CN111454317B - 具有抗炎活性的人参二醇型三萜皂苷、三七叶提取物、药物组合物和化妆品组合物 - Google Patents
具有抗炎活性的人参二醇型三萜皂苷、三七叶提取物、药物组合物和化妆品组合物 Download PDFInfo
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Abstract
本发明利用多种分离手段,包括正反相硅胶柱层析、大孔吸附树脂柱层析、凝胶柱层析和制备高效液相色谱法等,从三七叶中分离得到13个新颖的人参二醇型三萜皂苷类化合物。经活性测定实验表明这13个新化合物中的一些化合物具有抗炎活性,为今后进一步的药理活性筛选及临床研究开发出疗效确切、毒副作用小的抗炎药物奠定了物质基础。
Description
技术领域
本发明属于天然药物领域,具体而言,涉及一类具有抗炎活性的新型人参二醇型三萜皂苷。
背景技术
炎症是一种正常的免疫反应,是具有血管系统的活体组织对各种损伤因子的刺激所发生的一种以防御反应为主的基本病理过程。任何能够引起组织损伤的因素都可成为炎症的原因。炎症的基本病理变化通常包括局部组织的变质、渗出和增生等。慢性炎症反应通常与II型糖尿病、痛风、动脉粥样硬化、肠炎、癌症、心脑血管疾病等疾病的发生与发展密切相关。
三七Panax notoginseng(Burk.)F.H.Chen为五加科人参属宿根草本植物,又名田七、血参、田三七、滇三七、参三七,主产于云南文山州,在广西、广东等地亦有分布。作为传统常用名贵药材,三七不仅应用于治疗跌打损伤,民间也常用于预防血栓。
三七的入药部位主要是其根和根茎,三萜皂苷类成分是其发挥作用的主要物质之一。但是,由于三七的适宜生长环境较为局限,导致三七的药用资源不足。为了扩大其资源的利用度,有必要对三七的除了根和根茎之外的其它部位(例如,三七叶)的化学成分及药理活性进行研究。
发明内容
本发明的目的在于通过多种提取、分离手段,从三七叶中提取、分离并鉴定具有抗炎活性的活性单体化合物。
本发明的目的是通过如下的技术方案实现的:利用多种提取、分离手段,包括溶剂提取法、溶剂萃取法、大孔吸附树脂法、正反硅胶柱层析、凝胶柱层析和制备HPLC等方法,系统研究了三七叶的化学成分。
具体而言,本发明提供:下述化学式1至化学式13所示的人参二醇型三萜皂苷或其可药用的盐,
本发明还提供一种三七叶提取物,其包含上述化学式1至化学式13所示的人参二醇型三萜皂苷或其可药用的盐中的至少一者。
另外,本发明还提供一种药物组合物,其包含治疗有效量的上述化学式1至化学式13所示的人参二醇型三萜皂苷或其可药用的盐中的至少一者、以及药学可接受的赋形剂。或者,本发明还提供一种药物组合物,其包含治疗有效量的上述三七叶提取物、以及药学可接受的赋形剂。
本发明进一步提供一种化妆品组合物,其包含上述化学式1至化学式13所示的人参二醇型三萜皂苷或其可药用的盐中的至少一者、以及至少一种生理学上可接受的赋形剂。或者,本发明进一步提供一种化妆品组合物,其包含上述三七叶提取物、以及至少一种生理学上可接受的赋形剂。
发明的效果
本发明提供三七叶皂苷NL-E1(以下简称为“化合物1”)、三七叶皂苷NL-E2(以下简称为“化合物2”)、三七叶皂苷NL-E3(以下简称为“化合物3”)、三七叶皂苷NL-E4(以下简称为“化合物4”)、三七叶皂苷NL-F1(以下简称为“化合物5”)、三七叶皂苷NL-F2(以下简称为“化合物6”)、三七叶皂苷NL-G1(以下简称为“化合物7”)、三七叶皂苷NL-G2(以下简称为“化合物8”)、三七叶皂苷NL-H1(以下简称为“化合物9”)、三七叶皂苷NL-H2(以下简称为“化合物10”)、三七叶皂苷NL-H3(以下简称为“化合物11”)、三七叶皂苷NL-I(以下简称为“化合物12”)、三七叶皂苷NL-J(以下简称为“化合物13”)这13个新型人参二醇型三萜皂苷化合物,其中,化合物2~7、10、12和13在25μM浓度下能够抑制脂多糖诱导的RAW264.7细胞中一氧化氮的释放,提示它们具有抗炎作用,因而预期可以作为抗炎药物的候选化合物。
具体实施方式
以下通过具体实施方式的描述对本发明进行详细说明,但这并非是对本发明的限制,本领域技术人员根据本发明的基本思想,可以做出各种修改或改进,但是只要不脱离本发明的基本思想,均在本发明的范围之内。
本发明的新颖人参二醇型三萜皂苷可以从三七叶中分离得到。具体来说,将三七叶用含水乙醇溶液回流提取,减压回收溶剂,得到浸膏。将该浸膏悬浮于水中,经大孔吸附树脂色谱柱分离,分别得到水洗脱物和95%乙醇洗脱物,其中95%乙醇洗脱物为富含包括上述化学式1至化学式13所示的化合物在内的人参二醇型三萜皂苷的三七叶提取物。
接下来,将95%乙醇洗脱物经硅胶柱层析得到多个流份,分别对各个流份进一步采用正反硅胶柱层析、凝胶柱层析和制备HPLC等方法进行精制,从而获得上述纯的化合物1~化合物13。
可以采用1H-NMR、13C-NMR等一维核磁共振谱以及1H 1H COSY、HSQC、HMBC、HSQC-TOCSY、NOESY等二维核磁共振谱等波谱技术和化学反应对上述所得到的化合物1~化合物13的结构进行鉴定确证。
上述提取、分离、精制、以及结构鉴定过程中的具体操作对于本领域技术人员来说是公知的,可以参考相应的技术手册或教科书中记载的内容来进行。例如,参见吴继洲主编《天然药物化学》(高等教育出版社)、裴月湖主编《有机化合物波谱解析》(中国医药科技出版社)。本说明书中省略其详细的描述。
本发明中,可药用的盐类指的是在上述化学式1至化学式13所表示的本发明化合物当中,羟基与金属或有机碱形成的盐类。作为金属,可列举出钠或钾等碱金属或者镁或钙等碱土类金属;作为有机碱,可列举出三乙胺或二异丙胺等。
本发明还提供一种药物组合物,包含治疗有效量的上述化学式1至化学式13所表示的人参二醇型三萜皂苷中的至少一者、以及任选的药学可接受的赋形剂。或者,本发明还提供一种药物组合物,包含治疗有效量的上述三七叶提取物、以及任选的药学可接受的赋形剂。
上述药学可接受的赋形剂可以是药物制剂领域中任何常规的赋形剂,特定赋形剂的选择将取决于用于治疗特定患者的给药方式或疾病类型和状态,用于特定给药模式的合适药物组合物的制备方法完全在药物领域技术人员的知识范围内。例如,可以作为药学可接受的赋形剂包括药学领域常规的稀释剂、载体、填充剂、粘合剂、湿润剂、崩解剂等。
上述药物组合物可以制成片剂、粉剂、颗粒剂、胶囊、口服液、注射乳剂、注射用无菌粉针等多种形式。上述各种剂型的药物均可以按照药学领域的常规方法制备。
本发明进一步提供一种化妆品组合物,包含上述化学式1至化学式13所表示的人参二醇型三萜皂苷中的至少一者、以及任选的至少一种生理学上可接受的赋形剂。或者,本发明进一步提供一种化妆品组合物,包含上述三七叶提取物、以及任选的至少一种生理学上可接受的赋形剂。
术语“生理学上可接受的赋形剂”是指适合于局部或口服使用并且当与哺乳动物(特别是人类)的粘膜、指甲、头皮、头发、体毛和皮肤等接触时不存在任何毒性、不相容性等的风险的物质。根据本发明,生理学上可接受的赋形剂优选是美容上可接受的赋形剂。可适用的这些赋形剂是本领域技术人员熟知的,包括例如润肤剂、有机溶剂、螯合剂、渗透剂、增稠剂、填充剂、乳化剂或表面活性剂、防腐剂、着色剂、芳香剂、和其混合物。
上述化妆品组合物可以呈凝胶、乳液、微乳液、精华、油、面膜、药膏、软膏、化妆水、浓缩液、悬浮液、泡沫、固体棒或气溶胶的形式。
除了上述人参二醇型三萜皂苷以外,根据本发明的化妆品组合物还可以含有一种或多种第二活性剂,所述第二活性剂能够增强上述人参二醇型三萜皂苷的活性并且与其相容,即不易相互反应或者掩盖或限制其作用。特别地,第二活性剂可以例如选自保湿剂、湿润剂、抗氧化剂、皮肤保护剂、抗老化活性剂、防射线剂特别是防UV射线剂、及其混合物。
实施例
以下通过例子进一步解释或说明本发明的内容,但是这些例子不应被理解为对本发明保护范围的限制。
需要说明的是,以下实施例中所用的各种试剂等是本领域已知的,可通过商购得到。
实施例1
三七叶提取物的制备
干燥的三七叶8kg,剪碎,经10倍量50%乙醇溶液依次加热回流提取3次,时间为3小时、2小时、2小时,合并滤液,减压回收溶剂,得浸膏2.67kg。取浸膏2.1kg溶于20L水中,经D101大孔吸附树脂色谱柱分离,洗脱溶剂为水→95%乙醇,从而得到了水以及95%乙醇洗脱物,分别为760.0g和695.0g。其中,95%乙醇洗脱物作为富含人参二醇型三萜皂苷的三七叶提取物用于后续的实验。
实施例2
人参二醇型三萜皂苷化合物1~13的分离制备及结构鉴定
化合物1~13分离是同时进行的,因而在一个实施例中进行描述。
1.[化合物1~13的分离制备]
取上述实施例1中所获得的95%乙醇洗脱物150.0g,经硅胶柱层析[CH2Cl2→CH2Cl2/MeOH(体积比为100:3→100:7→10:1→8:1→3:1→2:1→1:1)→MeOH],得到12个组分[其中,Fr.1(1.3g)、Fr.2(6.2g)、Fr.3(2.1g)、Fr.4(5.4g)、Fr.5(6.8g)、Fr.6(6.5g)、Fr.7(56.3g)、Fr.8(28.2g)、Fr.9(16.4g)、Fr.10(7.2g)、Fr.11(3.7g)、Fr.12(2.0g)]。
Fr.7(30.0g)经MCI gel CHP 20P柱层析[MeOH/H2O(65:35→70:30→75:25→80:20→100:0,v/v)],得到12个组分[Fr.7-1(80.6mg)、Fr.7-2(1.3g)、Fr.7-3(582.8mg)、Fr.7-4(447.3mg)、Fr.7-5(482.1mg)、Fr.7-6(2.4g)、Fr.7-7(4.9g)、Fr.7-8(12.1g)、Fr.7-9(2.8g)、Fr.7-10(1.1g)、Fr.7-11(169.3mg)、Fr.7-12(1.3g)]。Fr.7-4(447.3mg)经PHPLC分离[CH3CN-1%HAc(26:74,v/v),Cosmosil 5C18-MS-II柱],得到三七叶皂苷NL-E1(化合物1,10.4mg)。Fr.7-5(480.0mg)经PHPLC分离[CH3CN-1%HAc(30:70,v/v),Cosmosil 5C18-MS-II柱],得到三七叶皂苷NL-H1(化合物9,23.1mg)和三七叶皂苷NL-H2(化合物10,22.8mg)。Fr.7-6(800.0mg)经PHPLC分离制备[MeOH-1%HAc(70:30,v/v),Cosmosil 5C18-MS-II柱],得到7个组分[Fr.7-6-1(17.1mg),Fr.7-6-2(34.3mg),Fr.7-6-3(141.5mg),Fr.7-6-4(179.5mg),Fr.7-6-5(20.7mg),Fr.7-6-6(51.3mg),Fr.7-6-7(87.1mg)]。Fr.7-6-4(179.5mg)经PHPLC分离纯化[CH3CN-1%HAc(32:68,v/v),Cosmosil 5C18-MS-II柱],得到三七叶皂苷NL-G1(化合物7,32.6mg)和三七叶皂苷NL-I(化合物12,8.7mg)。
