CN104710392B - A kind of baicalin prepares the method for scutellarin - Google Patents
A kind of baicalin prepares the method for scutellarin Download PDFInfo
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Abstract
The present invention provides a kind of method that baicalin prepares scutellarin, is take eutectic solvent as hydrolysis medium, and enzymatic hydrolysis baicalin prepares the novel method of scutellarin. It is an advantage of the current invention that to adopt that volatility is low, safety non-toxic green solvent--the aqueous solution of eutectic solvent is hydrolysis medium, overcome the destruction to baicalin existing for prior art big, low conversion rate, seriously polluted, the shortcomings such as separation purifying technique is complicated. This preparation method is simple, safety and environmental protection, utilize content of baicalin be 80% raw material prepare scutellarin, the transformation efficiency of baicalin can reach more than 90%, the purity of scutellarin can reach more than 75%.
Description
Technical field:
The present invention relates to the preparation method of scutellarin, specifically a kind of baicalin prepares the method for scutellarin.
Background technology:
Baicalin and scutellarin are the main active ingredient of baikal skullcap root. Current high amount of drug metabolism research shows, after baicalin oral administration, in Digestive tract, it is converted into glycosides unit by intestinal microflora just can be absorbed and used (Lai, etal., 2003), therefore, the bioavailability of baicalin is lower, and scutellarin is easily absorbed, bioavailability height (Zhao Jing etc., 1998). In addition, a large amount of inside and outsides pharmacology activity research shows, the pharmacologically active of scutellarin is also far above baicalin, especially scavenging free radicals and anti-oxidant (Gao, etal., 1999), anti AIDS virus (Wu, eaal., 2001), the aspect such as angiogenesis inhibitor (Liu, etal., 2003) effect. Owing to scutellarin content in radix scutellariae medicinal materials is humble, it is worth without extracting directly, so the preparation relating to scutellarin at present mainly contains three kinds of modes. First is utilize industrial chemicals to carry out organic synthesis preparation (application number 200410008987.8), a large amount of preparations of organic synthesis method, it is possible to cost is lower, but owing to using a large amount of organic solvent, there is the problem that environmental pollution is bigger. 2nd is the extraction with aqueous solution radix scutellariae medicinal materials utilized containing the root of large-flowered skullcap self enzyme or other enzyme, while baicalin is extracted, it is converted into scutellarin by the root of large-flowered skullcap self enzyme or other enzymic hydrolysis again, and then utilizes the mode such as organic solvent extraction, post separation to be further purified the scutellarin (application number 201110422999.5) obtaining high purity. Although the method has certain advantage, but owing to containing the aqueous solution of enzyme, the solubleness of baicalin is less, and thus hydrolysis efficiency is lower. In addition, thus subsequent disposal is more complicated. 3rd is adopt acid hydrolysis (application number 200410019726.6,200302129372.4) and the aqueous solution direct hydrolysis baicalin containing baicalin lytic enzyme to prepare scutellarin (application number 200410020649.6). Acid-hydrolysis method needs to be hydrolyzed 16-20 hour at 100 DEG C, long reaction time, and is destroyed by baicalin relatively big as entered strong acid, and environmental pollution is serious. Although the method that enzymatic hydrolysis baicalin glucal acidic group prepares scutellarin overcomes with serious pollution shortcoming, but equally owing to the aqueous solution containing enzyme is less to the solubleness of baicalin, long reaction time, hydrolysis efficiency is lower.
Eutectic solvent is that a class is synthesized by crude substance, novel green solvent renewable, easily a large amount of synthesis, it has the fusing point lower than room temperature, low volatility and high thermostability, the more important thing is that lipase hydrolysis enzyme, glycoside hydrolase etc. still show good catalytic activity in eutectic solvent. Such as, lipase can be converted into the transesterification reaction (JohnathanT.Gorke, Chem.Commun., 2008) of butyl valerate by the Valeric acid ethylester of catalysis preferably in eutectic solvent. Therefore, eutectic solvent is with a wide range of applications in Hydrolases catalyze bioconversion. Having not yet to see about taking eutectic solvent as solvent, enzymatic hydrolysis baicalin prepares the report of scutellarin.
