CN103242335A - Method for extracting and purifying artemisinin - Google Patents
Method for extracting and purifying artemisinin Download PDFInfo
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- CN103242335A CN103242335A CN2013101555667A CN201310155566A CN103242335A CN 103242335 A CN103242335 A CN 103242335A CN 2013101555667 A CN2013101555667 A CN 2013101555667A CN 201310155566 A CN201310155566 A CN 201310155566A CN 103242335 A CN103242335 A CN 103242335A
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Abstract
The invention discloses a method for extracting and purifying artemisinin. The method comprises the following steps of: (1) crushing artemisia apiacea and preparing artemisinin extractum; (2) melting the extractum: mixing the extractum and silica gel and drying to obtain material mixed silica gel; (3) performing wet column packing to obtain a silica gel column; (4) flatly paving the material mixed silica gel obtained in the step (2) on the silica gel column obtained in the step (3), standing, flushing the column and eluting; (5) collecting the eluent, concentrating, placing for 24 hours, crystallizing and centrifuging to obtain an artemisinin coarse product; and (6) refining the artemisinin coarse product obtained in the step (5). By adopting the method, the extraction efficiency is high, the artemisinin content is high, the using amount of solvents is small, and the method is favorable for industrial application.
Description
Technical field
The present invention relates to the traditional Chinese medicine extraction field, specifically a kind of extracting and purifying method of Artemisinin.
Background technology
Artemisinin (Artemesinin) is a kind of a kind of colourless acicular crystal that obtains that extracts from feverfew Herba Artemisiae annuae (Artemisia annua L.), and molecular formula is C
15H
22O
5Subtertian malaria and the brain malaria of Artemisinin antagonism chloroquine have special efficacy, have characteristics of high efficiency and low toxicity.
The preparation method of Artemisinin mainly comprises chemosynthesis, biosynthesizing, plant tissue culture synthetic artemisinin and extract Artemisinin from sweet wormwood plant.At present, natural extract remains most widely used Artemisinin preparation method.The method of natural extract mainly includes methods such as machine solvent extraction, supercritical CO 2 extraction, microwave extracting.
Traditional organic solvent extraction method, extraction yield is low, and the time is long, and the organic solvent usage quantity is big.Supercritical carbon dioxide extraction method also has its shortcoming, namely is applicable to the extraction of lipotropy, the less material of molecular weight; Big to polarity, to add entrainment agent during the separation and Extraction of the material that molecular weight is too big, and under very high pressure, carry out, bring certain degree of difficulty and cost higher to industrialization.Microwave extraction can be saved a large amount of solvents, and the time is short, but the shortcoming of its existence is to need polar solvent, equipment comparatively expensive.Generally speaking, extraction yield is low, purity is not high, and follow-up refining complex process is the ubiquitous problem of present Artemisinin silica gel column chromatography extracting method.So, seek the Artemisinin extracting method that a kind of extraction efficiency height, artemislnin content height, solvent usage quantity are low, be beneficial to industrial application, be that the problem that solves is endeavoured in this area all the time.
Summary of the invention
The objective of the invention is low at the extraction yield that exists in the prior art, purity is not high, the problem of follow-up refining complex process provides the Artemisinin extracting method that a kind of extraction efficiency height, artemislnin content height, solvent usage quantity are low, be beneficial to industrial application.
The present invention is achieved through the following technical solutions: a kind of extracting and purifying method of Artemisinin may further comprise the steps:
(1) the sweet wormwood grass meal is broken, adds 8 times～12 times (L/ ㎏) No. 6 solvent oils, 50 ℃～55 ℃ refluxing extraction 3 hours～5 hours, and extracting solution concentrates, and receives cream and gets Artemisinin medicinal extract;
(2) medicinal extract hot melt cream below 70 ℃; Take by weighing medicinal extract behind the hot melt by 110 ㎏/post, medicinal extract mixing silica gel, oven dry gets spice silica gel; Described silica gel amount=medicinal extract amount * silica gel activity, described silica gel activity are the required silica gel amount of every suction 1ml water;
(3) No. 6 solvent oils and ethyl acetate are done elutriant with the solvent of 93～97:7～3(V/V) mix, and wet method dress post gets silicagel column, the described silica gel amount * M of described dress post silica gel amount=step (2), described M=1.1～1.5;
(4) the described spice silica gel of step (2) is tiled on the interior described silicagel column of step (3) of post, leave standstill, do elutriant with No. 6 solvent oils and ethyl acetate with the solvent of 93～97:7～3(V/V) mix, must not have Artemisinin, contain assorted Artemisinin and do not have assorted Artemisinin towards post, respectively to no Artemisinin, contain assorted Artemisinin and do not have the Artemisinin of mixing and carry out wash-out;
(5) collect elutriant, concentrate, place crystallization in 24 hours, centrifugal, get the Artemisinin crude product;
(6) the described Artemisinin crude product of step (5) is made with extra care.
