets the requirements of people on food safety, but also is beneficial to improving the functionality of health food and widening the application field of the carotenoid.
Description
Technical Field
The invention relates to a preparation method of oil-based high-solubility non-oxygen-containing carotenoid, which is characterized in that absolute ethyl alcohol is adopted as cosolvent, CO is pressurized 2 As oxygen-isolating protective gas and high-temp. reaction flame-retarding gas in oil-alcohol-CO 2 In the ternary system, trans non-oxygenated carotenoids are solubilized in the oil by converting them to their cis configuration. Belongs to the technical field of food ingredients and health-care food production.
Background
Carotenoids are a class of fat-soluble pigments with important physiological activities, which are ubiquitous in animals, plants, fungi and algae. Because the molecule of the compound contains a large number of conjugated double bonds, the compound has the capability of capturing singlet oxygen free radicals, and has obvious effects on cancer prevention and resistance, cardiovascular diseases, age-related macular degeneration, cataract and the like. Carotenoids can be roughly divided into two groups according to the difference of polyene chain connecting terminal groups, wherein one group is non-oxygen-containing carotenoid, and comprises beta-carotene, lycopene and the like; another class is the oxygen-containing carotenoids, such as lutein, astaxanthin and the like. At present, the research on non-oxygen-containing carotenoid is more, the physiological activity is proved, and the non-oxygen-containing carotenoid is widely applied to the fields of food, medicines and cosmetics. Natural carotenoids mostly exist in the form of crystals in the all-trans configuration, with low solubility in lipids (less than 1 mg/mL). Research has shown that more than 50% of carotenoids in human serum and tissues are cis-isomers, indicating that cis-isomers of carotenoids are readily soluble in lipids and thus are more readily absorbed and utilized by the human body. In fact, in the human body test, two tomato juices were drunk, one obtained from specially cultivated tomatoes (lycopene total cis ratio is 94%), and the other obtained from ordinary red tomatoes (lycopene total cis ratio is 10%), and the bioavailability of lycopene in the former is found to be 9.5 times that in the latter. The cis-lycopene isomer is more readily digested and absorbed, and a general view is likely to be due to the fact that the cis-isomer is less prone to crystallization and has a lower melting point. In addition, the carotenoid cis-isomer is more excellent in reducing the risk of certain cancers, cardiovascular and cerebrovascular diseases and the like. Therefore, it is of great importance to develop a method for isomerizing carotenoid products with a high cis ratio and solubilizing the same in fats and oils.
At present, the common isomerization methods at home and abroad mainly comprise thermal isomerization reaction, thermal-promoted isomerization reaction, photoisomerization, microwave isomerization and electrolytic isomerization. Thermal isomerization is the most reported isomerization method due to simple operation and relatively low cost. By thermally induced isomerization is meant direct heating in the organic phase or under conditions to promote such heatingThe carotenoid configuration is converted from all-trans to cis. The existing thermal isomerization technology is mainly used for dissolving carotenoid through an organic solvent or grease, so that the all-trans configuration of the carotenoid is converted into the cis configuration. Patent document CN02120720.8 discloses a technology for preparing cis-lycopene by heating tomato paste in oil, the percentage of cis-isomer is 48.1%, but this method is liable to cause oxidation of unsaturated fatty acid in oil and thermal degradation of lycopene, and the content of lycopene in tomato paste is very limited, thus limiting the application range. Honda et al * Using CHCl 3 Lycopene with the concentration of 0.1mg/mL is heated at 50 ℃ for 24h as a reaction solvent to finally obtain the lycopene with the total cis-form ratio of 48.4 percent, but the method has lower carotenoid concentration in the process of preparing cis-isomer, and the reaction time is too long, so the used solvent is toxic and is not beneficial to the industrial production. Patent document CN201210516713.4 discloses a technology for preparing lycopene oil by using ultrasound and microwave heating in oil, but the reaction takes a long time, which is not favorable for industrial production. In recent years, in the field of food processing, people pay more and more attention to the importance of food safety and green environmental protection, but the existing isomerization technology has the problems of high edible safety risk, low preparation efficiency, low carotenoid concentration and the like, and the problems cause great obstacles to the industrial production of carotenoid isomers.
