CN103110671B - Method for removing ginkgolic acid and heavy metals in ginkgo biloba extract by using nanometer material - Google Patents
Method for removing ginkgolic acid and heavy metals in ginkgo biloba extract by using nanometer material Download PDFInfo
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- CN103110671B CN103110671B CN201310033052.4A CN201310033052A CN103110671B CN 103110671 B CN103110671 B CN 103110671B CN 201310033052 A CN201310033052 A CN 201310033052A CN 103110671 B CN103110671 B CN 103110671B
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Abstract
The invention discloses a method for removing ginkgolic acid and heavy metals in a ginkgo biloba extract by using a nanometer material. The method is characterized in that the ginkgo biloba extract is obtained by extraction, column chromatography, adsorption of the nanometer material, separation of the nanometer material, concentration and drying of separation liquid; a ferroferric oxide nanometer material is used as the nanometer material; and a magnetic separation process is used as a nanometer material separation process. As the improvement, the method further can comprise a step of recovering the nanometer material. According to the method provided by the invention, the ginkgolic acid, urushiol, isourushiol and the heavy metals are adsorbed by a Fe3O4 nanometer material; solid-liquid separation is carried out by using the magnetic separation process; and a finished product can be obtained by concentrating and drying the medicine liquid. The method provided by the invention has the double effects of environmental friendliness and simultaneous removal of the ginkgolic acid and the heavy metals.
Description
Technical field
The invention belongs to technical field of natural product preparation, be specifically related to a kind of method utilizing nano material adsorption to remove Ginkgolic Acid in Extract of Ginkgo biloba Leaves and heavy metal.
Background technology
Folium Ginkgo is the dried leaves of Ginkgoaceae plant Ginkgo biloba (Ginkgo biloba L.), and property is sweet, bitter, puckery, flat, GUIXIN, lung meridian, there is astringing the lung, relieving asthma, blood circulation promoting and blood stasis dispelling, the effect such as pain relieving, for coronary heart diseases and angina pectoris and hyperlipemia.Folium Ginkgo extract is the extract of Folium Ginkgo through being processed into, activating blood circulation to dissipate blood stasis and dredge the collateral, is used for the treatment of obstruction of qi in the chest and cardialgia that obstruction of collaterals by blood stasis causes, apoplexy, hemiplegia, stiff tongue are tongue-tied; Treating Stable Angina Pectoris of Coronary Artery Disease, cerebral infarction are shown in above-mentioned patient.Folium Ginkgo and Folium Ginkgo extract are as raw material, be widely used in the preparation for the treatment of cardiovascular and cerebrovascular disease, only " Chinese Pharmacopoeia " has just recorded 5 the relevant kinds comprising Folium Ginkgo, " European Pharmacopoeia " defines the standard of Folium Ginkgo and Folium Ginkgo extract, and Folium Ginkgo and preparation thereof are also included as food supplement by " American Pharmacopeia ".But also containing a kind of toxic component-ginkgoic acid in ginkgo agent, there is the effect such as sensitization, cytotoxicity, so international standard requires that the content of ginkgoic acid is less than 5ppm, require that content of beary metal is less than 10ppm simultaneously.In the ginkgo agent that China produces at present, the content of ginkgoic acid and heavy metal substantially exceeds international standard.Cause major part Folium Ginkgo extract manufacturing enterprise of China to be in stop production or half state stopped production, how effectively the ginkgoic acid in removing Folium Ginkgo extract and heavy metal are the subject matter of current China chemist research.
At present, the method removing ginkgoic acid has: (1) Schwabe company propose acetone extraction+extraction; (2) acetone extraction+chromatography+organic solvent extraction; (3) ethanol extraction+chromatography+organic solvent extraction; (4) supercritical extraction.Solvent extraction very easily produce emulsifying and cause the production time to extend and extraction not exclusively, have dissolvent residual in product, simultaneously to operator and environment unfriendly.Patent documentation the removing process of gingkolic acid " in the Folium Ginkgo extract " (CN101194918A) adopts twin columns to superpose way and removes ginkgoic acid, but affected more complicated, and the pretreatment of twin columns and activation can produce a certain amount of industrial wastewater.
