三七皂甙 R1 | 80418-24-2

• 物质功能分类: 生物化工 - 提取物
• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: 三七皂甙 R1
• 中文别名: 三七皂苷R1；三七皂甙R1；三七皂苷；三七皂苷 R1
• 英文名称: notoginsenoside R1
• 英文别名: (3β,6α,12β)-20-(β-D-glucopyranosyloxy)-3,12-dihydroxydammar-24-en-6-yl-2-O-β-D-xylopyranosyl-β-D-glucopyranoside；notoginsenoside R₁；notoginsenoside-R1；notogisenoside R1；NGR1；(2S,3R,4S,5S,6R)-2-[(2S)-2-[(3S,5R,6S,8R,9R,10R,12R,13R,14R,17S)-6-[(2R,3R,4S,5S,6R)-4,5-dihydroxy-6-(hydroxymethyl)-3-[(2S,3R,4S,5R)-3,4,5-trihydroxyoxan-2-yl]oxyoxan-2-yl]oxy-3,12-dihydroxy-4,4,8,10,14-pentamethyl-2,3,5,6,7,9,11,12,13,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-17-yl]-6-methylhept-5-en-2-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol
• CAS: 80418-24-2
• 化学式: C₄₇H₈₀O₁₈
• mdl: MFCD00210535
• 分子量: 933.141
• InChiKey: LLPWNQMSUYAGQI-OOSPGMBYSA-N

物化性质

• 熔点：
  215～217℃
• 沸点：
  1010.5±65.0 °C(Predicted)
• 密度：
  1.39±0.1 g/cm3(Predicted)
• 溶解度：
  水中的溶解度为1mg/mL，透明，无色
• LogP：
  1.354 (est)
• 颜色/状态：
  White to off-white powder
• 蒸汽压力：
  6.7X10-38 mm Hg at 25 °C (est)
• 稳定性/保质期：
  Stable under recommended storage conditions.
• 分解：
  Hazardous decomposition products formed under fire conditions. - Carbon oxides Other decomposition products - no data available

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  65
• 可旋转键数：
  12
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.957
• 拓扑面积：
  298
• 氢给体数：
  12
• 氢受体数：
  18

ADMET

代谢

斑马鱼，作为研究脊椎动物发育和基因功能的常见模式生物，近年来在药物研究中被用作一种新的强大工具。在当前的研究中，研究者们应用斑马鱼...进行人参皂苷R1、人参皂苷Rg1和人参皂苷Rb1的代谢研究，这些皂苷是从三七中分离出来的。通过使用Zorbax C-18柱进行分离的高效液相色谱-电喷雾质谱法（HPLC-ESI-MS），在斑马鱼暴露于这三种皂苷化合物24小时后，鉴定出了它们的代谢物，使用的是0.05%甲酸乙腈-0.05%甲酸水的二元梯度洗脱。化合物的准分子离子是在负模式下检测到的。发现了这三种皂苷的逐步去糖基化代谢物和羟基化代谢物，这与常规的代谢分析方法是一致的...

Zebrafish, a common model organism for studies of vertebrate development and gene function, has been used in pharmaceutical research as a new and powerful tool in recent years. In the present study, /the researchers/ applied zebrafish ...in a metabolic study of notoginsenoside (R1), ginsenoside (Rg1) and ginsenoside (Rb1), which are saponins isolated from Panax notoginseng. Metabolites of these three saponin compounds in zebrafish after exposure for 24 hr were identified by high performance liquid chromatography - electrospray mass spectrometry (HPLC-ESI-MS) with a Zorbax C-18 column for separation using a binary gradient elution of 0.05% formic acid acetonitrile - 0.05% formic acid water. The quasi-molecular ions of compounds were detected in negative mode. Step-wise deglycosylation metabolites and hydroxylation metabolites of the three saponins were found, which were /consistant/ with regular methods for metabolic analysis...

