CN105294626B - A kind of scutellarin aglycone derivative and its preparation method and application - Google Patents
A kind of scutellarin aglycone derivative and its preparation method and application Download PDFInfo
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- DJSISFGPUUYILV-UHFFFAOYSA-N UNPD161792 Natural products O1C(C(O)=O)C(O)C(O)C(O)C1OC(C(=C1O)O)=CC2=C1C(=O)C=C(C=1C=CC(O)=CC=1)O2 DJSISFGPUUYILV-UHFFFAOYSA-N 0.000 title claims abstract description 63
- NPLTVGMLNDMOQE-UHFFFAOYSA-N carthamidin Natural products C1=CC(O)=CC=C1C1OC2=CC(O)=C(O)C(O)=C2C(=O)C1 NPLTVGMLNDMOQE-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229930190376 scutellarin Natural products 0.000 title claims abstract description 63
- DJSISFGPUUYILV-ZFORQUDYSA-N scutellarin Chemical compound O1[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1OC(C(=C1O)O)=CC2=C1C(=O)C=C(C=1C=CC(O)=CC=1)O2 DJSISFGPUUYILV-ZFORQUDYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- TWCMVXMQHSVIOJ-UHFFFAOYSA-N Aglycone of yadanzioside D Natural products COC(=O)C12OCC34C(CC5C(=CC(O)C(O)C5(C)C3C(O)C1O)C)OC(=O)C(OC(=O)C)C24 TWCMVXMQHSVIOJ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- PLMKQQMDOMTZGG-UHFFFAOYSA-N Astrantiagenin E-methylester Natural products CC12CCC(O)C(C)(CO)C1CCC1(C)C2CC=C2C3CC(C)(C)CCC3(C(=O)OC)CCC21C PLMKQQMDOMTZGG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- PFOARMALXZGCHY-UHFFFAOYSA-N homoegonol Natural products C1=C(OC)C(OC)=CC=C1C1=CC2=CC(CCCO)=CC(OC)=C2O1 PFOARMALXZGCHY-UHFFFAOYSA-N 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- -1 scutellarin aglycon derivatives Chemical class 0.000 claims abstract description 33
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 239000012043 crude product Substances 0.000 claims abstract description 10
- 239000003814 drug Substances 0.000 claims abstract description 10
- 229940079593 drug Drugs 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 7
- 241000736800 Vernonia Species 0.000 claims abstract description 5
- 238000010898 silica gel chromatography Methods 0.000 claims abstract description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000002000 scavenging effect Effects 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 abstract description 2
- 238000000338 in vitro Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
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- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 description 11
- 238000002835 absorbance Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 4
- DKVBOUDTNWVDEP-NJCHZNEYSA-N teicoplanin aglycone Chemical compound N([C@H](C(N[C@@H](C1=CC(O)=CC(O)=C1C=1C(O)=CC=C2C=1)C(O)=O)=O)[C@H](O)C1=CC=C(C(=C1)Cl)OC=1C=C3C=C(C=1O)OC1=CC=C(C=C1Cl)C[C@H](C(=O)N1)NC([C@H](N)C=4C=C(O5)C(O)=CC=4)=O)C(=O)[C@@H]2NC(=O)[C@@H]3NC(=O)[C@@H]1C1=CC5=CC(O)=C1 DKVBOUDTNWVDEP-NJCHZNEYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
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- 230000000144 pharmacologic effect Effects 0.000 description 2
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- 241000208838 Asteraceae Species 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 241001013934 Erigeron breviscapus Species 0.000 description 1
- 206010016654 Fibrosis Diseases 0.000 description 1
- 206010063837 Reperfusion injury Diseases 0.000 description 1
- 208000005392 Spasm Diseases 0.000 description 1
- IAJILQKETJEXLJ-QTBDOELSSA-N aldehydo-D-glucuronic acid Chemical group O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-QTBDOELSSA-N 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
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- 230000002526 effect on cardiovascular system Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000004761 fibrosis Effects 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
- C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/40—Separation, e.g. from natural material; Purification
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明公开了一种具有新型结构的灯盏乙素苷元衍生物，以及它的制备方法和在制备抗氧化药物中的应用。本发明所述的灯盏乙素苷元衍生物的制备方法为：乙醇浸泡斑鸠菊全草得浸取液、浸取液过滤浓缩得到浸膏I、乙酸乙酯萃取浸膏I后浓缩得到浸膏II、用浸膏II制备得到过柱样品、过柱样品经硅胶柱层析后浓缩得到浓缩液、浓缩液进行吸附和解吸后得到灯盏乙素苷元衍生物粗品、灯盏乙素苷元衍生物粗品经乙醇重结晶并过滤和干燥后得到灯盏乙素苷元衍生物精制品。体外检测抗氧化剂清除自由基的实验结果表明，本发明提供的灯盏乙素苷元衍生物的抗氧化活性要强于灯盏乙素，有望作为抗氧化药物而得到广泛的应用。The invention discloses a scutellarin aglycone derivative with a novel structure, its preparation method and its application in the preparation of antioxidant drugs. The preparation method of the scutellarin aglycon derivatives of the present invention is: soaking the whole Vernonia herb in ethanol to obtain the extract, filtering and concentrating the extract to obtain extract I, extracting extract I with ethyl acetate, and then concentrating to obtain extract II. Use the extract II to prepare a column sample, and the column sample is concentrated through silica gel column chromatography to obtain a concentrated solution. After the concentrated solution is adsorbed and desorbed, the crude product of scutellarin aglycon derivatives and scutellarin aglycon derivatives are obtained. The crude product was recrystallized by ethanol, filtered and dried to obtain the refined product of scutellarin aglycon derivatives. The experimental results of in vitro detection of antioxidants for scavenging free radicals show that the antioxidant activity of the scutellarin aglycon derivatives provided by the present invention is stronger than that of scutellarin, and it is expected to be widely used as antioxidant drugs.