Artemisinin extracting and purifying method of the present invention is taked the silica gel column chromatography method of " wet method is adorned post, sample on the dry method ".Wet method dress post is after silica gel and appropriate solvent (generally namely using elutriant) are mixed thoroughly, reinstalls the dress column method of pillar.Sample on the dry method is that medicinal extract to be separated and silica gel are mixed thoroughly, again spice silica gel is added to the pillar upper strata after the drying.The contriver is through big quantity research, find breakthroughly, in the silica gel column chromatography method of " sample on wet method dress post, the dry method ", the silica gel amount and the silica gel amount that is used for the dress post that are used for spice by the strictness screening, and control is for the silica gel of spice and for the ratio between the silica gel amount of dress post, not only not having Artemisinin in the elutriant, contain assorted Artemisinin, do not have assorted Artemisinin can separate fully, and contains assorted Artemisinin, do not have the enrichment degree height of assorted Artemisinin, gives the follow-up refining convenience of having brought.
As preferred version, the sweet wormwood grass meal in the described step (1) is broken to be that the sweet wormwood grass is crossed the 10-20 mesh sieve.The applicant finds after deliberation, in the Artemisinin extraction and purification process of the present invention, the grinding particle size of Artemisinin is not the smaller the better, when the grinding particle size of sweet wormwood grass is too small or excessive, the extraction yield of Artemisinin is not high, and when grinding particle size was too small, not only extraction effect did not have obvious improvement also can influence the recovery of extracting solvent.The contriver finds that through repeated screening when Artemisinin was pulverized the 10-20 order, the Artemisinin extraction effect significantly improved, and it is easy to extract solvent recuperation, and it is convenient to handle.
As preferred version, the bake out temperature in the described step (2) is 50 ℃～60 ℃.Spice silica gel will influence the polarity of elutriant, thereby influence elute effect if brings moisture into, and, no Artemisinin, contain assorted Artemisinin, do not have that the Artemisinin of mixing is difficult to be separated.When spice silica gel is dried, need strict control bake out temperature.Bake out temperature is low, and drying effect is poor; The bake out temperature height, the Artemisinin in the spice silica gel easily is decomposed into dihydroarteannuin, causes Artemisinin extraction yield and purity drop.
As priority scheme, in described step (2) and step (3), silica gel is 100 orders ~ 200 order silica gel.
As priority scheme, in described step (3), M=1.3.
As priority scheme, the flow velocity towards post in described step (4) is 300L/h.
As priority scheme, not have the flow velocity of Artemisinin be 200 L/h to wash-out in described step (4), and the flow velocity that wash-out contains assorted Artemisinin is 300 L/h, and the flow velocity that wash-out does not have assorted Artemisinin is 600 L/h.
As priority scheme, making with extra care in the described step (6) further comprises the steps:
(6.1) the Artemisinin crude product adds described Artemisinin crude product amount 5%～10% gac stirring at normal temperature decolouring with 60 times～80 times (L/ ㎏) 95% methyl alcohol stirring and dissolving;
(6.2) filter, filter residue 95% washed with methanol, washing lotion is incorporated suction filtration liquid into, and the smart filter of millipore filtration gets clear filtrate;
(6.3) 50 ℃～60 ℃ vacuum concentration of clear filtrate;
(6.4) placed 12 hours, crystallization, centrifugal, dry more than 60 ℃.
As priority scheme, this extracting and purifying method also comprises step (7) silica gel activating, and described activation is 700 ℃～750 ℃ oven dry with silica gel.
The present invention compared with prior art has the following advantages and beneficial effect:
(1) Artemisinin extracting and purifying method of the present invention contains assorted Artemisinin, does not have the enrichment degree height of assorted Artemisinin, and the purity of not having assorted Artemisinin crude product can reach more than 95%, can reach more than 98% after refining.