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

/SRP:/ 立即急救：确保已经进行了充分的中和。如果患者停止呼吸，请开始人工呼吸，最好使用需求阀复苏器、球囊阀面罩设备或口袋面罩，按训练操作。如有必要，执行心肺复苏。立即用缓慢流动的水冲洗受污染的眼睛。不要催吐。如果患者呕吐，让患者向前倾或将其置于左侧（如果可能的话，头部向下），以保持呼吸道畅通，防止吸入。保持患者安静，维持正常体温。寻求医疗帮助。 /毒物A和B/

/SRP:/ Immediate first aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR if necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on the left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Poisons A and B/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

/SRP:/ 基本治疗：建立专利气道（如有需要，使用口咽或鼻咽气道）。如有必要，进行吸痰。观察呼吸不足的迹象，如有需要，辅助通气。通过非循环呼吸面罩以10至15升/分钟的速度给予氧气。监测肺水肿，如有必要，进行治疗……。监测休克，如有必要，进行治疗……。预防癫痫发作，如有必要，进行治疗……。对于眼睛污染，立即用水冲洗眼睛。在运输过程中，用0.9%的生理盐水（NS）持续冲洗每只眼睛……。不要使用催吐剂。对于摄入，如果患者能吞咽、有强烈的干呕反射且不流口水，则用温水冲洗口腔，并给予5毫升/千克，最多200毫升的水进行稀释……。在去污后，用干燥的无菌敷料覆盖皮肤烧伤……。/毒药A和B/

/SRP:/ Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if needed. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Monitor for shock and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 mL/kg up to 200 mL of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool ... . Cover skin burns with dry sterile dressings after decontamination ... . /Poisons A and B/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

/SRP:/ 高级治疗：对于无意识、严重肺水肿或严重呼吸困难的病人，考虑进行口咽或鼻咽气管插管以控制气道。使用气囊面罩装置的正压通气技术可能有益。考虑使用药物治疗肺水肿……。对于严重的支气管痉挛，考虑给予β激动剂，如沙丁胺醇……。监测心率和必要时治疗心律失常……。开始静脉输注D5W /SRP: "保持开放"，最小流量/。如果出现低血容量的迹象，使用0.9%的生理盐水（NS）或乳酸林格氏液。对于伴有低血容量迹象的低血压，谨慎给予液体。注意液体过载的迹象……。使用地西泮或劳拉西泮治疗癫痫……。使用丙美卡因氢氯化物协助眼部冲洗……。 /Poisons A and B/

/SRP:/ Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in severe respiratory distress. Positive-pressure ventilation techniques with a bag valve mask device may be beneficial. Consider drug therapy for pulmonary edema ... . Consider administering a beta agonist such as albuterol for severe bronchospasm ... . Monitor cardiac rhythm and treat arrhythmias as necessary ... . Start IV administration of D5W /SRP: "To keep open", minimal flow rate/. Use 0.9% saline (NS) or lactated Ringer's if signs of hypovolemia are present. For hypotension with signs of hypovolemia, administer fluid cautiously. Watch for signs of fluid overload ... . Treat seizures with diazepam or lorazepam ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Poisons A and B/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 人类毒性摘录

备选和体外测试 本研究的目的是探讨人参皂苷（PNS）对人类CD34(+)干细胞/祖细胞增殖和分化的影响。通过使用Dynal M-450系统的免疫珠从人类骨髓中分离CD34(+)细胞。将这些细胞在不同浓度的PNS下，在液体和半固体培养基中暴露14天。培养后，用单克隆抗体标记细胞并通过流式细胞仪进行分析。对来自CD34(+)细胞的CFU-Mix集落形成进行了检测。结果显示： （1）通过免疫珠筛选后的CD34(+)细胞产量为骨髓核细胞的（1.03 +/- 0.74）%，纯度为86% - 93%。 （2）PNS（10 - 25 mg/L）刺激了CD34(+)细胞的增殖，并显著提高了体外CFU-Mix集落的数量。PNS 25 mg/L是促进CD34(+)细胞增殖的最佳浓度，CFU-Mix集落增加率为（34.7 +/- 16.0）%。 （3）将CD34(+)细胞暴露于PNS（25, 50和100 mg/L）的液体培养基中14天，诱导了细胞的分化。PNS暴露后，CD33(+)和CD15(+)细胞的百分比增加，显著高于对照组（P < 0.01），然而CD71(+)和G-A(+)细胞在PNS处理后没有明显差异。 总之，人参皂苷不仅促进了CD34(+)细胞的增殖，还诱导了向粒细胞分化的分化承诺。