At present, the utilization of grease-ethanol-CO is not seen 2 Ternary system preparation oil based highly soluble non-oxygenated carotenoids rich reports.
*Honda,M.；Takahashi,N.；Kuwa,T.；Takehara,M.；Inoue,Y.；Kumagai,T.,Spectral characterisation of Z-isomers of lycopene formed during heat treatment and solvent effects on the E/Z isomerisation process.Food Chem 2015,171,323-329.
Disclosure of Invention
The invention aims to provide a preparation method of oil-based high-solubility non-oxygen-containing carotenoid, which can ensure that the relative content of cis-isomer of lycopene reaches more than 60 percent and the relative content of cis-isomer of beta-carotenoid reaches more than 40 percent. The method not only reduces the thermal degradation loss of the non-oxygen-containing carotenoid in the preparation process of the product, but also can greatly increase the concentration of the non-oxygen-containing carotenoid in the product. The product can be used as common food ingredient, functional food material or dietary supplement material.
The technical scheme of the invention is as follows:
a preparation method of oil-based high-solubility non-oxygen-containing carotenoid comprises the following specific reaction steps:
adding non-oxygen-containing carotenoid, grease and absolute ethyl alcohol into a medium-pressure reaction kettle to obtain initial reaction mixed liquid; introducing CO from the bottom end of the reaction kettle at room temperature 2 Gas, replacing oxygen in the reaction kettle, and closing a gas outlet valve; continuously introducing CO 2 Closing the air inlet valve when the gauge pressure reaches 0.1-2 MPa; stirring and reacting at the reaction temperature of 100-140 ℃ for 15-90 min under the condition that the volume ratio of ethanol to grease (ethanol for short) is 10-100 percent; after the reaction is finished, cooling the reaction device to room temperature, and slowly releasing pressure to obtain a mixed solution of the oil rich in the high-solubility non-oxygen-containing carotenoid and the ethanol; the solution is further evaporated under negative pressure to remove ethanol to obtain the oil-based product rich in the high-solubility non-oxygenated carotenoid.
Further, the high-solubility non-oxygen-containing carotenoid is lycopene with cis-form ratio of more than 60% or beta-carotene with cis-form ratio of more than 40%; the oil base is rich in high-solubility non-oxygen-containing carotenoid, and the concentration of the non-oxygen-containing carotenoid in the oil is 1.70-11.40 mg/mL; the retention rate of the non-oxygen-containing carotenoid after reaction is 85-95%.
Further, the oil is one of caprylic capric glyceride, corn oil, sunflower seed oil, soybean oil, olive oil, rapeseed oil, grape seed oil, evening primrose oil and fish oil; the non-oxygen-containing carotenoid is one of lycopene and beta-carotene.
The solubility of all-trans lycopene in absolute ethyl alcohol is only 0.6mg/L, and the solubility of lycopene with cis proportion of 76% can reach 2410.7mg/L. Thus, with respect to the isomerization equilibrium system,ethanol is used as a reaction auxiliary agent, which is beneficial to improving the proportion of the cis-configuration of the carotenoid. In addition, under certain conditions CO 2 And ethanol solution can form its subcritical CO 2 Expanded ethanol system (CXE) comprising ethanol as the main component and a small amount of compressed CO 2 To make CO 2 Dissolved in ethanol to form a single phase system. The physicochemical properties of the system, such as density, viscosity, diffusion, and polarity, are likely to change with changes in conditions such as temperature, pressure, and carbon dioxide mole fraction. The application constructs oil-ethanol-CO 2 The ternary system is used for preparing oil-based high-solubility non-oxygenated carotenoid, and the volume ratio of ethanol to grease and CO in the system are regulated and controlled 2 Initial pressure and reaction temperature, so as to change the physical and chemical properties of the reaction system, promote the configurational transformation of trans-non-oxygen-containing carotenoid, and prevent the carotenoid from reacting with trace oxygen in the system, thereby improving the retention rate of the carotenoid. The oil and fat contained in the product obtained after the reaction and the carotenoid can construct a co-digestion system and can be directly used as food ingredients or raw materials of health-care capsules. In addition, the edible safety risk brought by the low ethanol residue of the product obtained by the ternary system method is negligible.