Summary of the invention:
The object of the invention is to provide a kind of environmental protection, efficiency height, the simple method preparing scutellarin by baicalin.
A kind of method preparing scutellarin by baicalin provided by the invention, comprises the steps:
(1) preparation of the root of large-flowered skullcap thick enzyme powder: the fresh root of large-flowered skullcap is got and pH is the damping fluid of 4��6 in 1:1.5��2.5 in mass ratio, adds a small amount of quartz sand, grinding, centrifuging, obtain root of large-flowered skullcap crude enzyme liquid, crude enzyme liquid after filtration, is dialysed, and vacuum lyophilization obtains the thick enzyme powder of the root of large-flowered skullcap;
(2) enzymic hydrolysis baicalin: the baicalin getting content at least 80%, dissolve with eutectic solvent, add damping fluid, the thick enzyme powder of the root of large-flowered skullcap that pH is 4��6 more successively, mix, it is heated to 40��50 DEG C, insulation, stirring reaction 2.0��4.0 hours, it is cooled to room temperature, filtering, reclaim throw out, filtrate can again for being hydrolyzed baicalin; Wherein: the mass ratio of the thick enzyme powder of baicalin, eutectic solvent, damping fluid, the root of large-flowered skullcap is 1:40��60:150��250:0.025��0.1;
(3) scutellarin purifying: by throw out obtained above with the dissolve with ethanol of 95%, filter, abandon insolubles; Adding 5��6 times amount deionized waters (volume ratio) in filtrate, stir evenly, leave standstill, precipitate out scutellarin, filter and obtain precipitation, precipitation with deionized water wash at least 3 times, filters again, dry, obtains refining scutellarin.
The preferred 1:2 of mass ratio of the fresh root of large-flowered skullcap and damping fluid in step (1).
Preferred 1:50:200:0.025��0.1 of mass ratio of baicalin, eutectic solvent, damping fluid, the root of large-flowered skullcap thick enzyme powder in step (2).
Eutectic solvent described in step (2) is that a kind of ammonium salt and a kind of hydrogen-bond donor compound mix in the ratio of 1:0.5��2 (mol ratio), heats, is stirred to formation transparent and homogeneous liquid under 60��90 DEG C of conditions. The preferred choline chloride 60 of ammonium salt wherein, the preferred urea of hydrogen-bond donor compound.
Described damping fluid can be any one damping fluid in acetic acid-acetate buffer, citric acid-citrate damping fluid, phosphoric acid-phosphate buffered saline buffer.
The present invention utilize content of baicalin be 80% raw material prepare scutellarin, the transformation efficiency of baicalin can reach more than 90%, the purity of scutellarin can reach more than 75%.
Compared with prior art tool of the present invention has the following advantages:
(1) root of large-flowered skullcap enzyme and baicalin are all had good solubleness by the eutectic solvent aqueous solution that the preparation method of the present invention uses, and therefore, baicalin hydrolysis efficiency height, the transformation efficiency of baicalin can reach more than 90%, the purity of scutellarin can reach more than 75%.
(2) the present invention uses solvent for eutectic solvent, has the fusing point lower than room temperature, low volatility, high thermostability and safety non-toxic, and recyclable recycling, it is a kind of green and environment-friendly solvent.
(3) preparation method of the present invention does not use organic solvent (except a small amount of ethanol) and soda acid, environmentally safe.
Accompanying drawing illustrates:
Fig. 1. the HPLC collection of illustrative plates of baicalin prepared by this laboratory
Fig. 2. the HPLC collection of illustrative plates of scutellarin prepared by present example 3 preparation method
Embodiment:
The present invention described in further detail by following examples it should be understood that embodiment described herein only for illustration of with understand the present invention, be not limited to the present invention.
Embodiment 1
A. the preparation of the root of large-flowered skullcap thick enzyme powder: get the fresh medicinal material 200g of the root of large-flowered skullcap and shred, it is placed in mortar, add a small amount of quartz sand and 400mlpH value be 4.0 acetic acid-acetate buffer, grinding, filtration, filtrate is put in dialysis tubing, with deionized water dialysis, until outer liquid is colourless, get dialysis tubing endoenzyme liquid, vacuum lyophilization, obtain the thick enzyme powder 0.18g of the root of large-flowered skullcap.