Fr.8(25.0g)经MCI gel CHP 20P柱层析[MeOH/H2O(40:60→60:40→70:30→80:20→100:0,v/v)],得到11个组分[Fr.8-1(83.1mg)、Fr.8-2(46.0mg)、Fr.8-3(202.4mg)、Fr.8-4(98.6mg)、Fr.8-5(303.6mg)、Fr.8-6(1.7g)、Fr.8-7(611.2mg)、Fr.8-8(6.7g)、Fr.8-9(11.6g)、Fr.8-10(811mg)、Fr.8-11(838.1mg)]。Fr.8-6(1.6g)经PHPLC分离制备[MeOH-1%HAc(60:40,v/v),Venusil PrepG C18柱],得到13个组分[Fr.8-6-1(53.3mg)、Fr.8-6-2(13.9mg)、Fr.8-6-3(10.1mg)、Fr.8-6-4(39.0mg)、Fr.8-6-5(40.3mg)、Fr.8-6-6(135.3mg)、Fr.8-6-7(264.4mg)、Fr.8-6-8(244.2mg)、Fr.8-6-9(223.8mg)、Fr.8-6-10(207.5mg)、Fr.8-6-11(73.6mg)、Fr.8-6-12(97.2mg)、Fr.8-6-13(146.0mg)]。Fr.8-6-6(135.3mg)经PHPLC分离纯化[CH3CN-1%HAc(26:74,v/v),Cosmosil 5C18-MS-II柱],得到三七叶皂苷NL-H3(化合物11,18.4mg)。
Fr.9(15.0g)经MCI gel CHP 20P柱层析[MeOH/H2O(60:40→70:30→80:20→100:0,v/v)],得到10个组分[Fr.9-1(119.0mg)、Fr.9-2(129.6mg)、Fr.9-3(254.2mg)、Fr.9-4(1.6g)、Fr.9-5(261.0mg)、Fr.9-6(1.3g)、Fr.9-7(7.1g)、Fr.9-8(2.7g)、Fr.9-9(139.9mg)、Fr.9-10(323.0mg)]。其中,Fr.9-3(254.2mg)经PHPLC分离纯化[CH3CN-1%HAc(22:78,v/v),Cosmosil 5C18-MS-II柱],得到三七叶皂苷NL-E2(化合物2,5.1mg),三七叶皂苷NL-E3(化合物3,6.4mg),三七叶皂苷NL-E4(化合物4,3.4mg),三七叶皂苷NL-F1(化合物5,13.0mg),三七叶皂苷NL-F2(化合物6,5.1mg)和三七叶皂苷NL-J(化合物13,3.2mg)。Fr.9-4(500.0mg)经PHPLC分离制备[CH3CN-1%HAc(26:74,v/v),Cosmosil 5C18-MS-II柱],得到11个组分[Fr.9-4-1(95.8mg)、Fr.9-4-2(3.6mg)、Fr.9-4-3(42.3mg)、Fr.9-4-4(9.7mg)、Fr.9-4-5(103.2mg)、Fr.9-4-6(86.0mg)、Fr.9-4-7(57.2mg)、Fr.9-4-8(21.4mg)、Fr.9-4-9(23.2mg)、Fr.9-4-10(10.1mg)]。Fr.9-4-3(42.3mg)经PHPLC分离纯化[MeOH-1%HAc(60:40,v/v),Wakopak Navi C30-5柱],得到三七叶皂苷NL-H3(化合物11,27.4mg)。Fr.9-4-6(86.0mg)经PHPLC分离纯化[MeOH-1%HAc(60:40,v/v),Cosmosil 5C18-MS-II柱],得到三七叶皂苷NL-G2(化合物8,16.5mg)。
2.[结构鉴定]
主要利用光谱技术,包括红外、质谱、核磁共振谱(1H-NMR、13C-NMR、1H 1H COSY、HSQC、HMBC、HSQC-TOCSY、NOESY)和旋光度,鉴定上述所得到的化合物1~化合物13的结构。
运用二维核磁共振谱波谱技术,确定了取代基的位置和糖的连接位置,结合高分辨质谱,对它们的全部碳信号和氢信号进行了确切的归属。化合物1~化合物13的理化数据如下所示。
三七叶皂苷NL-E1(化合物1):3β,12β,20S,24R,25-五羟基达玛烷-3-O-β-D-吡喃葡萄糖基-20-O-α-L-呋喃阿拉伯糖基(1→6)-β-D-吡喃葡萄糖苷
白色粉末;
[α]D 25-4.8(conc 0.50,MeOH);
IRνmax(KBr)cm-1:3351,2940,2877,1570,1411,1160,1074,1033;
1H NMR(C5D5N,600MHz)δ:0.77、1.53(1H each,both m,H2-1),1.82、2.22(1Heach,both m,overlapped,H2-2),3.37(1H,dd,J=3.6、11.4Hz,H-3),0.73(1H,br.d,ca.J=12Hz,H-5),[1.35(1H,m),1.49(1H,m,overlapped),H2-6],[1.20(1H,m),1.48(1H,m,overlapped),H2-7],1.38(1H,m,overlapped,H-9),1.49、1.96(1H each,both m,overlapped,H2-11),4.06(1H,m,H-12),2.07(1H,dd,J=10.2、10.2Hz,H-13),[0.97(1H,m),1.57(1H,m,overlapped),H2-15],1.45、1.82(1H each,both m,overlapped,H2-16),2.50(1H,q like,ca.J=10Hz,H-17),0.96(3H,s,H3-18),0.80(3H,s,H3-19),1.65(3H,s,H3-21),[2.10(1H,m,overlapped),2.90(1H,m),H2-22],2.07、2.20(1H each,both m,overlapped,H2-23),3.83(1H,br.d,ca.J=8Hz,H-24),1.57(6H,s,H3-26 and 27),1.32(3H,s,H3-28),1.00(3H,s,H3-29),0.91(3H,s,H3-30),4.96(1H,d,J=7.2Hz,H-1'),4.05(1H,dd,J=7.2、9.0Hz,H-2'),4.26(1H,dd,J=8.4、9.0Hz,H-3'),4.23(1H,dd,J=9.0、9.6Hz,H-4'),4.03(1H,m,overlapped,H-5'),[4.42(1H,dd,J=4.8、10.2Hz),4.62(1H,br.d,ca.J=11Hz),H2-6'],5.14(1H,d,J=7.8Hz,H-1”),3.91(1H,dd,J=7.8、7.8Hz,H-2”),4.15(1H,dd,J=7.8、8.4Hz,H-3”),3.94(1H,dd,J=8.4、9.0Hz,H-4”),4.03(1H,m,H-5”),[4.10(1H,dd,J=6.0、10.2Hz),4.71(1H,br.d,ca.J=11Hz),H2-6”],5.69(1H,br.s,H-1”),4.90(1H,br.s,H-2”),4.78(1H,m,overlapped,H-3”),4.78(1H,m,overlapped,H-4”),[4.19(1H,dd,J=6.0、12.0Hz),4.32(1H,br.d,ca.J=12Hz),H2-5”];
13C NMR(C5D5N,150MHz)δ:39.2(C-1),26.8(C-2),89.0(C-3),39.7(C-4),56.4(C-5),18.5(C-6),35.1(C-7),40.0(C-8),50.2(C-9),37.0(C-10),30.9(C-11),70.5(C-12),49.4(C-13),51.5(C-14),30.8(C-15),26.6(C-16),52.1(C-17),16.0(C-18),16.3(C-19),83.5(C-20),22.7(C-21),34.4(C-22),26.9(C-23),79.7(C-24),73.0(C-25),26.5(C-26),25.9(C-27),28.1(C-28),16.8(C-29),17.2(C-30),107.0(C-1'),75.8(C-2'),78.8(C-3'),71.9(C-4'),78.4(C-5'),63.1(C-6'),98.1(C-1”),75.0(C-2”),79.1(C-3”),72.0(C-4”),76.8(C-5”),68.4(C-6”),110.1(C-1”'),83.8(C-2”'),78.9(C-3”'),85.8(C-4”'),62.8(C-5”');
ESI-Q-Orbitrap MS:负离子模式:m/z 949.53735[M-H]-(calcd for C47H81O19,949.53666),确定其分子式为C47H82O19。
三七叶皂苷NL-E2(2):3β,12β,20S,24R,25-五羟基达玛烷-3-O-[β-D-吡喃葡萄糖基(1→2)-β-D-吡喃葡萄糖基]-20-O-α-L-呋喃阿拉伯糖基(1→6)-β-D-吡喃葡萄糖苷
白色粉末;
[α]D 25-3.1(conc 0.26,MeOH);
IRνmax(KBr)cm-1:3355,2939,2877,1569,1413,1157,1074,1033;
1H NMR(C5D5N,600MHz)δ:0.73、1.54(1H each,both m,H2-1),1.82、2.22(1Heach,both m,overlapped,H2-2),3.27(1H,dd,J=4.2、12.0Hz,H-3),0.66(1H,br.d,ca.J=11Hz,H-5),1.35、1.45(1Heach,both m,overlapped,H2-6),[1.19(1H,m),1.43(1H,m,overlapped),H2-7],1.35(1H,m,overlapped,H-9),1.49、1.96(1H each,both m,overlapped,H2-11),4.06(1H,m,H-12),2.06(1H,dd,J=10.8、10.8Hz,H-13),[0.96(1H,m),1.58(1H,m,overlapped),H2-15],1.43、1.82(1H each,both m,overlapped,H2-16),2.50(1H,q like,ca.J=11Hz,H-17),0.96(3H,s,H3-18),0.80(3H,s,H3-19),1.65(3H,s,H3-21),[2.08(1H,m,overlapped),2.90(1H,m),H2-22],2.06、2.20(1H each,both m,overlapped,H2-23),3.84(1H,br.d,ca.J=9Hz,H-24),1.58(3H,s,H3-26),1.58(3H,s,H3-27),1.29(3H,s,H3-28),1.11(3H,s,H3-29),0.91(3H,s,H3-30),4.94(1H,d,J=7.8Hz,H-1'),4.26(1H,dd,J=7.8、9.0Hz,H-2'),4.33(1H,m,overlapped,H-3'),4.34(1H,m,overlapped,H-4'),3.94(1H,m,overlapped,H-5'),[4.37(1H,dd,J=5.4、12.0Hz),4.59(1H,dd,J=1.8、12.0Hz),H2-6'],5.39(1H,d,J=7.8Hz,H-1”),4.14(1H,m,overlapped,H-2”),4.28(1H,dd,J=9.0、9.0Hz,H-3”),4.15(1H,m,overlapped,H-4”),3.93(1H,m,overlapped,H-5”),[4.48(1H,dd,J=3.6、11.4Hz),4.51(1H,dd,J=2.4、11.4Hz),H2-6”],5.15(1H,d,J=7.8Hz,H-1”),3.91(1H,dd,J=7.8、8.4Hz,H-2”),4.17(1H,dd,J=8.4、9.0Hz,H-3”),3.93(1H,dd,J=9.0、9.5Hz,H-4”),4.03(1H,m,H-5”),[4.11(1H,dd,J=6.6、10.8Hz),4.71(1H,dd,J=1.2、10.8Hz),H2-6”],5.71(1H,d,J=1.8Hz,H-1”'),4.91(1H,br.s,H-2”'),4.79(1H,m,overlapped,H-3”'),4.78(1H,m,overlapped,H-4”'),[4.21(1H,dd,J=4.8、11.4Hz),4.32(1H,m,overlapped),H2-5”'];