/ALTERNATIVE and IN VITRO TESTS/ The object of this study was to explore the effects of Panax notoginosides (PNS) on proliferation and differentiation of human CD34(+) stem/progenitor cells. CD34(+) cells were isolated from human bone marrow by using immune beads of Dynal M- 450 system. The cells were exposed to PNS at different concentrations in both liquid and semi-solid culture for 14 days. The cells were marked with monoclonal antibodies and analyzed by flow cytometry after culture. The CFU-Mix colony formation from CD34(+) cells was assayed. The results showed that: (1) The yield of CD34(+) cells after being selected by immune beads were (1.03 +/- 0.74)% out of bone marrow nuclear cells with purity of 86% - 93%. (2) PNS (10 - 25 mg/L) stimulated the proliferation of CD34(+) cells, and raised the colony numbers of CFU-Mix obviously in vitro. PNS 25 mg/L was the optimal concentration to promote proliferation of CD34(+) cells, the increasing rate of CFU-Mix colony was (34.7 +/- 16.0)%. (3) The differentiation of CD34(+) cells was induced by exposure to PNS (25, 50 and 100 mg/L) in liquid culture for 14 days. The percentages of CD33(+) and CD15(+) cells were increased after PNS exposure, which were significantly higher than those of control (P < 0.01), however CD71(+) and G-A(+) cells were no obviously difference after PNS treatment. In conclusion, Panax notoginosides not only promote the proliferation of CD34(+) cells, but also induce the differentiation committed to granulocytes.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 人类毒性摘录

/替代和体外测试/ 在其他中药中，三七被用于治疗心血管疾病。为了阐明这种药物在体外对止血系统可能的效应，研究者分析了其一个主要活性成分对培养的人脐静脉内皮细胞（HUVECs）纤维蛋白溶解参数的影响。当HUVECs（传代2到3）被纯化的人参皂苷R1（NR1）处理后，观察到剂量（0.01至100微克NR1/毫升）和时间依赖性的组织型纤溶酶原激活剂（TPA）合成的增加，从0.1微克NR1/毫升开始以及100微克NR1/毫升孵化6小时后显著。在加入100微克NR1/毫升后，TPA抗原从每10^5细胞每24小时的3.9 +/- 0.2纳克增加到8.0 +/- 0.5纳克。相比之下，尿激酶型纤溶酶原激活剂和纤溶酶原激活剂抑制剂-1（PAI-1）抗原合成没有变化。NR1对细胞外基质中PAI-1沉积也没有影响。根据纤维蛋白自描和反向纤维蛋白自描判断，TPA活性和TPA-PAI-1复合物在100微克NR1/毫升的条件下达到了最大刺激，分别超过三倍和两倍。相反，NR1在同一浓度的NR1条件下导致PAI-1活性降低了超过五倍。在Northern blot分析中，从NR1刺激和对照HUVECs获得的RNA显示，NR1显著增加了TPA mRNA（在100微克NR1/毫升时为对照值的192%），而PAI-1 mRNA保持不变。

