CN108484712B - 一种制备达木林a的方法 - Google Patents
一种制备达木林a的方法 Download PDFInfo
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- CN108484712B CN108484712B CN201810243218.8A CN201810243218A CN108484712B CN 108484712 B CN108484712 B CN 108484712B CN 201810243218 A CN201810243218 A CN 201810243218A CN 108484712 B CN108484712 B CN 108484712B
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- Prior art keywords
- damulin
- gynostemma
- chitosan
- silica gel
- gynostemma pentaphylla
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- BMSPHMYCTYOUPF-SNVBIOCGSA-N (2s,3r,4s,5s,6r)-2-[(2r,3r,4s,5s,6r)-2-[[(2r,3r,5r,8r,9r,10r,12r,13r,14r,17s)-2,12-dihydroxy-4,4,8,10,14-pentamethyl-17-[(2e)-6-methylhepta-2,5-dien-2-yl]-2,3,5,6,7,9,11,12,13,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-dihydroxy-6-(hyd Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@H]1[C@H](O)C[C@]2(C)[C@H]3C[C@@H](O)[C@H]4[C@@]([C@@]3(CC[C@H]2C1(C)C)C)(C)CC[C@@H]4C(/C)=C/CC=C(C)C)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O BMSPHMYCTYOUPF-SNVBIOCGSA-N 0.000 title claims abstract description 29
- BMSPHMYCTYOUPF-HYIBBFQISA-N damulin A Natural products CC(=CCC=C(C)[C@H]1CC[C@]2(C)[C@@H]1[C@H](O)C[C@@H]3[C@@]4(C)C[C@@H](O)[C@H](O[C@@H]5O[C@H](CO)[C@@H](O)[C@H](O)[C@H]5O[C@@H]6O[C@H](CO)[C@@H](O)[C@H](O)[C@H]6O)C(C)(C)[C@H]4CC[C@@]23C)C BMSPHMYCTYOUPF-HYIBBFQISA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 18
- 240000006509 Gynostemma pentaphyllum Species 0.000 claims abstract description 53
- 235000002956 Gynostemma pentaphyllum Nutrition 0.000 claims abstract description 51
- 241000519324 Cardiospermum microcarpum Species 0.000 claims abstract description 15
- 238000000746 purification Methods 0.000 claims abstract description 15
- 238000000605 extraction Methods 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 229920001661 Chitosan Polymers 0.000 claims description 21
- 229960000892 attapulgite Drugs 0.000 claims description 18
- 239000004927 clay Substances 0.000 claims description 18
