CN105859805A - Preparation method and application of novel phenolic glycoside compound extracted from green peel of Juglans mandshurica Maxim - Google Patents
Preparation method and application of novel phenolic glycoside compound extracted from green peel of Juglans mandshurica Maxim Download PDFInfo
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- CN105859805A CN105859805A CN201610296216.6A CN201610296216A CN105859805A CN 105859805 A CN105859805 A CN 105859805A CN 201610296216 A CN201610296216 A CN 201610296216A CN 105859805 A CN105859805 A CN 105859805A
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- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/20—Carbocyclic rings
- C07H15/203—Monocyclic carbocyclic rings other than cyclohexane rings; Bicyclic carbocyclic ring systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
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Abstract
The invention belongs to the technical field of medicines, and relates to a novel phenolic glycoside compound and a preparation method thereof. The novel novel phenolic glycoside compound is extracted and separated from green peel of Juglans mandshurica Maxim and has antitumor activity in vitro. The preparation method includes subjecting green peel of Juglans mandshurica Maxim to alcohol extraction, enrichment and purification by macroporous resin, chromatography by silicagel columns and chromatography by gel columns sequentially, and then preparing HPLC and purifying the same to obtain the novel phenolic glycoside compound: 4 -hydroxypropiophenone-4-O-Beta-D-glucopyranosyl (1->6) -Beta-D-glucopyranoside. The raw material for preparing the compound is wide in source and easy to obtain; the novel compound has effective inhabitation effect to gastric carcinoma cells, liver cancer cells, breast cancer cells and the like as proved by tests.
Description
Technical field
The invention belongs to pharmaceutical technology field, be specifically related to the preparation of a kind of noval chemical compound with inhibition of cancer cell effect
Method and the application in preparation tumor.
Background technology
Malignant tumour is a class disease of serious threat human life, and the World Health Organization (WHO) scholarly forecast, to 2020
Year population in the world will reach 8,000,000,000 cancer new cases and be up to 20,000,000, and 12,000,000 people will be had to die from cancer.Cancer has become danger
And the primary killers of human health.So far, the methods for the treatment of of the Common Chemotherapy of tumour uses antineoplastic chemical drugs exactly
Tumor patient is treated by product, and this method all has therapeutic action to primary tumor, MET and subclinical MET, but shortcoming is also
Fairly obvious, as to cells, having powerful toxic and side effect, develop immunity to drugs.So theoretically, chemotherapy
Internal all of tumour cell can not be killed, the most always have residual tumor cell, be its recurrence, the root of transfer.Cause
The needs that this new excellent effect medicine of exploitation meets clinical treatment are pendulum tasks the most urgent in face of medical personal.
Confirming through substantial amounts of clinical report, the Several Kinds of Malignancies such as esophagus cancer and stomach cancer, liver cancer and breast cancer are had by pericarpium juglandis
Obviously inhibitory action, can alleviate the clinical symptoms of tumour patient, alleviates it painful.But at present it is produced antitumor work
The most inconsistent by the determination suggestion of effective substance, it would be highly desirable to build pericarpium juglandis active ingredient molecule storehouse.
Summary of the invention
The invention aims to solve the problems referred to above, expand the resource of tumor, source, it is provided that Yi Zhongxin
The compound with inhibiting tumour cells effect.
In order to achieve the above object, the invention provides 4-hydroxypropiophenonepreparation-4-O-β-D-glucopyranosyl (1 → 6)-
β-D-glucopyranoside, its structural formula is as follows:
Present invention also offers 4-hydroxypropiophenonepreparation-4-O-β-D-glucopyranosyl (1 → 6)-β-D-glucopyranose
The preparation method of glycosides: with green peel of walnut as raw material, passes sequentially through alcohol extracting, column chromatography prepares.
Above-mentioned column chromatography includes macroporous resin column, normal phase silicagel column, sephadex column and preparation HPLC successively.