/ALTERNATIVE and IN VITRO TESTS/ Among other Chinese herb drugs, Panax notoginseng is used to treat cardiovascular diseases. To elucidate any possible effects of this drug on the hemostatic system in vitro, /the researchers/ analyzed the influence of one of its major active constituents on fibrinolytic parameters of cultured human umbilical vein endothelial cells (HUVECs). When confluent cultures of HUVECs (passages 2 to 3) were conditioned with purified notoginsenoside R1 (NR1), a dose- (0.01 to 100 ug NR1/mL) and time-dependent increase in tissue-type plasminogen activator (TPA) synthesis was observed, which was significant from 0.1 ug NR1/mL and from 6 hours of incubation with 100 ug NR1/mL on. TPA antigen increased from 3.9 +/- 0.2 ng per 10(5) cells per 24 hours to 8.0 +/- 0.5 ng per 10+5 cells per 24 hours on addition of 100 ug NR1/mL. In contrast, no change in urokinase-type plasminogen activator and plasminogen activator inhibitor-1 (PAI-1) antigen synthesis was seen. There was also no effect of NR1 on PAI-1 deposition in the extracellular matrix. As judged from fibrin autography and reverse fibrin autography, TPA activity and TPA-PAI-1 complexes reached a maximal stimulation of more than threefold and twofold, respectively, at a concentration of 100 micrograms NR1/mL in conditioned media. On the contrary, NR1 induced a more than fivefold decrease in PAI-1 activity at the same concentration of NR1 in conditioned media. On Northern blot analysis of RNA obtained from NR1-stimulated and control HUVECs, NR1 induced a significant increase in TPA mRNA (192% of control value at 100 ug NR1/mL) while PAI-1 mRNA remained unchanged.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• WGK Germany：
  3

制备方法与用途

概述

三七皂苷R1来源于五加科植物三七（Panax notoginseng (Burk.) F.H.Chen）的干燥根和根茎，具有散瘀止血、消肿定痛的功效。现代药理研究表明，三七不仅能够延缓衰老、扩张血管、改善微循环，其主要有效成分——三七总皂苷（Panax Notoginseng Saponins, PNS），包括多种单体皂苷，也显示出促进血液循环和改善能量代谢的作用。

药材提取与对照品溶液的配制 药材的提取

精密称取过四号筛三七粉末0.5678g，加入甲醇50ml，密闭放置过夜后，在80℃水浴微沸2小时。冷却后用甲醇补足减失的重量，摇匀过滤，即得待测样品。

对照品溶液的制备

分别精密称取人参皂苷Rg1、Rb1和三七皂苷R1对照品各适量（分别为14.7mg、13.2mg和8.0mg），置于10ml容量瓶中，用甲醇溶解并稀释至刻度，摇匀。再精密量取上述三种对照品溶液加入流动相制成混合液。

用途 改善认知与学习记忆能力

本发明通过实验证明三七皂苷R1（NTR1）可改善APP/PS1转基因阿尔茨海默病（AD）小鼠的认知和学习记忆能力，回复其脑内胆碱能神经元（ChAT）水平，降低丙二醛含量，并提高细胞色素C氧化酶活性。此外，NTR1还能提升β-淀粉样蛋白降解相关酶IDE的表达，从而抑制Aβ积累。

改善微循环及保护心血管作用

研究发现NTR1能促进纤维蛋白溶解系统合成，通过对内皮细胞E-选择素和中性粒细胞CD18蛋白表达的抑制作用。此外，在TNF-a介导的静脉内皮细胞功能障碍模型中，NTR1通过抑制ERK激活及NADPH氧化酶介导的ROS生成减轻炎症。

抗炎作用

尾静脉注射NTR1可以降低脂多糖（LPS）诱导的小鼠死亡率，并抑制人全血培养液中的TNF-a分泌。最新研究发现，NTR1能通过上调雌激素受体a (ERα)及PI3K/Akt通路减轻心脏功能障碍小鼠模型的心肌炎症反应和细胞凋亡。

其他作用

三七皂苷R1还具有一定的抗肿瘤与抗氧化作用。

化学性质

来源于五加科(araliaceae)人参属植物的干燥根，用于含量测定、鉴定及药理实验等。

药理药效

活血化瘀功效，并据报道有神经保护及抗高血压等作用。

参考资料

1. 三七皂苷R1 .国家标准物质网,2010-5-12 [引用日期2013-01-4]
2. 三七 .国家标准物质网,2013-1-1 [引用日期2013-01-4]
3. 张文生, 李智. 三七皂苷R1的用途[P]. 北京：CN103877107A, 2014-06-25.
4. 张雁, 宋建国, 鱼红闪, 金凤燮. 三七皂苷R_1的分离提纯[J]. 大连工业大学学报, 2011, 30(03):161-164.

