CN105087707A - Method for catalytically synthesizing dihydromyricetin mono-esterification material by aid of lipase - Google Patents
Method for catalytically synthesizing dihydromyricetin mono-esterification material by aid of lipase Download PDFInfo
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- CN105087707A CN105087707A CN201410222489.7A CN201410222489A CN105087707A CN 105087707 A CN105087707 A CN 105087707A CN 201410222489 A CN201410222489 A CN 201410222489A CN 105087707 A CN105087707 A CN 105087707A
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- lipase
- dibydro myricetrin
- dihydromyricetin
- monoesters compound
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Abstract
The invention discloses a method for catalytically synthesizing a dihydromyricetin mono-esterification material by the aid of lipase, and belongs to the field of biological catalysis. The method includes steps of dissolving dihydromyricetin and acyl donors in organic solvents, adding the free or immobilized lipase into the organic solvents and carrying out reaction by the aid of shaking tables at the temperatures of 30-40 DEG C and the speed of 200-300r/min for 1-2 days; centrifuging reaction liquid after reaction is completed, acquiring supernatant and volatilizing the solvents to obtain solid which is the dihydromyricetin mono-esterification material. The method has the advantages that the dihydromyricetin mono-esterification material is catalytically synthesized by the aid of the free or immobilized lipase for the first time, an esterification position of the product is located at 3-hydroxyl with the lowest antioxidant activity, accordingly, the antioxidant activity of the dihydromyricetin can be kept to the greatest extent, the oil solubility of the dihydromyricetin can be improved, and the dihydromyricetin has high practical value; the method is low in catalyst cost and production cost and high in reaction specificity and selectivity, reaction conditions are mild, the lipase can be reused, and the like.
Description
Technical field
The invention belongs to biocatalysis field, relate to a kind of method utilizing lipase-catalyzed synthesis dibydro myricetrin monoesters compound.
Background technology
Dibydro myricetrin is a kind of Flavone aglycone compound, and chemistry 3,5,7,3', 4', 5'-hexahydroxy--2,3-flavanonol (dihydromyricetin, DMY) by name, has another name called dihydromyricetin, Ampeloptin, ampelopsin.The massfraction of dibydro myricetrin in dry Ampelopsis grossedentata cauline leaf can up to more than 30%.Dibydro myricetrin has multiple pharmacologically active, as anti-inflammatory, analgesia, cough-relieving, eliminate the phlegm, hypertension, liver protecting and relieve the effect of alcohol, the fat that disappears, hypoglycemic, strengthening immunity, anti-oxidant and bacteriostatic action etc., be expected to be developed to food antioxidant, protective foods, makeup, pharmaceuticals etc.
Dibydro myricetrin molecule oil soluble is poor, limits its dispersiveness in oil phase, is unfavorable for the performance of its antioxygenation.Certain hydroxyl in dibydro myricetrin molecule is carried out esterification and can improve its oil soluble, strengthen its anti-oxidant activity, practical value is larger.
Esterification is modified and is usually adopted chemical method and enzyme process.Adopt chemical method position to lack specificity, the hydroxyl with antioxygenation may be made esterified, although the lipophilicity of adding, reduce the antioxidant effect of compound itself.Enzymatic esterification generally adopts lipase to carry out esterification to hydroxyl, because enzyme has good specificity to substrate, can optionally esterification monohydroxy, and reaction conditions is gentle, and by product is few, has important using value in food service industry.The report of current most enzyme process esterification chromocor compound, for hydroxyl on flavonoid glycoside glycosyl, rarely has report to the esterification of hydroxyl on Flavone aglycone.Dibydro myricetrin hydroxyl is be directly connected in phenyl ring mostly, and due to the sucting electronic effect of phenyl ring, the Sauerstoffatom cloud density of hydroxyl reduces, and makes reactive esterify hydroxy become difficulty.Have no the report about the esterification of dibydro myricetrin enzyme process at present.