Compared with the prior reported process, the oil-based carotenoid rich in high solubility and non-oxygen-containing has the beneficial effects that:
(1) The invention relates to grease-ethanol-CO 2 The ternary system is used for carrying out isomerization reaction of the non-oxygen-containing carotenoid, the reaction system is a green reaction system, the initial concentration of the carotenoid relative to the grease in the reaction is high, and therefore the use cost of the solvent is reduced, and the application safety of the carotenoid is guaranteed. Ethanol is used as a cosolvent, and the cis-isomerization proportion of the carotenoid can be efficiently improved. Simultaneously utilizes the grease-ethanol-CO 2 The ternary system can block the interaction between the carotenoid and oxygen to improve the retention rate, and the oil and the carotenoid can construct a co-digestion system, which is beneficial to improving the bioavailability of the carotenoid, thereby improving the production benefit of the product.
(2) The total cis-form ratio in the lycopene isomerized product obtained by the invention reaches more than 60 percent, the total cis-form ratio in the beta-carotene isomerized product reaches more than 40 percent, and the content in grease reaches more than 1.7 mg/mL. In addition, the retention rate of lycopene or beta-carotene in the preparation process of the method reaches more than 85 percent. The isomerization reaction process has the characteristics of simplicity, high efficiency, economy and environmental friendliness. The cis-non-oxygen-containing carotenoid obtained under the reaction condition is beneficial to improving the functionality of the health food, so that the application field of the carotenoid is widened.
Drawings
FIG. 1 shows the HPLC chromatogram of the lycopene product obtained in example 4 of the present invention after 30min of isomerization reaction of all-trans lycopene according to the detection method in the present invention. As can be seen from FIG. 1, the relative percentage of total cis-lycopene is 68.62, with the relative percentage of 5-cis-lycopene being 25.49. The oil-based concentration of lycopene in this product was 9.50mg/mL.
FIG. 2 shows an HPLC chromatogram of a beta-carotene product obtained in example 5 of the present invention after a reaction of isomerizing all-trans beta-carotene for 30min, wherein the detection wavelength is 450nm according to the detection base in the present invention. As can be seen from FIG. 2, the relative percentage of total cis- β -carotene is 41.31. The oil-based concentration of beta-carotene in this product was 4.75mg/mL.
Detailed Description
In order to better understand the present invention, the present invention will be further described in detail with reference to the following examples, which are an alternative embodiment of the present invention and use lycopene and olive oil to perform the isomerization reaction, but the scope of the present invention is not limited by the examples.
The purity of all-trans lycopene and all-trans beta-carotene adopted in the following examples of the invention are more than or equal to 90% and more than or equal to 92%.
Example 1
Adding 60mg of lycopene, 30mL of olive oil and 3mL of absolute ethyl alcohol into a 50mL medium-pressure reaction kettle to obtain initial reaction mixed liquid; introducing CO from the bottom end of the reaction kettle at room temperature 2 Gas, replacing oxygen in the reaction kettle, and closing a gas outlet valve; continuously introducing intoCO 2 Closing the air inlet valve after the pressure reaches 0.1 Mpa; stirring and reacting at the reaction temperature of 100 ℃ for 15 min; after the reaction is finished, cooling the reaction device to room temperature, and slowly releasing pressure to obtain a lycopene oil-ethanol mixed solution with high cis-ratio; the solution is further evaporated under negative pressure to remove ethanol, so that the oil-based lycopene product rich in high solubility is obtained.
Product detection: taking 50 mu L of reaction liquid, using ethyl acetate to fix the volume to 10mL, filtering the reaction liquid by using a filter membrane with the diameter of 0.22 mu m, and using a liquid chromatograph to detect the relative percentage content of each isomer of the lycopene at 472nm by an area normalization method respectively. A chromatographic column: YMC C30 column (5 μm,250 mm. Times.4.6 mm); mobile phase: phase A: methanol: acetonitrile = 25: 75, phase b: 100% of methyl tert-butyl ether; gradient conditions: 0-20min, reducing phase A from 100% to 50%, 20-40min, keeping phase A at 50%; sample solvent: ethyl acetate; flow rate: 1mL/min; column temperature: 20 ℃; sample introduction amount: 5 μ L. The relative percentage content of the total cis-lycopene is 60.38. The oil-based concentration of lycopene in this product was 1.70mg/mL.