图片

图1 三七皂苷R1高效液相色谱图

反应信息

• 作为反应物：
  描述：

  三七皂甙 R1 在 Sphingomonas sp. JB13 GH39 β-xylosidase 、 水 作用下， 反应 24.0h， 生成 人参皂苷 Rg1
  参考文献：
  名称：

  Glycoside Hydrolase Family 39 β-Xylosidases Exhibit β-1,2-Xylosidase Activity for Transformation of Notoginsenosides: A New EC Subsubclass

  摘要：

  beta-1,2-Xylosidase activity has not been recorded as an EC subsubclass. In this study, phylogenetic analysis and multiple sequence alignments revealed that characterized beta-xylosidases of glycoside hydrolase family (GH) 39 were classified into the same subgroup with conserved amino acid residue positions participating in substrate recognition. Protein-ligand docking revealed that seven of these positions were probably essential to bind xylose-glucose, which is linked by a beta-1,2-glycosidic bond. Amino acid residues in five of the seven positions are invariant, while those in two of the seven positions are variable with low frequency. Both the wild-type beta-xylosidase rJB13GH39 and its mutants with mutation at the two positions exhibited beta-1,2-xylosidase activity, as they hydrolyzed o-nitrophenyl-beta-D-xylopyranoside and transformed notoginsenosides R-1 and R-2 to ginsenosides Rg(1) and Rh-1, respectively. The results suggest that all of these characterized GH 39 beta-xylosidases probably show beta-1,2-xylosidase activity, which should be assigned an EC number with these beta-xylosidases as representatives.

  DOI：

  10.1021/acs.jafc.9b00027

文献信息

• Enzymatic Synthesis of Unnatural Ginsenosides Using a Promiscuous UDP-Glucosyltransferase from Bacillus subtilis
  作者：Ting-Ting Zhang、Ting Gong、Zong-Feng Hu、An-Di Gu、Jin-Ling Yang、Ping Zhu

  DOI：10.3390/molecules23112797

  日期：——

  Glycosylation, which is catalyzed by UDP-glycosyltransferases (UGTs), is an important biological modification for the structural and functional diversity of ginsenosides. In this study, the promiscuous UGT109A1 from Bacillus subtilis was used to synthesize unnatural ginsenosides from natural ginsenosides. UGT109A1 was heterologously expressed in Escherichia coli and then purified by Ni-NTA affinity chromatography. Ginsenosides Re, Rf, Rh1, and R1 were selected as the substrates to produce the corresponding derivatives by the recombinant UGT109A1. The results showed that UGT109A1 could transfer a glucosyl moiety to C3-OH of ginsenosides Re and R1, and C3-OH and C12-OH of ginsenosides Rf and Rh1, respectively, to produce unnatural ginsenosides 3,20-di-O-β-d-glucopyranosyl-6-O-[α-l-rhamnopyrano-(1→2)-β-d-glucopyranosyl]-dammar-24-ene-3β,6α,12β,20S-tetraol (1), 3,20-di-O-β-d-glucopyranosyl-6-O-[β-d-xylopyranosyl-(1→2)-β-d-glucopyranosyl]-dammar-24-ene-3β,6α,12β,20S-tetraol (6), 3-O-β-d-glucopyranosyl-6-O-[β-d-glucopyranosyl-(1→2)-β-d-glucopyranosyl]-dammar-24-ene-3β,6α,12β,20S-tetraol (3), 3,12-di-O-β-d-glucopyranosyl-6-O-[β-d-glucopyranosyl-(1→2)-β-d-glucopyranosyl]-dammar-24-ene-3β,6α,12β,20S-tetraol (2), 3,6-di-O-β-d-glucopyranosyl-dammar-24-ene-3β,6α,12β,20S-tetraol (5), and 3,6,12-tri-O-β-d-glucopyranosyl-dammar-24-ene-3β,6α,12β,20S-tetraol (4). Among the above products, 1, 2, 3, and 6 are new compounds. The maximal activity of UGT109A1 was achieved at the temperature of 40 °C, in the pH range of 8.0–10.0. The activity of UGT109A1 was considerably enhanced by Mg2+, Mn2+, and Ca2+, but was obviously reduced by Cu2+, Co2+, and Zn2+. The study demonstrated that UGT109A1 was effective in producing a series of unnatural ginsenosides through enzymatic reactions, which could pave a way to generate promising leads for new drug discovery.