Containing multiple hydroxyl on dibydro myricetrin molecule, its anti-oxidant activity difference is larger, the most weak hydroxyl of anti-oxidant activity by quantum chemistry calculation dibydro myricetrin 3 hydroxyls (3-OH), thus 3-OH is carried out esterification can improve dibydro myricetrin oil-soluble while retain its anti-oxidant activity to greatest extent.
Enzyme immobilization (Enzymeimmobilization) technology utilizes the method for physics or chemistry to make resolvase be positioned the area of space limited, and keeps it active, and by the method recycled.Enzyme immobilization can improve the enzyme density of unit volume, the advantage such as strengthen (as pH value, temperature, organic solvent, toxic substance etc.) to the tolerance of environment, enzyme easily reclaims.Enzyme immobilization technology is the emerging biometric technology grown up the sixties in 20th century, and in industries such as chemical industry, fermentative production, the energy, medicine, practical application effect is remarkable.
Summary of the invention
The object of the present invention is to provide a kind of method utilizing lipase-catalyzed synthesis dibydro myricetrin monoesters compound.The advantages such as the method strengthens its oil soluble while the anti-oxidant activity remaining dibydro myricetrin to greatest extent, and reaction conditions is gentle, reaction specificity is high, selectivity is high, lipase can repeatedly reuse, production cost is low.
Object of the present invention is achieved through the following technical solutions:
A kind of method of lipase-catalyzed synthesis dibydro myricetrin monoesters compound that utilizes is for by free-fat enzyme or fixed lipase catalyzed dibydro myricetrin and acry radical donor synthesizing dihydro ampelopsin monoesters compound; Described dibydro myricetrin monoesters compound is 3 hydroxy esterifications of dibydro myricetrin.
Described free-fat enzyme comprises: penicillium cammenberti lipase (LPC), zhizopchin lipase (LipaseRC), pseudomonas cepacia lipase (PCL), porcine pancreatic lipase (PPL), Rhizopus niveus lipase (LipaseRN), penicillium expansum lipase (PEL), aspergillus niger HGD0823 lipase.Described immobilized lipase comprises: Lipozyme
iMtL, Lipozyme
iMrM, Novozym435, Immobilized Aspergillus niger HGD0823 lipase.
Penicillium cammenberti lipase (LPC), zhizopchin lipase (LipaseRC), pseudomonas cepacia lipase (PCL), porcine pancreatic lipase (PPL), Rhizopus niveus lipase (LipaseRN), penicillium expansum lipase (PEL), Lipozyme in above-mentioned lipase
iMtL, Lipozyme
iMrM, Novozym435 are commercially produced product, directly can buy from businessman and obtain.Aspergillus niger HGD0823 lipase is fermented by aspergillus niger HGD0823 and prepares.Adopt being fixed of absorption method fixed black aspergillus HGD0823 lipase aspergillus niger HGD0823 lipase again, the method of absorption method fixed fat enzyme specifically comprises the steps: 1. thick enzyme powder to be dissolved in (0.05M, pH9.4) in Glycine-NaOH damping fluid, at 30 ~ 40 DEG C, stir 1 ~ 2h with 150 ~ 200r/min; 2. centrifugal with 5000r/min at 4 ~ 10 DEG C, get supernatant liquor; 3. by D4020 resin with after 95% alcohol immersion 24h, till being washed till filtrate clarification with deionized water, added to 2. in supernatant liquor; 4. 35 ~ 40 DEG C, under 150 ~ 200r/min, after vibration 4 ~ 5h, filter with sand core funnel, with above-mentioned wash buffer 3 times, being fixed of suction filtration postlyophilization lipase, 0 ~ 4 DEG C of preservation.
Preferably, the described method of lipase-catalyzed synthesis dibydro myricetrin monoesters compound that utilizes comprises the steps:
(1) dibydro myricetrin and acry radical donor are dissolved in organic solvent, then add free-fat enzyme or immobilized lipase, in 30 ~ 40 DEG C, 200 ~ 300r/min shaking table reaction 1 ~ 2 day.
