CN103073611B - A kind of ginseng saponin C-K hemi-hydrate crystalline and preparation method - Google Patents
A kind of ginseng saponin C-K hemi-hydrate crystalline and preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of ginseng saponin C-K hemi-hydrate crystalline and preparation method, ginseng saponin C-K raw material is joined in the mixed solvent of acetone and water, adopt the mode of crystallisation by cooling, in process of cooling, crystal seed is joined in the supersaturated solution of ginseng saponin C-K, it is induced to go out crystalline substance, control the nucleation of crystal, promote crystal growth.The 2 θ values that the powdery diffractometry characteristic peak of products obtained therefrom ginseng saponin C-K hemi-hydrate crystalline is corresponding are 5.4 ± 0.2,6.6 ± 0.2,11.0 ± 0.2,12.6 ± 0.2,13.2 ± 0.2,14.5 ± 0.2,15.5 ± 0.2,15.9 ± 0.2,17.1 ± 0.2,20.6 ± 0.2.The present invention prepares ginseng saponin C-K semihydrate by the method for crystallisation by cooling, improves the crystallization yield of C-K; Avoid breaking out nucleation in crystallisation process, obtain even particle size distribution, stable product.
Description
Technical field
The present invention relates to a kind of ginseng saponin C-K hemi-hydrate crystalline and preparation method, specifically a kind of method adopting crystallisation by cooling to produce ginseng saponin C-K semihydrate.The ginseng saponin C-K semihydrate obtained by this method is long pillar-shaped crystal, and even particle size distribution do not occur coalescent, and yield is high.
Background technology
Ginseng is widely used in the traditional Chinese medicine of curing the disease that takes care of health simply, and the formidable enemy's cancer for human health has certain therapeutic action, this with it on secreting, the impact of the aspect such as immunity and metabolism is relevant.Ginsenoside is a kind of main active ingredient of ginseng, there is the effects such as the breeding of T suppression cell tumour cell, anti-metastasis, its drug action has diversity, for neural system, small intestine transmitting function, internal secretion, immunity system etc. all tool have a certain impact, also there is antidotal effect, it is divided into protopanoxadiol class, Protopanaxatriol's saponins and Oleanolic Acid saponins (Yang Na etc., ginseng antitumor and the restraining effect to chemicotherapy remote effect, Shandong tumour magazine, 1995(4); Wang Hainan, personal saponin(e pharmacological research progress, Chinese Clinical pharmacology and therapeutics, 2006(11)).
(molecular formula is C to ginseng saponin C-K
36h
62o
8) its structural formula is as follows:
For (2OS)-O-β-D-protopanoxadiol glucoside, belong to glycols saponin(e, do not exist in natural ginseng, being the meta-bolites of other diol type ginsenoside in people's enteron aisle, is one of main active ingredient of ginseng.Research show C-K have Tumor suppression growth and transfer, anti-transgenation, cell death inducing isoreactivity.At present, the pharmaceutical composition of ginseng saponin C-K can oral or drug administration by injection (CN1623554).
Ginseng saponin C-K can be obtained by the method for enzymatic conversion.Korean Patent 1020030037005 discloses a kind of method preparing ginsenoside, first by water-soluble for ginseng Saponin/TSM or organic solution, then add shaddock ped enzyme or polygalacturonase and carry out conversion preparation, last shaddock ped enzyme is separated by Penicillium notatum, and polygalacturonase is separated by aspergillus tubigensis; Korean Patent 1020080094275 discloses a kind of method using zymin citrozym process ginsenoside to prepare, and the condition of process is 4.0-6.0 in pH value, and temperature is 48-52 DEG C.
The report of present this area also not in ginseng saponin C-K hydrate in the solution crystallization, we obtain a kind of semihydrate of ginseng saponin C-K in the solution, its X-ray powder diffraction characteristic peak is obviously different from other solvated compounds, can not occur coalescent, preparation method is simpler.