Example 2
Adding 240mg of lycopene, 20mL of olive oil and 20mL of absolute ethyl alcohol into a 50mL reaction kettle to obtain initial reaction mixed liquid; introducing CO into the reaction kettle at room temperature 2 Gas, replacing oxygen in the reaction kettle, and closing a gas outlet valve; continuously introducing CO 2 Closing the air inlet valve after the pressure reaches 2 MPa; stirring and reacting at the reaction temperature of 140 ℃ for 90min; after the reaction is finished, cooling the reaction device to room temperature, and slowly releasing pressure to obtain a lycopene oil-ethanol mixed solution with high cis-ratio; the solution is further rotated and evaporated to remove ethanol to obtain the oil-based lycopene product rich in high cis-ratio. The relative percentage of total cis-lycopene in this product was 65.89 according to the assay described in example 1. The oil-based concentration of lycopene in this product was 11.40mg/mL.
Example 3
Adding 100mg of lycopene, 20mL of olive oil and 10mL of absolute ethyl alcohol into a 50mL reaction kettle to obtain initial reaction mixed liquid; introducing CO into the reaction kettle at room temperature 2 Gas, replacing oxygen in the reaction kettle, and closing a gas outlet valve; continuously introducing CO 2 Closing the air inlet valve after the pressure reaches 0.6 Mpa; stirring and reacting at the reaction temperature of 120 ℃ for 50 min; after the reaction is finished, cooling the reaction device to room temperature, and slowly releasing pressure to obtain a lycopene oil-ethanol mixed solution with a high cis-to-ethanol ratio; the solution is further rotated and evaporated to remove ethanol to obtain the oil-based lycopene product rich in high cis-ratio. The relative percentage of total cis-lycopene in this product was 60.34 according to the assay described in example 1. The oil-based concentration of lycopene in this product was 4.75mg/mL.
Example 4
Adding 200mg of lycopene, 20mL of olive oil and 20mL of absolute ethyl alcohol into a 50mL reaction kettle to obtain initial reaction mixed liquid; introducing CO into the reaction kettle at room temperature 2 Gas, replacing oxygen in the reaction kettle, and closing a gas outlet valve; continuously introducing CO 2 Closing the air inlet valve after the pressure reaches 0.8 Mpa; stirring and reacting at the reaction temperature of 120 ℃ for 30 min; after the reaction is finished, cooling the reaction device to room temperature, and slowly releasing pressure to obtain a lycopene oil-ethanol mixed solution with high cis-ratio; the solution is further rotated and evaporated to remove ethanol to obtain the oil-based lycopene product rich in high cis-ratio. The relative percentage of total cis-lycopene in this product was 68.62 following the assay of example 1. The oil-based concentration of lycopene in this product was 9.50mg/mL.
Comparative example 1 in which 200mg of lycopene and 20mL of olive oil were added without adding ethanol, the isomerization reaction of lycopene was carried out according to example 4 under other conditions. The relative percentage of total cis-lycopene in the product of comparative example 1 was 47.28. The oil-based concentration of lycopene in this product was 8.2mg/mL.
Comparative example 2 lycopene was added in an amount of 200mg and 20mL of ethanol without adding olive oil, and lycopene isomerization reaction was performed according to example 4 under other conditions. The relative percentage of total cis-lycopene in the product of comparative example 2 was 27.05. The oil-based concentration of lycopene in this product was 7.70mg/mL.
Comparative example 3 was conducted without using CO 2 Instead of using N 2 200mg of lycopene, 20mL of olive oil and 20mL of absolute ethanol were added, and the isomerization reaction of lycopene was carried out according to example 4 under other conditions. The relative percentage of total cis-lycopene in the product of comparative example 3 was 40.39. The oil-based concentration of lycopene in this product was 8.1mg/mL.