It is the bottleneck that restriction China Folium Ginkgo extract exports that Ginkgolic Acid in Extract of Ginkgo biloba Leaves and content of beary metal exceed standard, and also have impact on the safety of domestic pharmacy simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of method utilizing nano material to remove Ginkgolic Acid in Extract of Ginkgo biloba Leaves and heavy metal, the method has environmental friendliness, removes the double effects of ginkgoic acid and heavy metal simultaneously.
A kind of method utilizing nano material to remove Ginkgolic Acid in Extract of Ginkgo biloba Leaves and heavy metal provided by the invention, the method obtains Folium Ginkgo extract by extraction, column chromatography, nano material absorption, nano material separation, separating medium concentrate drying; Described nano material is ferriferrous oxide nanometer material, and described nano material isolation technics is magnetic separation technique.
One as technique scheme is improved, and the method also comprises nano material recycling step.
Another kind as technique scheme improves, described extraction comprises following detailed process: Folium Ginkgo adds 60-70% ethanol respectively, the mass volume ratio of Folium Ginkgo and alcoholic solution is 1: 5-1: 10, reflux, extract, at least 2 times, each 1-3 hour, merge extractive liquid, decompression recycling ethanol, adds the water of 3-5 times of Folium Ginkgo weight, leaves standstill, filter, filtrate is for subsequent use.
As another improvement of technique scheme, described column chromatography comprises following detailed process: adopt any one dress post in these the 4 kinds of resins of AB-8, HP-20, DA201, D101 after activation, by the filtrate of gained in extraction step, with the washing post of 3-6 times of resin bed volume, adopt the 60-80% ethanol desorbing of 2-4 times of resin bed volume, collection ethanol elution part is for subsequent use.
As the further improvement of technique scheme, described nano material adsorbs following detailed process: in the ethanol elution collected, add ferriferrous oxide nanometer material, the quality of ferroso-ferric oxide is 0.01%-1% with the ratio of ethanol elution volume, ultrasonic absorption 0.5-8h.
Improving further again as technique scheme, the mode of described separating medium concentrate drying is vacuum drying or spraying dry.
As the further improvement of technique scheme, described nano material removal process is: the ferriferrous oxide nanometer material obtained by nano material separating step is collected, with 0.05%-2% soak with hydrochloric acid 0.5-24h, then dry for several times with deionized water rinsing.
Fe
3o
4nano material and catechol and derivant thereof have higher affinity, the therefore phytochemicals of some carboxyls of selective absorption or ortho position phenolic hydroxyl group.Semen Ginkgo total acid comprises ginkgoic acid, Semen Ginkgo laccol, different Semen Ginkgo laccol, ginkgolic acid etc., and its basic structure all has carboxyl or ortho-phenolic hydroxyl, Fe
3o
4nano material can adsorb ginkgoic acid, laccol, different laccol etc., utilizes magnetic separation technique to be separated from mother solution by Semen Ginkgo total acid.The invention has the advantages that and utilize Fe
3o
4nano material not only can remove ginkgoic acid, and can removal heavy metal, reaches the effect of killing two birds with one stone, simultaneously can also by Fe
3o
4nano material is by pickling recycling, and the ginkgoic acid of industrialized great production enrichment can make biological insecticides and other purposes.
Detailed description of the invention
What the specific embodiment of the invention provided utilizes nano material to remove the method for Ginkgolic Acid in Extract of Ginkgo biloba Leaves and heavy metal, completes especially by following steps:
1st step is extracted: Folium Ginkgo adds 60-70% ethanol respectively, and the proportioning of Folium Ginkgo and alcoholic solution is 5-10 (W/V), reflux, extract, at least 2 times, each 1-3 hour, merge extractive liquid, decompression recycling ethanol, adds the water of 3-5 times of Folium Ginkgo weight, leave standstill, filter, filtrate is for subsequent use.
2nd step column chromatography: adopt any one dress post in these the 4 kinds of resins of AB-8, HP-20, DA201, D101 after activation, the filtrate upper prop of gained will be extracted, with 3-6 times of volume washing post, adopt the 60-80% ethanol desorbing of 2-4 times of resin bed volume, collection ethanol elution part is for subsequent use.