(2) Artemisinin extracting and purifying method of the present invention, the omnidistance extraction yield from the sweet wormwood grass to the Artemisinin elaboration can reach more than 75%.
(3) the Artemisinin its related substances that obtains of Artemisinin extracting and purifying method of the present invention is few, and follow-up process for refining is simple.
(4) Artemisinin extracting and purifying method of the present invention, because consumption and the ratio of silica gel have been controlled in strictness, so the silica gel consumption is little, and activation method is simple.
Embodiment
Be described in further detail below in conjunction with the present invention of embodiment, but embodiments of the present invention are not limited thereto.Not breaking away under the above-mentioned technological thought situation of the present invention, according to ordinary skill knowledge and customary means, make various replacements and change, all should comprise within the scope of the invention.
Embodiment 1
The extracting and purifying method of Artemisinin is mainly to pulverize that the sweet wormwood grass makes medicinal extract, changes cream, spice, oven dry, dress post, towards post, wash-out etc., specific as follows:
(1) gets sweet wormwood grass 2200 ㎏, pulverized 10 mesh sieves, add No. 6 solvent oils of 8 times of volumes (L/ ㎏), 55 ℃ of refluxing extraction 3.5 hours concentrate the vat liquor normal pressure, reclaim nearly No. 50%6 solvent oils, concentrate behind the moisture again that concentrating under reduced pressure reclaims No. 6 solvent oils, receive cream and get Artemisinin medicinal extract;
(2) hot melt cream below 70 ℃ in putting into of the medicinal extract cream pond dissolves to medicinal extract and to be fluid state and can freely to topple over to feed intake and get final product; Take by weighing medicinal extract by 110 ㎏/post;
Method with test silica gel water regain is measured the silica gel activity, obtains the active 1.5/ml of being of silica gel.Press the active 1.5/ml of silica gel amount=medicinal extract amount 110 ㎏ * silica gel, the silica gel amount that calculates for spice is 198 ㎏; Medicinal extract mixing silica gel, 60 ℃ of oven dry get spice silica gel;
(3) No. 6 solvent oil 9300L and ethyl acetate 700L(V/V=93:7) mix, obtain mixed solvent as elutriant (hereinafter to be referred as No. 67 oil); 1.2 times of (2) silica gel amount take by weighing silica gel 198 ㎏ set by step; To adorn post silica gel and aforementioned elutriant 700L mixes thoroughly, the pillar of packing into;
(4) the described spice silica gel of step (2) is tiled on the interior described silicagel column of step (3) of post, left standstill 30 minutes, do elutriant with No. 67 oil, with the flow velocity of 300L/h towards post, cross post with the speed of 200L/h after finishing towards post, contain assorted Artemisinin and do not have assorted Artemisinin with thin-layer chromatography monitoring, wherein to contain the flow velocity of assorted Artemisinin be 300L/h to wash-out, and the flow velocity that wash-out does not have assorted Artemisinin is 600L/h;
Particularly, the thin-layer chromatography monitoring method is collected the liquid points on the silica gel G version for getting different sections, and with sherwood oil: ethyl acetate (3:1) is launched, and develops the color with 1% vanillin food grade,1000.000000ine mesh (65%) sulphuric acid soln; The spot that shows same color in contrast liquid phase position together is Artemisinin; Otherwise, no Artemisinin.
(5) collect respectively no Artemisinin, contain assorted Artemisinin and do not have the Artemisinin elutriant of mixing, be concentrated into 60 ℃ of the 5%-10%(temperature of original volume respectively), placed 24 hours, crystallization, centrifugal, get Artemisinin crude product 10.35 ㎏;
(6) Artemisinin crude product 10.35 ㎏ add 95% methyl alcohol (Artemisinin coarse crystal volume 60 times) the stirring at normal temperature dissolving in 30 minutes of 621L, add the gac stirring at normal temperature decolouring in 30 minutes of Artemisinin crude product weight 10%; Decolouring back suction filtration, filter residue are with 3 95% washed with methanol of accompanying volume, and washing lotion is incorporated suction filtration liquid into, filters with 0.45 micron millipore filtration essence, obtains clear filtrate; 50 ℃ of vacuum concentration of filtrate whenever concentrate 2h and receive liquid once; Place 12h, crystallization, centrifugal; After centrifugal, at 50 ℃ of dry 3h, get Artemisinin elaboration 9.21 ㎏.