- 229910052625 palygorskite Inorganic materials 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 239000000741 silica gel Substances 0.000 claims description 15
- 229910002027 silica gel Inorganic materials 0.000 claims description 15
- 229960001866 silicon dioxide Drugs 0.000 claims description 15
- 238000010828 elution Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000003480 eluent Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
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- YHVZKDRAJHNHJX-UDBICBSZSA-N (2s,3r,4s,5s,6r)-2-[(2r,3r,4s,5s,6r)-2-[[(2r,3r,5r,8r,9r,10r,12r,13r,14r,17s)-2,12-dihydroxy-4,4,8,10,14-pentamethyl-17-(6-methylhepta-1,5-dien-2-yl)-2,3,5,6,7,9,11,12,13,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-dihydroxy-6-(hydroxym Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@H]1[C@H](O)C[C@]2(C)[C@H]3C[C@@H](O)[C@H]4[C@@]([C@@]3(CC[C@H]2C1(C)C)C)(C)CC[C@@H]4C(=C)CCC=C(C)C)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O YHVZKDRAJHNHJX-UDBICBSZSA-N 0.000 abstract description 21
- YHVZKDRAJHNHJX-UHFFFAOYSA-N damulin B Natural products CC(C)=CCCC(=C)C1CCC(C2(CCC3C4(C)C)C)(C)C1C(O)CC2C3(C)CC(O)C4OC1OC(CO)C(O)C(O)C1OC1OC(CO)C(O)C(O)C1O YHVZKDRAJHNHJX-UHFFFAOYSA-N 0.000 abstract description 21
- TXEWRVNOAJOINC-UHFFFAOYSA-N ginsenoside Rb2 Natural products CC(=CCCC(OC1OC(COC2OCC(O)C(O)C2O)C(O)C(O)C1O)C3CCC4(C)C3C(O)CC5C6(C)CCC(OC7OC(CO)C(O)C(O)C7OC8OC(CO)C(O)C(O)C8O)C(C)(C)C6CCC45C)C TXEWRVNOAJOINC-UHFFFAOYSA-N 0.000 abstract description 21
- NZXNJMVGDPUWMR-UHFFFAOYSA-N gypenoside LVI Natural products CC(=CCCC(C)(OC1OC(COC2OCC(O)C(O)C2O)C(O)C(O)C1O)C3CCC4(C)C5CCC6C(C)(C)C(OC7OC(CO)C(O)C(O)C7OC8OC(CO)C(O)C(O)C8O)C(O)CC6(C)C5CC(O)C34C)C NZXNJMVGDPUWMR-UHFFFAOYSA-N 0.000 abstract description 21
- 241000671596 Gynostemma cardiospermum Species 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 description 16
- 238000010898 silica gel chromatography Methods 0.000 description 16
- 238000004587 chromatography analysis Methods 0.000 description 15