Summary of the invention
The invention provides semihydrate of a kind of ginseng saponin C-K and preparation method thereof, its technical scheme is as follows:
Prepare a method for ginseng saponin C-K hemi-hydrate crystalline, step is as follows:
1) ginseng saponin C-K crude product is joined in acetone/water mixed solvent, be warming up to more than 50 DEG C and it is all dissolved, obtain ginseng saponin C-K saturated solution;
2) by saturated solution obtained above with 0.05 DEG C/min ~ 0.2 DEG C/min cooling, in solution, add crystal seed when being down to 42 ~ 37 DEG C, and maintain in this temperature and stir 60min;
3) after constant temperature stirs and terminates, be down to 4 DEG C with the cooling rate of 0.1 DEG C/min ~ 0.3 DEG C/min, at 4 DEG C of growing the grains 1 hour, filtration washing, in vacuum drying oven, 45 ~ 65 DEG C of dryings 1 hour, obtain ginseng saponin C-K hemi-hydrate crystalline.
Described acetone and water mixed solvent mass ratio are 10:1 to 1:2.The massfraction adding the amount of crystal seed is initially add CK crude product quality 0.5% ~ 5%.The water-content of products obtained therefrom ginseng saponin C-K hemi-hydrate crystalline is 1.4% ~ 1.8%.
The present invention prepares ginseng saponin C-K hemi-hydrate crystalline, it is characterized in that: the 2 θ values that the powdery diffractometry characteristic peak of products obtained therefrom ginseng saponin C-K hemi-hydrate crystalline is corresponding are 5.4 ± 0.2,6.6 ± 0.2,11.0 ± 0.2,12.6 ± 0.2,13.2 ± 0.2,14.5 ± 0.2,15.5 ± 0.2,15.9 ± 0.2,17.1 ± 0.2,20.6 ± 0.2.
Products obtained therefrom ginseng saponin C-K semihydrate, use Fourier transform infrared spectroscopy meter to detect, the characteristic peak obtained is respectively 3359cm
-1, 2948cm
-1, 1709cm
-1, 1656cm
-1, 1453cm
-1, 1389cm
-1, 1076cm
-1, 1034cm
-1, 641cm
-1.
Products obtained therefrom ginseng saponin C-K hemi-hydrate crystalline is long column shape.
In the preparation method of ginseng saponin C-K semihydrate of the present invention, the mass ratio using the mixed solvent of acetone and water is 10:1 to 1:2, use mixed solvent ginseng saponin C-K to be had to the effect of solubilising, ginseng saponin C-K solubleness in a solvent can be increased, thus improve yield.If the ratio of mixed solvent is lower than 10:1 or higher than 1:2, then the solubleness of C-K is too little, and the concentration of initial soln is too little, makes final productive rate too low.
In the preparation method of ginseng saponin C-K semihydrate of the present invention, by add in the supersaturated solution of ginseng saponin C-K initially add CK crude product quality 0.5% ~ 5% crystal seed, the degree of supersaturation of solution is made to maintain lower level, thus effectively control crystal nucleation, inhibit product to break out nucleation, promote crystal growth.If the crystal seed added is less than 0.5%, the vegetative point of system can be made very little, produce a large amount of thin brilliant; If the crystal seed added is greater than 5%, makes the vegetative point of system too much, thus the main granularity of crystal is diminished.
In the preparation method of ginseng saponin C-K semihydrate of the present invention, be cooled to 42 ~ 37 DEG C and add crystal seed in the supersaturated solution of ginseng saponin C-K, if temperature is too high, the degree of supersaturation in solution is too little, adds the effect that crystal seed can not reach graining; If temperature is too low, the degree of supersaturation in solution is excessive, after adding crystal seed, can produce thin crystalline substance in solution.