Comparative example 4A reaction vessel was charged with CO 2 Then, the regulated gauge pressure before the unheated reaction is 0MPa, and at the moment, the CO of the reaction system 2 The molar fraction is lower than that of the lycopene prepared in example 4, 200mg of lycopene, 20mL of olive oil and 20mL of absolute ethanol are added, and the isomerization reaction of lycopene is carried out according to example 4 under other conditions. The relative percentage of total cis-lycopene in the product of comparative example 1 was 51.63. The oil-based concentration of lycopene in this product was 7.7mg/mL.
As is clear from comparison of the results obtained in comparative examples 1, 2, 3 and 4 with those obtained in example 4, the fat and oil-ethanol-CO used in the present invention 2 The isomerization reaction of the ternary system can greatly improve the cis-form ratio and retention rate of the lycopene, and is more suitable for the requirement of industrial production.
Example 5
Adding 100mg of beta-carotene, 20mL of olive oil and 20mL of absolute ethyl alcohol into a 50mL reaction kettle to obtain initial reaction mixed liquid; introducing CO into the reaction kettle at room temperature 2 Gas, replacing oxygen in the reaction kettle, and closing a gas outlet valve; continuously introducing CO 2 Closing the air inlet valve after the pressure reaches 1.0 Mpa; stirring and reacting at the reaction temperature of 120 ℃ for 30 min; after the reaction is finished, cooling the reaction device to room temperature, and slowly releasing pressure to obtain a grease-ethanol mixed solution containing the beta-carotene with high cis-ratio; the solution is further evaporated under negative pressure to remove ethanol, and the oil-based beta-carotene product rich in high solubility is obtained. The relative percentage of total cis-lycopene in this product was 41.3 according to the detection method of example 1 (detection wavelength 450 nm). The oil-based concentration of beta-carotene in this product was 4.75mg/mL.
The above embodiments do not limit the technical solutions of the present invention in any way, and all technical solutions obtained by means of equivalent replacement or equivalent transformation fall within the protection scope of the present invention.
Claims (5)
1. A preparation method of oil-based high-solubility non-oxygen-containing carotenoid is characterized by comprising the following steps: in oil-ethanol-CO 2 The method for preparing the oil-based lycopene or beta-carotene rich in high solubility by utilizing a thermal isomerization method in a ternary system comprises the following steps:
adding non-oxygen-containing carotenoid, grease and absolute ethyl alcohol into a medium-pressure reaction kettle, wherein the volume ratio of the ethyl alcohol to the grease is 10-100%, so as to obtain initial reaction mixed liquid; introducing CO from the bottom end of the reaction kettle at room temperature 2 Gas, replacing oxygen in the reaction kettle, and closing a gas outlet valve; continuously introducing CO 2 Controlling the gauge pressure within the range of 0.1-2 MPa, and closing the air inlet valve; stirring for 15-90 min at the reaction temperature of 100-140 ℃; after the reaction is finished, cooling the reaction device to room temperature, and slowly releasing pressure to obtain a mixed solution of the oil rich in the high-solubility non-oxygen-containing carotenoid and the ethanol; the solution is further evaporated under negative pressure to remove ethanol to obtain the oil-based product rich in the high-solubility non-oxygenated carotenoid.
2. The method of producing oil-based highly soluble non-oxygenated carotenoids according to claim 1, characterized in that: the high-solubility non-oxygen-containing carotenoid is lycopene with cis-form ratio of more than 60% or beta-carotene with cis-form ratio of more than 40%.
3. The method for producing oil-based high-solubility non-oxygenated carotenoids rich in oil according to claim 1 or 2, wherein: the oil base is rich in high-solubility non-oxygen-containing carotenoid, and the concentration of the non-oxygen-containing carotenoid in the oil is 1.70-11.40 mg/mL.
4. The method for producing oil-based high-solubility non-oxygenated carotenoids rich in oil according to claim 1 or 2, wherein: the retention rate of the non-oxygen-containing carotenoid after reaction is 85-95%.
5. The method of producing oil-based highly soluble non-oxygenated carotenoids according to claim 3, characterized in that: the oil is one of caprylic capric glyceride, corn oil, sunflower seed oil, soybean oil, olive oil, rapeseed oil, grape seed oil, evening primrose oil and fish oil; the non-oxygen-containing carotenoid is one of lycopene and beta-carotene.
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