- LTJZMSTVPKBWKB-HGZKDYFJSA-N (2s,3r,4s,5s,6r)-2-[(2r,3r,4s,5s,6r)-2-[[(2r,3r,5r,8r,9r,10r,12r,13r,14r,17s)-2,12-dihydroxy-17-[(2s)-2-hydroxy-6-methylhept-5-en-2-yl]-4,4,8,10,14-pentamethyl-2,3,5,6,7,9,11,12,13,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-dihydroxy-6 Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@H]1[C@H](O)C[C@]2(C)[C@H]3C[C@@H](O)[C@H]4[C@@]([C@@]3(CC[C@H]2C1(C)C)C)(C)CC[C@@H]4[C@@](C)(O)CCC=C(C)C)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O LTJZMSTVPKBWKB-HGZKDYFJSA-N 0.000 description 14
- 239000012071 phase Substances 0.000 description 12
- 239000012535 impurity Substances 0.000 description 7
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- 235000017709 saponins Nutrition 0.000 description 5
- LTJZMSTVPKBWKB-XUYZQZLKSA-N (2s,3r,4s,5s,6r)-2-[(2r,3r,4s,5s,6r)-2-[[(2r,3r,5r,8r,9r,10r,12r,13r,14r,17s)-2,12-dihydroxy-17-[(2r)-2-hydroxy-6-methylhept-5-en-2-yl]-4,4,8,10,14-pentamethyl-2,3,5,6,7,9,11,12,13,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-dihydroxy-6 Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@H]1[C@H](O)C[C@]2(C)[C@H]3C[C@@H](O)[C@H]4[C@@]([C@@]3(CC[C@H]2C1(C)C)C)(C)CC[C@@H]4[C@](C)(O)CCC=C(C)C)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O LTJZMSTVPKBWKB-XUYZQZLKSA-N 0.000 description 4
- VENRSYBHHVDBDC-UHFFFAOYSA-N 2-[2-[[2,12-dihydroxy-4,4,8,10,14-pentamethyl-17-[6-methyl-2-[3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyhept-5-en-2-yl]-2,3,5,6,7,9,11,12,13,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-dihydroxy-6-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound C1CC(C2(CCC3C(C)(C)C(OC4C(C(O)C(O)C(CO)O4)OC4C(C(O)C(O)C(CO)O4)O)C(O)CC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC1OC(CO)C(O)C(O)C1O VENRSYBHHVDBDC-UHFFFAOYSA-N 0.000 description 4
- CYPYEPJSRSWKLA-UHFFFAOYSA-N Gypenoside XLVI Natural products CC(=CCCC(C)(OC1OC(CO)C(O)C(O)C1O)C2CCC3(C)C4CCC5C(C)(C)C(OC6OC(CO)C(O)C(O)C6OC7OC(CO)C(O)C(O)C7O)C(O)CC5(C)C4CC(O)C23C)C CYPYEPJSRSWKLA-UHFFFAOYSA-N 0.000 description 4
- LTJZMSTVPKBWKB-UHFFFAOYSA-N gypenoside LI Natural products CC(C)=CCCC(C)(O)C1CCC(C2(CCC3C4(C)C)C)(C)C1C(O)CC2C3(C)CC(O)C4OC1OC(CO)C(O)C(O)C1OC1OC(CO)C(O)C(O)C1O LTJZMSTVPKBWKB-UHFFFAOYSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 210000003323 beak Anatomy 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 229930182470 glycoside Natural products 0.000 description 3
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- 241000345998 Calamus manan Species 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 229930187479 gypenoside Natural products 0.000 description 2
- ZRBFCAALKKNCJG-UHFFFAOYSA-N gypenoside-XVII Natural products C1CC(C2(CCC3C(C)(C)C(OC4C(C(O)C(O)C(CO)O4)O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC(C(C(O)C1O)O)OC1COC1OC(CO)C(O)C(O)C1O ZRBFCAALKKNCJG-UHFFFAOYSA-N 0.000 description 2
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- 208000004078 Snake Bites Diseases 0.000 description 1
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 0.000 description 1
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- 230000002218 hypoglycaemic effect Effects 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J17/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, having an oxygen-containing hetero ring not condensed with the cyclopenta(a)hydrophenanthrene skeleton
- C07J17/005—Glycosides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Medicines Containing Plant Substances (AREA)
- Steroid Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
本发明公开了一种制备达木林A的方法,该方法以同属但不同亚属的心籽绞股蓝Gynostemma cardiospermum Cogn.ex Oliv替代绞股蓝Gynostemma pentaphyllum(Thunb.)Makino作为原料,可以提取分离纯化制备得到大量绞股蓝皂苷LVI、XLVI、L、LI、达木林A和达木林B,绞股蓝皂苷LVI、XLVI、L、LI、达木林A和达木林B在心籽绞股蓝Gynostemma cardiospermum Cogn.ex Oliv叶中的含量分别是在绞股蓝Gynostemmapentaphyllum(Thunb.)Makino叶中的含量的10‑50倍;而心籽绞股蓝Gynostemma cardiospermum Cogn.ex Oliv没有商品化,漫田遍野无人问津,成本可以忽略。
Description
技术领域
本发明属于生物医药领域,具体涉及一种制备达木林A的方法。
背景技术
绞股蓝Gynostemma pentaphyllum(Thunb.)Makino又名甘茶蔓、神仙草、遍地生根等,是葫芦科绞股蓝属的多年生草质藤本植物,在我国主要生长在秦岭及长江以南的地区。其始载于明代的《救荒本草》,作野菜使用,《本草纲目》中开始将其以“乌蔹莓”之名入药。《中国壮药学》:“通调三道两路,清热解毒,止咳祛痰。用于慢性气管炎,病毒性肝炎,肾盂肾炎,胃肠炎,泄泻,高血压,动脉硬化症,高血脂,痈疮肿毒,蛇咬伤”。绞股蓝中主要化学成分为皂苷和多糖,另外还含有少量的黄酮类化合物、萜类、有机酸、蛋白质、维生素、脂肪、纤维等成分以及锌、铜、镁、铁、锰、硒等微量元素。绞股蓝具有抗肿瘤、降血糖、抗衰老、抗肝纤维化等药理作用,其主要有效成分绞股蓝皂苷过量服用亦无副作用,因而在保健食品和新型药品研发上都有巨大的应用前景,是一种新的药食两用植物资源。
绞股蓝中含有的皂苷成分众多,研究较多、活性较好的有绞股蓝皂苷LVI、XLVI、L、LI、达木林A(DamulinA)和达木林B(Damulin B)。其中,绞股蓝皂苷LVI、XLVI含量较高,其他四种为含量极低的稀有皂苷(为绞股蓝皂苷LVI、XLVI的转化产物)。
目前,绞股蓝皂苷LVI、XLVI以绞股蓝为原料提取分离纯化得到,绞股蓝皂苷L、LI、达木林A和达木林B以经过加热炮制的绞股蓝为原料提取分离纯化得到(文献:Determination by UPLC-MS of four dammaranetype saponins from heat-processedGynostemma pentaphyllum;Bioscience,Biotechnology,andBiochemistry,2014;Vol.78,No.2,311-316)。以绞股蓝为原料制备绞股蓝皂苷LVI、XLVI、L、LI、达木林A和达木林B存在两点不足:
第一,绞股蓝价格相对较高,成本高。自从1986年国家科委在“星火计划”中把绞股蓝列为待开发的“名贵中药材”之首位,绞股蓝的市场价格就明显上涨。
第二,未加热炮制的绞股蓝中绞股蓝皂苷L、LI、达木林A和达木林B非常低,分离纯化难度大;加热炮制费事,且加热后绞股蓝皂苷L、LI、达木林A和达木林B的含量并非同步增加,加热温度和时间难以掌控(上述引用文献也可体现这种现象)。
绞股蓝属共有2亚属13种2变种,2亚属为绞股蓝亚属、喙果藤亚属,上述的绞股蓝Gynostemma pentaphyllum(Thunb.)Makino即为绞股蓝亚属中的一种(文献:绞股蓝属植物的分类系统和分布,植物分类学报,1995)。研究发明,绞股蓝属植物基本都含有绞股蓝皂苷,且种类基本相同,但是该属不同植物中特定绞股蓝皂苷的含量差别较大。产自湖北西部、陕西南部和四川的心籽绞股蓝Gynostemma cardiospermum Cogn.ex Oliv属于喙果藤亚属,其主要特征是果为蒴果,成熟时顶端沿腹缝线开裂,具宿存的3枚喙状花柱,其他特征则与绞股蓝Gynostemma pentaphyllum(Thunb.)Makino基本一致。目前尚未有报道公开绞股蓝皂苷LVI、XLVI、L、LI、达木林A、B在心籽绞股蓝Gynostemma cardiospermum Cogn.exOliv中的含量显著高于绞股蓝Gynostemma pentaphyllum(Thunb.)Makino。
发明内容
本发明目的在于提供一种制备达木林A的方法。
上述目的通过如下技术方案实现:
绞股蓝皂苷LVI、XLVI、L、LI、达木林A和达木林B的制备方法包括如下步骤:
步骤S1,收集心籽绞股蓝Gynostemma cardiospermum Cogn.ex Oliv的叶,阴干,用乙醇水溶液加热回流提取,纱布过滤,合并滤液浓缩至无醇味;
步骤S2,将浓缩至无醇味的提取液上样于D101大孔吸附树脂柱,树脂径高比为1:10,拌样树脂占树脂总量的1/10,湿法装柱,拌树脂上样;先用10BV的30%乙醇以10BV/h的流速洗脱除杂,再用10BV的85%乙醇以10BV/h的流速洗脱,收集3-10BV洗脱液,浓缩至无醇味得到总皂苷水溶液;
步骤S3,将总皂苷水溶液调节pH值至6.0,加入壳聚糖/凹凸棒石黏土复合物,常温搅拌、静置、过滤,收集滤液,调节pH值至中性,冷冻干燥得到精制总皂苷粉末;
步骤S4,将精制总皂苷粉末上样于正相硅胶柱,硅胶径高比为1:10,拌样硅胶占硅胶总量的1/10,干法装柱,拌硅胶上样;依次用体积比为20:1:2、10:1:2、5:1:2、2:1:2的二氯甲烷/甲醇/丙酮混合溶剂以12BV/h的速度梯度洗脱,分别洗脱10BV、6BV、5BV、3BV;
步骤S5,分别收集20:1:2二氯甲烷/甲醇/丙酮洗脱7-8BV、9-10BV的洗脱液浓缩干燥得到达木林B、达木林A;分别收集10:1:2二氯甲烷/甲醇/丙酮洗脱3-4BV、5-6BV的洗脱液浓缩干燥得到绞股蓝皂苷L、绞股蓝皂苷LI;收集5:1:2二氯甲烷/甲醇/丙酮洗脱4-5BV的洗脱液浓缩干燥得到绞股蓝皂苷XLVI;收集2:1:2二氯甲烷/甲醇/丙酮洗脱2-3BV的洗脱液浓缩干燥得到绞股蓝皂苷LVI。
优选地,壳聚糖/凹凸棒石黏土复合物制备方法为:1g壳聚糖溶于100mL质量分数为1%的醋酸水溶液中得到壳聚糖溶胶,向该溶胶中加入8g凹凸棒石黏土,常温搅拌48h,静置2h后将上层溶液倾倒出,剩余物50℃烘干,研磨、干燥。
优选地,步骤S1乙醇水溶液体积百分浓度为75%。
优选地,步骤S1提取的固液比为1:20。
优选地,步骤S3中1L总皂苷水溶液加入50g壳聚糖/凹凸棒石黏土复合物。
优选地,步骤S3加入壳聚糖/凹凸棒石黏土复合物后搅拌24h,静置2h后过滤。
优选地,步骤S3用盐酸和氨水调节pH。
