金银花水溶性化学成分研究
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摘要
本博士学位论文重点研究了产自河南省的中药金银花水提取物中的高含量环烯醚萜苷类成分和具有特殊UV吸收的微量成分,对其进行了分离纯化和结构鉴定,并对分离得到的对杏仁β-葡萄糖苷酶水解抵抗的两个新化合物及其异构体和类似物进行了半合成;在抗炎、神经保护、抗氧化、肝保护、抗肿瘤和钾通道调节等多种药理模型上,对以上化学成分进行了初步活性筛选。
利用多种色谱技术、波谱分析和化学方法,从金银花中分离并鉴定了31个化合物,化学名称和结构分别见表1和Figure 1,其中,包括23个环烯醚萜苷及其新型衍生物(1*～12*和15～25)、2个烟酸氮苷衍生物(13*和14*)和3个核苷(29～31),以及绿原酸(26)、咖啡酸(27)和丁香苷(28)。发现新化合物14个,其中,4个是具有由环烯醚萜苷与烟酸衍生物通过碳碳键连接的新颖骨架并以内盐形式存在的强水溶性化合物(1*～4*),4个为具有由环烯醚萜苷与吡啶衍生物以碳碳键连接的新颖骨架并以内盐形式存在的强水溶性化合物(5*～8*),2个是由环烯醚萜苷与β-羟基氨基酸缩合偶联的化合物(9*和10*),2个为分别多2个和3个碳的高环烯醚萜苷衍生物(11*和12*),2个是从天然生物资源中首次发现的烟酸葡萄糖氮苷内盐化合物(13*和14*)。另外,已知化合物18、28～30是从忍冬中首次分离得到的。
另外,以分离得到的17和21为原料,通过与不同构型的(L-或D-)β-羟基氨基酸或β-巯基氨基酸进行缩合偶联反应,半合成得到了9*和10*(S1*和S3*)、及其异构体和类似物(S2*、S4*、S5和S6)。通过不同条件下的酶水解反应初步探讨了1*、5*、9*(S1*)、10*(S3*)、S2*、S4*、S5和S6的β-葡萄糖苷酶水解特性。
经多种药理模型的活性筛选,发现金银花水提取物和部分分离组分具有较显著的抗炎活性。在浓度为10~(-5)M时,从活性组分中分离鉴定的新化合物3*、4*、7*、8*和10*,以及已知化合物16～24和26,对PAF刺激的大鼠多形核白细胞β-葡萄糖苷酸酶释放有抑制活性(50.5%～88.2%),5*、22和23对LPS刺激的小鼠腹腔巨噬细胞PGE_2产生有抑制活性(62.3%～65.4%),10*、S4*、S5和S6去血清损伤的PC12细胞具有较明显的保护活性(76.3%～79.0%),S2*、S4*、S5和S6对DL-半乳糖胺诱导的WB-F344细胞损伤有保护活性(42%～49%)。在浓度10~(-4)～10~(-6)M下,筛选的化合物对肿瘤细胞(BGC-823、A2780、A549、HCT-8和Be17402)等模型均未显示明显的活性。
This PhD dissertation focused on an investigation of main iridoids and minor constituents with specific UV absorption bands of the more polar fractions from a water extract of the flower buds of Lonicerajaponica collected from Henan province.By using various chromatographic techniques,31 compounds were isolated,and their structures were elucidated by spectroscopic and chemical methods.Their chemical names and structures are listed in Table 1 and Figure 1,including 23 iridoids(1~*～12~* and 15～25), 2 nicotinic acid N-glycosides(13~* and 14~*),3 nucleosides(29～31),chiorogenic acid (26),caffeic acid(27),and syringin(28).Among them,1~*～14~* were new,and 18 and 28～30 were isolated from L.japonica for the first time.Compounds 1~*～4~* are based on a novel carbon skeleton derived from a N-substituted nicotinic acid nucleus coupled through C-5 with C-7 of a secoiridoid.5~*～8~* possesses another novel carbon skeleton derived from a N-substituted pyridine nucleus coupled through C-5 with C-7 of a secoiridoid.9~* and 10~* are unusual secoiridoids coupling withβ-hydroxy amino acids, and 11~* and 12~* are two homosecoiridoids with two and three additional carbons in their skeleton,respectively.13~* and 14~* are the first natural examples of N-β-D-glucopyranosyl nicotinic acid derivatives.1~*～8~*,13~* and 14~* were obtained as their inner salt forms.