3rd step nano material absorption: the ferriferrous oxide nanometer material adding 0.01-1% (W/V) in the ethanol elution collected, ultrasonic absorption 0.5-8h.
4th step nano material is separated: adopt permanent magnetism or electromagnetism to be adsorbed by ferriferrous oxide nanometer material, complete solid-liquid separation.
5th step separating medium concentrate drying: vacuum drying or spraying dry.
6th step nano material reclaims: the ferriferrous oxide nanometer material obtained by nano material separating step is collected, with 0.05%-2% soak with hydrochloric acid 0.5-24h, then dry for several times with deionized water rinsing.
Below in conjunction with example, the specific embodiment of the present invention is described further.It should be noted that at this, the explanation for these embodiments understands the present invention for helping, but does not form limitation of the invention.In addition, if below in described each embodiment of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
Embodiment 1
Get Folium Ginkgo 500g, add 10,8 times amount 60% ethanol, respectively reflux, extract, 2h, leaching medicinal liquid, merge, decompression recycling ethanol not containing alcohol, then adds water to 1500ml to medicinal liquid, leave standstill, filter, filtrate is added on processed DA201 resin column, and pure water crosses post cleaning, when effluent is more limpid, use 2000mL80% ethanol elution, collect ethanol elution, add 0.2g ferriferrous oxide nanometer material, ultrasonic absorption 2h, Magnet puts into the liquid absorption ferriferrous oxide nanometer material, and medicinal liquid concentrating under reduced pressure reclaims ethanol, extractum vacuum drying.Collect ferriferrous oxide nanometer material, put into 0.1% hydrochloric acid and soak 4h, Magneto separate, for several times, vacuum drying is for subsequent use for deionized water rinsing.Dry rear Folium Ginkgo extract is weighed, sampling and measuring total flavones, total lactones, ginkgoic acid and content of beary metal.Result is: Folium Ginkgo extract 9.1g, and general flavone content is 28.3%, total lactones 8.6%, ginkgoic acid 2ppm, heavy metal 4ppm.
Embodiment 2
Get Folium Ginkgo 500g, add 8, 6 times amount 70% ethanol, reflux, extract, 1.5h respectively, leaching medicinal liquid, merge, decompression recycling ethanol does not contain alcohol to medicinal liquid, then 1500ml is added water to, leave standstill, filter, filtrate is added on processed D101 resin column, pure water crosses post cleaning, when effluent is more limpid, use 2500mL80% ethanol elution, collect ethanol elution, when decompression recycling ethanol to medicinal liquid solid content reaches 1.08-1.10, stop concentrated, 0.5g ferriferrous oxide nanometer material is added in medicinal liquid, ultrasonic absorption 5h, electric magnet puts into the liquid absorption ferriferrous oxide nanometer material, medicinal liquid concentrating under reduced pressure, when solid content reaches 1.25-1.30, spraying dry.Collect ferriferrous oxide nanometer material, put into 1% hydrochloric acid and soak 2h, Magneto separate, for several times, vacuum drying is for subsequent use for deionized water rinsing.Dry rear Folium Ginkgo extract is weighed, sampling and measuring total flavones, total lactones, ginkgoic acid and content of beary metal.Result is: Folium Ginkgo extract 10.2g, and general flavone content is 27.2%, total lactones 8.2%, ginkgoic acid 2ppm, heavy metal 5ppm.
Embodiment 3
Get Folium Ginkgo 500g, add 10,5 times amount 70% ethanol, reflux, extract, 3h respectively, leaching medicinal liquid, merges, and decompression recycling ethanol does not contain alcohol to medicinal liquid, then 1500ml is added water to, leave standstill, filter, filtrate is added on processed AB-8 resin column, pure water crosses post cleaning, when effluent is more limpid, use 2000mL60% ethanol elution, collect ethanol elution, add 1.0g ferriferrous oxide nanometer material, ultrasonic absorption 8h, Magnet puts into the liquid absorption ferriferrous oxide nanometer material, medicinal liquid concentrating under reduced pressure, when solid content reaches 1.25-1.30, spraying dry.Collect ferriferrous oxide nanometer material, put into 2% hydrochloric acid and soak 24h, Magneto separate, for several times, vacuum drying is for subsequent use for deionized water rinsing.Dry rear Folium Ginkgo extract is weighed, sampling and measuring total flavones, total lactones, ginkgoic acid and content of beary metal.Result is: Folium Ginkgo extract 8.8g, and general flavone content is 26.6%, total lactones 7.4%, ginkgoic acid 1ppm, heavy metal 3ppm.