(2), after reaction terminates, reaction solution is centrifugal, and get supernatant liquor, by solvent recuperation, the solid obtained is the product containing dibydro myricetrin monoesters compound.
Acry radical donor described in step (1) comprises: vinyl-acetic ester, propionate, vinyl butyrate, sad vinyl acetate, vinyl benzoate, stearic acid vinyl ester.
In step (1), the mol ratio of dibydro myricetrin and acry radical donor is preferably 1:20 ~ 30.
Organic solvent described in step (1) comprises: acetonitrile, acetone, tetrahydrofuran (THF), the trimethyl carbinol, dimethyl sulfoxide (DMSO).
The amount of the lipase described in step (1) is preferably 250U/mL.
The present invention has the following advantages and effect relative to prior art tool:
The present invention utilizes lipase-catalyzed synthesis dibydro myricetrin monoesters compound first.Relative to conventional chemical methods synthesizing dihydro ampelopsin monoesters compound, reaction conditions of the present invention is gentle, processing step is simple, environmental friendliness, can reuse and the easy large-scale industrial production of continuous prodution.
The present invention uses immobilized lipase, has fatty enzyme-to-substrate and the segregative feature of product, and the long service life of lipase, can reuse and continuous prodution, greatly reduce production cost.
The esterified positions of product of the present invention, at the minimum 3-hydroxyl of anti-oxidant activity, remains the anti-oxidant activity of dibydro myricetrin to greatest extent, strengthens its oil soluble simultaneously.
Embodiment
Below in conjunction with embodiment, further detailed description is done to the present invention, but embodiments of the present invention are not limited thereto.
Formula I is dibydro myricetrin molecular structure, and the anti-oxidant activity of dibydro myricetrin molecule 6 hydroxyls is different.Before and after molecule dehydrogenation, the difference (△ HOF) of Heat of Formation can judge the anti-oxidant activity of flavones and polyphenols preferably, and the free radical formed after the dehydrogenation of △ HOF value less explanation molecule is more stable, and the anti-oxidant activity of molecule is stronger.By comparing dibydro myricetrin 6 hydroxyl anti-oxidant activities with △ HOF.Dibydro myricetrin each hydroxyl △ HOF sees the following form:
According to the △ HOF result of quantum chemistry calculation in table, dibydro myricetrin 6 hydroxyl resistance of oxidation are followed successively by: 4'-OH > 5'-OH > 3'-OH > 7-OH > 5-OH > 3-OH.As can be seen from dibydro myricetrin molecule 6 hydroxyl resistance of oxidation calculation result, 3 hydroxyl (3-OH) anti-oxidant activities are the most weak.The Heat of Formation (HOF) of dibydro myricetrin molecule is 281.3931kJ/mol.
Embodiment 1
(1) dibydro myricetrin is dissolved in 2mL organic solvent, vinyl-acetic ester (starting point concentration of dibydro myricetrin and vinyl-acetic ester be respectively 20,500mmol/L) is added again after whole dissolving, add the Immobilized Aspergillus niger HGD0823 lipase of 500U again, react 24 hours under the condition of temperature 35 DEG C, shaking speed 200r/min.
(2), after reaction terminates, reaction solution is centrifugal, and get supernatant liquor, by solvent recuperation, the solid obtained is the product containing dibydro myricetrin monoesters compound.
In the present embodiment, organic solvent used is respectively acetonitrile, acetone, tetrahydrofuran (THF), the trimethyl carbinol, dimethyl sulfoxide (DMSO).In different organic solvents, the transformation efficiency of dibydro myricetrin under Immobilized Aspergillus niger HGD0823 is lipase-catalyzed (being measured by HPLC) is in table 1.