B. eutectic solvent preparation: get 140g choline chloride 60 and 60g urea, be placed in the round-bottomed flask of 250ml, heats under 80 DEG C of conditions, is stirred to formation transparent and homogeneous liquid.
C. enzymic hydrolysis baicalin prepares scutellarin: get baicalin (content of baicalin 80%) 2g, dissolve with 100g eutectic solvent, add successively again 400mLpH value for pH value be 4.0 acetic acid-acetate buffer, the thick enzyme powder 100mg of the root of large-flowered skullcap, mix. Above-mentioned solution is heated to 45 DEG C, and insulation, stirring reaction 2.5 hours, after react, be cooled to room temperature, filters, recovery throw out (filtrate can again for being hydrolyzed baicalin). By throw out obtained above 95% dissolve with ethanol, filter, abandon insolubles. Filtrate adds 5 times amount deionized waters (volume ratio), stirs evenly, leave standstill, scutellarin precipitates out, and filters and obtains precipitation, and precipitation is again with deionized water wash 3 times, filtration, drying, obtaining scutellarin 1.081g. through HPLC detection purity is 80.2%, and baicalin transformation efficiency is 90.3%.
Embodiment 2
A. the preparation of the root of large-flowered skullcap thick enzyme powder: get the fresh medicinal material 200g of the root of large-flowered skullcap and shred, it is placed in mortar, add a small amount of quartz sand and 400mlpH value be 4.5 citric acid-citrate damping fluid, grinding, filtration, filtrate is put in dialysis tubing, with deionized water dialysis, until outer liquid is colourless, get dialysis tubing endoenzyme liquid, vacuum lyophilization, obtain the thick enzyme powder 0.20g of the root of large-flowered skullcap.
B. eutectic solvent preparation: get 140g choline chloride 60 and 60g urea, be placed in the round-bottomed flask of 250ml, heats under 60 DEG C of conditions, is stirred to formation transparent and homogeneous liquid.
C. enzymic hydrolysis baicalin prepares scutellarin: get baicalin (content of baicalin 80%) 2g, dissolves with 100g eutectic solvent, then adds citric acid-citrate damping fluid, the thick enzyme powder 100mg of the root of large-flowered skullcap that 400mLpH value is 4.5 successively, mixes. Above-mentioned solution is heated to 45 DEG C, and insulation, stirring reaction 2.6 hours, after react, be cooled to room temperature, filters, recovery throw out (filtrate can again for being hydrolyzed baicalin). By throw out obtained above 95% dissolve with ethanol, filter, abandon insolubles. Adding 5 times amount deionized waters (volume ratio) in filtrate, stir evenly, leave standstill, scutellarin precipitates out, and filters and obtains precipitation, and precipitation with deionized water wash 3 times, filters again, dry, obtains scutellarin 1.07g. Detecting purity through HPLC is 83.0%, and baicalin transformation efficiency is 92.5%.
Embodiment 3
A. the preparation of the root of large-flowered skullcap thick enzyme powder: get the fresh medicinal material 200g of the root of large-flowered skullcap and shred, it is placed in mortar, add a small amount of quartz sand and 400mlpH value be 6.0 phosphoric acid-phosphate buffered saline buffer, grinding, filtration, filtrate is put in dialysis tubing, with deionized water dialysis, until outer liquid is colourless, get dialysis tubing endoenzyme liquid, vacuum lyophilization, obtain the thick enzyme powder 0.22g of the root of large-flowered skullcap.
B. eutectic solvent preparation: get 140g choline chloride 60 and 60g urea, be placed in the round-bottomed flask of 250ml, heats under 90 DEG C of conditions, is stirred to formation transparent and homogeneous liquid.
C. enzymic hydrolysis baicalin prepares scutellarin: get baicalin (content of baicalin 80%) 2g, dissolves with 100g eutectic solvent, then adds phosphoric acid-phosphate buffered saline buffer, the thick enzyme powder 100mg of the root of large-flowered skullcap that 400mLpH value is 6.0 successively, mixes. Above-mentioned solution is heated to 45 DEG C, and insulation, stirring reaction 2.5 hours, after react, be cooled to room temperature, filters, recovery throw out (filtrate can again for being hydrolyzed baicalin). By throw out obtained above 95% dissolve with ethanol, filter, abandon insolubles. Adding 5 times amount deionized waters (volume ratio) in filtrate, stir evenly, leave standstill, scutellarin precipitates out, and filters and obtains precipitation, and precipitation with deionized water wash 3 times, filters again, dry, obtains scutellarin 1.076g. Detecting purity through HPLC is 85.0%, and baicalin transformation efficiency is 95.3%.
Embodiment 4
A. the preparation of the root of large-flowered skullcap thick enzyme powder: get the fresh medicinal material 200g of the root of large-flowered skullcap and shred, it is placed in mortar, add a small amount of quartz sand and 400mlpH value be 4.5 phosphoric acid-phosphate buffered saline buffer, grinding, filtration, filtrate is put in dialysis tubing, with deionized water dialysis, until outer liquid is colourless, get dialysis tubing endoenzyme liquid, vacuum lyophilization, obtain the thick enzyme powder 0.18g of the root of large-flowered skullcap.
B. eutectic solvent preparation: get 140g choline chloride 60 and 30g urea, be placed in the round-bottomed flask of 250ml, heats under 80 DEG C of conditions, is stirred to formation transparent and homogeneous liquid.
C. enzymic hydrolysis baicalin prepares scutellarin: get baicalin (content of baicalin 80%) 2g, dissolves with 100g eutectic solvent, then adds phosphoric acid-phosphate buffered saline buffer, the thick enzyme powder 50mg of the root of large-flowered skullcap that 400mLpH value is 4.5 successively, mixes. Above-mentioned solution is heated to 50 DEG C, and insulation, stirring reaction 4.0 hours, after react, be cooled to room temperature, filters, recovery throw out (filtrate can again for being hydrolyzed baicalin). By throw out obtained above 95% dissolve with ethanol, filter, abandon insolubles. Adding 5 times amount deionized waters (volume ratio) in filtrate, stir evenly, leave standstill, scutellarin precipitates out, and filters and obtains precipitation, and precipitation with deionized water wash 3 times, filters again, dry, obtains scutellarin 1.07g. Detecting purity through HPLC is 82.8%, and baicalin transformation efficiency is 92.3%.
Embodiment 5
A. the preparation of the root of large-flowered skullcap thick enzyme powder: get the fresh medicinal material 200g of the root of large-flowered skullcap and shred, it is placed in mortar, add a small amount of quartz sand and 400mlpH value be 5.0 citric acid-citrate damping fluid, grinding, filtration, filtrate is put in dialysis tubing, with deionized water dialysis, until outer liquid is colourless, get dialysis tubing endoenzyme liquid, vacuum lyophilization, obtain the thick enzyme powder 0.18g of the root of large-flowered skullcap.
B. eutectic solvent preparation: get 140g choline chloride 60 and 120g urea, be placed in the round-bottomed flask of 250ml, heats under 90 DEG C of conditions, is stirred to formation transparent and homogeneous liquid.
C. enzymic hydrolysis baicalin prepares scutellarin: get baicalin (content of baicalin 80%) 2g, dissolves with 100g eutectic solvent, then adds citric acid-citrate damping fluid, the thick enzyme powder 200mg of the root of large-flowered skullcap that 400mLpH value is 5.0 successively, mixes. Above-mentioned solution is heated to 40 DEG C, and insulation, stirring reaction 2.0 hours, after react, be cooled to room temperature, filters, recovery throw out (filtrate can again for being hydrolyzed baicalin). By throw out obtained above 95% dissolve with ethanol, filter, abandon insolubles. Adding 5 times amount deionized waters (volume ratio) in filtrate, stir evenly, leave standstill, scutellarin precipitates out, filtering and obtain precipitation, precipitation, again with deionized water wash 3 times, is filtered, dry, obtaining scutellarin 1.177g, detecting purity through HPLC is 78.2%, and baicalin transformation efficiency is 95.6%.