Description
技术领域technical field
本发明涉及药物化学研究领域，尤其涉及一种新型的灯盏乙素苷元衍生物，以及其制备方法和在制备抗氧化药物中的应用。The invention relates to the field of medicinal chemistry research, in particular to a novel scutellarin aglycone derivative, a preparation method thereof and an application in preparation of antioxidant drugs.
背景技术Background technique
灯盏乙素(scutellarin，又称灯盏花素)是从菊科植物短亭飞蓬[Erigeronbreviscapus(Van.t)Hand.-Mazz.]的干燥全草中提取分离得到的黄酮类化合物，是临床用药灯盏花素的主要成分，其结构式如下：Scutellarin (also known as scutellarin) is a flavonoid compound extracted and isolated from the dried whole herb of the Compositae plant Erigeronbreviscapus (Van.t) Hand.-Mazz. The main component of flower element, its structural formula is as follows:
灯盏乙素Scutellarin
灯盏乙素在临床上主要用于治疗心脑血管疾病、风湿性关节炎和中风后遗症。现代药理研究证明，灯盏乙素具有增加脑血流量、降低脑血管阻力、改善脑循环、缓解微动脉痉挛、提高血脑屏障通透性、拮抗心肌缺血再灌注损伤、抑制血小板凝集、促进纤溶活性以及抗血栓形成的作用。但是灯盏花素临床应用并不理想，原因主要有两点：(1)灯盏乙素水溶性和脂溶性较差；(2)灯盏乙素生物利用度低，体内易于代谢，不利于发挥药效。Scutellarin is mainly used clinically to treat cardiovascular and cerebrovascular diseases, rheumatoid arthritis and sequelae of stroke. Modern pharmacological studies have proved that scutellarin can increase cerebral blood flow, reduce cerebrovascular resistance, improve cerebral circulation, relieve arteriolar spasm, improve blood-brain barrier permeability, antagonize myocardial ischemia-reperfusion injury, inhibit platelet aggregation, and promote fibrosis. lytic activity and antithrombotic effect. However, the clinical application of scutellarin is not ideal. There are two main reasons: (1) scutellarin has poor water and fat solubility; .
灯盏乙素的刚性结构，是限制其透膜吸收的主要原因，水解掉葡萄糖醛酸基，分子的结构变小，刚性降低，有利于被人体吸收。有研究表明，灯盏乙素可能在人体内被水解为苷元而被吸收，推断口服灯盏乙素在体内真正起效的可能是苷元。灯盏乙素苷元是灯盏乙素7位脱去糖基的化合物，其结构如下所示：The rigid structure of scutellarin is the main reason for limiting its transmembrane absorption. The glucuronic acid group is hydrolyzed, the molecular structure becomes smaller, and the rigidity is reduced, which is conducive to being absorbed by the human body. Studies have shown that scutellarin may be hydrolyzed into aglycone and absorbed in the human body, and it is deduced that aglycone may be the real effect of oral scutellarin in the body. Scutellarin aglycon is a compound deglycosylated at the 7-position of scutellarin, and its structure is as follows:
灯盏乙素苷元scutellarin aglycone
由于灯盏乙素苷元比灯盏乙素具有更好的药理作用和生物利用度，因此，对生物利用度相对较高的灯盏乙素苷元进行结构修饰，提取、开发并合成出具有新型结构的灯盏乙素苷元衍生物，在药物研究方面将具有重大的意义。Since scutellarin aglycon has better pharmacological effects and bioavailability than scutellarin, the structural modification of scutellarin aglycon with relatively high bioavailability was carried out to extract, develop and synthesize a new structure The scutellarin aglycon derivative will have great significance in drug research.