  糖基化是由UDP-糖基转移酶（UGTs）催化的，对人参皂苷的结构和功能多样性是一种重要的生物修饰。在这项研究中，来自枯草芽孢杆菌的多功能UGT109A1被用来从天然人参皂苷合成非天然人参皂苷。UGT109A1在大肠杆菌中异源表达，然后通过Ni-NTA亲和层析纯化。选择人参皂苷Re、Rf、Rh1和R1作为底物，通过重组UGT109A1产生相应的衍生物。结果显示UGT109A1能够将葡萄糖基转移至人参皂苷Re和R1的C3-OH，以及人参皂苷Rf和Rh1的C3-OH和C12-OH，从而分别产生非天然人参皂苷3,20-二-O-β-d-葡萄糖吡喃基-6-O-[α-l-鼠李糖吡喃-(1→2)-β-d-葡萄糖吡喃]-丹麦-24-烯-3β,6α,12β,20S-四醇（1）、3,20-二-O-β-d-葡萄糖吡喃基-6-O-[β-d-木糖吡喃-(1→2)-β-d-葡萄糖吡喃]-丹麦-24-烯-3β,6α,12β,20S-四醇（6）、3-O-β-d-葡萄糖吡喃基-6-O-[β-d-葡萄糖吡喃-(1→2)-β-d-葡萄糖吡喃]-丹麦-24-烯-3β,6α,12β,20S-四醇（3）、3,12-二-O-β-d-葡萄糖吡喃基-6-O-[β-d-葡萄糖吡喃-(1→2)-β-d-葡萄糖吡喃]-丹麦-24-烯-3β,6α,12β,20S-四醇（2）、3,6-二-O-β-d-葡萄糖吡喃基-丹麦-24-烯-3β,6α,12β,20S-四醇（5）和3,6,12-三-O-β-d-葡萄糖吡喃基-丹麦-24-烯-3β,6α,12β,20S-四醇（4）。在上述产物中，1、2、3和6是新化合物。UGT109A1的最大活性在40℃的温度下，在8.0-10.0的pH范围内达到。UGT109A1的活性受到Mg2+、Mn2+和Ca2+的显著增强，但受到Cu2+、Co2+和Zn2+的明显降低。该研究表明，UGT109A1通过酶反应有效地产生了一系列非天然人参皂苷，为新药发现提供了有希望的线索。
• Dammarane-saponins of sanchi-ginseng, roots of Panax notoginseng (Burk.) F.H. Chen (araliaceae): Structures of new saponins, notoginsenosides-R1 and -R2, and identification of ginsenosides-Rg2 and -Rh1.
  作者：JUN ZHOU、MINGZHU WU、SHIGENORI TANIYASU、HIROMICHI BESSO、OSAMU TANAKA、YUICHIRO SARUWATARI、TOHRU FUWA

  DOI：10.1248/cpb.29.2844

  日期：——

  From Sanchi-Ginseng, roots of Panax notoginseng cultivated in Yunnan, China, two new dammarane-saponins named notoginsenosides-R1 (5) and -R2 (7S) were isolated by means of reverse phase high performance liquid chromatography. The structures of these saponins were established as 20 (S)-protopanaxatriol 6-[O-β-D-xylopyranosyl-(1→2)-β-D-glucopyranosyl]-20-O-β-D-glucopyranoside (5) and 20 (S)-protopanaxatriol 6-O-β-D-xylopyranosyl (1→2)-β-D-glucopyranoside (7S), respectively, mainly by 13C NMR spectroscopy and mass spectrometry. In connection with this study, assignments of carbon signals of ginsenoside-Rf (11), a minor saponin of Ginseng roots, were substantiated by the application of selective deuteration of the sugar moiety as reported by Stuart et al. Besides these saponins, two known saponins, ginsenosides-Rh1 (12) and -Rg2 (13) which have previously been isolated from Ginseng roots, were also isolated and identified.