In the preparation method of ginseng saponin C-K semihydrate of the present invention, the temperature adopted in vacuum drying process is 45 ~ 65 DEG C, if bake out temperature is lower than 45 DEG C, can extend manufacture cycle, acetone solvent also has residual; If bake out temperature is higher than 65 DEG C, then energy consumption increases, and has higher requirement to equipment
In the preparation method of ginseng saponin C-K semihydrate of the present invention, crystallizer is connected with refrigerating unit, the timely condensation of solvent being convenient to volatilize is got off, and reduces the vapor pressure in crystallizer.
Ginseng saponin C-K semihydrate prepared by the present invention, use Cu-K α radiation, the XRD powdery diffractometry represented with 2 θ angles 5.4 ± 0.2,6.6 ± 0.2,11.0 ± 0.2,12.6 ± 0.2,13.2 ± 0.2,14.5 ± 0.2,15.5 ± 0.2,15.9 ± 0.2,17.1 ± 0.2,20.6 ± 0.2 have characteristic peak.
Ginseng saponin C-K semihydrate prepared by the present invention, use Nicolet Magna560 Fourier transform infrared spectroscopy meter to detect, the characteristic peak obtained is respectively 3359cm
-1, 2948cm
-1, 1709cm
-1, 1656cm
-1, 1453cm
-1, 1389cm
-1, 1076cm
-1, 1034cm
-1, 641cm
-1.Wherein, 3359cm
-1and 2948cm
-1peak be because the stretching vibration of O-H key and c h bond is formed, at 1656cm respectively
-1the small peak existed is then the stretching vibration of C=C key.In addition, CH
3and CH
2asymmetric deformation appear at 1453cm
-1and 1389cm
-1.At 1076cm
-1and 1034cm
-1the strong absorption peak occurred is the stretching vibration due to C-O key, and at 641cm
-1the absorption peak at place is the distortion formation of C-C key.
The invention has the beneficial effects as follows the method production ginseng saponin C-K hemi-hydrate crystalline by crystallisation by cooling in the mixed solvent of acetone and water, improve the crystallization yield of ginseng saponin C-K semihydrate; Avoid breaking out nucleation in crystallisation process, obtain even particle size distribution, stable product.
Accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum of the ginseng saponin C-K semihydrate that application present invention process obtains; Length axis represents diffracted intensity (counts), and axis of abscissa represents diffraction angle (2 θ).
Fig. 2 is that the Fourier of the ginseng saponin C-K semihydrate that application present invention process obtains changes infared spectrum;
Fig. 3 is the electron scanning micrograph of the ginseng saponin C-K semihydrate that application present invention process obtains.
Embodiment
Embodiment 1:
The method of this examples produce ginseng saponin C-K hemi-hydrate crystalline specifically comprises the following steps:
1) mass ratio 22.3950g ginseng saponin C-K crude product being joined acetone and water is in 4:1 mixed solvent 290ml, at 50 DEG C, it is all dissolved, be warming up to 53 DEG C again to ensure that ginseng saponin C-K all dissolves, and add condensation reflux unit in order to avoid solvent evaporates;
2) saturated solution obtained above is lowered the temperature, lower the temperature with 0.1 DEG C/min, when being down to 40 DEG C, add the crystal seed of 1%, maintain 60min, to run out of the degree of supersaturation in solution in the temperature adding crystal seed;
3) after constant temperature stirs and terminates, continue to be down to 4 DEG C with the cooling rate of 0.2 DEG C/min, at 4 DEG C of growing the grains 1 hour, filtration washing, at 50 DEG C, vacuum tightness is under 0.08Mp-0.1Mp dry 1 hour, and obtain product ginseng saponin C-K semihydrate, yield is greater than 92%.
Products obtained therefrom X-ray powder diffraction carries out characterizing (2 θ value): 5.3,6.6,11.2,12.5,13.3,14.6,15.4,16.0,17.3,20.8.