It is 75.21% that the whole process of present method from the sweet wormwood grass to the Artemisinin elaboration is extracted the rate of transform.
Can get after testing: Artemisinin purity is 99.5%.Detection method is: high performance liquid chromatography, and chromatographic condition is as follows:
Acetonitrile: water (7:3) for flow to, 210mm is for detecting wavelength, C
18Silicagel column, 25 ℃ of flow velocity 1ml/min column temperatures.
Embodiment 2
This embodiment only is the different of partial parameters with the difference of embodiment 1, and the extracting and purifying method of Artemisinin is as follows:
(1) gets sweet wormwood grass 2200 ㎏, pulverized 20 mesh sieves, add No. 6 solvent oils of 12 times of volumes (L/ ㎏), 50 ℃ of refluxing extraction 5 hours concentrate the vat liquor normal pressure, reclaim nearly No. 50%6 solvent oils, concentrate to divide behind the water again that concentrating under reduced pressure reclaims No. 6 solvent oils, receive cream and get Artemisinin medicinal extract;
(2) hot melt cream below 70 ℃ in putting into of the medicinal extract cream pond dissolves to medicinal extract and to be fluid state and can freely to topple over to feed intake and get final product; Take by weighing medicinal extract by 110 ㎏/post;
Method with embodiment 1 is measured the silica gel activity, obtains the active 1.5g/ml of being of silica gel.Press the active 1.5g/ml of silica gel amount=medicinal extract amount 110 ㎏ * silica gel, the silica gel amount that calculates for spice is 198 ㎏; Medicinal extract mixing silica gel, 50 ℃ of oven dry get spice silica gel;
(3) No. 6 solvent oil 9700L and ethyl acetate 300L(V/V=97:3) mix, obtain No. 67 oily elutriants (hereinafter to be referred as); 1.5 times of (2) silica gel amount take by weighing silica gel 247.5 ㎏ set by step; To adorn post silica gel and aforementioned elutriant 700L mixes thoroughly, the pillar of packing into;
(4) the described spice silica gel of step (2) is tiled on the described silicagel column of step (3), left standstill 30 minutes, do elutriant with No. 67 oil, with the flow velocity of 300L/h towards post, cross post with the speed of 200L/h after finishing towards post, contain assorted Artemisinin and do not have assorted Artemisinin with thin-layer chromatography monitoring, wherein to contain the flow velocity of assorted Artemisinin be 300L/h to wash-out, and the flow velocity that wash-out does not have assorted Artemisinin is 600L/h;
The thin-layer chromatography monitoring method is not being given unnecessary details here with embodiment 1.
(5) collect respectively no Artemisinin, contain assorted Artemisinin and do not have the Artemisinin elutriant of mixing, be concentrated into 55 ℃ of the 5%-10%(temperature of original volume respectively), placed 24 hours, crystallization, centrifugal, get Artemisinin crude product 10.46 ㎏;
(6) Artemisinin crude product 10.46 ㎏ add 95% methyl alcohol (Artemisinin coarse crystal volume 80 times) the stirring at normal temperature dissolving in 30 minutes of 836L, add 10% gac of Artemisinin crude product weight, stirring at normal temperature decolouring in 30 minutes; Decolouring back suction filtration, filter residue are with 95% washed with methanol of 2 times of volumes, and washing lotion is incorporated suction filtration liquid into, filters with 0.45 micron millipore filtration essence, obtains clear filtrate; 50 ℃ of vacuum concentration of filtrate whenever concentrate 2h and receive liquid once; Place 12h, crystallization, centrifugal; The centrifugal crystal that goes out gets Artemisinin elaboration 9.03 ㎏ at 55 ℃ of dry 3h.
The omnidistance extraction yield of present method from the sweet wormwood grass to the Artemisinin elaboration is 73.70%.
Can get after testing: Artemisinin purity is 99.66%.Detection method is with embodiment 1.