13C NMR(C5D5N,150MHz)δ:39.2(C-1),26.9(C-2),89.0(C-3),39.7(C-4),56.4(C-5),18.4(C-6),35.1(C-7),40.0(C-8),50.2(C-9),36.9(C-10),30.8(C-11),70.5(C-12),49.4(C-13),51.5(C-14),30.8(C-15),26.6(C-16),52.1(C-17),15.9(C-18),16.3(C-19),83.4(C-20),22.7(C-21),34.4(C-22),26.8(C-23),79.7(C-24),73.0(C-25),26.5(C-26),25.9(C-27),28.1(C-28),16.6(C-29),17.2(C-30),105.2(C-1'),83.5(C-2'),78.3(C-3'),71.7(C-4'),78.2(C-5'),62.9(C-6'),106.1(C-1”),77.2(C-2”),78.0(C-3”),71.7(C-4”),78.4(C-5”),62.7(C-6”),98.1(C-1”'),75.1(C-2”'),79.1(C-3”'),72.0(C-4”'),76.8(C-5”'),68.4(C-6”'),110.1(C-1””),83.8(C-2””),78.9(C-3””),85.8(C-4””),62.8(C-5””);
ESI-Q-Orbitrap MS:负离子模式:m/z 1111.59045[M-H]-(calcd for C53H91O24,1111.58948),确定其分子式为C53H92O24。
三七叶皂苷NL-E3(3):3β,12β,20S,24R,25-五羟基达玛烷-3-O-[β-D-吡喃木糖基(1→2)-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃葡萄糖基]-20-O-α-L-呋喃阿拉伯糖基(1→6)-β-D-吡喃葡萄糖苷
白色粉末;
[α]D 25-5.6(conc 0.32,MeOH);
IRνmax(KBr)cm-1:3358,2939,2877,1565,1417,1157,1072,1043;
1H NMR(C5D5N,600MHz)δ:0.74、1.52(1H each,both m,H2-1),[1.83(1H,m,overlapped),2.19(1H,m),H2-2],3.29(1H,dd,J=4.2、12.0Hz,H-3),0.68(1H,br.d,ca.J=11Hz,H-5),1.36、1.47(1H each,both m,overlapped,H2-6),1.20、1.46(1H each,bothm,H2-7),1.36(1H,m,overlapped,H-9),1.48、1.94(1H each,both m,H2-11),4.06(1H,m,H-12),2.06(1H,m,overlapped,H-13),[1.00(1H,m),1.58(1H,m,overlapped),H2-15],[1.44(1H,m),1.83(1H,m,overlapped),H2-16],2.51(1H,q like,ca.J=10Hz,H-17),0.95(3H,s,H3-18),0.78(3H,s,H3-19),1.65(3H,s,H3-21),[2.08(1H,m),2.89(1H,m),H2-22],2.07、2.22(1H each,both m,H2-23),3.84(1H,br.d,ca.J=9Hz,H-24),1.58(3H,s,H3-26),1.59(3H,s,H3-27),1.28(3H,s,H3-28),1.11(3H,s,H3-29),0.90(3H,s,H3-30),4.94(1H,d,J=7.8Hz,H-1'),4.12(1H,dd,J=7.8、9.0Hz,H-2'),4.35(1H,m,overlapped,H-3'),4.10(1H,m,overlapped,H-4'),3.97(1H,m,H-5'),[4.36(1H,m,overlapped),4.59(1H,dd,J=1.8、10.8Hz),H2-6'],5.54(1H,d,J=7.8Hz,H-1”),4.20(1H,dd,J=7.8、9.0Hz,H-2”),4.29(1H,dd,J=9.0、9.0Hz,H-3”),4.22(1H,dd,J=9.0、9.0Hz,H-4”),3.88(1H,m,H-5”),[4.36(1H,m,overlapped),4.51(1H,dd,J=2.5、11.0Hz),H2-6”],5.40(1H,d,J=7.2Hz,H-1”'),4.11(1H,m,overlapped,H-2”'),4.14(1H,m,overlapped,H-3”'),4.15(1H,m,overlapped,H-4”'),[3.70(1H,dd,J=9.6、9.6Hz),4.31(1H,m,overlapped),H2-5”'],5.13(1H,d,J=7.2Hz,H-1””),3.92(1H,dd,J=7.2、9.0Hz,H-2””),4.17(1H,m,overlapped,H-3””),3.93(1H,dd,J=9.0、9.0Hz,H-4””),4.03(1H,m,H-5””),[4.09(1H,m,overlapped),4.70(1H,br.d,ca.J=10Hz),H2-6””],5.71(1H,br.s,H-1””'),4.91(1H,br.s,H-2””'),4.79(1H,m,overlapped,H-3””'),4.78(1H,m,overlapped,H-4””'),[4.21(1H,dd,J=5.4、12.6Hz),4.31(1H,m,overlapped),H2-5””'];
13C NMR(C5D5N,150MHz)δ:39.2(C-1),26.7(C-2),89.0(C-3),39.8(C-4),56.4(C-5),18.4(C-6),35.1(C-7),40.0(C-8),50.2(C-9),36.9(C-10),30.8(C-11),70.5(C-12),49.4(C-13),51.5(C-14),30.8(C-15),26.6(C-16),52.0(C-17),15.9(C-18),16.3(C-19),83.8(C-20),22.7(C-21),34.4(C-22),26.9(C-23),79.7(C-24),73.0(C-25),26.5(C-26),25.9(C-27),28.1(C-28),16.7(C-29),17.2(C-30),104.8(C-1'),82.9(C-2'),78.7(C-3'),71.1(C-4'),78.3(C-5'),63.0(C-6'),103.2(C-1”),84.6(C-2”),78.0(C-3”),71.8(C-4”),77.8(C-5”),62.9(C-6”),106.5(C-1”'),76.0(C-2”'),77.8(C-3”'),70.7(C-4”'),67.4(C-5”'),98.1(C-1””),75.0(C-2””),79.1(C-3””),72.0(C-4””),76.8(C-5””),68.4(C-6””),110.1(C-1””'),83.5(C-2””'),78.9(C-3””'),85.8(C-4””'),62.8(C-5””');
ESI-Q-Orbitrap MS:负离子模式:m/z 1243.63171[M-H]-(calcd for C58H99O28,1243.63174),确定其分子式为C58H100O28。
三七叶皂苷NL-E4(4):3β,12β,20S,24R,25-五羟基达玛烷-3-O-[β-D-吡喃木糖基(1→2)-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃葡萄糖基]-20-O-β-D-吡喃木糖基(1→6)-β-D-吡喃葡萄糖苷
白色粉末;
[α]D 25-3.5(conc 0.17,MeOH);
IRνmax(KBr)cm-1:3354,2933,2873,1571,1414,1072,1043;
1H NMR(C5D5N,600MHz)δ:0.75、1.53(1H each,both m,H2-1),[1.83(1H,m,overlapped),2.20(1H,m),H2-2],3.30(1H,dd,J=3.6、12.0Hz,H-3),0.69(1H,br.d,ca.J=12Hz,H-5),1.36、1.47(1H each,both m,overlapped,H2-6),[1.20(1H,m),1.44(1H,m,overlapped),H2-7],1.36(1H,m,overlapped,H-9),[1.48(1H,m,overlapped),1.95(1H,m),H2-11],4.08(1H,m,H-12),2.06(1H,dd,J=10.2、10.2Hz,H-13),[0.98(1H,m),1.57(1H,m,overlapped),H2-15],1.42、1.83(1H each,both m,overlapped,H2-16),2.52(1H,qlike,ca.J=11Hz,H-17),0.94(3H,s,H3-18),0.80(3H,s,H3-19),1.64(3H,s,H3-21),2.08、2.90(1H each,both m,H2-22),[2.11(1H,m),2.22(1H,m,overlapped),H2-23],3.84(1H,br.d,ca.J=10Hz,H-24),1.57(3H,s,H3-26),1.56(3H,s,H3-27),1.28(3H,s,H3-28),1.12(3H,s,H3-29),0.93(3H,s,H3-30),4.94(1H,d,J=7.8Hz,H-1'),4.13(1H,dd,J=7.8、9.0Hz,H-2'),4.37(1H,m,overlapped,H-3'),4.10(1H,dd,J=9.0、9.0Hz,H-4'),3.97(1H,m,H-5'),[4.35(1H,m,overlapped),4.59(1H,br.d,ca.J=12Hz),H2-6'],5.53(1H,d,J=7.8Hz,H-1”),4.21(1H,dd,J=7.8、9.0Hz,H-2”),4.30(1H,dd,J=9.0、9.0Hz,H-3”),4.21(1H,m,overlapped,H-4”),3.87(1H,m,H-5”),[4.37(1H,m,overlapped),4.50(1H,br.d,ca.J=10Hz),H2-6”],5.41(1H,d,J=7.2Hz,H-1”'),4.12(1H,dd,J=7.2、9.0Hz,H-2”'),4.15(1H,m,overlapped,H-3”'),4.15(1H,m,overlapped,H-4”'),[3.70(1H,dd,J=10.2、10.2Hz),4.33(1H,m,overlapped),H2-5”'],5.13(1H,m,overlapped,H-1””),3.87(1H,dd,J=7.2、9.0Hz,H-2””),4.15(1H,m,overlapped,H-3””),4.04(1H,m,overlapped,H-4””),4.04(1H,m,overlapped,H-5””),[4.25(1H,dd,J=3.6、12.0Hz),4.78(1H,br.d,ca.J=12Hz),H2-6””],4.99(1H,d,J=7.2Hz,H-1””'),4.06(1H,dd,J=7.2、8.4Hz,H-2””'),4.16(1H,m,overlapped,H-3””'),4.21(1H,m,overlapped,H-4””'),[3.74(1H,dd,J=10.2、10.2Hz),4.32(1H,m,overlapped),H2-5””'];
