CN115819176B - A method for preparing high-cis-content lycopene by catalysis of iodine-containing anion compounds - Google Patents
A method for preparing high-cis-content lycopene by catalysis of iodine-containing anion compounds Download PDFInfo
- Publication number
- CN115819176B CN115819176B CN202211734218.0A CN202211734218A CN115819176B CN 115819176 B CN115819176 B CN 115819176B CN 202211734218 A CN202211734218 A CN 202211734218A CN 115819176 B CN115819176 B CN 115819176B
- Authority
- CN
- China
- Prior art keywords
- lycopene
- cis
- iodine
- reaction
- containing anion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000001751 lycopene Substances 0.000 title claims abstract description 90
- OAIJSZIZWZSQBC-GYZMGTAESA-N lycopene Chemical compound CC(C)=CCC\C(C)=C\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C=C(/C)CCC=C(C)C OAIJSZIZWZSQBC-GYZMGTAESA-N 0.000 title claims abstract description 87
- 229960004999 lycopene Drugs 0.000 title claims abstract description 81
- UPYKUZBSLRQECL-UKMVMLAPSA-N Lycopene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1C(=C)CCCC1(C)C)C=CC=C(/C)C=CC2C(=C)CCCC2(C)C UPYKUZBSLRQECL-UKMVMLAPSA-N 0.000 title claims abstract description 78
- 235000012661 lycopene Nutrition 0.000 title claims abstract description 78
- JEVVKJMRZMXFBT-XWDZUXABSA-N Lycophyll Natural products OC/C(=C/CC/C(=C\C=C\C(=C/C=C/C(=C\C=C\C=C(/C=C/C=C(\C=C\C=C(/CC/C=C(/CO)\C)\C)/C)\C)/C)\C)/C)/C JEVVKJMRZMXFBT-XWDZUXABSA-N 0.000 title claims abstract description 69
- ZCIHMQAPACOQHT-ZGMPDRQDSA-N trans-isorenieratene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/c1c(C)ccc(C)c1C)C=CC=C(/C)C=Cc2c(C)ccc(C)c2C ZCIHMQAPACOQHT-ZGMPDRQDSA-N 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 21
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 19
- 239000011630 iodine Substances 0.000 title claims abstract description 19
- -1 anion compounds Chemical class 0.000 title claims abstract description 17
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- 239000003054 catalyst Substances 0.000 claims description 23
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 15
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 12
- OAIJSZIZWZSQBC-UHFFFAOYSA-N (7Z,9Z,7'Z,9'Z)-ψ,ψ-carotene Chemical compound CC(C)=CCCC(C)=CC=CC(C)=CC=CC(C)=CC=CC=C(C)C=CC=C(C)C=CC=C(C)CCC=C(C)C OAIJSZIZWZSQBC-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 235000009518 sodium iodide Nutrition 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 5
- 150000002664 lycopenes Chemical class 0.000 abstract description 4
- 235000013402 health food Nutrition 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 25
- OAIJSZIZWZSQBC-OUUYXACASA-N cis-lycopene Natural products CC(=CCCC(=CC=CC(=C/C=C/C(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C=C(C)/CCC=C(C)C)/C)C)C)C OAIJSZIZWZSQBC-OUUYXACASA-N 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 14
- 238000006317 isomerization reaction Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013376 functional food Nutrition 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000008601 oleoresin Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 206010004446 Benign prostatic hyperplasia Diseases 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000016720 allyl isothiocyanate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 125000005626 carbonium group Chemical group 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000005417 food ingredient Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种含碘负离子化合物催化制备高顺占比番茄红素的方法。该方法采用含碘负离子化合物催化制备总顺式占比75％以上的番茄红素。该绿色反应体系保障了番茄红素异构体的食用安全性。方法具有简单、高效、经济、环境友好，5Z‑番茄红素占比较高的特点。该催化所得的富含顺式番茄红素产品有助于提高保健食品的功能性和拓宽番茄红素应用领域。
The present invention relates to a method for preparing lycopene with a high cis-ratio by catalysis of an iodine-containing anion compound. The method uses an iodine-containing anion compound to catalyze the preparation of lycopene with a total cis-ratio of more than 75%. The green reaction system ensures the edible safety of lycopene isomers. The method is simple, efficient, economical, environmentally friendly, and has the characteristics of a high 5Z-lycopene ratio. The cis-ratio lycopene-rich product obtained by the catalysis helps to improve the functionality of health foods and broaden the application field of lycopene.