Embodiment 3
This embodiment only is the different of partial parameters with the difference of embodiment 1 and embodiment 2, and the extracting and purifying method of Artemisinin is as follows:
(1) gets sweet wormwood grass 2200 ㎏, pulverized 10 mesh sieves, add No. 6 solvent oils of 10 times of volumes (L/ ㎏), 50 ℃ of refluxing extraction 3 hours concentrate the vat liquor normal pressure, reclaim nearly No. 50%6 solvent oils, concentrate to divide behind the water again that concentrating under reduced pressure reclaims No. 6 solvent oils, receive cream and get Artemisinin medicinal extract;
(2) hot melt cream below 70 ℃ in putting into of the medicinal extract cream pond dissolves to medicinal extract and to be fluid state and can freely to topple over to feed intake and get final product; Take by weighing medicinal extract by 110 ㎏/post;
Method with embodiment 1 is measured the silica gel activity, obtains the active 1.5g/ml of being of silica gel.Press the active 1.5g/ml of silica gel amount=medicinal extract amount 110 ㎏ * silica gel, the silica gel amount that calculates for spice is 198 ㎏; Medicinal extract mixing silica gel, 55 ℃ of oven dry get spice silica gel;
(3) No. 6 solvent oil 9300L and ethyl acetate 700L(V/V=93:7) mix, obtain No. 67 oily elutriants (hereinafter to be referred as); 1.1 times of (2) silica gel amount take by weighing silica gel 181.5 ㎏ set by step; To adorn post silica gel and aforementioned elutriant 700L mixes thoroughly, the pillar of packing into;
(4) the described spice silica gel of step (2) is tiled on the described silicagel column of step (3), left standstill 30 minutes, do elutriant with No. 67 oil, with the flow velocity of 300L/h towards post, cross post with the speed of 200L/h after finishing towards post, contain assorted Artemisinin and do not have assorted Artemisinin with thin-layer chromatography monitoring, wherein to contain the flow velocity of assorted Artemisinin be 300L/h to wash-out, and the flow velocity that wash-out does not have assorted Artemisinin is 600L/h;
The thin-layer chromatography monitoring method is not being given unnecessary details here with embodiment 1.
(5) collect respectively no Artemisinin, contain assorted Artemisinin and do not have the Artemisinin elutriant of mixing, be concentrated into 55 ℃ of the 5%-10%(temperature of original volume respectively), placed 24 hours, crystallization, centrifugal, get Artemisinin crude product 10.11 ㎏;
(6) Artemisinin crude product 10.11 ㎏ add 95% methyl alcohol (Artemisinin coarse crystal volume 70 times) the stirring at normal temperature dissolving in 30 minutes of 707.7L, add 10% gac of Artemisinin crude product weight, stirring at normal temperature decolouring in 30 minutes; Decolouring back suction filtration, filter residue are with 95% washed with methanol of 3 times of volumes, and washing lotion is incorporated suction filtration liquid into, filters with 0.45 micron millipore filtration essence, obtains clear filtrate; 50 ℃ of vacuum concentration of filtrate whenever concentrate 2h and receive liquid once; Place 12h, crystallization, centrifugal; The centrifugal crystal that goes out gets Artemisinin elaboration 9.0 ㎏ at 60 ℃ of dry 3h.
The omnidistance extraction yield of present method from the sweet wormwood grass to the Artemisinin elaboration is 73.45%.
Can get after testing: Artemisinin purity is 99.86%.Detection method is with embodiment 1.
Embodiment 4
This embodiment only is the different of partial parameters with the difference of embodiment 1, embodiment 2 and embodiment 3, and the several important parameters among the embodiment have been carried out test and research.The extracting and purifying method of Artemisinin is as follows:
(1) gets sweet wormwood grass 2200 ㎏, pulverized 10 mesh sieves, add No. 6 solvent oils of 12 times of volumes (L/ ㎏), 50 ℃ of refluxing extraction 3.5 hours concentrate the vat liquor normal pressure, reclaim nearly No. 50%6 solvent oils, concentrate to divide behind the water again that concentrating under reduced pressure reclaims No. 6 solvent oils, receive cream and get Artemisinin medicinal extract; Hot melt cream below 70 ℃ in putting into of the medicinal extract cream pond dissolves to medicinal extract and to be fluid state and can freely to topple over to feed intake and get final product;
(2) take by weighing medicinal extract by 110 ㎏/post;
Method with embodiment 1 is measured the silica gel activity, obtains the active 1.5g/ml of being of silica gel.Press the active 1.5g/ml of silica gel amount=medicinal extract amount 110 ㎏ * silica gel, the silica gel amount that calculates for spice is 198 ㎏; Medicinal extract mixing silica gel, 50 ℃ of oven dry get spice silica gel;
(3) No. 6 solvent oil 9700L and ethyl acetate 300L(V/V=97:3) mix, obtain No. 67 oily elutriants (hereinafter to be referred as); 1.0 times of (2) silica gel amount take by weighing silica gel 165 ㎏ set by step; To adorn post silica gel and aforementioned elutriant 700L mixes thoroughly, the pillar of packing into;
(4) the described spice silica gel of step (2) is tiled on the described silicagel column of step (3), left standstill 30 minutes, do elutriant with No. 67 oil, with the flow velocity of 300L/h towards post, cross post with the speed of 200L/h after finishing towards post, contain assorted Artemisinin and do not have assorted Artemisinin with thin-layer chromatography monitoring, wherein to contain the flow velocity of assorted Artemisinin be 300L/h to wash-out, and the flow velocity that wash-out does not have assorted Artemisinin is 600L/h;
The thin-layer chromatography monitoring method is with embodiment 1.