Embodiment 4
Get Folium Ginkgo 500g, add 10, 8 times amount 65% ethanol, reflux, extract, 2h respectively, leaching medicinal liquid, merge, decompression recycling ethanol does not contain alcohol to medicinal liquid, then 1500ml is added water to, leave standstill, filter, filtrate is added on processed HP-20 resin column, pure water crosses post cleaning, when effluent is more limpid, use 2800mL80% ethanol elution, collect ethanol elution, when decompression recycling ethanol to medicinal liquid solid content reaches 1.08-1.10, stop concentrated, add 5.0g ferriferrous oxide nanometer material, ultrasonic absorption 3h, Magnet puts into the liquid absorption ferriferrous oxide nanometer material, medicinal liquid concentrating under reduced pressure, when solid content reaches 1.25-1.30, spraying dry.Collect ferriferrous oxide nanometer material, put into 2% hydrochloric acid and soak 3h, Magneto separate, for several times, vacuum drying is for subsequent use for deionized water rinsing.Dry rear Folium Ginkgo extract is weighed, sampling and measuring total flavones, total lactones, ginkgoic acid and content of beary metal.Result is: Folium Ginkgo extract 9.5g, and general flavone content is 28.6%, total lactones 7.6%, ginkgoic acid 1ppm, heavy metal 2ppm.
In the present invention, the concentration of ethanol and hydrochloric acid all refers to concentration of volume percent.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the content disclosed in this embodiment.The equivalence completed under not departing from spirit disclosed in this invention so every or amendment, all fall into the scope of protection of the invention.
Claims (1)
1. utilize nano material to remove a method for Ginkgolic Acid in Extract of Ginkgo biloba Leaves and heavy metal, it is characterized in that, comprised the following steps:
1st step is extracted: Folium Ginkgo adds 60-70% ethanol respectively, and the proportioning of Folium Ginkgo and alcoholic solution is 5W/V ~ 10W/V, reflux, extract, at least 2 times, each 1-3 hour, merge extractive liquid, decompression recycling ethanol, adds the water of 3-5 times of Folium Ginkgo weight, leave standstill, filter, filtrate is for subsequent use;
2nd step column chromatography: adopt any one dress post in these the 4 kinds of resins of AB-8, HP-20, DA201, D101 after activation, the filtrate upper prop of gained will be extracted, with 3-6 times of volume washing post, adopt the 60%-80% ethanol desorbing of 2-4 times of resin bed volume, collection ethanol elution part is for subsequent use;
3rd step nano material absorption: the ferriferrous oxide nanometer material adding 0.01W/V%-1W/V% in the ethanol elution collected, ultrasonic absorption 0.5h-8h, and in the process for removing ginkgoic acid and heavy metal simultaneously;
4th step nano material is separated: adopt permanent magnetism or electromagnetism to be adsorbed by ferriferrous oxide nanometer material, complete solid-liquid separation;
5th step separating medium concentrate drying: vacuum drying or spraying dry;
6th step nano material reclaims: the ferriferrous oxide nanometer material obtained by nano material separating step is collected, with 0.05%-2% soak with hydrochloric acid 0.5-24h, then dry for several times with deionized water rinsing.
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Address after: 430074 Hubei Province, Wuhan city Hongshan District Luoyu Road No. 1037 Patentee after: Huazhong University of Science and Technology Patentee after: Hubei Nuo Kete medicine company limited-liability company Address before: 430074 Hubei Province, Wuhan city Hongshan District Luoyu Road No. 1037 Patentee before: Huazhong University of Science and Technology Patentee before: Hubei Nuokete Pharmaceutical Co., Ltd. |