Description
Technical Field
The invention relates to a method for preparing Gao Shunzhan-ratio lycopene by using an iodine-containing negative ion compound as a catalyst, in particular to a method for catalyzing trans-lycopene to be isomerized into cis-lycopene in a supercritical CO 2 -ethanol system. Belonging to the technical field of functional food production.
Background
Lycopene is a carotenoid with special biological activity, and has the functions of inhibiting benign hyperplasia of prostate, reducing the incidence risk of cardiovascular and cerebrovascular diseases and the like. Common lycopene isomers mainly include All-trans (All-E), 5-cis (5Z), 9-cis (9Z) and 13-cis (13Z), and the antioxidant activity of the lycopene cis isomer is generally higher than that of All-trans lycopene, wherein the antioxidant activity of 5Z-lycopene is the highest. In addition, natural lycopene (more than 90% is in all-trans configuration) has the defects of low bioavailability (less than 30%) because of high melting point and poor fat solubility (far lower than 1 mg/mL) of crystalline substances, which greatly limits the application range.
Under the condition of room temperature, the solubility of lycopene with the cis-form ratio of 76% in absolute ethyl alcohol can reach 2410.7mg/L, which is about 4000 times of all-trans lycopene. Therefore, the green solvent ethanol is selected as a reaction solvent or a cosolvent to carry out lycopene isomerization reaction under specific conditions to improve the cis-configuration ratio in lycopene, which is expected to greatly improve the physiological activity and bioavailability of lycopene products, and meanwhile, the low ethanol residue can also ensure the edible safety of the products.
In terms of the conversion of trans lycopene to cis lycopene, the thermal isomerization reaction refers to the isomerization of lycopene in the organic phase with a catalyst. Honda et al (HondaM, kawanaT, takeharaM, et al, journalofFoodScience, 2015) use FeCl 3 as a catalyst and the total cis-lycopene ratio can reach 79.9%. Although the total cis content of lycopene in the reaction is relatively high, the outstanding problem is that FeCl 3 is a strong oxidant, is difficult to remove from the product after homogeneous reaction, and uses acetone as a solvent, which seriously affects the stability and edible safety of lycopene isomerization products. In addition, honda et al (Honda M, ICHIHASHI K, takada W, et al, journal of Agricultural and Food Chemistry, 2020) reacted at 160 ℃ for 1h with allyl isothiocyanate as a catalyst and lycopene oleoresin as a raw material, different oils and fats as diluents, with a total cis-lycopene ratio of up to 86.7%. Although the total cis ratio of the reacted lycopene is high, the high temperature reaction at 160 ℃ can cause lycopene oleoresin to generate other harmful substances, and the harmful substances are difficult to remove from the reacted product, so that the quality of lycopene isomerization products is seriously affected. Honda et al (Honda M, KAGEYAMA H, hibino T, et al, journal of Agricultural and Food Chemistry, 2020) reacted lycopene in ethyl acetate at 60 ℃ for 1h at a lycopene concentration of 0.02mmol/L with isothiocyanate as catalyst to increase the cis-isomer content by about 2.5 times, respectively, compared to the absence of catalyst. Through researches, wang et al (Wang Q, yang C, liu Y, et al, LWT, 2022) found that under the condition of lycopene concentration of 0.1mmol/L, alCl 3 isomerization efficiency and lycopene retention rate were optimal, the isomerization rate and 5Z-lycopene ratio were 81.1% and 33.0%, respectively, but the reaction system utilized acetone as a solvent and heavy metal salt as a catalyst, so that the obtained product had high food safety risk. In addition, the lycopene reaction concentration of the method reported by Honda et al and Wang et al is far lower than 1mg/mL, which seriously affects the preparation efficiency of lycopene cis-isomer and is not beneficial to industrial production. ZL201410736320.3 and ZL201510021309.3 respectively disclose methods for heterogeneously catalyzing trans-lycopene configuration conversion by using iodine-doped titanium dioxide nanocatalysts. However, the method for preparing the iodine-doped titanium dioxide nano catalyst has the defects of higher raw material cost (especially titanate cost ratio) of the catalyst, longer catalyst preparation process period (at least 26 hours are needed for preparing the catalyst by the hydrothermal method at least), difficult separation of the solid nano catalyst and the like no matter the catalyst is prepared by a sol-gel method or a hydrothermal method, and the industrialized application of the catalyst is limited.