Claims (5)
1. prepare the method for scutellarin with baicalin for one kind, it is characterised in that comprise the steps:
(1) preparation of the root of large-flowered skullcap thick enzyme powder: the fresh root of large-flowered skullcap is got and pH is the damping fluid of 4��6 in 1:1.5��2.5 in mass ratio, adds a small amount of quartz sand, grinding, centrifuging, obtain root of large-flowered skullcap crude enzyme liquid, crude enzyme liquid after filtration, is dialysed, and vacuum lyophilization obtains the thick enzyme powder of the root of large-flowered skullcap;
(2) enzymic hydrolysis baicalin: the baicalin getting content at least 80%, dissolve with eutectic solvent, add damping fluid, the thick enzyme powder of the root of large-flowered skullcap that pH is 4��6 more successively, mix, it is heated to 40��50 DEG C, insulation, stirring reaction 2.0��4.0 hours, it is cooled to room temperature, filtering, reclaim throw out, filtrate can again for being hydrolyzed baicalin; Wherein: the mass ratio of the thick enzyme powder of baicalin, eutectic solvent, damping fluid, the root of large-flowered skullcap is 1:40��60:150��250:0.025��0.1;
(3) scutellarin purifying: by throw out obtained above with the dissolve with ethanol of 95%, filter, abandon insolubles; Adding 5��6 times amount deionized waters in filtrate, stir evenly, leave standstill, precipitate out scutellarin, filter and obtain precipitation, precipitation with deionized water wash at least 3 times, filters again, dry, obtains refining scutellarin.
2. a kind of baicalin prepares the method for scutellarin as claimed in claim 1, it is characterised in that, the mass ratio 1:2 of the fresh root of large-flowered skullcap and damping fluid in described step (1).
3. a kind of baicalin prepares the method for scutellarin as claimed in claim 1, it is characterised in that, in described step (2), the mass ratio of baicalin, eutectic solvent, damping fluid, the thick enzyme powder of the root of large-flowered skullcap is 1:50:200:0.025��0.1.
4. a kind of baicalin as described in claim 1,2 or 3 prepares the method for scutellarin, it is characterized in that, described eutectic solvent prepares by the following method: choline chloride 60 and urea are mixed by 1:0.5��2 in molar ratio, heats, is stirred to formation transparent and homogeneous liquid under 60��90 DEG C of conditions.
5. a kind of baicalin as described in claim 1,2 or 3 prepares the method for scutellarin, it is characterised in that, described damping fluid is acetic acid-acetate buffer, citric acid-citrate damping fluid or phosphoric acid-phosphate buffered saline buffer.
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| CN106749442B (en) * | 2016-12-08 | 2019-04-19 | 河西学院 | A kind of method that Salt treatment eutectic solvent extracts benzyl carbinol glycosides in Herba Cistanches |
| CN106950318A (en) * | 2017-04-20 | 2017-07-14 | 广西壮族自治区梧州食品药品检验所 | A kind of method that ASE HPLC methods determine baicalin in Scutellaria baicalensis Georgi content |
| CN107091889A (en) * | 2017-04-20 | 2017-08-25 | 广西壮族自治区梧州食品药品检验所 | A kind of method that ASE methods extract baicalin in Scutellaria baicalensis Georgi |
| CN108088943A (en) * | 2018-02-13 | 2018-05-29 | 沈阳药科大学 | Extractant-eutectic is dissolved in the application during effective component of chinese medicine measures |
| CN115948488A (en) * | 2022-12-28 | 2023-04-11 | 东北林业大学 | Method for efficiently converting baicalin in scutellaria baicalensis raw material into baicalein |
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| CN103160549A (en) * | 2011-12-16 | 2013-06-19 | 东北林业大学 | Method of preparing, separating and purifying baicalein and wogonin by endogenous enzymatic hydrolysis of baicalin and wogonoside in scutellaria |
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Effective date of registration: 20190816 Address after: 030600, No. 8, Yuci Industrial Park, Shanxi, Jinzhong Patentee after: Shanxi Huawei Pharmaceutical Co., Ltd. Address before: 030006 Taiyuan, Xiaodian District, Shanxi City Road, No. 92 Patentee before: Shanxi Univeristy |