13C NMR(C5D5N,150MHz)δ:39.2(C-1),26.8(C-2),89.0(C-3),39.8(C-4),56.4(C-5),18.5(C-6),35.1(C-7),40.0(C-8),50.2(C-9),36.9(C-10),30.9(C-11),70.4(C-12),49.4(C-13),51.5(C-14),30.8(C-15),26.7(C-16),51.9(C-17),16.0(C-18),16.3(C-19),83.8(C-20),22.8(C-21),34.2(C-22),26.9(C-23),79.6(C-24),73.0(C-25),26.4(C-26),26.0(C-27),28.1(C-28),16.7(C-29),17.3(C-30),104.8(C-1'),82.8(C-2'),78.7(C-3'),71.2(C-4'),78.3(C-5'),63.0(C-6'),103.1(C-1”),84.6(C-2”),78.0(C-3”),71.8(C-4”),77.9(C-5”),62.9(C-6”),106.5(C-1”'),76.0(C-2”'),77.8(C-3”'),70.7(C-4”'),67.4(C-5”')。
ESI-Q-Orbitrap MS:负离子模式:m/z 1243.63049[M-H]-(calcd for C58H99O28,1243.63174),确定其分子式为C58H100O28。
三七叶皂苷NL-F1(5):3β,12β,20S,24S,25-五羟基达玛烷-3-O-[β-D-吡喃葡萄糖基(1→2)-β-D-吡喃葡萄糖基]-20-O-β-D-吡喃木糖基(1→6)-β-D-吡喃葡萄糖苷
白色粉末;
[α]D 25+2.8(conc 0.65,MeOH);
IRνmax(KBr)cm-1:3358,2940,2877,1568,1387,1076,1035;
1H NMR(C5D5N,600MHz)δ:[0.72(1H,m),1.52(1H,m,overlapped),H2-1],[1.82(1H,m,overlapped),2.20(1H,m),H2-2],3.27(1H,dd,J=4.2、12.0Hz,H-3),0.66(1H,br.d,ca.J=11Hz,H-5),[1.34(1H,m,overlapped),1.47(1H,m),H2-6],1.17、1.42(1Heach,both m,H2-7),1.35(1H,m,overlapped,H-9),[1.51(1H,m,overlapped),1.93(1H,m),H2-11],4.14(1H,m,overlapped,H-12),2.11(1H,dd,J=10.8、10.8Hz,H-13),[0.95(1H,m),1.52(1H,m,overlapped),H2-15],1.35、1.82(1H each,both m,overlapped,H2-16),2.55(1H,q like,ca.J=10Hz,H-17),0.93(3H,s,H3-18),0.80(3H,s,H3-19),1.63(3H,s,H3-21),2.47(2H,m,H2-22),1.91、2.42(1H each,both m,H2-23),3.85(1H,br.d,ca.J=10Hz,H-24),1.51(3H,s,H3-26),1.55(3H,s,H3-27),1.27(3H,s,H3-28),1.10(3H,s,H3-29),0.94(3H,s,H3-30),4.92(1H,d,J=7.8Hz,H-1'),4.26(1H,dd,J=7.8、8.4Hz,H-2'),4.32(1H,m,overlapped,H-3'),4.33(1H,m,overlapped,H-4'),3.95(1H,m,overlapped,H-5'),[4.35(1H,dd,J=5.4、10.5Hz),4.58(1H,br.d,ca.J=11Hz),H2-6'],5.39(1H,d,J=7.8Hz,H-1”),4.13(1H,dd,J=7.8、8.4Hz,H-2”),4.26(1H,dd,J=7.8、8.4Hz,H-3”),4.15(1H,m,overlapped,H-4”),3.95(1H,m,overlapped,H-5”),[4.46(1H,dd,J=3.6、11.4Hz),4.52(1H,dd,J=3.0、11.4Hz),H2-6”],5.14(1H,d,J=7.8Hz,H-1”'),3.92(1H,dd,J=7.8、7.8Hz,H-2”'),4.17(1H,m,overlapped,H-3”'),4.08(1H,dd,J=7.8、7.8Hz,H-4”'),4.06(1H,m,overlapped,H-5”'),[4.30(1H,m,overlapped),4.74(1H,br.d,ca.J=11Hz),H2-6”'],5.00(1H,d,J=7.2Hz,H-1””),4.04(1H,dd,J=7.2、7.8Hz,H-2””),4.17(1H,m,overlapped,H-3””),4.21(1H,m,H-4””),[3.74(1H,dd,J=9.6、9.6Hz),4.32(1H,m,overlapped),H2-5””];
13C NMR(C5D5N,150MHz)δ:39.2(C-1),26.8(C-2),89.1(C-3),39.7(C-4),56.4(C-5),18.4(C-6),35.2(C-7),40.0(C-8),50.3(C-9),36.9(C-10),30.9(C-11),70.4(C-12),49.3(C-13),51.5(C-14),30.8(C-15),26.7(C-16),52.0(C-17),16.0(C-18),16.3(C-19),84.1(C-20),22.6(C-21),33.9(C-22),26.6(C-23),79.6(C-24),73.0(C-25),26.2(C-26),26.1(C-27),28.1(C-28),16.6(C-29),17.3(C-30),105.1(C-1'),83.3(C-2'),78.4(C-3'),71.7(C-4'),78.3(C-5'),62.9(C-6'),106.0(C-1”),77.1(C-2”),78.1(C-3”),71.7(C-4”),78.0(C-5”),62.7(C-6”),98.1(C-1”'),74.9(C-2”'),79.2(C-3”'),71.5(C-4”'),76.8(C-5”'),69.8(C-6”'),105.6(C-1””),74.9(C-2””),78.0(C-3””),71.2(C-4””),67.0(C-5””)。
ESI-Q-Orbitrap MS:负离子模式:m/z 1111.58997[M-H]-(calcd for C53H91O24,1111.58948),确定其分子式为C53H92O24。
三七叶皂苷NL-F2(6):3β,12β,20S,24S,25-五羟基达玛烷-3-O-[β-D-吡喃木糖基(1→2)-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃葡萄糖基]-20-O-β-D-吡喃木糖基(1→6)-β-D-吡喃葡萄糖苷
白色粉末;
[α]D 25+0.8(conc 0.26,MeOH);
IRνmax(KBr)cm-1:3356,2937,2877,1570,1415,1164,1072,1042;
1H NMR(C5D5N,600MHz)δ:[0.75(1H,m),1.56(1H,m,overlapped),H2-1],[1.83(1H,m,overlapped),2.20(1H,m),H2-2],3.30(1H,dd,J=3.0、12.0Hz,H-3),0.68(1H,br.d,ca.J=12Hz,H-5),1.35、1.45(1H each,both m,overlapped,H2-6),[1.19(1H,m),1.44(1H,m,overlapped),H2-7],1.37(1H,m,overlapped,H-9),[1.51(1H,m,overlapped),1.96(1H,m),H2-11],4.15(1H,m,overlapped,H-12),2.11(1H,dd,J=10.2、10.2Hz,H-13),[0.97(1H,m),1.55(1H,m,overlapped),H2-15],[1.37(1H,m,overlapped),1.79(1H,m),H2-16],2.55(1H,q like,ca.J=10Hz,H-17),0.93(3H,s,H3-18),0.80(3H,s,H3-19),1.64(3H,s,H3-21),[2.47(2H,m),H2-22],[1.91(1H,m),2.44(1H,m,overlapped),H2-23],3.86(1H,br.d,ca.J=10Hz,H-24),1.51(3H,s,H3-26),1.55(3H,s,H3-27),1.28(3H,s,H3-28),1.11(3H,s,H3-29),0.95(3H,s,H3-30),4.94(1H,d,J=7.8Hz,H-1'),4.13(1H,dd,J=7.8、9.0Hz,H-2'),4.36(1H,m,overlapped,H-3'),4.10(1H,dd,J=8.5、8.5Hz,H-4'),3.98(1H,m,H-5'),[4.35(1H,m,overlapped),4.59(1H,br.d,ca.J=11Hz),H2-6'],5.53(1H,d,J=7.2Hz,H-1”),4.21(1H,m,overlapped,H-2”),4.29(1H,dd,J=9.6、9.6Hz,H-3”),4.21(1H,m,overlapped,H-4”),3.89(1H,m,H-5”),[4.37(1H,m,overlapped),4.51(1H,br.d,ca.J=11Hz),H2-6”],5.40(1H,d,J=7.2Hz,H-1”'),4.11(1H,dd,J=7.2、9.0Hz,H-2”'),4.14(1H,m,overlapped,H-3”'),4.15(1H,m,overlapped,H-4”'),[3.70(1H,dd,J=9.6、9.6Hz),4.33(1H,m,overlapped),H2-5”'],5.13(1H,m,overlapped,H-1””),3.92(1H,dd,J=7.2、9.0Hz,H-2””),4.17(1H,m,overlapped,H-3””),4.06(1H,m,overlapped,H-4””),4.05(1H,m,overlapped,H-5””),[4.28(1H,dd,J=2.4、10.8Hz),4.75(1H,br.d,ca.J=11Hz),H2-6””],5.00(1H,d,J=7.2Hz,H-1””'),4.05(1H,dd,J=7.2、8.4Hz,H-2””'),4.16(1H,m,overlapped,H-3””'),4.22(1H,m,overlapped,H-4””'),[3.76(1H,dd,J=9.0、9.0Hz),4.33(1H,m,overlapped),H2-5””'];