At present, no report of catalyzing all-trans lycopene to be converted into cis-isomer by utilizing an iodine-containing anion compound in a supercritical CO 2 -ethanol system is yet seen.
Disclosure of Invention
The invention aims to provide a method for efficiently catalyzing all-trans lycopene configuration conversion by an iodine-containing negative ion compound, so that lycopene with high cis configuration ratio and 5Z-lycopene with higher cis ratio are obtained and used as common food ingredients, functional food raw materials or dietary supplement raw materials.
The technical scheme of the invention is as follows:
A method for catalyzing trans-lycopene configuration conversion by an iodine-containing anion compound comprises the following specific catalytic reaction steps:
Adding lycopene, an iodine-containing anion compound catalyst and absolute ethyl alcohol into a supercritical CO 2 reaction kettle to obtain an initial reaction mixed solution; introducing CO 2 gas from the bottom end of the supercritical reaction kettle at room temperature to replace oxygen in the reaction kettle; closing the air outlet valve, continuously introducing CO 2, and stirring for reaction at the reaction temperature of 80-110 ℃ and the pressure of 25-35 MPa for 0.5-2.0 h; after the reaction is completed, the reaction device is cooled to room temperature and slowly depressurized to obtain an ethanol solution containing Gao Shunzhan portions of lycopene; the solution is further subjected to reduced pressure evaporation to remove ethanol, so that a lycopene product with high cis-to-cis ratio is obtained.
Further, the iodine-containing negative ion compound is potassium iodide or sodium iodide.
Further, the mass ratio of the iodine-containing negative ion compound to the lycopene is 0.2:100-1.0:100; the concentration of lycopene in ethanol is 1.0-2.5 mg/mL.
Further, the yield of lycopene with the cis-form ratio of more than 75% is 80% -92%.
The beneficial effects of the invention are that
Compared with the prior reported method, the innovation of the preparation method of Gao Shunzhan to lycopene is that:
(1) The catalyst used in the invention is potassium iodide or sodium iodide, can be used as a food additive, has the advantage of easily available raw materials, and the residue can ensure the edible safety of the product;
(2) The invention has the advantages of catalyzing reaction in a supercritical CO 2 -ethanol system, high reaction initial concentration (higher than 1 mg/mL) and short reaction time, belongs to a green chemical method, ensures the application safety of lycopene and improves the preparation efficiency of products. In addition, the oxidation degradation rate of lycopene is greatly reduced by utilizing the oxygen isolation effect and the high-efficiency catalysis effect of the CO 2 -ethanol system. In summary, these innovative measures improve the productivity of lycopene isomerisation products;
(3) Under the preferred condition of the invention, the total cis-lycopene ratio and the yield of the lycopene isomerization product obtained in the reaction for 1h can reach more than 87%, and 5Z-lycopene with the content of more than 20% can be obtained. This benefits from possible reaction mechanisms: under the action of an iodine-containing anion catalyst in a supercritical CO 2 -ethanol system, lycopene molecules firstly generate a stable all-trans lycopene allyl carbonium intermediate, and the carbonium is difficult to rotate by a single bond. The I-has more outer electrons, is easy to polarize and deform, can be used as a nucleophilic reagent to attack allylcarbanion, so that the rotation and distortion of single bonds of the lycopene allylcarbanion intermediate occur, and the lycopene molecular intermediate with low iodine-containing energy is generated at the moment; because the radius of the I-is larger, and the conjugated double bond of the lycopene molecule has high-density electron cloud, the generated C-I single bond is extremely unstable, the I-is easy to leave under the action of hydride (H-) and the catalyst is reduced, so that different lycopene isomers are generated;
(4) The catalytic reaction method has the characteristics of simplicity, high efficiency, economy and environmental friendliness. The obtained cis-lycopene product is helpful for widening lycopene application field and improving functionality of derivative health food.