Infrared spectra: 3358cm
-1, 2946cm
-1, 1712cm
-1, 1658cm
-1, 1453cm
-1, 1390cm
-1, 1073cm
-1, 1036cm
-1, 642cm
-1.
It is 1.5% that products obtained therefrom uses Karl_Fischer method to record its moisture content.
Embodiment 2:
The method of this examples produce ginseng saponin C-K hemi-hydrate crystalline specifically comprises the following steps:
1) mass ratio 15.0205g ginseng saponin C-K crude product being joined acetone and water is in 10:1 mixed solvent 320ml, at 50 DEG C, it is all dissolved, be warming up to 53 DEG C again to ensure that ginseng saponin C-K all dissolves, and add condensation reflux unit in order to avoid solvent evaporates;
2) saturated solution obtained above is lowered the temperature, lower the temperature with 0.05 DEG C/min, when being down to 42 DEG C, add the crystal seed of 0.5%, maintain 60min, to run out of the degree of supersaturation in solution in the temperature adding crystal seed;
3) after constant temperature stirs and terminates, continue to be down to 4 DEG C with the cooling rate of 0.1 DEG C/min, at 4 DEG C of growing the grains 1 hour, filtration washing, at 45 DEG C, vacuum tightness is under 0.08Mp-0.1Mp dry 1 hour, and obtain product ginseng saponin C-K semihydrate, yield is greater than 91%.
Products obtained therefrom X-ray powder diffraction carries out characterizing (2 θ value): 5.3,6.4,11.2,12.8,13.1,14.3,15.6,15.8,17.2,20.8.
Infrared spectra: 3359cm
-1, 2948cm
-1, 1709cm
-1, 1656cm
-1, 1453cm
-1, 1389cm
-1, 1076cm
-1, 1034cm
-1, 641cm
-1.
It is 1.4% that products obtained therefrom uses Karl_Fischer method to record its moisture content.
Embodiment 3:
The method of this examples produce ginseng saponin C-K hemi-hydrate crystalline specifically comprises the following steps:
1) mass ratio 18.1238g ginseng saponin C-K crude product being joined acetone and water is in 8:1 mixed solvent 300ml, at 50 DEG C, it is all dissolved, be warming up to 53 DEG C again to ensure that ginseng saponin C-K all dissolves, and add condensation reflux unit in order to avoid solvent evaporates;
2) saturated solution obtained above is lowered the temperature, lower the temperature with 0.2 DEG C/min, when being down to 38 DEG C, add the crystal seed of 3%, maintain 60min, to run out of the degree of supersaturation in solution in the temperature adding crystal seed;
3) after constant temperature stirs and terminates, continue to be down to 4 DEG C with the cooling rate of 0.3 DEG C/min, at 4 DEG C of growing the grains 1 hour, filtration washing, at 60 DEG C, vacuum tightness is under 0.08Mp-0.1Mp dry 1 hour, and obtain product ginseng saponin C-K semihydrate, yield is greater than 90%.
Products obtained therefrom X-ray powder diffraction carries out characterizing (2 θ value): 5.4,6.8,11.0,12.8,13.1,14.5 ± 0.2,15.6,15.8,17.0,20.6.
Infrared spectra: 3356cm
-1, 2952cm
-1, 1711cm
-1, 1656cm
-1, 1455cm
-1, 1390cm
-1, 1078cm
-1, 1036cm
-1, 642cm
-1.
It is 1.8% that products obtained therefrom uses Karl_Fischer method to record its moisture content.