发明内容Contents of the invention
本发明的目的是要克服现有技术不足，提供一种具有新型结构的灯盏乙素苷元衍生物。The purpose of the present invention is to overcome the deficiencies of the prior art and provide a scutellarin aglycon derivative with a novel structure.
本发明的另一个目的是提供一种本发明所述灯盏乙素苷元衍生物的制备方法。Another object of the present invention is to provide a preparation method of the scutellarin aglycon derivative of the present invention.
本发明进一步的目的是提供本发明所述灯盏乙素苷元衍生物在制备抗氧化药物中的应用。A further object of the present invention is to provide the application of the scutellarin aglycon derivatives of the present invention in the preparation of antioxidant drugs.
为解决上述技术问题，本发明提出的技术方案为：In order to solve the problems of the technologies described above, the technical solution proposed by the present invention is:
本发明提供一种灯盏乙素苷元衍生物，其结构式如下所示：The present invention provides a scutellarin aglycon derivative, the structural formula of which is as follows:
本发明提供上述灯盏乙素苷元衍生物的制备方法，具体包括以下步骤：The present invention provides a preparation method for the above-mentioned scutellarin aglycon derivatives, which specifically includes the following steps:
(1)取自然晾干后的斑鸠菊全草，用质量分数为10％～90％的乙醇浸泡30天，乙醇体积用量为原料重量的5～20倍；(1) Take the whole Vernonia herb after natural drying, soak it with ethanol with a mass fraction of 10% to 90% for 30 days, and the volume of ethanol used is 5 to 20 times the weight of the raw material;
(2)将上一步得到的浸取液过滤，滤液于50～60℃下浓缩至干，得浸膏I；(2) Filtrate the leaching solution obtained in the previous step, and concentrate the filtrate to dryness at 50-60° C. to obtain extract I;
(3)将浸膏I用乙酸乙酯萃取，再将得到的萃取液进行浓缩，得浸膏II；(3) extracting extract I with ethyl acetate, and then concentrating the obtained extract to obtain extract II;
(4)将浸膏II用甲醇溶解，加入硅胶搅拌，得过柱样品；(4) Dissolve the extract II with methanol, add silica gel and stir to obtain a column sample;
(5)将过柱样品经硅胶柱层析，依次用石油醚、丙酮和正丙醇洗脱，收集正丙醇洗脱液，然后将得到的正丙醇洗脱液进行浓缩，得浓缩液；(5) The column sample is subjected to silica gel column chromatography, eluted successively with petroleum ether, acetone and n-propanol, and the n-propanol eluate is collected, and then the obtained n-propanol eluate is concentrated to obtain a concentrated solution;
(6)采用D101大孔树脂对得到的浓缩液进行吸附，然后用乙醇进行解吸，得到灯盏乙素苷元衍生物粗品；(6) Adsorb the obtained concentrated solution with D101 macroporous resin, and then desorb with ethanol to obtain the crude product of scutellarin aglycone derivative;
(7)将灯盏乙素苷元衍生物粗品用乙醇重结晶，再过滤和干燥，得到灯盏乙素苷元衍生物精制品。(7) The crude product of scutellarin aglycon derivative is recrystallized with ethanol, then filtered and dried to obtain the refined product of scutellarin aglycon derivative.
优选的，以上所述灯盏乙素苷元衍生物的制备方法，所述步骤(1)中的乙醇体积用量为原料重量的10倍。Preferably, in the above-mentioned preparation method of scutellarin aglycon derivatives, the volume of ethanol used in the step (1) is 10 times the weight of raw materials.
本发明还提供上述灯盏乙素苷元衍生物在制备抗氧化药物中的应用。The present invention also provides the application of the above-mentioned scutellarin aglycon derivatives in the preparation of antioxidant drugs.
与现有技术相比，本发明的有益效果是：Compared with prior art, the beneficial effect of the present invention is:
本发明提供的灯盏乙素苷元衍生物的DPPH(1,1-二苯基-2-三硝基苯肼)抗氧化活性要强于灯盏乙素，有望作为抗氧化药物得到广泛的应用。The scutellarin aglycone derivatives provided by the present invention have stronger DPPH (1,1-diphenyl-2-trinitrophenylhydrazine) antioxidant activity than scutellarin, and are expected to be widely used as antioxidant drugs.