本发明技术优势:
1、本发明以同属但不同亚属的心籽绞股蓝Gynostemma cardiospermum Cogn.exOliv替代绞股蓝Gynostemma pentaphyllum(Thunb.)Makino作为原料,可以提取分离纯化制备得到大量绞股蓝皂苷LVI、XLVI、L、LI、达木林A和达木林B,绞股蓝皂苷LVI、XLVI、L、LI、达木林A和达木林B在心籽绞股蓝Gynostemma cardiospermum Cogn.ex Oliv叶中的含量分别是在绞股蓝Gynostemma pentaphyllum(Thunb.)Makino叶中的含量的10-50倍;而心籽绞股蓝Gynostemma cardiospermum Cogn.ex Oliv没有商品化,漫田遍野无人问津,成本可以忽略。
2、本发明步骤S3用壳聚糖/凹凸棒石黏土复合物对总皂苷水溶液进行精制,有效降低了总皂苷中的杂质,极大简化了后续正相硅胶柱色谱工艺,产物纯度高。
附图说明
图1为步骤S2总皂苷水溶液的高效液相色谱分析谱图;
图2为步骤S3精制总皂苷粉末的高效液相色谱分析谱图;
图3为硅胶柱色谱纯化得到的达木林B的高效液相色谱分析谱图;
图4为硅胶柱色谱纯化得到的达木林A的高效液相色谱分析谱图;
图5为硅胶柱色谱纯化得到的绞股蓝皂苷L的高效液相色谱分析谱图;
图6为硅胶柱色谱纯化得到的绞股蓝皂苷LI的高效液相色谱分析谱图;
图7为硅胶柱色谱纯化得到的绞股蓝皂苷XLVI的高效液相色谱分析谱图;
图8为硅胶柱色谱纯化得到的绞股蓝皂苷LVI的高效液相色谱分析谱图。
具体实施方式
下面结合实施例具体介绍本发明的实质性内容,但本领域技术人员应当知道,不应将本发明的保护范围局限于这些具体实施例。
一、实验材料
心籽绞股蓝Gynostemma cardiospermum Cogn.ex Oliv的叶收集自湖北十堰市房县,绞股蓝Gynostemma pentaphyllum(Thunb.)Makino的叶收集自湖南邵阳绥宁,阴干后使用。
壳聚糖/凹凸棒石黏土复合物制备方法为:1g壳聚糖溶于100mL质量分数为1%的醋酸水溶液中得到壳聚糖溶胶,向该溶胶中加入8g凹凸棒石黏土,常温搅拌48h,静置2h后将上层溶液倾倒出,剩余物50℃烘干,研磨、干燥。
不同浓度乙醇均指不同体积百分浓度的乙醇水溶液。
二、实验方法
1、绞股蓝皂苷LVI、XLVI、L、LI、达木林A和达木林B的制备
包括如下步骤:
步骤S1,收集心籽绞股蓝Gynostemma cardiospermum Cogn.ex Oliv的叶,阴干,用体积百分浓度为75%的乙醇水溶液加热回流提取,固液比为1:20,提取3次,每次2h,纱布过滤,合并滤液浓缩至无醇味;
步骤S2,将浓缩至无醇味的提取液上样于D101大孔吸附树脂柱,树脂径高比为1:10,拌样树脂占树脂总量的1/10,湿法装柱,拌树脂上样;先用10BV的30%乙醇以10BV/h的流速洗脱除杂,再用10BV的85%乙醇以10BV/h的流速洗脱,收集3-10BV洗脱液,浓缩至无醇味得到总皂苷水溶液;
步骤S3,将总皂苷水溶液用盐酸调节pH值至6.0,加入壳聚糖/凹凸棒石黏土复合物,1L总皂苷水溶液加入50g壳聚糖/凹凸棒石黏土复合物,搅拌24h,静置2h后过滤,收集滤液,氨水调节pH值至中性,冷冻干燥得到精制总皂苷粉末;
步骤S4,将精制总皂苷粉末上样于正相硅胶柱,硅胶径高比为1:10,拌样硅胶占硅胶总量的1/10,干法装柱,拌硅胶上样(精制总皂苷粉末用甲醇溶解后与拌样硅胶混合均匀、干燥,精制总皂苷粉末与拌样硅胶的质量比1:1);依次用体积比为20:1:2、10:1:2、5:1:2、2:1:2的二氯甲烷/甲醇/丙酮混合溶剂以12BV/h的速度梯度洗脱,分别洗脱10BV、6BV、5BV、3BV;
步骤S5,分别收集20:1:2二氯甲烷/甲醇/丙酮洗脱7-8BV、9-10BV的洗脱液浓缩干燥得到达木林B、达木林A;分别收集10:1:2二氯甲烷/甲醇/丙酮洗脱3-4BV、5-6BV的洗脱液浓缩干燥得到绞股蓝皂苷L、绞股蓝皂苷LI;收集5:1:2二氯甲烷/甲醇/丙酮洗脱4-5BV的洗脱液浓缩干燥得到绞股蓝皂苷XLVI;收集2:1:2二氯甲烷/甲醇/丙酮洗脱2-3BV的洗脱液浓缩干燥得到绞股蓝皂苷LVI。
2、高效液相色谱分析条件
色谱仪:LC-20ADXR高压泵;SPD-M20A二极管阵列紫外可见光检测器;CTO-20AC柱温箱;CBM-20A系统控制器;SIL-20ACXR自动进样器;
色谱柱:Agilent ZORBAX Extend-C18(250mm×4.6mm,5μm);
流动相A相:水(含万分之五四氢呋喃);
流动相B相:乙腈(含万分之五四氢呋喃);
洗脱程序:0-3min,20%B相;3-15min,20%→40%B相;15-30min,40%→80%B相;
流速:1.0mL/min;
柱温:30℃;
检测波长:203nm;
进样量:10μL。
三、实验结果
取步骤S2总皂苷水溶液稀释5倍作为高效液相色谱进样溶液,取步骤S3精制总皂苷粉末用初始比例的流动相溶解成0.5mg/mL的溶液作为高效液相色谱进样溶液。图1为步骤S2总皂苷水溶液的高效液相色谱分析谱图,图2为步骤S3精制总皂苷粉末的高效液相色谱分析谱图。从图1、2可见,步骤S2所得总皂苷水溶液成分复杂,步骤S3精制总皂苷中杂质成分极大降低,说明壳聚糖/凹凸棒石黏土复合物在pH 6.0条件下可以有效吸附去除总皂苷水溶液中的杂质成分。经过除杂,有助于降低后续硅胶柱层析的工艺难度。
精制总皂苷经过步骤S4、S5硅胶柱层析分离纯化后得到绞股蓝皂苷LVI、XLVI、L、LI、达木林A和达木林B单体。图3为硅胶柱色谱纯化得到的达木林B的高效液相色谱分析谱图,图4为硅胶柱色谱纯化得到的达木林A的高效液相色谱分析谱图,图5为硅胶柱色谱纯化得到的绞股蓝皂苷L的高效液相色谱分析谱图,图6为硅胶柱色谱纯化得到的绞股蓝皂苷LI的高效液相色谱分析谱图,图7为硅胶柱色谱纯化得到的绞股蓝皂苷XLVI的高效液相色谱分析谱图,图8为硅胶柱色谱纯化得到的绞股蓝皂苷LVI的高效液相色谱分析谱图。从图3-8可见,绞股蓝皂苷LVI、XLVI、L、LI、达木林A和达木林B纯度非常高,在95%以上。经过一次硅胶柱层析即可制备得到如此高纯度的绞股蓝皂苷LVI、XLVI、L、LI、达木林A和达木林B,主要得益于步骤S3壳聚糖/凹凸棒石黏土复合物的精制除杂。
本发明具有如下优点:
本发明以同属但不同亚属的心籽绞股蓝Gynostemma cardiospermum Cogn.exOliv替代绞股蓝Gynostemma pentaphyllum(Thunb.)Makino作为原料,可以提取分离纯化制备得到大量绞股蓝皂苷LVI、XLVI、L、LI、达木林A和达木林B,绞股蓝皂苷LVI、XLVI、L、LI、达木林A和达木林B在心籽绞股蓝Gynostemma cardiospermum Cogn.ex Oliv叶中的含量分别是在绞股蓝Gynostemma pentaphyllum(Thunb.)Makino叶中的含量的12、11、45、37、42、55倍(操作方法:直接用甲醇提取两种绞股蓝的干燥叶,固体比1:40,超声40min,过滤,然后用高效液相色谱法对滤液进行分析,根据绞股蓝皂苷LVI、XLVI、L、LI、达木林A和达木林B的峰面积比值粗略计算其在两种滤液中的含量比值);而心籽绞股蓝Gynostemmacardiospermum Cogn.ex Oliv没有商品化,漫田遍野无人问津,原料成本可以忽略。
本发明步骤S3用壳聚糖/凹凸棒石黏土复合物对总皂苷水溶液进行精制,有效降低了总皂苷中的杂质,极大简化了后续正相硅胶柱色谱工艺,产物纯度高。
Claims (6)
1.一种制备达木林A的方法,其特征在于,包括如下步骤:
步骤S1,收集心籽绞股蓝Gynostemma cardiospermum Cogn. ex Oliv的叶,阴干,用乙醇水溶液加热回流提取,纱布过滤,合并滤液浓缩至无醇味;
步骤S2,将浓缩至无醇味的提取液上样于D101大孔吸附树脂柱,树脂径高比为1:10,拌样树脂占树脂总量的1/10,湿法装柱,拌树脂上样;先用10BV的30%乙醇以10BV/h的流速洗脱除杂,再用10BV的85%乙醇以10BV/h的流速洗脱,收集3-10BV洗脱液,浓缩至无醇味得到总皂苷水溶液;
步骤S3,将总皂苷水溶液调节pH值至6.0,加入壳聚糖/凹凸棒石黏土复合物,常温搅拌、静置、过滤,收集滤液,调节pH值至中性,冷冻干燥得到精制总皂苷粉末;
步骤S4,将精制总皂苷粉末上样于正相硅胶柱,硅胶径高比为1:10,拌样硅胶占硅胶总量的1/10,干法装柱,拌硅胶上样;用体积比为20:1:2的二氯甲烷/甲醇/丙酮混合溶剂以12BV/h的速度洗脱10BV;
步骤S5,收集20:1:2二氯甲烷/甲醇/丙酮洗脱9-10BV的洗脱液浓缩干燥得到达木林A;
其中,壳聚糖/凹凸棒石黏土复合物制备方法为:1g壳聚糖溶于100 mL质量分数为1%的醋酸水溶液中得到壳聚糖溶胶,向该溶胶中加入8g凹凸棒石黏土,常温搅拌48h,静置2h后将上层溶液倾倒出,剩余物50℃烘干,研磨、干燥。
2.根据权利要求1所述的方法,其特征在于:步骤S1乙醇水溶液体积百分浓度为75%。
3.根据权利要求2所述的方法,其特征在于:步骤S1提取的固液比为1:20。
4.根据权利要求1所述的方法,其特征在于:步骤S3中1L总皂苷水溶液加入50g壳聚糖/凹凸棒石黏土复合物。
5.根据权利要求4所述的方法,其特征在于:步骤S3加入壳聚糖/凹凸棒石黏土复合物后搅拌24h,静置2h后过滤。
6.根据权利要求1所述的方法,其特征在于:步骤S3用盐酸和氨水调节pH。
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