(5) collect respectively no Artemisinin, contain assorted Artemisinin and do not have the Artemisinin elutriant of mixing, be concentrated into 60 ℃ of the 5%-10%(temperature of original volume respectively), placed 24 hours, crystallization, centrifugal, get Artemisinin crude product 10.165 ㎏;
(6) Artemisinin crude product 10.165 ㎏ add 95% methyl alcohol (Artemisinin coarse crystal volume 80 times) the stirring at normal temperature dissolving in 30 minutes of 852L, add 10% gac of Artemisinin crude product weight, stirring at normal temperature decolouring in 30 minutes; Decolouring back suction filtration, filter residue are with 95% washed with methanol of 3 times of volumes, and washing lotion is incorporated suction filtration liquid into, filters with 0.45 micron millipore filtration essence, obtains clear filtrate; 50 ℃ of vacuum concentration of filtrate whenever concentrate 2h and receive liquid once; Place 12h, crystallization, centrifugal; The centrifugal crystal that goes out gets Artemisinin elaboration 9.19 ㎏ at 55 ℃ of dry 3h.
The omnidistance extraction yield of present method from the sweet wormwood grass to the Artemisinin elaboration is 75.05%.
Can get after testing: Artemisinin purity is 99.86%.Detection method is with embodiment 1.
From above-mentioned several embodiment, we can find out that the extracting and purifying method core point of Artemisinin is the following aspects: when 1, medicinal extract is mixed silica gel the ratio of medicinal extract consumption and silica gel consumption and mix cream after water content; 2, No. 67 oily proportionings of eluent and elution speed; 3, the consumption of silica gel in wet method dress post, dry feed and the dress post front pillar; 4, the speed of solvent elution Artemisinin; 5, the temperature in Tuo Se activated carbon dosage and when decolouring; 6, Jing Zhi molten coal concentration and proportioning and refining temperature; 7, the pulverizing order number of raw material.Above-mentioned key element all can have influence on extraction yield and the purity of Artemisinin, and below with the different ratios of silica gel amount, the silica gel amount that is used for spice and the silica gel amount that is used for the dress post and different spice silica gel bake out temperatures the experiment of being correlated with have been done in the influence of Artemisinin extraction and purification process with regard to different spices as follows.
The present invention studies the influence of Artemisinin extraction and purification process with the silica gel amount different spices, below is the part summary of the present invention to result of study:
Totally 5 groups for the treatment of group, the concrete steps of Artemisinin extraction and purification process such as embodiment 1 investigate step (2) and are used for the silica gel amount difference of spice to the influence of extraction yield and purity.Wherein the 1st group of silica gel amount that is used for spice is identical with embodiment 1, and the 2nd group is 195 ㎏, and the 3rd group is 180 ㎏, the 4th group of 150 ㎏, and the 5th group is 135 ㎏.Every group of extracting method got average for parallel three parts, respectively organized extraction yield, measures content with HPLC, the results are shown in Table 1.
Table 1 spice silica gel amount is to the influence of Artemisinin extraction yield and purity
| Group | 1 | 2 | 3 | 4 | 5 |
| Extraction yield % | 75.03 | 73.60 | 71.02 | 69.96 | 66.32 |
| Related substance | 0.98% | 1.00% | 1.36% | 1.49% | 3.18% |
By table 1 as seen, the 1st group extraction efficiency is the highest, and the Artemisinin elaboration related substance that obtains is minimum.Reason is that the present invention is by the amount of control for the silica gel of spice, and the adsorption and desorption of effectively having controlled Artemisinin medicinal extract and silica gel is attached, and the Artemisinin loss is few, the enrichment degree height.
The present invention studies the influence of Artemisinin extraction and purification process with the different ratios of the silica gel amount that is used for the dress post the silica gel amount that is used for spice, below is the part summary of the present invention to result of study:
Totally 5 groups for the treatment of group, the concrete steps of Artemisinin extraction and purification process such as embodiment 4 investigate the different ratios (M value) of step (3) the silica gel amount that is used for spice and the silica gel amount that is used for the dress post to the influence of Artemisinin extraction and purification process.
The 1st group of M=1.2 wherein, the 2nd group of M=1.5, the 3rd group of M=1.1, the 4th group of M=1.0, the 5th group of M=1.6.Every group of extracting method got average for parallel three parts, respectively organized extraction yield, measures content with HPLC, the results are shown in Table 2.
Table 2 M value value is to the influence of Artemisinin extraction yield and purity
| Group | 1 | 2 | 3 | 4 | 5 |
| Extraction yield % | 75.21 | 73.70 | 73.45 | 69.66 | 68.32 |
| Related substance % | 0.92 | 0.96 | 0.93 | 3.08 | 2.36 |
By table 2 as seen, the 1st, 2,3 group, the extraction yield height of Artemisinin, its related substances is few.And the 4th group since the M value less than span of control of the present invention, the extraction yield of Artemisinin is low, Artemisinin is difficult to separate with impurity, its related substances height; The 5th group since M value greater than span of control of the present invention, elution time is grown (greater than 150 hours), extraction yield is low, its related substances is also high.
The present invention studies the influence of Artemisinin extraction and purification process different spice silica gel bake out temperatures, below is the part summary of the present invention to result of study:
4 groups for the treatment of group are pressed embodiment 1 technology, make the spice silica gel that step (2) obtains, and claim the method for deciding to measure, calculate the artemislnin content of oven dry front and back with precision, investigate the described spice silica gel of step (2) bake out temperature difference to the influence of extraction yield and purity.Wherein the 1st group of bake out temperature is 50 ℃, and the 2nd group is 60 ℃, and the 3rd group is 65 ℃, the 4th group 70 ℃.Every group of extracting method got average for parallel three parts, the results are shown in Table 3.
Table 3 bake out temperature is to the influence of artemislnin content
| Group | 1 | 2 | 3 | 4 |
| % before the oven dry | 99.65 | 99.52 | 99.37 | 99.62 |
| Oven dry back % | 99.43 | 99.30 | 99.00 | 98.50 |
| Wastage rate % | 0.22 | 0.20 | 0.37 | 1.12 |
By table 3 as seen, the bake out temperature of control spice silica gel is one of key process parameter in the Artemisinin extraction and purification process.50 ℃-60 ℃ of the bake out temperature of the present invention by screening spice silica gel have effectively been avoided the loss of artemislnin content.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction, and every foundation technical spirit of the present invention all falls within protection scope of the present invention any simple modification, equivalent variations that above embodiment does.
Claims (9)
1. the extracting and purifying method of an Artemisinin is characterized in that, may further comprise the steps:
(1) the sweet wormwood grass meal is broken, adds 8 times～12 times (L/ ㎏) No. 6 solvent oils, 50 ℃～55 ℃ refluxing extraction 3 hours～5 hours, and extracting solution concentrates, and receives cream and gets Artemisinin medicinal extract;
(2) medicinal extract hot melt cream below 70 ℃; Take by weighing medicinal extract behind the hot melt by 110 ㎏/post, medicinal extract mixing silica gel, oven dry gets spice silica gel; Described silica gel amount=medicinal extract amount * silica gel activity, described silica gel activity are the required silica gel amount of every suction 1ml water;
(3) No. 6 solvent oils and ethyl acetate are done elutriant with the solvent of 93～97:7～3(V/V) mix, and wet method dress post gets silicagel column, the described silica gel amount * M of described dress post silica gel amount=step (2), described M=1.1～1.5;
(4) the described spice silica gel of step (2) is tiled on the interior described silicagel column of step (3) of post, leave standstill, do elutriant with No. 6 solvent oils and ethyl acetate with the solvent of 93～97:7～3(V/V) mix, must not have Artemisinin, contain assorted Artemisinin and do not have assorted Artemisinin towards post, respectively to no Artemisinin, contain assorted Artemisinin and do not have the Artemisinin of mixing and carry out wash-out;
(5) collect elutriant, concentrate, place crystallization in 24 hours, centrifugal, get the Artemisinin crude product;
(6) the described Artemisinin crude product of step (5) is made with extra care.
2. the extracting and purifying method of a kind of Artemisinin according to claim 1 is characterized in that, the sweet wormwood grass meal in the described step (1) is broken to be that the sweet wormwood grass is crossed the 10-20 mesh sieve.
3. the extracting and purifying method of a kind of Artemisinin according to claim 1 and 2 is characterized in that, the bake out temperature in the described step (2) is 50 ℃～60 ℃.
4. the extracting and purifying method of a kind of Artemisinin according to claim 3 is characterized in that, in described step (2) and step (3), silica gel is 100 orders ~ 200 order silica gel.
5. the extracting and purifying method of a kind of Artemisinin according to claim 4 is characterized in that, in described step (3), and M=1.3.
6. the extracting and purifying method of a kind of Artemisinin according to claim 5 is characterized in that, the flow velocity towards post in described step (4) is 300L/h.
7. the extracting and purifying method of a kind of Artemisinin according to claim 6, it is characterized in that, not have the flow velocity of Artemisinin be 200 L/h to wash-out in described step (4), and the flow velocity that wash-out contains assorted Artemisinin is 300 L/h, and the flow velocity that wash-out does not have assorted Artemisinin is 600 L/h.
8. the extracting and purifying method of a kind of Artemisinin according to claim 7 is characterized in that, making with extra care in the described step (6) further comprises the steps:
(6.1) the Artemisinin crude product adds described Artemisinin crude product amount 5%～10% gac stirring at normal temperature decolouring with 60 times～80 times (L/ ㎏) 95% methyl alcohol stirring and dissolving;
(6.2) filter, filter residue 95% washed with methanol, washing lotion is incorporated suction filtration liquid into, and the smart filter of millipore filtration gets clear filtrate;
(6.3) 50 ℃～60 ℃ vacuum concentration of clear filtrate;
(6.4) placed 12 hours, crystallization, centrifugal, dry more than 60 ℃.
9. the extracting and purifying method of a kind of Artemisinin according to claim 8 is characterized in that, also comprises step (7) silica gel activating, and described activation is 700 ℃～750 ℃ oven dry with silica gel.
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| CN103694249A (en) * | 2013-12-28 | 2014-04-02 | 湘西自治州奥瑞克医药化工有限责任公司 | Production technology for extracting artemisinin from artemisia annua |
| WO2016110864A1 (en) * | 2015-01-05 | 2016-07-14 | Mantri Ashish Ompakash | Process for purification of artemisinin and other constituents from artemisia annua in high yield and high purity |
| CN106543199A (en) * | 2016-09-24 | 2017-03-29 | 合肥信达膜科技有限公司 | A kind of arteannuin film extraction process |
| CN107235989A (en) * | 2017-06-21 | 2017-10-10 | 禹州市天源生物科技有限公司 | A kind of extraction and purification process of qinghaosu |
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| CN107793430A (en) * | 2017-12-25 | 2018-03-13 | 禹州市天源生物科技有限公司 | A kind of method of purification of qinghaosu |
| CN110038322A (en) * | 2019-04-24 | 2019-07-23 | 上海复旦复华药业有限公司 | A kind of tripterygium glycosides chromatographic silica gel dress column method |
| CN111141846A (en) * | 2019-12-31 | 2020-05-12 | 广西仙草堂制药有限责任公司 | Method for measuring content of artemisinin in sweet wormwood herb |
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| CN107793430A (en) * | 2017-12-25 | 2018-03-13 | 禹州市天源生物科技有限公司 | A kind of method of purification of qinghaosu |
| CN110038322A (en) * | 2019-04-24 | 2019-07-23 | 上海复旦复华药业有限公司 | A kind of tripterygium glycosides chromatographic silica gel dress column method |
| CN111141846A (en) * | 2019-12-31 | 2020-05-12 | 广西仙草堂制药有限责任公司 | Method for measuring content of artemisinin in sweet wormwood herb |
| CN115466647A (en) * | 2022-08-12 | 2022-12-13 | 湖南斯依康生物科技有限公司 | Preparation method of itching-relieving essential oil |
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