具体实施方式detailed description
实施例1Example 1
一种本发明提供的灯盏乙素苷元衍生物，其结构式如下所示：A kind of scutellarin aglycon derivative provided by the present invention, its structural formula is as follows:
本实施例的灯盏乙素苷元衍生物的具体制备过程为：取斑鸠菊全草1千克，自然晾干，用20升浓度为50％的乙醇浸泡30天；将浸取液过滤，所得滤液在50℃浓缩至干，得浸膏I；将浸膏I用5升乙酸乙酯萃取，得萃取液，再将萃取液浓缩，得浸膏II；将浸膏II用3升甲醇溶解，加入100g硅胶搅拌，得过柱样品；将过柱样品经硅胶柱层析，依次用石油醚、丙酮和正丙醇洗脱，收集正丙醇洗脱液，将所得的正丙醇洗脱液进行浓缩，得浓缩液；采用D101大孔树脂对所得的浓缩液进行吸附，然后用乙醇进行解吸，获得0.25g灯盏乙素苷元衍生物粗品；将灯盏乙素苷元衍生物粗品用乙醇重结晶，然后过滤和干燥，得到0.19g灯盏乙素苷元衍生物精制品。The specific preparation process of the scutellarin aglycone derivative in this example is as follows: take 1 kg of the whole Vernonia herb, dry it naturally, soak it in 20 liters of 50% ethanol for 30 days; filter the leaching solution, and obtain the filtrate Concentrate to dryness at 50°C to obtain extract I; extract extract I with 5 liters of ethyl acetate to obtain extract, then concentrate the extract to obtain extract II; dissolve extract II with 3 liters of methanol, add 100g of silica gel was stirred to obtain a column sample; the column sample was subjected to silica gel column chromatography, eluted with petroleum ether, acetone and n-propanol in sequence, and the n-propanol eluate was collected, and the obtained n-propanol eluate was concentrated , to obtain a concentrated solution; adopt D101 macroporous resin to absorb the obtained concentrated solution, and then desorb with ethanol to obtain 0.25g scutellarin aglycon derivative crude product; the scutellarin aglycon derivative crude product is recrystallized with ethanol, Then it was filtered and dried to obtain 0.19 g of refined product of scutellarin aglycon derivative.
本实施例制备的灯盏乙素苷元衍生物精制品经1H-NMR和MS确认，数据如下：The refined product of scutellarin aglycon derivatives prepared in this example was confirmed by 1 H-NMR and MS, and the data are as follows:
1H-NMR(400MHz,DMSO-d6)δ:4.40-4.71(m,2H,CH)，5.0(s,1H,-OH)，5.12(s,1H,-OH)，5.84(s,1H,-CH)，6.58(d,1H,-CH)，6.68(d,2H,-CH)，6.71(s,1H,-CH)，7.13(d,2H,-CH)，7.36(d,1H,-CH)。ESI-MS:m/z 363[M-H]-。 1 H-NMR (400MHz, DMSO-d 6 ) δ: 4.40-4.71 (m, 2H, CH), 5.0 (s, 1H, -OH), 5.12 (s, 1H, -OH), 5.84 (s, 1H ,-CH), 6.58(d,1H,-CH), 6.68(d,2H,-CH), 6.71(s,1H,-CH), 7.13(d,2H,-CH), 7.36(d,1H ,-CH). ESI-MS: m/z 363 [MH] - .
将获得的精制品用乙醇和正己烷混合溶剂(体积比3:1)重结晶，得到单晶。经元素分析确认其分子式为：C18H12O6F2。The obtained refined product was recrystallized with a mixed solvent of ethanol and n-hexane (volume ratio 3:1) to obtain a single crystal. Its molecular formula is confirmed by elemental analysis: C 18 H 12 O 6 F 2 .
实施例2Example 2
一种本发明提供的灯盏乙素苷元衍生物，其结构式同实施例1的结构式。A scutellarin aglycon derivative provided by the present invention, the structural formula of which is the same as that of Example 1.