In addition,9~* and 10~*,which can not be hydrolyzed byβ-glucosidase from almonds, as well as their epimers and anologues(S2~*,S4~*,S5,and S6) were stereoselectively semi-synthesized by condensation of 17 or 21 withβ-hydroxy- orβ-thiol- amino acids. By using several glucosidases includingβ-glucosidase from almonds,hesperidinase from Aspergillus niger and heloxpomatiase,enzymatic hydrolysic properties of 1~*,5~*,S1~*～S4~*,S5,and S6 were investigated.S1~*(9~*),S3~*(10~*),S4~*,and S5 were completely resisitant toβ-glucosidase and hesperidinase while S2~*,S6,1~*,and 5~* were partially resistant to them.However,they were readily hydrolyzed by heloxpomatiase.
The isolates,and semi-synthetic products were assayed on several pharmacological models.3~*,4~*,7~*,8~*,10~*,16～24 and 26 showed inhibitory activities against the release of glucuronidase in rat polymorphonuclear leukocytes(PMNs) induced by platelet-activating factor(PAF) with inhibition rates of 50.5%～88.2%at 10~(-5) M.5~*, 22 and 23 were active against the release of PGE_2 in mouse peritoneal macrophages induced by lipopolysaccharide(LPS),with inhibition rates of 62.3%～65.4%at 10~(-5) M. 10~*,S4~*,S5,and S6 exhibited protective activities against serum deprivation-induced PC12 cell apoptosis with cell survival rates of 76.3%～79.0%at 10~(-5) M.26 showed DPPH free radical scavenging acticity with an inhibition rate of 92%at 10~(-3) M.S2~*,S4~*, S5,and S6 showed protective activities against hepatocyte(WB-F344) damage caused by DL-GalN with cell survival rates of 42%～49%at 10 10~(-5) M.Moreover,biological activities of the extracts,isolates,and semi-synthetic products were evaluated on human cancer cell lines(BGC-823,A2780,A549,HCT-8,and Be17402),a potassium channel regulation model,and etc.,but they were inactive at 10~(-4)～10~(-6)M.
利用多种色谱技术、波谱分析和化学方法,从金银花中分离并鉴定了31个化合物,化学名称和结构分别见表1和Figure 1,其中,包括23个环烯醚萜苷及其新型衍生物(1*～12*和15～25)、2个烟酸氮苷衍生物(13*和14*)和3个核苷(29～31),以及绿原酸(26)、咖啡酸(27)和丁香苷(28)。发现新化合物14个,其中,4个是具有由环烯醚萜苷与烟酸衍生物通过碳碳键连接的新颖骨架并以内盐形式存在的强水溶性化合物(1*～4*),4个为具有由环烯醚萜苷与吡啶衍生物以碳碳键连接的新颖骨架并以内盐形式存在的强水溶性化合物(5*～8*),2个是由环烯醚萜苷与β-羟基氨基酸缩合偶联的化合物(9*和10*),2个为分别多2个和3个碳的高环烯醚萜苷衍生物(11*和12*),2个是从天然生物资源中首次发现的烟酸葡萄糖氮苷内盐化合物(13*和14*)。另外,已知化合物18、28～30是从忍冬中首次分离得到的。
另外,以分离得到的17和21为原料,通过与不同构型的(L-或D-)β-羟基氨基酸或β-巯基氨基酸进行缩合偶联反应,半合成得到了9*和10*(S1*和S3*)、及其异构体和类似物(S2*、S4*、S5和S6)。通过不同条件下的酶水解反应初步探讨了1*、5*、9*(S1*)、10*(S3*)、S2*、S4*、S5和S6的β-葡萄糖苷酶水解特性。
经多种药理模型的活性筛选,发现金银花水提取物和部分分离组分具有较显著的抗炎活性。在浓度为10~(-5)M时,从活性组分中分离鉴定的新化合物3*、4*、7*、8*和10*,以及已知化合物16～24和26,对PAF刺激的大鼠多形核白细胞β-葡萄糖苷酸酶释放有抑制活性(50.5%～88.2%),5*、22和23对LPS刺激的小鼠腹腔巨噬细胞PGE_2产生有抑制活性(62.3%～65.4%),10*、S4*、S5和S6去血清损伤的PC12细胞具有较明显的保护活性(76.3%～79.0%),S2*、S4*、S5和S6对DL-半乳糖胺诱导的WB-F344细胞损伤有保护活性(42%～49%)。在浓度10~(-4)～10~(-6)M下,筛选的化合物对肿瘤细胞(BGC-823、A2780、A549、HCT-8和Be17402)等模型均未显示明显的活性。