4-hydroxypropiophenonepreparation-4-O-β-D-glucopyranosyl (1 → 6)-β-D-glucopyranoside of the present invention is specifically made
Standby step is as follows:
(1) alcohol extracting: by green peel of walnut (the Chinese olive skin for Juglans mandshurica Juglans mandshurica Maxim of originating) fresh goods low temperature
40 DEG C of drying, the 5kg dry product obtained is raw material, uses alcohol reflux to extract 3 times, is respectively, and the 1st time with 30L 60% ethanol
Extract 2.5h, the 2nd 25L 60% alcohol extract 2h, with 20L 60% alcohol extract 2h, filter, merge 3 filtrates, subtract for the 3rd time
Pressure recycling design, drying under reduced pressure, get dry extract shape extract；
(2) enriching and purifying: alcohol extracting gained in above-mentioned steps (1) is done paste extract moisture be dissipated to relative density be 1.30 ±
The solution of 0.05, through AB-8 type macroporous resin column chromatography enriching and purifying, elutes with water, 20% ethanol, 30% ethanol respectively successively, receives
Collecting 30% ethanol eluate, decompression and solvent recovery obtains 30% ethanol elution part；
(3) normal phase silicagel column separates: gained 30% ethanol elution part in above-mentioned steps (2) is carried out normal phase silica gel column chromatography and divides
From, respectively with volume proportion as 8:1, the methylene chloride-methanol mixed solvent gradient elution of 3:1,1:1 and 0:1, each ratio
3.5 column volumes of example drip washing, by the methylene chloride-methanol mixed solvent wash-out that wherein methylene chloride-methanol volume proportion is 3:1
Part reduced pressure recycling design obtains separating product；
(4) sephadex column separates: the product after above-mentioned steps of learning from else's experience (3) separation, by sephadex column, with methyl alcohol:
Water=2:3(V/V) elute 3 column volumes, discard first column volume eluent.Collect two column volume eluents below, reclaim
Solvent, obtains crude product；
(5) preparing HPLC to separate: use methyl alcohol to dissolve gained crude product in above-mentioned steps (4) and enter preparation HPLC, flow phase
For methyl alcohol that volume ratio is 32:68 and water mixed solution, elution flow rate is 3mL/min, retention time tR=22.6min～
After collecting cut in the 22.8min stage, recovery is drying to obtain.
Present invention also offers 4-hydroxypropiophenonepreparation-4-O-β-D-glucopyranosyl (1 → 6)-β-D-glucopyranose
Glycosides application in terms of preparation prevention and tumor.It is preferably at preparation prevention and treatment people's cancer of the stomach, liver cancer and mammary gland
Application in terms of cancer drug.
Above achievement in research not yet has patent or document report.
Beneficial effects of the present invention and meaning are: the raw material of employing is the black cloth of walnut shell, is generally taken as refuse
Abandon, carry out compound extraction as raw material, this plant resources can be made full use of；Additionally, green peel of walnut is carried out by this research
Go deep into composition research and development, search out and there is unique chemical moieties and the stronger compound of activity, provide newly for clinical research
Type antineoplastic.
Accompanying drawing explanation
Fig. 1 is the chemical structural formula of the compounds of this invention；
Fig. 2 is the positivity HR-ESI-MS spectrogram of the compounds of this invention；
Fig. 3 is the compounds of this invention1H-NMR spectrum；
Fig. 4 is the compounds of this invention13C-NMR spectrogram；
Fig. 5 is the DEPT spectrogram of the compounds of this invention；
Fig. 6 is the hsqc spectrum figure of the compounds of this invention；
Fig. 7 is the HMBC spectrogram of the compounds of this invention.
Detailed description of the invention
According to technology contents disclosed in this invention, those skilled in the art will be apparent from other embodiments of the present invention,
Following embodiment only makees example.In the case of not violating present subject matter and scope, the present invention can be carried out various adjustment
And improvement.These changes should be within the scope of the present invention.Below in conjunction with specific embodiment, the present invention is described in detail.
The preparation method of case study on implementation one the compounds of this invention:
(1) alcohol extracting: by green peel of walnut (the Chinese olive skin for Juglans mandshurica Juglans mandshurica Maxim of originating) fresh goods low temperature
40 DEG C of drying, the 5kg dry product obtained is raw material, uses alcohol reflux to extract 3 times, is respectively, and the 1st time with 30L 60% ethanol
Extract 2.5h, the 2nd 25L 60% alcohol extract 2h, with 20L 60% alcohol extract 2h, filter, merge 3 filtrates, subtract for the 3rd time
Pressure recycling design, drying under reduced pressure, get dry extract shape extract 311g；
(2) enriching and purifying: alcohol extracting gained in above-mentioned steps (1) is done paste extract moisture be dissipated to relative density be 1.30 ±
The solution of 0.05, through AB-8 type macroporous resin column chromatography enriching and purifying, (the long 1.30m of chromatographic column internal diameter 6cm, wherein resin is the highest
Degree 0.95m), elute successively with water, 20% ethanol, 30% ethanol respectively, collect 30% ethanol eluate, decompression and solvent recovery obtains 30%
Ethanol elution part 22.5g；
(3) normal phase silicagel column separates: gained 30% ethanol elution part in above-mentioned steps (2) is used normal phase silicagel column (chromatographic column
The long 1.5m of internal diameter 3cm, wherein silica gel effective depth 1.0m), use methylene chloride-methanol (8:1, V/V, 3.5 column volume) successively
→ methylene chloride-methanol (3:1, V/V, 3.5 column volume) → methylene chloride-methanol (1:1, V/V, 3.5 column volume) → methyl alcohol is molten
Liquid (3.5 column volumes) carries out system gradient elution, by dichloromethane-first that wherein methylene chloride-methanol volume proportion is 3:1
Alcohol mixed solvent elution fraction decompression and solvent recovery is to dry, and weigh 0.98 g；
(4) sephadex column separates: the product after the separation of above-mentioned steps of learning from else's experience (3) purification on normal-phase silica gel, passes through sephadex column
(internal diameter 1.5cm, column length 1.5m), with methyl alcohol: water=2:3(V/V) elute 3 column volumes, discard first column volume eluent.