Embodiment 4:
The method of this examples produce ginseng saponin C-K hemi-hydrate crystalline specifically comprises the following steps:
1) mass ratio 10.3216g ginseng saponin C-K crude product being joined acetone and water is in 1:2 mixed solvent 310ml, at 50 DEG C, it is all dissolved, be warming up to 53 DEG C again to ensure that ginseng saponin C-K all dissolves, and add condensation reflux unit in order to avoid solvent evaporates;
2) saturated solution obtained above is lowered the temperature, lower the temperature with 0.1 DEG C/min, when being down to 37 DEG C, add the crystal seed of 5%, maintain 60min, to run out of the degree of supersaturation in solution in the temperature adding crystal seed;
3) after constant temperature stirs and terminates, continue to be down to 4 DEG C with the cooling rate of 0.2 DEG C/min, at 4 DEG C of growing the grains 1 hour, filtration washing, at 65 DEG C, vacuum tightness is under 0.08Mp-0.1Mp dry 1 hour, and obtain product ginseng saponin C-K semihydrate, yield is greater than 91%.
Products obtained therefrom X-ray powder diffraction carries out characterizing (2 θ value): 5.5,6.6,11.1,12.6,13.1,14.5,15.4,15.8,17.1,20.6.
Infrared spectra: 3359cm
-1, 2946cm
-1, 1709cm
-1, 1658cm
-1, 1456cm
-1, 1392cm
-1, 1079cm
-1, 1034cm
-1, 645cm
-1.
It is 1.5% that products obtained therefrom uses Karl_Fischer method to record its moisture content.
Claims (6)
1. prepare a method for ginseng saponin C-K hemi-hydrate crystalline, it is characterized in that:
1) ginseng saponin C-K crude product is joined in acetone/water mixed solvent, be warming up to more than 50 DEG C and it is all dissolved, obtain ginseng saponin C-K saturated solution;
2) by saturated solution obtained above with 0.05 DEG C/min ~ 0.2 DEG C/min cooling, in solution, add crystal seed when being down to 42 ~ 37 DEG C, and maintain in this temperature and stir 60min;
3) after constant temperature stirs and terminates, be down to 4 DEG C with the cooling rate of 0.1 DEG C/min ~ 0.3 DEG C/min, at 4 DEG C of growing the grains 1 hour, filtration washing, in vacuum drying oven, 45 ~ 65 DEG C of dryings 1 hour, obtain ginseng saponin C-K hemi-hydrate crystalline;
The 2 θ values that the powdery diffractometry characteristic peak of gained crystal is corresponding are 5.4 ± 0.2,6.6 ± 0.2,11.0 ± 0.2,12.6 ± 0.2,13.2 ± 0.2,14.5 ± 0.2,15.5 ± 0.2,15.9 ± 0.2,17.1 ± 0.2,20.6 ± 0.2.
2. method according to claim 1, is characterized in that: acetone and water mixed solvent mass ratio are 10:1 to 1:2.
3. method according to claim 1, is characterized in that: the massfraction adding the amount of crystal seed is initially add C-K crude product quality 0.5% ~ 5%.
4. according to the ginseng saponin C-K hemi-hydrate crystalline that claim 1 method prepares, it is characterized in that: the water-content of this crystal is 1.4% ~ 1.8%.
5., according to the ginseng saponin C-K hemi-hydrate crystalline that claim 1 method prepares, use Fourier transform infrared spectroscopy meter to detect, the characteristic peak obtained is respectively 3359cm
-1, 2948cm
-1, 1709cm
-1, 1656cm
-1, 1453cm
-1, 1389cm
-1, 1076cm
-1, 1034cm
-1, 641cm
-1.
6., according to the ginseng saponin C-K hemi-hydrate crystalline that claim 1 method prepares, crystal is long column shape.
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| KR100377546B1 (en) * | 2000-07-26 | 2003-03-26 | 주식회사 케이티앤지 | Manufacturing Method for Ginsenoside Compound K by Enzymatic Reaction |
| KR101158846B1 (en) * | 2010-04-09 | 2012-06-27 | (주) 위디어 | The manufacturing method for ginsenoside compound K |
| KR101156204B1 (en) * | 2010-05-13 | 2012-06-18 | 건국대학교 산학협력단 | Beta-glycosidase and Production of aglycon protopanaxadiol and compound K by the thermostable beta-glycosidase |
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