本实施例的灯盏乙素苷元衍生物的具体制备过程为：取斑鸠菊全草1千克，自然晾干，用10升浓度为90％的乙醇浸泡30天；将浸取液过滤，所得滤液在60℃浓缩至干，得浸膏I；将浸膏I用5升乙酸乙酯萃取，得萃取液，再将萃取液浓缩，得浸膏II；将浸膏II用3升甲醇溶解，加入100g硅胶搅拌，得过柱样品；将过柱样品经硅胶柱层析，依次用石油醚、丙酮和正丙醇洗脱，收集正丙醇洗脱液，将所得的正丙醇洗脱液进行浓缩，得浓缩液；采用D101大孔树脂对所得的浓缩液进行吸附，然后用乙醇进行解吸，获得0.28g灯盏乙素苷元衍生物粗品；将灯盏乙素苷元衍生物粗品用乙醇重结晶，然后过滤和干燥，得到0.20g灯盏乙素苷元衍生物精制品。The specific preparation process of the scutellarin aglycone derivative in this example is as follows: take 1 kg of the whole Vernonia herb, dry it naturally, soak it in 10 liters of ethanol with a concentration of 90% for 30 days; filter the leaching solution, and obtain the filtrate Concentrate to dryness at 60°C to obtain extract I; extract extract I with 5 liters of ethyl acetate to obtain extract, then concentrate the extract to obtain extract II; dissolve extract II with 3 liters of methanol, add 100g of silica gel was stirred to obtain a column sample; the column sample was subjected to silica gel column chromatography, eluted with petroleum ether, acetone and n-propanol in sequence, and the n-propanol eluate was collected, and the obtained n-propanol eluate was concentrated , to obtain a concentrated solution; adopt D101 macroporous resin to absorb the obtained concentrated solution, and then desorb with ethanol to obtain 0.28g scutellarin aglycon derivative crude product; the scutellarin aglycon derivative crude product is recrystallized with ethanol, Then it was filtered and dried to obtain 0.20 g refined product of scutellarin aglycon derivative.
本实施例制备的灯盏乙素苷元衍生物精制品的1H-NMR和MS数据同实施例1。The 1 H-NMR and MS data of refined scutellarin aglycon derivatives prepared in this example are the same as those in Example 1.
体外检测抗氧化剂清除自由基的方法中以清除DPPH(1,1-二苯基-2-三硝基苯肼)自由基最为常用。DPPH溶液在517nm处具有较强吸收，当有供氢能力的抗氧化剂存在时，与DPPH耦合使DPPH紫色消退或减弱，且吸光度与自由基被清除的程度呈线性关系，通过加入抗氧化剂前后吸光度的线性变化计算自由基清除率。研究比较灯盏乙素苷元衍生物对自由基的清除作用，对于抗氧化药物的开发具有重要意义。Among the methods for in vitro detection of antioxidant scavenging free radicals, scavenging DPPH (1,1-diphenyl-2-trinitrophenylhydrazine) free radicals is the most commonly used. The DPPH solution has a strong absorption at 517nm. When there is an antioxidant with the ability to donate hydrogen, it will be coupled with DPPH to make the DPPH purple fade or weaken, and the absorbance is linearly related to the degree of free radical removal. By adding the antioxidant before and after the absorbance The linear change of free radical scavenging rate was calculated. Studying and comparing the scavenging effect of scutellarin aglycon derivatives on free radicals is of great significance for the development of antioxidant drugs.
将实施例1制备得到的灯盏乙素苷元衍生物与DPPH用无水乙醇溶解。分别把100μL受试物(浓度为300μmol·L-1)加到96孔板中，然后加入100μLDPPH溶液(浓度为45μmol·L-1)，振摇均匀，避光反应30分钟，在517nm处测定吸光值。按照以下公式计算自由基清除率：The scutellarin aglycone derivative prepared in Example 1 and DPPH were dissolved in absolute ethanol. Add 100 μL of the test substance (concentration: 300 μmol·L -1 ) to a 96-well plate, then add 100 μL DPPPH solution (concentration: 45 μmol·L -1 ), shake evenly, react in the dark for 30 minutes, and measure at 517 nm absorbance value. Calculate the free radical scavenging rate according to the following formula:
A0：溶剂与DPPH作用后的吸光度；A1：本发明提供的灯盏乙素苷元衍生物与DPPH作用后的吸光度；A2：未加DPPH时的吸光度。具体实验数据如表1所示：A 0 : the absorbance after the solvent reacts with DPPH; A 1 : the absorbance after the scutellarin aglycone derivative provided by the present invention reacts with DPPH; A 2 : the absorbance without adding DPPH. The specific experimental data are shown in Table 1:
表1灯盏乙素苷元衍生物DPPH抗氧化活性数据Table 1 Antioxidant activity data of scutellarin aglycon derivative DPPH
从表1可以看出，本发明提供的灯盏乙素苷元衍生物的DPPH抗氧化活性要强于灯盏乙素，可以作为抗氧化药物进行后续开发。It can be seen from Table 1 that the scutellarin aglycon derivatives provided by the present invention have stronger DPPH antioxidant activity than scutellarin, and can be used as antioxidant drugs for subsequent development.
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