Drawings
FIG. 1 is a HPLC chart of lycopene product obtained in example 4 of the present invention after catalyzing isomerization of all-trans lycopene for 1 hour according to the detection method in the summary of the invention. As can be seen from FIG. 1, the relative percentage of total cis-lycopene is 87.16, wherein the relative percentage of 5Z-lycopene is 20.39.
Detailed Description
For a better understanding of the present invention, the present invention will be described in further detail with reference to the following examples, but the scope of the present invention is not limited to the scope of the examples.
The reagents ethanol, potassium iodide and sodium iodide used in the following examples of the present invention were all analytically pure, and the all-trans lycopene purity was 91.2%.
Example 1
20Mg of lycopene, 0.04mg of catalyst KI and 20mL of absolute ethyl alcohol are added into a 100mL supercritical CO 2 reaction kettle, and an initial reaction mixed solution is obtained; introducing CO 2 gas from the bottom end of the supercritical reaction kettle at room temperature to replace oxygen in the reaction kettle; continuously introducing CO 2, closing an air outlet valve, and stirring for reaction at the reaction temperature of 80 ℃ and the pressure of 25MPa for 0.5 h; after the reaction is completed, the reaction device is cooled to room temperature and slowly depressurized to obtain lycopene ethanol solution with high cis-to-cis ratio; the solution is further subjected to reduced pressure evaporation to remove ethanol, so that a lycopene product with high cis-to-cis ratio is obtained.
And (3) detecting products: taking 100 mu L of ethanol solution after reaction, fixing the volume to 5mL by using ethyl acetate, filtering by using a 0.22 mu m filter membrane, detecting and analyzing by using an HPLC method, detecting the relative percentage content of each lycopene isomer at 472nm by using an area normalization method, quantifying the total lycopene content of the product by using an external standard method (standard curve manufactured by all-trans lycopene standard), and calculating the yield. Chromatographic column: YMCC30 column (5 μm,250 mm. Times.4.6 mm); mobile phase: phase A: methanol:acetonitrile=25:75, phase b: methyl tertiary butyl ether 100%; gradient conditions: 0-20 min, wherein the A phase is reduced from 100% to 50%, 20-40 min, and the A phase is kept at 50%; flow rate: 1mL/min; column temperature: 30 ℃; sample injection amount: 20. Mu.L. The total cis-lycopene content was 75.26, the 5Z-lycopene content was 11.16, and the yield was 80%.
Example 2
50Mg of lycopene, 0.5mg of catalyst KI and 20mL of absolute ethyl alcohol are added into a 100mL supercritical CO 2 reaction kettle, and an initial reaction mixed solution is obtained; introducing CO 2 gas from the bottom end of the supercritical reaction kettle at room temperature to replace oxygen in the reaction kettle; continuously introducing CO 2, closing an air outlet valve, and stirring for reaction at the reaction temperature of 110 ℃ under the pressure of 35MPa for 2.0 h; after the reaction is completed, the reaction device is cooled to room temperature and slowly depressurized to obtain lycopene ethanol solution with high cis-to-cis ratio; the solution is further subjected to reduced pressure evaporation to remove ethanol, so that a lycopene product with high cis-to-cis ratio is obtained. According to the method of example 1, the total cis-lycopene content of the product was 88.78, the 5Z-lycopene content was 22.43, and the yield was 88%.