Collect two column volume eluents, recycling design below, obtain crude product 0.22g；
(5) prepare HPLC to separate: with preparation HPLC prepared by gained crude product in above-mentioned steps (4) (Waters 515-further
2414, SunFireTMPrep C18,250 mm × 10 mm i.d., 5 μm), with flowing for the volume ratio methyl alcohol as 32:68
And water mixed solution, elution flow rate is 3mL/min, retention time tRAfter collecting cut in=22.6min～22.8min stage, return
Receipts are drying to obtain sterling 11.5mg.
The sign of case study on implementation two the compounds of this invention:
The compounds of this invention is white amorphous powder, is soluble in methyl alcohol.Maximum suction is presented at 256nm in UV spectrum (MeOH)
Receive.In positivity HR-ESI-MS spectrum, [M+H] seen from m/z 475.1865+Quasi-molecular ions, shows the molecule of the compounds of this invention
Amount is 474.In conjunction with1H-NMR、13The spectral datas such as C-NMR and DEPT spectrum speculate that the compounds of this invention molecular formula is C21H30O12, meter
Calculating its degree of unsaturation is 7.Its concrete spectral data is shown in Table 1.
Effect example
MTT(tetrazolium salts) method mensuration 4-hydroxypropiophenonepreparation-4-O-β-D-glucopyranosyl (1 → 6)-β-D-glucopyranoside
Lethal effect to human tumor cells.
(1) tumour cell: human gastric cancer, people's HepG-2 cell line and MCF-7 Human Breast Cancer Cells.
(2) experiment concrete operation method: tumour cell is the (tire containing 10% Glu in being incubated at DMEM matrix
Cow's serum, 100 μ g mL−1Penicillin, 100 μ g mL−1Streptomysin).Take the tumour cell being in exponential phase, add
Enter 0.25% Trypsin Induced, with concentration for 10 × 104Individual mL-1, the cell suspension taking 180 μ L is placed in 96 orifice plates, often group
Being all provided with 3 parallel holes, separately set blank well and control wells, the non-inoculating cell of blank well, control wells is the nutrient solution of not drug containing.In
37℃、5%CO2Under the conditions of cultivate after 24h, add in nutrient solution testing sample (sample is dissolved in DMSO, with culture medium by
Step dilution, adds DMSO final concentration≤1% of cell herb liquid), make final concentration of 0,10,30,50,70,90 μMs of medicine.Solution
Continue at 37 DEG C of 5% CO2Co-incubation 48h in incubator.Every hole adds 20 μ L MTT solution, and (5 mg/mL, are dissolved in
In PBS, after continuing to cultivate 4 h, terminate cultivating.Careful suction abandons supernatant, and every hole adds 150 μ L DMSO, and shaking table shakes
10min, makes crystal dissolve cmpletely.At 570nm, survey the light absorption value (A) in every hole with ELIASA, calculate cell survival
Inhibiting rate: cell survival inhibiting rate %=[1-(experimental group A-blank group A)/(control group A-blank group A)] × 100%.Data use
SPSS software analysis system processes.
(3) experimental result: this noval chemical compound of variable concentrations is shown in Table 2 to the survival inhibiting rate experimental data of tumour cell.Knot
Fruit shows, noval chemical compound all has preferable growth inhibition effect to above-mentioned tumour cell, to human gastric cancer, people liver
Cancer HepG-2 cell and the IC of human breast carcinoma MCF-750It is respectively 28.15 μMs and 22.64 μMs and 35.62 μMs.
In sum, the phenolic glycoside compound 4-hydroxy base propiophenone-4-O-of isolated from pericarpium juglandis of the present invention
β-D-glucopyranosyl (1 → 6)-β-D-glucopyranoside has the prospect of preparation clinical cancer therapy medicine.