  通过反相高效液相色谱法，从中国云南栽培的三七根中分离出两种新的达玛烷皂苷，分别命名为三七皂苷-R1（5）和-R2（7S）。通过反相高效液相色谱法，确定了这两种皂苷的结构为 20 (S)-protopanaxatriol 6-[O-β-D-xylopyranosyl-(1→2)-β-D-glucopyranosyl]-20-O-β-D-glucopyranoside (5) 和 20 (S)-protopanaxatriol 6-O-β-D-xylopyranosyl (1→2)-β-D-glucopyranoside (7S)、主要通过 13C NMR 光谱法和质谱法分别对其进行了分析。除这些皂苷外，还分离鉴定了两种已知的皂苷，人参皂苷-Rh1（12）和-Rg2（13），这两种皂苷之前已从人参根中分离出来。
• A Novel Ginsenosidase from an Aspergillus Strain Hydrolyzing 6-O-Multi-Glycosides of Protopanaxatriol-Type Ginsenosides, Named Ginsenosidase Type IV
  作者：Dong-Ming Wang

  DOI：10.4014/jmb.1101.01044

  日期：2011.10.28

  Herein, a novel ginsenosidase, named ginsenosidase type IV, hydrolyzing 6-O-multi-glycosides of protopanaxatriol-type ginsenosides (PPT), such as Re, R1, Rf, and Rg2, was isolated from the Aspergillus sp. 39g strain, purified, and characterized. Ginsenosidase type IV was able to hydrolyze the 6-O-alpha-L-(1 -> 2)-rhamnoside of Re and the 6-O-beta-D-(1 -> 2)-xyloside of R1 into ginsenoside Rg1. Subsequently, it could hydrolyze the 6-O-beta-D-glucoside of Rg1 into F1. Similarly, it was able to hydrolyze the 6-O-alpha-L-(1 -> 2)-rhamnoside of Rg2 and the 6-O-beta-D-(1 -> 2)-glucoside of Rf into Rh1, and then further hydrolyze Rh1 into its aglycone. However, ginsenosidase type IV could not hydrolyze the 3-O- or 20-O-glycosides of protopanaxadiol-type ginsenosides (PPD), such as Rb1, Rb2, Rb3, Rc, and Rd. These exhibited properties are significantly different from those of glycosidases described in Enzyme Nomenclature by the NC-IUBMB. The optimal temperature and pH for ginsenosidase type IV were 40 degrees C and 6.0, respectively. The activity of ginsenosidase type IV was slightly improved by the Mg2+ ion, and inhibited by Cu2+ and Fe2+ ions. The molecular mass of the enzyme, based on SDS-PAGE, was noted as being approximately 56 kDa.
• Glycoside Hydrolase Family 39 β-Xylosidases Exhibit β-1,2-Xylosidase Activity for Transformation of Notoginsenosides: A New EC Subsubclass
  作者：Rui Zhang、Na Li、Shujing Xu、Xiaowei Han、Chunyan Li、Xin Wei、Yu Liu、Tao Tu、Xianghua Tang、Junpei Zhou、Zunxi Huang

  DOI：10.1021/acs.jafc.9b00027

  日期：2019.3.20

  beta-1,2-Xylosidase activity has not been recorded as an EC subsubclass. In this study, phylogenetic analysis and multiple sequence alignments revealed that characterized beta-xylosidases of glycoside hydrolase family (GH) 39 were classified into the same subgroup with conserved amino acid residue positions participating in substrate recognition. Protein-ligand docking revealed that seven of these positions were probably essential to bind xylose-glucose, which is linked by a beta-1,2-glycosidic bond. Amino acid residues in five of the seven positions are invariant, while those in two of the seven positions are variable with low frequency. Both the wild-type beta-xylosidase rJB13GH39 and its mutants with mutation at the two positions exhibited beta-1,2-xylosidase activity, as they hydrolyzed o-nitrophenyl-beta-D-xylopyranoside and transformed notoginsenosides R-1 and R-2 to ginsenosides Rg(1) and Rh-1, respectively. The results suggest that all of these characterized GH 39 beta-xylosidases probably show beta-1,2-xylosidase activity, which should be assigned an EC number with these beta-xylosidases as representatives.