13C NMR(C5D5N,150MHz)δ:39.2(C-1),26.8(C-2),89.0(C-3),39.8(C-4),56.4(C-5),18.5(C-6),35.2(C-7),40.0(C-8),50.3(C-9),36.9(C-10),30.9(C-11),70.4(C-12),49.3(C-13),51.5(C-14),30.8(C-15),26.7(C-16),52.0(C-17),16.0(C-18),16.3(C-19),84.1(C-20),22.6(C-21),34.0(C-22),26.6(C-23),79.6(C-24),73.0(C-25),26.2(C-26),26.1(C-27),28.1(C-28),16.7(C-29),17.4(C-30),104.8(C-1'),82.8(C-2'),78.7(C-3'),71.2(C-4'),78.3(C-5'),63.0(C-6'),103.2(C-1”),84.6(C-2”),78.0(C-3”),71.8(C-4”),77.9(C-5”),62.9(C-6”),106.5(C-1”'),76.0(C-2”'),77.8(C-3”'),70.7(C-4”'),67.4(C-5”'),98.1(C-1””),74.9(C-2””),79.2(C-3””),71.5(C-4””),76.8(C-5””),69.8(C-6””),105.6(C-1””'),74.9(C-2””'),78.0(C-3””'),71.2(C-4””'),67.0(C-5””')。
ESI-Q-Orbitrap MS:负离子模式:m/z 1243.63147[M-H]-(calcd for C58H99O28,1243.63174),确定其分子式为C58H100O28。
三七叶皂苷NL-G1(7):3β,12β,20S,24R-四羟基达玛-25-烯-3-O-β-D-吡喃葡萄糖基-20-O-β-D-吡喃木糖基(1→6)-β-D-吡喃葡萄糖苷
白色粉末;
[α]D 25+5.5(conc 1.01,MeOH);
IRνmax(KBr)cm-1:3362,2943,2877,1648,1452,1387,1162,1075,1038;
1H NMR(C5D5N,500MHz)δ:[0.77(1H,m),1.54(1H,m,overlapped),H2-1],[1.83(1H,m,overlapped),2.22(1H,m),H2-2],3.36(1H,dd,J=4.5、12.0Hz,H-3),0.73(1H,br.d,ca.J=12Hz,H-5),1.37、1.51(1H each,both m,overlapped,H2-6),[1.20(1H,m),1.48(1H,m,overlapped),H2-7],1.39(1H,m,overlapped,H-9),[1.54(1H,m,overlapped),1.96(1H,m),H2-11],4.12(1H,m,H-12),2.04(1H,m,overlapped,H-13),0.98、1.54(1Heach,both m,overlapped,H2-15),1.39、1.83(1H each,both m,overlapped,H2-16),2.55(1H,q like,ca.J=11Hz,H-17),0.98(3H,s,H3-18),0.81(3H,s,H3-19),1.65(3H,s,H3-21),[1.95(1H,m,overlapped),2.62(1H,dt like,ca.J=5、14Hz),H2-22],[2.04(1H,m,overlapped),2.33(1H,m),H2-23],4.45(1H,t like,ca.J=7Hz,H-24),4.93、5.25(1Heach,both br.s,H2-26),1.95(3H,s,H3-27),1.31(3H,s,H3-28),0.99(3H,s,H3-29),0.96(3H,s,H3-30),4.94(1H,d,J=7.5Hz,H-1'),4.05(1H,dd,J=7.5、9.0Hz,H-2'),4.27(1H,dd,J=9.0、9.0Hz,H-3'),4.19(1H,m,overlapped,H-4'),4.00(1H,m,H-5'),[4.40(1H,dd,J=5.5、11.5Hz),4.60(1H,dd,J=2.0、11.5Hz),H2-6'],5.12(1H,d,J=7.5Hz,H-1”),3.88(1H,dd,J=7.5、8.0Hz,H-2”),4.15(1H,m,overlapped,H-3”),4.03(1H,m,overlapped,H-4”),4.03(1H,m,overlapped,H-5”),[4.25(1H,m,overlapped),4.74(1H,br.d,ca.J=11Hz),H2-6”],4.99(1H,d,J=8.0Hz,H-1”'),4.03(1H,m,overlapped,H-2”'),4.15(1H,m,overlapped,H-3”'),4.17(1H,m,overlapped,H-4”'),[3.73(1H,dd,J=10.0、11.5Hz),4.32(1H,dd,J=5.0、11.5Hz),H2-5”'];
13C NMR(C5D5N,125MHz)δ:39.2(C-1),26.7(C-2),88.9(C-3),39.7(C-4),56.4(C-5),18.5(C-6),35.1(C-7),40.0(C-8),50.2(C-9),36.9(C-10),30.9(C-11),70.3(C-12),49.4(C-13),51.5(C-14),30.8(C-15),26.7(C-16),51.8(C-17),15.9(C-18),16.3(C-19),83.5(C-20),22.7(C-21),32.7(C-22),30.6(C-23),76.1(C-24),149.5(C-25),110.4(C-26),18.2(C-27),28.1(C-28),16.8(C-29),17.3(C-30),106.9(C-1'),75.8(C-2'),78.7(C-3'),71.9(C-4'),78.3(C-5'),63.1(C-6'),98.1(C-1”),74.9(C-2”),79.1(C-3”),71.6(C-4”),76.8(C-5”),69.9(C-6”),105.6(C-1”'),74.8(C-2”'),77.9(C-3”'),71.1(C-4”'),66.9(C-5”')。
ESI-Q-Orbitrap MS:负离子模式:m/z 931.52795[M-H]-(calcd for C47H79O18,931.52609),确定其分子式为C47H80O18。
三七叶皂苷NL-G2(8):3β,12β,20S,24R-四羟基达玛-25-烯-3-O-[β-D-吡喃木糖基(1→2)-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃葡萄糖基]-20-O-β-D-吡喃木糖基(1→6)-β-D-吡喃葡萄糖苷
白色粉末;
[α]D 25-0.6(conc 0.72,MeOH);
IRνmax(KBr)cm-1:3358,2941,2877,1646,1456,1386,1166,1073,1040;
1H NMR(C5D5N,500MHz)δ:[0.74(1H,m),1.49(1H,m,overlapped),H2-1],[1.83(1H,m,overlapped),2.19(1H,m),H2-2],3.29(1H,dd,J=3.5、11.0Hz,H-3),0.67(1H,br.d,ca.J=12Hz,H-5),[1.37(1H,m,overlapped),1.50(1H,m),H2-6],1.19、1.45(1Heach,both m,H2-7),1.37(1H,m,overlapped,H-9),1.55、1.95(1H each,both m,overlapped,H2-11),4.14(1H,m,overlapped,H-12),2.06(1H,m,overlapped,H-13),0.99、1.55(1H each,both m,overlapped,H2-15),[1.39(1H,m),1.83(1H,m,overlapped),H2-16],2.57(1H,q like,ca.J=10Hz,H-17),0.97(3H,s,H3-18),0.79(3H,s,H3-19),1.66(3H,s,H3-21),[1.95(1H,m,overlapped),2.66(1H,t like,ca.J=5Hz),H2-22],[2.06(1H,m,overlapped),2.36(1H,m),H2-23],4.48(1H,t like,ca.J=6Hz,H-24),4.95、5.27(1Heach,both br.s,H2-26),1.97(3H,s,H3-27),1.28(3H,s,H3-28),1.11(3H,s,H3-29),0.96(3H,s,H3-30),4.96(1H,d,J=8.5Hz,H-1'),4.17(1H,m,overlapped,H-2'),4.38(1H,m,overlapped,H-3'),4.11(1H,dd,J=9.0、9.0Hz,H-4'),4.00(1H,m,H-5'),[4.38(1H,m,overlapped),4.62(1H,br.d,ca.J=11Hz),H2-6'],5.56(1H,d,J=7.5Hz,H-1”),4.23(1H,m,overlapped,H-2”),4.32(1H,m,overlapped,H-3”),4.23(1H,m,overlapped,H-4”),3.91(1H,m,H-5”),[4.38(1H,m,overlapped),4.54(1H,br.d,ca.J=10Hz),H2-6”],5.44(1H,d,J=7.0Hz,H-1”'),4.14(1H,m,overlapped,H-2”'),4.17(1H,m,overlapped,H-3”'),4.17(1H,m,overlapped,H-4”'),[3.71(1H,dd,J=10.0、10.0Hz),4.35(1H,m,overlapped),H2-5”'],5.15(1H,d,J=8.0Hz,H-1””),3.93(1H,dd,J=8.0、8.0Hz,H-2””),4.18(1H,dd,J=7.0、8.0Hz,H-3””),4.08(1H,m,overlapped,H-4””),4.07(1H,m,overlapped,H-5””),[4.29(1H,m),4.78(1H,br.d,ca.J=11Hz),H2-6””],5.02(1H,d,J=7.5Hz,H-1””'),4.07(1H,m,overlapped,H-2””'),4.20(1H,dd,J=8.5、8.5Hz,H-3””'),4.23(1H,m,overlapped,H-4””'),[3.76(1H,dd,J=11.0、11.0Hz),4.35(1H,m,overlapped),H2-5””'];
13C NMR(C5D5N,125MHz)δ:39.2(C-1),26.7(C-2),89.0(C-3),39.7(C-4),56.3(C-5),18.2(C-6),35.1(C-7),40.0(C-8),50.2(C-9),36.8(C-10),30.8(C-11),70.3(C-12),49.4(C-13),51.4(C-14),30.7(C-15),26.7(C-16),51.8(C-17),15.9(C-18),16.3(C-19),83.5(C-20),22.6(C-21),32.7(C-22),30.5(C-23),76.1(C-24),149.6(C-25),110.4(C-26),18.4(C-27),28.1(C-28),16.7(C-29),17.3(C-30),104.8(C-1'),82.6(C-2'),78.7(C-3'),71.1(C-4'),78.3(C-5'),62.9(C-6'),103.0(C-1”),84.5(C-2”),77.9(C-3”),71.7(C-4”),78.0(C-5”),62.8(C-6”),106.4(C-1”'),76.0(C-2”'),77.8(C-3”'),70.7(C-4”'),67.4(C-5”'),98.1(C-1””),74.9(C-2””),79.2(C-3””),71.5(C-4””),76.9(C-5””),69.9(C-6””),105.7(C-1””'),74.9(C-2””'),78.1(C-3””'),71.2(C-4””'),67.0(C-5””')。
ESI-Q-Orbitrap MS:负离子模式:m/z 1225.62292[M-H]-(calcd for C58H97O27,1225.62117),确定其分子式为C58H98O27。
三七叶皂苷NL-H1(9):3β,12β,20S,24S-四羟基达玛-25-烯-3-O-β-D-吡喃葡萄糖基-20-O-α-L-呋喃阿拉伯糖基(1→6)-β-D-吡喃葡萄糖苷
白色粉末;
[α]D 25-4.5(conc 1.15,MeOH);
IRνmax(KBr)cm-1:3366,2943,2877,1649,1455,1388,1313,1075,1033;
1H NMR(C5D5N,500MHz)δ:[0.76(1H,m),1.53(1H,m,overlapped),H2-1],1.80、2.22(1H each,both m,H2-2),3.36(1H,dd,J=4.5、12.0Hz,H-3),0.72(1H,br.d,ca.J=12Hz,H-5),[1.36(1H,m),1.48(1H,m,overlapped),H2-6],[1.19(1H,m),1.48(1H,m,overlapped),H2-7],1.39(1H,m,H-9),[1.52(1H,m,overlapped),1.98(1H,m),H2-11],4.14(1H,m,H-12),2.07(1H,dd,J=10.5、10.5Hz,H-13),[0.97(1H,m,overlapped),1.55(1H,m),H2-15],1.36、1.82(1H each,both m,H2-16),2.55(1H,q like,ca.J=10Hz,H-17),0.94(3H,s,H3-18),0.78(3H,s,H3-19),1.64(3H,s,H3-21),[2.24(1H,dd like,ca.J=3、14Hz),2.46(1H,dt like,ca.J=3、14Hz),H2-22],[2.05(1H,m,overlapped),2.32(1H,tt like,ca.J=3、14Hz),H2-23],4.46(1H,dd,J=4.5、8.0Hz,H-24),4.91、5.25(1H each,bothbr.s,H2-26),1.95(3H,s,H3-27),1.31(3H,s,H3-28),0.99(3H,s,H3-29),0.95(3H,s,H3-30),4.96(1H,d,J=8.0Hz,H-1'),4.06(1H,dd,J=8.0、8.5Hz,H-2'),4.28(1H,dd,J=8.5、9.0Hz,H-3'),4.22(1H,dd,J=9.0、9.0Hz,H-4'),4.03(1H,m,overlapped,H-5'),[4.42(1H,dd,J=5.5、11.5Hz),4.63(1H,dd,J=2.0、11.5Hz),H2-6'],5.16(1H,d,J=7.5Hz,H-1”),3.98(1H,dd,J=7.5、8.0Hz,H-2”),4.20(1H,dd,J=8.0、8.5Hz,H-3”),4.02(1H,dd,J=8.5、8.5Hz,H-4”),4.03(1H,m,overlapped,H-5”),[4.11(1H,dd,J=6.0、10.5Hz),4.68(1H,dd,J=1.5、10.5Hz),H2-6”],5.68(1H,d,J=1.5Hz,H-1”'),4.89(1H,dd,J=1.5、3.5Hz,H-2”'),4.81(1H,dd,J=3.5、6.0Hz,H-3”'),4.78(1H,m,H-4”'),[4.24(1H,dd,J=4.0、12.0Hz),4.35(1H,dd,J=3.0、12.0Hz),H2-5”'];
13C NMR(C5D5N,125MHz)δ:39.2(C-1),26.8(C-2),88.8(C-3),39.7(C-4),56.4(C-5),18.4(C-6),35.1(C-7),40.0(C-8),50.2(C-9),36.9(C-10),30.8(C-11),70.4(C-12),49.3(C-13),51.4(C-14),30.7(C-15),26.7(C-16),51.9(C-17),16.0(C-18),16.3(C-19),83.7(C-20),22.6(C-21),32.7(C-22),30.5(C-23),76.1(C-24),149.9(C-25),110.2(C-26),18.3(C-27),28.1(C-28),16.8(C-29),17.4(C-30),107.0(C-1'),75.8(C-2'),78.8(C-3'),71.9(C-4'),78.4(C-5'),63.1(C-6'),98.1(C-1”),75.0(C-2”),79.2(C-3”),72.0(C-4”),76.4(C-5”),68.3(C-6”),110.0(C-1”'),83.4(C-2”'),78.9(C-3”'),85.9(C-4”'),62.7(C-5”')。
ESI-Q-Orbitrap MS:负离子模式:m/z 931.52588[M-H]-(calcd for C47H79O18,931.52609),确定其分子式为C47H80O18。
三七叶皂苷NL-H2(10):3β,12β,20S,24S-四羟基达玛-25-烯-3-O-β-D-吡喃葡萄糖基-20-O-β-D-吡喃木糖基(1→6)-β-D-吡喃葡萄糖苷
白色粉末;
[α]D 25+2.6(conc 1.14,MeOH);
IRνmax(KBr)cm-1:3391,2943,2877,1648,1454,1387,1163,1077,1039;
1H NMR(C5D5N,500MHz)δ:0.78、1.55(1H each,both m,overlapped,H2-1),[1.83(1H,m,overlapped),2.23(1H,m),H2-2],3.37(1H,dd,J=4.5、11.5Hz,H-3),0.72(1H,br.d,ca.J=12Hz,H-5),[1.37(1H,m),1.48(1H,m,overlapped),H2-6],[1.19(1H,m),1.48(1H,m,overlapped),H2-7],1.38(1H,m,H-9),[1.55(1H,m,overlapped),1.98(1H,m),H2-11],4.19(1H,m,overlapped,H-12),2.09(1H,dd,J=10.5、10.5Hz,H-13),0.97、1.55(1Heach,both m,overlapped,H2-15),1.37、1.83(1H each,both m,overlapped,H2-16),2.55(1H,q like,ca.J=11Hz,H-17),0.93(3H,s,H3-18),0.79(3H,s,H3-19),1.65(3H,s,H3-21),[2.28(1H,dd like,ca.J=4、13Hz),2.50(1H,dt like,ca.J=3、13Hz),H2-22],[2.07(1H,m),2.38(1H,tt like,ca.J=4、13Hz),H2-23],4.46(1H,dd,J=4.0、8.0Hz,H-24),4.90、5.25(1H each,both br.s,H2-26),1.93(3H,s,H3-27),1.31(3H,s,H3-28),0.99(3H,s,H3-29),0.97(3H,s,H3-30),4.95(1H,d,J=7.5Hz,H-1'),4.06(1H,dd,J=7.5、8.0Hz,H-2'),4.28(1H,dd,J=8.0、9.5Hz,H-3'),4.23(1H,dd,J=9.0、9.5Hz,H-4'),4.03(1H,m,overlapped,H-5'),[4.42(1H,dd,J=5.5、11.5Hz),4.62(1H,dd,J=2.0、11.5Hz),H2-6'],5.14(1H,d,J=7.5Hz,H-1”),3.93(1H,dd,J=7.5、8.5Hz,H-2”),4.19(1H,dd,J=8.5、9.0Hz,H-3”),4.09(1H,dd,J=9.0、9.5Hz,H-4”),4.06(1H,m,overlapped,H-5”),[4.29(1H,dd,J=6.0、11.5Hz),4.75(1H,dd,J=2.0、11.5Hz),H2-6”],5.00(1H,d,J=7.5Hz,H-1”'),4.04(1H,dd,J=7.5、8.0Hz,H-2”'),4.17(1H,dd,J=8.0、8.5Hz,H-3”'),4.22(1H,m,overlapped,H-4”'),[3.73(1H,dd,J=10.0、11.0Hz),4.34(1H,dd,J=5.0、11.0Hz),H2-5”'];
13C NMR(C5D5N,125MHz)δ:39.2(C-1),26.8(C-2),88.8(C-3),39.7(C-4),56.4(C-5),18.4(C-6),35.1(C-7),40.0(C-8),50.2(C-9),36.9(C-10),30.9(C-11),70.3(C-12),49.4(C-13),51.4(C-14),30.7(C-15),26.7(C-16),51.9(C-17),16.0(C-18),16.3(C-19),83.7(C-20),22.6(C-21),32.8(C-22),30.6(C-23),76.0(C-24),149.9(C-25),110.0(C-26),18.6(C-27),28.1(C-28),16.8(C-29),17.4(C-30),107.0(C-1'),75.8(C-2'),78.8(C-3'),71.9(C-4'),78.4(C-5'),63.1(C-6'),98.1(C-1”),74.9(C-2”),79.3(C-3”),71.5(C-4”),76.8(C-5”),69.9(C-6”),105.7(C-1”'),74.9(C-2”'),78.0(C-3”'),71.2(C-4”'),67.0(C-5”')。
ESI-Q-Orbitrap MS:负离子模式:m/z 931.52771[M-H]-(calcd for C47H79O18,931.52609),确定其分子式为C47H80O18。
三七叶皂苷NL-H3(11):3β,12β,20S,24S-四羟基达玛-25-烯-3-O-[β-D-吡喃木糖基(1→2)-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃葡萄糖基]-20-O-β-D-吡喃木糖基(1→6)-β-D-吡喃葡萄糖苷
白色粉末;
[α]D 25-0.9(conc 0.92,MeOH);
IRνmax(KBr)cm-1:3378,2941,2877,1649,1456,1366,1167,1075,1042;
1H NMR(C5D5N,500MHz)δ:[0.76(1H,m),1.54(1H,m,overlapped),H2-1],[1.81(1H,m,overlapped),2.16(1H,m),H2-2],3.28(1H,dd,J=4.5、12.0Hz,H-3),0.68(1H,br.d,ca.J=12Hz,H-5),1.35、1.48(1H each,both m,H2-6),1.18、1.46(1H each,both m,H2-7),1.36(1H,m,overlapped,H-9),[1.50(1H,m,overlapped),1.96(1H,m),H2-11],4.16(1H,m,overlapped,H-12),2.07(1H,dd,J=10.5、10.5Hz,H-13),[0.96(1H,m),1.53(1H,m,overlapped),H2-15],1.36、1.81(1H each,both m,overlapped,H2-16),2.57(1H,q like,ca.J=10Hz,H-17),0.93(3H,s,H3-18),0.79(3H,s,H3-19),1.64(3H,s,H3-21),[2.25(1H,dd like,ca.J=4、14Hz),2.47(1H,dt like,ca.J=4、14Hz),H2-22],[2.04(1H,m),2.34(1H,tt like,ca.J=4、14Hz),H2-23],4.44(1H,dd,J=4.0、9.5Hz,H-24),4.89、5.25(1Heach,both br.s,H2-26),1.93(3H,s,H3-27),1.27(3H,s,H3-28),1.10(3H,s,H3-29),0.95(3H,s,H3-30),4.91(1H,d,J=7.5Hz,H-1'),4.07(1H,dd,J=7.5、9.5Hz,H-2'),4.33(1H,m,overlapped,H-3'),4.08(1H,m,overlapped,H-4'),3.94(1H,m,H-5'),[4.33(1H,m,overlapped),4.56(1H,dd,J=2.0、12.0Hz),H2-6'],5.49(1H,d,J=7.5Hz,H-1”),4.18(1H,m,overlapped,H-2”),4.27(1H,m,overlapped,H-3”),4.20(1H,dd,J=8.5、8.5Hz,H-4”),3.85(1H,m,H-5”),[4.36(1H,dd,J=5.0、12.0Hz),4.46(1H,dd,J=2.5、12.0Hz),H2-6”],5.39(1H,d,J=6.5Hz,H-1”'),4.09(1H,m,overlapped,H-2”'),4.12(1H,m,overlapped,H-3”'),4.13(1H,m,overlapped,H-4”'),[3.68(1H,dd,J=11.0、11.0Hz),4.31(1H,dd,J=3.0、11.0Hz),H2-5”'],5.12(1H,d,J=7.5Hz,H-1””),3.92(1H,dd,J=7.5、8.5Hz,H-2””),4.15(1H,dd,J=8.5、8.5Hz,H-3””),4.04(1H,m,overlapped,H-4””),4.04(1H,m,overlapped,H-5””),[4.26(1H,m,overlapped),4.73(1H,br.d,ca.J=11Hz),H2-6””],4.98(1H,d,J=7.5Hz,H-1””'),4.02(1H,dd,J=7.5、8.0Hz,H-2””'),4.19(1H,m,overlapped,H-3””'),4.20(1H,m,overlapped,H-4””'),[3.72(1H,dd,J=9.5、11.0Hz),4.34(1H,m,overlapped),H2-5””'];
13C NMR(C5D5N,125MHz)δ:39.3(C-1),26.8(C-2),89.0(C-3),39.8(C-4),56.4(C-5),18.5(C-6),35.2(C-7),40.1(C-8),50.3(C-9),36.9(C-10),31.0(C-11),70.3(C-12),49.4(C-13),51.5(C-14),30.8(C-15),26.7(C-16),51.9(C-17),16.0(C-18),16.3(C-19),83.7(C-20),22.6(C-21),32.8(C-22),30.7(C-23),76.0(C-24),149.9(C-25),110.0(C-26),18.6(C-27),28.1(C-28),16.7(C-29),17.4(C-30),104.8(C-1'),83.1(C-2'),78.7(C-3'),71.2(C-4'),78.3(C-5'),63.0(C-6'),103.2(C-1”),84.6(C-2”),77.9(C-3”),71.8(C-4”),77.7(C-5”),62.9(C-6”),106.5(C-1”'),76.0(C-2”'),77.8(C-3”'),70.7(C-4”'),67.4(C-5”'),98.2(C-1””),74.9(C-2””),79.3(C-3””),71.7(C-4””),76.8(C-5””),69.9(C-6””),105.6(C-1””'),74.8(C-2””'),77.9(C-3””'),71.2(C-4””'),67.0(C-5””')。
ESI-Q-Orbitrap MS:负离子模式:m/z 1225.62134[M-H]-(calcd for C58H97O27,1225.62117),确定其分子式为C58H98O27。
三七叶皂苷NL-I(12):3β,20S-二羟基-12β,23β-环氧达玛-24-烯-3-O-β-D-吡喃葡萄糖基-20-O-β-D-吡喃木糖基(1→6)-β-D-吡喃葡萄糖苷
白色粉末;
[α]D 25-10.4(conc 0.34,MeOH);
IRνmax(KBr)cm-1:3365,2941,2877,1632,1449,1380,1163,1074,1039;
1H NMR(C5D5N,500MHz)δ:0.82、1.50(1H each,both m,overlapped,H2-1),[1.83(1H,m,overlapped),2.25(1H,m),H2-2],3.37(1H,dd,J=4.5、11.5Hz,H-3),0.72(1H,br.d,ca.J=12Hz,H-5),[1.35(1H,m),1.49(1H,m,overlapped),H2-6],1.19、1.39(1Heach,both m,H2-7),1.49(1H,m,overlapped,H-9),1.35、1.93(1H each,both m,H2-11),3.67(1H,m,H-12),1.59(1H,dd,J=11.0、11.0Hz,H-13),[1.06(1H,m),1.48(1H,m,overlapped),H2-15],2.13、2.32(1H each,both m,H2-16),3.22(1H,dt,J=4.0、11.0Hz,H-17),0.94(3H,s,H3-18),0.82(3H,s,H3-19),1.51(3H,s,H3-21),[2.26(1H,dd,J=10.0、16.0Hz),2.85(1H,d,J=16.0Hz),H2-22],4.86(1H,dd,J=8.0、10.0Hz,H-23),5.55(1H,d,J=8.0Hz,H-24),1.68(3H,s,H3-26),1.83(3H,s,H3-27),1.31(3H,s,H3-28),1.01(3H,s,H3-29),1.11(3H,s,H3-30),4.97(1H,d,J=8.0Hz,H-1'),4.06(1H,dd,J=7.5、8.0Hz,H-2'),4.28(1H,dd,J=7.5、9.0Hz,H-3'),4.25(1H,m,overlapped,H-4'),4.05(1H,m,H-5'),[4.43(1H,m),4.63(1H,br.d,ca.J=12Hz),H2-6'],5.12(1H,d,J=8.0Hz,H-1”),3.94(1H,dd,J=8.0、8.0Hz,H-2”),4.22(1H,dd,J=8.0、9.0Hz,H-3”),4.17(1H,dd,J=9.0、9.0Hz,H-4”),4.15(1H,m,overlapped,H-5”),[4.40(1H,dd,J=6.0、11.0Hz),4.77(1H,br.d,ca.J=11Hz),H2-6”],4.99(1H,d,J=7.5Hz,H-1”'),4.09(1H,dd,J=7.5、8.5Hz,H-2”'),4.16(1H,dd,J=8.5、9.0Hz,H-3”'),4.26(1H,m,overlapped,H-4”'),[3.71(1H,dd,J=11.0、11.0Hz),4.38(1H,dd,J=5.0、11.0Hz),H2-5”'];
13C NMR(C5D5N,125MHz)δ:39.4(C-1),26.8(C-2),88.7(C-3),39.7(C-4),56.3(C-5),18.4(C-6),35.2(C-7),39.8(C-8),50.6(C-9),37.1(C-10),30.1(C-11),79.6(C-12),49.8(C-13),51.3(C-14),32.6(C-15),25.6(C-16),46.5(C-17),15.5(C-18),16.5(C-19),82.0(C-20),24.7(C-21),52.1(C-22),72.6(C-23),129.2(C-24),131.2(C-25),25.7(C-26),18.9(C-27),28.1(C-28),16.8(C-29),17.0(C-30),107.0(C-1'),75.8(C-2'),78.9(C-3'),71.9(C-4'),78.4(C-5'),63.1(C-6'),99.4(C-1”),75.3(C-2”),78.8(C-3”),71.7(C-4”),76.9(C-5”),70.9(C-6”),106.5(C-1”'),74.9(C-2”'),78.3(C-3”'),71.2(C-4”'),67.3(C-5”')。
ESI-Q-Orbitrap MS:负离子模式:m/z 913.51648[M-H]-(calcd for C47H77O17,913.51553),确定其分子式为C47H78O17。
三七叶皂苷NL-J(13):27-脱甲基-3β,20S-二羟基-12β,23β-环氧达玛-25-酮-3-O-[β-D-吡喃木糖基(1→2)-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃葡萄糖基]-20-O-β-D-吡喃木糖基(1→6)-β-D-吡喃葡萄糖苷
白色粉末;
[α]D 25-10.0(conc 0.16,MeOH);
IRνmax(KBr)cm-1:3356,2934,2877,1699,1568,1413,1167,1071,1041;
1H NMR(C5D5N,600MHz)δ:0.63、1.29(1H each,both m,H2-1),1.80、2.15(1Heach,both m,H2-2),3.29(1H,dd,J=2.4、12.0Hz,H-3),0.66(1H,br.d,ca.J=10Hz,H-5),1.37、1.46(1H each,both m,overlapped,H2-6),[1.19(1H,m),1.37(1H,m,overlapped),H2-7],1.37(1H,m,overlapped,H-9),1.22、1.77(1H each,both m,H2-11),3.57(1H,m,H-12),1.49(1H,dd,J=11.4、11.4Hz,H-13),1.02、1.43(1H each,both m,H2-15),2.09(2H,m,H2-16),3.02(1H,dt,J=3.6、11.4Hz,H-17),0.89(3H,s,H3-18),0.76(3H,s,H3-19),1.46(3H,s,H3-21),[1.98(1H,dd,J=9.0、15.0Hz),2.77(1H,br.d,ca.J=15Hz),H2-22],4.62(1H,m,overlapped,H-23),2.86(2H,m,H2-24),2.21(3H,s,H3-26),1.26(3H,s,H3-27),1.10(3H,s,H3-28),0.97(3H,s,H3-29),4.95(1H,d,J=8.4Hz,H-1'),4.15(1H,m,overlapped,H-2'),4.38(1H,m,overlapped,H-3'),4.11(1H,m,overlapped,H-4'),3.99(1H,m,H-5'),[4.38(1H,m,overlapped),4.61(1H,br.d,ca.J=11Hz),H2-6'],5.54(1H,d,J=7.2Hz,H-1”),4.21(1H,m,overlapped,H-2”),4.30(1H,dd,J=9.0、9.0Hz,H-3”),4.20(1H,m,overlapped,H-4”),3.89(1H,m,H-5”),[4.37(1H,m,overlapped),4.51(1H,br.d,ca.J=11Hz),H2-6”],5.41(1H,d,J=7.2Hz,H-1”'),4.12(1H,m,overlapped,H-2”'),4.15(1H,m,overlapped,H-3”'),4.16(1H,m,overlapped,H-4”'),[3.72(1H,dd,J=10.2、10.2Hz),4.34(1H,m,overlapped),H2-5”'],5.06(1H,d,J=7.8Hz,H-1””),3.96(1H,dd,J=7.8、8.0Hz,H-2””),4.26(1H,m,overlapped,H-3””),4.20(1H,m,overlapped,H-4””),4.12(1H,m,H-5””),[4.32(1H,m,overlapped),4.77(1H,br.d,ca.J=10Hz),H2-6””],4.93(1H,d,J=7.8Hz,H-1””'),4.06(1H,dd,J=7.8、9.0Hz,H-2””'),4.17(1H,m,overlapped,H-3””'),4.26(1H,m,overlapped,H-4””'),3.70、4.37(1H each,both m,overlapped,H2-5””');
13C NMR(C5D5N,150MHz)δ:39.2(C-1),26.8(C-2),88.8(C-3),39.7(C-4),56.4(C-5),18.4(C-6),35.1(C-7),39.7(C-8),50.5(C-9),37.0(C-10),29.9(C-11),80.0(C-12),49.4(C-13),51.2(C-14),32.5(C-15),25.2(C-16),47.0(C-17),15.4(C-18),16.5(C-19),81.6(C-20),24.1(C-21),50.2(C-22),71.0(C-23),51.6(C-24),207.2(C-25),30.5(C-26),28.0(C-28),16.7(C-29),16.8(C-30),104.8(C-1'),83.0(C-2'),78.7(C-3'),71.2(C-4'),78.4(C-5'),63.0(C-6'),103.2(C-1”),84.6(C-2”),78.0(C-3”),71.8(C-4”),77.8(C-5”),62.9(C-6”),106.5(C-1”'),76.0(C-2”'),77.8(C-3”'),70.8(C-4”'),67.4(C-5”'),99.0(C-1””),75.4(C-2””),78.7(C-3””),71.6(C-4””),76.7(C-5””),70.5(C-6””),106.1(C-1””'),74.9(C-2””'),78.4(C-3””'),71.2(C-4””'),67.2(C-5””')。
ESI-Q-Orbitrap MS:负离子模式:m/z 1209.59021[M-H]-(calcd for C57H93O27,1209.58987),确定其分子式为C57H94O27。
实施例3
人参二醇型三萜皂苷化合物1~化合物13的生物活性测定
巨噬细胞作为分布于全身的免疫细胞,在免疫监视系统中扮演着核心角色。病原体进入机体后,巨噬细胞可以立即通过释放各种炎症介质而间接地发挥免疫作用。RAW264.7细胞作为巨噬细胞的一种,因具有很强的黏附、吞噬抗原的能力,是研究微生物学、免疫学等相关学科的常用细胞株。脂多糖(Lipopolysaccharide,LPS)可刺激RAW 264.7细胞产生急性炎症反应,释放诱导型一氧化氮合酶(iNOS)等多种炎症因子,这些因子可参与调控机体炎症的发生发展。当RAW 264.7细胞受到LPS刺激时,与炎症有关的iNOS蛋白会过度表达,促进细胞中一氧化氮(Nitric oxide,NO)水平升高,而NO可直接参与炎症反应的发生与发展。因此,调节NO产生可能是治疗炎症的重要途径。
本发明采用LPS刺激诱导的RAW 264.7细胞模型,测定上述化合物1~13对NO释放的抑制作用。
I.RAW 264.7细胞的培养与处理
使用含有10%胎牛血清、100unit/mL青霉素和100μg/mL链霉素混合液的DMEM高糖酚红培养液,在37℃、5%CO2的恒温培养箱中培养RAW264.7细胞。待细胞融合至约90%时,用于下述实验。
II.化合物1~13对RAW 264.7细胞生长活力的影响
使用MTT比色法分析三七叶中的上述化合物1~13对RAW264.7细胞生长活力的影响。取对数生长期RAW264.7巨噬细胞(细胞融合至约90%)接种于24孔培养板中,细胞密度为1×106cells/mL,培养24h后所有细胞更换无酚红培基培养,分别为:正常组,给药组(25μM各化合物1~13)。培养18h后,弃去培养基,每孔加入1mL含MTT(500μg/ml)的培养基;培养4h后,弃去培养基,每孔加入1mL DMSO并震荡30s,酶标仪490nm检测吸光度。
III.化合物1~13对LPS刺激的RAW 264.7细胞释放NO的影响
取对数生长期RAW264.7巨噬细胞接种于24孔培养板中,细胞密度为1×106cells/mL,培养24h后所有细胞更换无酚红培基培养,分别为:正常组,模型组(LPS 0.5μg/mL),阳性药对照组(LPS 0.5μg/mL+1.5μg/mL地塞米松(DEX)),给药组(LPS 0.5μg/mL+25μM各化合物1~13)。培养18h后,吸取50μL培养基上清于96孔细胞培养板,室温状态下,各孔依次加入50μL Griess Reagent I及50μL Griess Reagent II并震荡30s,酶标仪540nm检测吸光度,并用校准曲线确定实验各组NO的浓度。
IV.实验结果
在采用RAW264.7细胞模型测定化合物1~13对NO抑制作用之前,首先研究了这些化合物在25μM浓度下的细胞毒性。在25μM浓度下,除了化合物8、9和11外,其余化合物未表现明显的细胞毒性。因此,本实验中以25μM为终浓度测定了化合物1、2~7、10、12、13对RAW264.7细胞释放NO的抑制作用。结果参见下表1。需要说明的是,在下表1中,亚硝酸盐相对浓度为相比于对照组(100%)的百分比;***表示P<0.001(给药组与对照组的差异);n=4;阳性药的终浓度为1.5μg/mL。另外,在表1中,表中数值代表平均值±标准偏差;并且化合物1~13的终浓度为25μM。
表1.化合物1、2~7、10、12和13对RAW 264.7细胞释放NO的抑制作用
上表1的测定结果表明,除了化合物1外,其它化合物2~7、10、12和13对NO产生均具有抑制活性。
工业实用性
本发明利用多种分离手段,包括正反相硅胶柱层析、大孔吸附树脂柱层析、凝胶柱层析和制备高效液相色谱法等,从三七叶中分离得到了包括13个新的人参二醇型三萜皂苷化合物,其中一些化合物对NO产生具有抑制活性,提示它们具有潜在的抗炎活性。这些新化合物的发现为三七叶作为抗炎药物的研究与开发奠定了物质基础,并且为三七资源的再利用提供了借鉴。
Claims (7)
2.一种三七叶提取物,包含权利要求1所述的人参二醇型三萜皂苷或其可药用的盐中的至少一者。
3.一种药物组合物,包含治疗有效量的权利要求1所述的人参二醇型三萜皂苷或其可药用的盐中的至少一者、以及药学可接受的赋形剂。
4.一种药物组合物,包含治疗有效量的权利要求2所述的三七叶提取物、以及药学可接受的赋形剂。
5.一种化妆品组合物,包含权利要求1所述的人参二醇型三萜皂苷或其可药用的盐中的至少一者、以及至少一种生理学上可接受的赋形剂。
6.一种化妆品组合物,包含权利要求2所述的三七叶提取物、以及至少一种生理学上可接受的赋形剂。
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