Claims (4)
1. a phenolic glycoside compound, it is characterised in that its structural formula as shown in the formula (I):
。
2. the preparation method of compound described in claim 1, it is characterised in that comprise the steps:
(1) alcohol extracting: by green peel of walnut (the Chinese olive skin for Juglans mandshurica Juglans mandshurica Maxim of originating) fresh goods low temperature
40 DEG C of drying, the 5kg dry product obtained is raw material, uses alcohol reflux to extract 3 times, is respectively, and the 1st time with 30L 60% ethanol
Extract 2.5h, the 2nd 25L 60% alcohol extract 2h, with 20L 60% alcohol extract 2h, filter, merge 3 filtrates, subtract for the 3rd time
Pressure recycling design, drying under reduced pressure, get dry extract shape extract；
(2) enriching and purifying: alcohol extracting gained in above-mentioned steps (1) is done paste extract moisture be dissipated to relative density be 1.30 ±
The solution of 0.05, through AB-8 type macroporous resin column chromatography enriching and purifying, elutes with water, 20% ethanol, 30% ethanol respectively successively, receives
Collecting 30% ethanol eluate, decompression and solvent recovery obtains 30% ethanol elution part；
(3) normal phase silicagel column separates: gained 30% ethanol elution part in above-mentioned steps (2) is carried out normal phase silica gel column chromatography and divides
From, respectively with volume proportion as 8:1, the methylene chloride-methanol mixed solvent gradient elution of 3:1,1:1 and 0:1, each ratio
3.5 column volumes of example drip washing, by the methylene chloride-methanol mixed solvent wash-out that wherein methylene chloride-methanol volume proportion is 3:1
Part reduced pressure recycling design obtains separating product；
(4) sephadex column separates: the product after above-mentioned steps of learning from else's experience (3) separation, by sephadex column, with methyl alcohol:
Water=2:3(V/V) elute 3 column volumes, discard first column volume eluent；Collect two column volume eluents below, reclaim
Solvent, obtains crude product；
(5) preparing HPLC to separate: use methyl alcohol to dissolve gained crude product in above-mentioned steps (4) and enter preparation HPLC, flow phase
For methyl alcohol that volume ratio is 32:68 and water mixed solution, elution flow rate is 3mL/min, retention time tR=22.6min～
After collecting cut in the 22.8min stage, recovery is drying to obtain.
3. phenolic glycoside compound described in claim 1,4-hydroxypropiophenonepreparation-4-O-β-D-glucopyranosyl (1 → 6)-β-D-pyrrole
The application in terms of preparing antineoplastic of the glucopyranoside glycosides.
4-hydroxypropiophenonepreparation-4-O-β-D-glucopyranosyl (1 → 6)-β-D-glucopyra the most according to claim 3
Glucosides application in preparing antineoplastic, it is characterised in that: described tumour behaviour gastric cancer tumor, people's hepatic carcinoma or people
Breast cancer tumour.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106841433A (en) * | 2017-01-17 | 2017-06-13 | 广州浩意万医药科技有限公司 | A kind of rascal reference extract and its application |
| CN109705188A (en) * | 2018-12-27 | 2019-05-03 | 黑龙江中医药大学 | A kind of new triterpene compound and the preparation method and application thereof in pericarpium juglandis |
| CN111349134A (en) * | 2020-04-23 | 2020-06-30 | 黑龙江中医药大学 | Dammarane type triterpene compound in walnut green seedcase and preparation method and application thereof |
| CN111704639A (en) * | 2020-06-03 | 2020-09-25 | 江南大学 | Separation method and application of phenolic acid glucoside compounds in diaphragma juglandis fructus |
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| WO2009105936A1 (en) * | 2008-02-28 | 2009-09-03 | Wang Tao | The use of phenolic glycosides derivatives in the manufacture of compositions for treating cell proliferation diseases |
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| JP2009179602A (en) * | 2008-01-31 | 2009-08-13 | Chiba Univ | Eleutherinoside a, b and c |
| WO2009105936A1 (en) * | 2008-02-28 | 2009-09-03 | Wang Tao | The use of phenolic glycosides derivatives in the manufacture of compositions for treating cell proliferation diseases |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106841433A (en) * | 2017-01-17 | 2017-06-13 | 广州浩意万医药科技有限公司 | A kind of rascal reference extract and its application |
| CN106841433B (en) * | 2017-01-17 | 2019-06-11 | 广州浩意万医药科技有限公司 | A kind of green peel reference extract and its application |
| CN109705188A (en) * | 2018-12-27 | 2019-05-03 | 黑龙江中医药大学 | A kind of new triterpene compound and the preparation method and application thereof in pericarpium juglandis |
| CN111349134A (en) * | 2020-04-23 | 2020-06-30 | 黑龙江中医药大学 | Dammarane type triterpene compound in walnut green seedcase and preparation method and application thereof |
| CN111349134B (en) * | 2020-04-23 | 2021-08-20 | 黑龙江中医药大学 | Preparation method of dammarane type triterpene compound in walnut green husk |
| CN111704639A (en) * | 2020-06-03 | 2020-09-25 | 江南大学 | Separation method and application of phenolic acid glucoside compounds in diaphragma juglandis fructus |
| US11384109B2 (en) | 2020-06-03 | 2022-07-12 | Jiangnan University | Method for separating phenolic acid glucoside compounds from Diaphragma juglandis Fructu |
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