This PhD dissertation focused on an investigation of main iridoids and minor constituents with specific UV absorption bands of the more polar fractions from a water extract of the flower buds of Lonicerajaponica collected from Henan province.By using various chromatographic techniques,31 compounds were isolated,and their structures were elucidated by spectroscopic and chemical methods.Their chemical names and structures are listed in Table 1 and Figure 1,including 23 iridoids(1~*～12~* and 15～25), 2 nicotinic acid N-glycosides(13~* and 14~*),3 nucleosides(29～31),chiorogenic acid (26),caffeic acid(27),and syringin(28).Among them,1~*～14~* were new,and 18 and 28～30 were isolated from L.japonica for the first time.Compounds 1~*～4~* are based on a novel carbon skeleton derived from a N-substituted nicotinic acid nucleus coupled through C-5 with C-7 of a secoiridoid.5~*～8~* possesses another novel carbon skeleton derived from a N-substituted pyridine nucleus coupled through C-5 with C-7 of a secoiridoid.9~* and 10~* are unusual secoiridoids coupling withβ-hydroxy amino acids, and 11~* and 12~* are two homosecoiridoids with two and three additional carbons in their skeleton,respectively.13~* and 14~* are the first natural examples of N-β-D-glucopyranosyl nicotinic acid derivatives.1~*～8~*,13~* and 14~* were obtained as their inner salt forms.
In addition,9~* and 10~*,which can not be hydrolyzed byβ-glucosidase from almonds, as well as their epimers and anologues(S2~*,S4~*,S5,and S6) were stereoselectively semi-synthesized by condensation of 17 or 21 withβ-hydroxy- orβ-thiol- amino acids. By using several glucosidases includingβ-glucosidase from almonds,hesperidinase from Aspergillus niger and heloxpomatiase,enzymatic hydrolysic properties of 1~*,5~*,S1~*～S4~*,S5,and S6 were investigated.S1~*(9~*),S3~*(10~*),S4~*,and S5 were completely resisitant toβ-glucosidase and hesperidinase while S2~*,S6,1~*,and 5~* were partially resistant to them.However,they were readily hydrolyzed by heloxpomatiase.
The isolates,and semi-synthetic products were assayed on several pharmacological models.3~*,4~*,7~*,8~*,10~*,16～24 and 26 showed inhibitory activities against the release of glucuronidase in rat polymorphonuclear leukocytes(PMNs) induced by platelet-activating factor(PAF) with inhibition rates of 50.5%～88.2%at 10~(-5) M.5~*, 22 and 23 were active against the release of PGE_2 in mouse peritoneal macrophages induced by lipopolysaccharide(LPS),with inhibition rates of 62.3%～65.4%at 10~(-5) M. 10~*,S4~*,S5,and S6 exhibited protective activities against serum deprivation-induced PC12 cell apoptosis with cell survival rates of 76.3%～79.0%at 10~(-5) M.26 showed DPPH free radical scavenging acticity with an inhibition rate of 92%at 10~(-3) M.S2~*,S4~*, S5,and S6 showed protective activities against hepatocyte(WB-F344) damage caused by DL-GalN with cell survival rates of 42%～49%at 10 10~(-5) M.Moreover,biological activities of the extracts,isolates,and semi-synthetic products were evaluated on human cancer cell lines(BGC-823,A2780,A549,HCT-8,and Be17402),a potassium channel regulation model,and etc.,but they were inactive at 10~(-4)～10~(-6)M.
引文
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