The transformation efficiency of table 1. dibydro myricetrin in different organic solvents
Embodiment 2
(1) dibydro myricetrin is dissolved in 2mL acetonitrile, vinyl-acetic ester (starting point concentration of dibydro myricetrin and vinyl-acetic ester be respectively 20,500mmol/L) is added again after whole dissolving, add the lipase of 500U again, react 24 hours under the condition of temperature 35 DEG C, shaking speed 200r/min.
(2), after reaction terminates, reaction solution is centrifugal, and get supernatant liquor, by solvent recuperation, the solid obtained is the product containing dibydro myricetrin monoesters compound.
In the present embodiment, lipase used is respectively free lipase: penicillium cammenberti lipase (LPC), zhizopchin lipase (LipaseRC), pseudomonas cepacia lipase (PCL), porcine pancreatic lipase (PPL), Rhizopus niveus lipase (LipaseRN), penicillium expansum lipase (PEL), aspergillus niger HGD0823 lipase; Immobilized lipase: Lipozyme
iMtL, Lipozyme
iMrM, Novozym435, Immobilized Aspergillus niger HGD0823 lipase.The transformation efficiency of dibydro myricetrin under difference is lipase-catalyzed is in table 2 and table 3:
The transformation efficiency of table 2. dibydro myricetrin under different free-fat enzyme catalysis
The transformation efficiency of table 3. dibydro myricetrin under difference is fixed lipase catalyzed
The product that embodiment 1 and embodiment 2 obtain turns out to be the dibydro myricetrin monoesters compound (hydroxy esterification that anti-oxidant activity is the most weak of dibydro myricetrin 3-OH esterification through nucleus magnetic resonance (NMR) analysis, such as formula II), its productive rate is between 2 ~ 40%.Being about 40% with Novozym435 lipase yield in acetonitrile, is about 25% with Immobilized Aspergillus niger HGD0823 lipase yield.
1HNMR(600MHz,CD
3OD/TMS):δ1.28(s,1H,OH
19),1.97(s,3H,H
25),4.20(d,J＝2.6Hz,1H,H
14),4.46(d,J＝11.3Hz,2H,H
2+H
6),5.23(d,J＝2.6Hz,1H,H
7+H
9),5.90(d,2H,H
16),5.89–5.99(d,1H,OH
20+OH
22),6.53(d,J＝7.7Hz,1H,OH
21),6.53(d,J＝7.7Hz,1H,OH
23).
13CNMR(151MHz,CD
3OD/TMS):δ21.70(C
25),73.34(C
16),83.13(C
14),96.46(C
6),97.42(C
2),102.05(C
4),107.85(C
7,C
9),128.24(C
8),134.50(C
11),147.00(C
10,C
12),164.59(C
5),165.50(C3),168.76(C
1),196.71(C
15),198.48(C
24).
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. utilize a method for lipase-catalyzed synthesis dibydro myricetrin monoesters compound, it is characterized in that: described method is
By free or fixed lipase catalyzed dibydro myricetrin and acry radical donor synthesizing dihydro ampelopsin monoesters compound; Described dibydro myricetrin monoesters compound is 3 hydroxy esterifications of dibydro myricetrin.
2. the method utilizing lipase-catalyzed synthesis dibydro myricetrin monoesters compound according to claim 1, is characterized in that:
Described free-fat enzyme comprises: penicillium cammenberti lipase, zhizopchin lipase, pseudomonas cepacia lipase, porcine pancreatic lipase, Rhizopus niveus lipase, penicillium expansum lipase, aspergillus niger HGD0823 lipase;
Described immobilized lipase comprises: LipozymeIMTL, LipozymeIMRM, Novozym435, Immobilized Aspergillus niger HGD0823 lipase.
3. the method utilizing lipase-catalyzed synthesis dibydro myricetrin monoesters compound according to claim 2, is characterized in that: penicillium cammenberti lipase, zhizopchin lipase, pseudomonas cepacia lipase, porcine pancreatic lipase, Rhizopus niveus lipase, penicillium expansum lipase, LipozymeIMTL, LipozymeIMRM, Novozym435 are directly bought from businessman and obtained; Aspergillus niger HGD0823 lipase is fermented by aspergillus niger HGD0823 and prepares; Immobilized Aspergillus niger HGD0823 lipase adopts absorption method fixedly to obtain.
4. the method utilizing lipase-catalyzed synthesis dibydro myricetrin monoesters compound according to claim 3, it is characterized in that: the method for absorption method fixed fat enzyme comprises the steps: 1. to be dissolved in Glycine-NaOH damping fluid by thick enzyme powder, at 30 ~ 40 DEG C, stir 1 ~ 2h with 150 ~ 200r/min; 2. centrifugal with 5000r/min at 4 ~ 10 DEG C, get supernatant liquor; 3. by D4020 resin with after 95% alcohol immersion 24h, till being washed till filtrate clarification with deionized water, added to 2. in supernatant liquor; 4. 35 ~ 40 DEG C, under 150 ~ 200r/min, after vibration 4 ~ 5h, filter with sand core funnel, with Glycine-NaOH wash buffer 3 times, being fixed of suction filtration postlyophilization lipase, 0 ~ 4 DEG C of preservation.
5. the method utilizing lipase-catalyzed synthesis dibydro myricetrin monoesters compound according to claim 1, is characterized in that comprising the steps:
(1) dibydro myricetrin and acyl donor are dissolved in organic solvent, then add free-fat enzyme or immobilized lipase, in 30 ~ 40 DEG C, 200 ~ 300r/min shaking table reaction 1 ~ 2 day;
(2), after reaction terminates, reaction solution is centrifugal, and get supernatant liquor, by solvent evaporates, the solid obtained is the product containing dibydro myricetrin monoesters compound.
6. the method utilizing lipase-catalyzed synthesis dibydro myricetrin monoesters compound according to claim 5, is characterized in that: the acry radical donor described in step (1) comprises: vinyl-acetic ester, propionate, vinyl butyrate, sad vinyl acetate, vinyl benzoate, stearic acid vinyl ester.
7. the method utilizing lipase-catalyzed synthesis dibydro myricetrin monoesters compound according to claim 5, is characterized in that: in step (1), the mol ratio of dibydro myricetrin and acyl donor is 1:20 ~ 30.
8. the method utilizing lipase-catalyzed synthesis dibydro myricetrin monoesters compound according to claim 5, is characterized in that: the organic solvent described in step (1) comprises: acetonitrile, acetone, tetrahydrofuran (THF), the trimethyl carbinol, dimethyl sulfoxide (DMSO).
9. the method utilizing lipase-catalyzed synthesis dibydro myricetrin monoesters compound according to claim 5, is characterized in that:
The amount of the lipase described in step (1) is 250U/mL.
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Cited By (3)
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| CN105385675A (en) * | 2015-12-31 | 2016-03-09 | 厦门大学 | Immobilization method of candida antarctica lipase B |
| CN113308506A (en) * | 2021-05-28 | 2021-08-27 | 华南理工大学 | Method for synthesizing dihydromyricetin-7-glucoside through biocatalysis |
| CN114807262A (en) * | 2022-05-25 | 2022-07-29 | 江南大学 | Dihydromyricetin acylated derivative and preparation method thereof |
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Cited By (4)
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|---|---|---|---|---|
| CN105385675A (en) * | 2015-12-31 | 2016-03-09 | 厦门大学 | Immobilization method of candida antarctica lipase B |
| CN113308506A (en) * | 2021-05-28 | 2021-08-27 | 华南理工大学 | Method for synthesizing dihydromyricetin-7-glucoside through biocatalysis |
| CN114807262A (en) * | 2022-05-25 | 2022-07-29 | 江南大学 | Dihydromyricetin acylated derivative and preparation method thereof |
| CN114807262B (en) * | 2022-05-25 | 2023-07-25 | 江南大学 | Dihydromyricetin acylated derivative and preparation method thereof |
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