Example 3
30Mg of lycopene, 0.20mg of NaI0.20mg of catalyst and 20mL of absolute ethyl alcohol are added into a 100mL supercritical CO 2 reaction kettle, so as to obtain an initial reaction mixed solution; introducing CO 2 gas from the bottom end of the supercritical reaction kettle to replace oxygen in the reaction kettle; continuously introducing CO 2, closing an air outlet valve, and stirring for reaction at the reaction temperature of 100 ℃ and the pressure of 30MPa for 1 hour; after the reaction is completed, the reaction device is cooled to room temperature and slowly depressurized to obtain lycopene ethanol solution with high cis-to-cis ratio; the solution is further subjected to reduced pressure evaporation to remove ethanol, so that a lycopene product with high cis-to-cis ratio is obtained. According to the method of example 1, the total cis-lycopene content of the product was 86.12, the 5Z-lycopene content was 19.59, and the yield was 87%.
Example 4
50Mg of lycopene, 0.40mg of catalyst KI and 20mL of absolute ethyl alcohol are added into a 100mL supercritical CO 2 reaction kettle, and an initial reaction mixed solution is obtained; introducing CO 2 gas from the bottom end of the supercritical reaction kettle to replace oxygen in the reaction kettle; continuously introducing CO 2, closing an air outlet valve, and stirring for reaction at the reaction temperature of 100 ℃ and the pressure of 30MPa for 1 hour; after the reaction is completed, the reaction device is cooled to room temperature and slowly depressurized to obtain lycopene ethanol solution with high cis-to-cis ratio; the solution is further subjected to reduced pressure evaporation to remove ethanol, so that a lycopene product with high cis-to-cis ratio is obtained. According to the detection method in the scheme, the total cis-lycopene relative percentage content in the product is 87.16, wherein the 5Z-lycopene relative percentage content is 20.39, and the yield is 92%.
In comparative example 1, lycopene isomerization was performed under the same conditions as in example 4 without adding a catalyst. The total cis-lycopene content in the product of comparative example 1 was 44.63, wherein the 5Z-lycopene content was 3.16, and the yield was 89%.
In comparative example 2, no catalyst was added, and the reaction time was prolonged from 1 hour to 4 hours based on the test of comparative example 1, and the isomerization reaction of lycopene was performed. The total cis-lycopene content in the product of comparative example 2 was 54.78, the 5Z-lycopene content was 5.16, and the yield was 67%.
As can be seen from comparison of the results obtained in comparative examples 1 and 2 and example 4, the present invention has the advantages of high total cis-lycopene ratio, high yield and short reaction time by using the catalytic isomerization method, and is more suitable for the industrial production requirements, thereby improving the production benefits.
The above embodiments do not limit the technical solutions of the present invention in any way, and all the technical solutions obtained by adopting equivalent substitution or equivalent transformation fall within the protection scope of the present invention.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211734218.0A CN115819176B (en) | 2022-12-30 | 2022-12-30 | A method for preparing high-cis-content lycopene by catalysis of iodine-containing anion compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211734218.0A CN115819176B (en) | 2022-12-30 | 2022-12-30 | A method for preparing high-cis-content lycopene by catalysis of iodine-containing anion compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115819176A CN115819176A (en) | 2023-03-21 |
| CN115819176B true CN115819176B (en) | 2024-11-22 |
Family
ID=85519830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211734218.0A Active CN115819176B (en) | 2022-12-30 | 2022-12-30 | A method for preparing high-cis-content lycopene by catalysis of iodine-containing anion compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115819176B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475134A (en) * | 2014-12-05 | 2015-04-01 | 江南大学 | Preparation method of iodine-doped titanium dioxide nano catalyst and use of catalyst in heterogeneous catalysis of configuration inversion of trans-carotenoids |
| WO2020158502A1 (en) * | 2019-01-30 | 2020-08-06 | カゴメ株式会社 | Method for supercritical extraction of lycopene, and method for producing lycopene-containing composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2757904B1 (en) * | 2011-09-19 | 2017-01-11 | OmniActive Health Technologies Limited | An efficient process for the preparation of lycopene containing oleoresin and lycopene crystals for human consumption |
| US20210214291A1 (en) * | 2020-01-10 | 2021-07-15 | Michael Lloyd | Rapid Thermal Isomerization of Lycopene |
-
2022
- 2022-12-30 CN CN202211734218.0A patent/CN115819176B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475134A (en) * | 2014-12-05 | 2015-04-01 | 江南大学 | Preparation method of iodine-doped titanium dioxide nano catalyst and use of catalyst in heterogeneous catalysis of configuration inversion of trans-carotenoids |
| WO2020158502A1 (en) * | 2019-01-30 | 2020-08-06 | カゴメ株式会社 | Method for supercritical extraction of lycopene, and method for producing lycopene-containing composition |
Non-Patent Citations (1)
| Title |
|---|
| The thermal Z-isomerization-induced change in solubility and physical properties of (all-E)-lycopene;Kazuya Murakami et al;Biochemical and Biophysical Research Communications;20170720;第491卷;317-322 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115819176A (en) | 2023-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10807938B2 (en) | Method for preparing maleate by selective catalytic oxidation of lignin | |
| CN104010996B (en) | The preparation method of p-Xylol and/or p-tolyl aldehyde | |
| Kieslich et al. | Transformation of terpenoids | |
| CN105585470B (en) | A method of 2- hydroxy-3-methyl -2- cyclopentene-1-ones are prepared by fructose | |
| CN109534977A (en) | One kind synthesizing α, γ-unsaturation dienone method and the catalyst for this method by propargyl alcohol | |
| Blume et al. | Chemoenzymatic total synthesis of (+)-& (−)-cis-osmundalactone | |
| CN112608219A (en) | Method for preparing 4-ethylphenol by depolymerizing lignin based on liquid phase reforming system | |
| Utsukihara et al. | Reduction of various ketones by red algae | |
| CN104710282B (en) | Method for producing ethanol co-production methanol | |
| CN115819176B (en) | A method for preparing high-cis-content lycopene by catalysis of iodine-containing anion compounds | |
| CN114950505A (en) | A catalyst for preparing β-phenethyl alcohol by hydrogenation of styrene oxide and its preparation method and application | |
| US9656250B2 (en) | Method for preparing iodine-doped TiO2 nano-catalyst and use thereof in heterogeneously catalyzing configuration transformation of trans-carotenoids | |
| CN116023226B (en) | Supercritical CO2Method for thermally induced transformation of trans-lycopene configuration in ethanol system | |
| CN102775276B (en) | A kind of preparation method of plant polyprenol and its hydrogenated derivatives with antibacterial and antioxidative activity | |
| CN111072477B (en) | A method for preparing p-hydroxycinnamate by copper-catalyzed depolymerization of lignin | |
| CN102173977B (en) | Cu/Al2O3 catalyst, preparation method and catalytic glycerol hydrogenolysis method | |
| CN101646642A (en) | Method for enantioselectively preparing optically active 4-hydroxy-2, 6, 6-trimethylcyclohex-2-enone derivatives | |
| CN102153446B (en) | Cu/MgO catalyst, preparation method thereof and method for catalyzing glycerin hydrogenolysis | |
| CN105399653A (en) | Industrialization method for preparing zeaxanthine from marigold oil resin in one step | |
| CN103880661A (en) | Method of preparing ethyl acetate by catalyzing alcohol to directly dehydrogenize | |
| CN106316839A (en) | One-step method for synthesizing methyl lactate from biomass glycerol | |
| KR102289190B1 (en) | A synthesis method of 9-cis Beta-carotene | |
| CN102206146B (en) | A kind of preparation method of vanillin | |
| CN102020556B (en) | Method for producing carboxylic ester by cellulose biomass | |
| CN118874549B (en) | Composite catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |