Phenylethanoid and Phenylmethanoid Glycosides from the Leaves of Ligustrum robustum and Their Bioactivities

The phytochemical study on the leaves of Ligustrum robustum, which have been used as Ku-Ding-Cha, led to the isolation and identification of three new phenylethanoid glycosides and three new phenylmethanoid glycosides, named ligurobustosides R₁ (1b), R_2–3 (2), R₄ (3), S₁ (4b), S₂ (5), and S₃ (6), and five reported phenylethanoid glycosides (7–11). In the bioactivity test, (Z)-osmanthuside B₆ (11) displayed strong fatty acid synthase (FAS) inhibitory activity (IC₅₀: 4.55 ± 0.35 μM) as the positive control orlistat (IC₅₀: 4.46 ± 0.13 μM), while ligurobustosides R₄ (3) and S₂ (5), ligupurpuroside B (7), cis-ligupurpuroside B (8), ligurobustoside N (9), osmanthuside D (10), and (Z)-osmanthuside B₆ (11) showed stronger ABTS radical scavenging activity (IC₅₀: 2.68 ± 0.05~4.86 ± 0.06 μM) than the positive control L-(+)-ascorbic acid (IC₅₀: 10.06 ± 0.19 μM). This research provided a theoretical basis for the leaves of L. robustum as a tea with function in treating obesity and diabetes.     

Two New Phenylethanoid Glycosides from Callicarpa longissima

Two new phenylethanoid glycosides, longissimosides A and B ( 1 and 2 , resp.), together with eight structurally related known compounds, were isolated from the EtOH extract of leaves and stems of Callicarpa longissima (Hemsl .) Merr . The structures of 1 and 2 were elucidated as 2‐(3,4‐dihydroxyphenyl)ethyl O‐(α‐L ‐rhamnopyranosyl)‐(1→3)‐O‐(2‐O‐syringoyl‐β‐D ‐xylopyranosyl)‐(1→6)‐ 4‐O‐[(E)‐caffeoyl]‐β‐D ‐glucopyranoside ( 1 ) and 2‐(3‐hydroxy‐4‐methoxyphenyl)ethyl O‐(α‐L ‐rhamnopyranosyl)‐(1→3)‐O‐(β‐D ‐apiofuranosyl)‐(1→6)‐4‐O‐[(E)‐isoferuloyl]‐β‐D ‐glucopyranoside ( 2 ) on the basis of spectroscopic data and acid hydrolysis.     

Phenylethanoid Glycosides from the Roots of Digitalis ciliata Trautv.

Three new phenylethanoid glycosides, named digicilisides A – C ( 1  –  3 , resp.), have been isolated from the roots of Digitalis ciliata, along with five known phenylethanoid glycosides. The structures of 1  –  3 were identified as 2‐(4‐hydroxy‐3‐methoxyphenyl)ethyl β‐d ‐glucopyranosyl‐(1→3)‐[α‐l ‐rhamnopyranosyl‐(1→6)]‐4‐O‐[(E)‐feruloyl]‐β‐d ‐glucopyranoside ( 1 ), 2‐(3,4‐dihydroxyphenyl)ethyl α‐l ‐arabinopyranosyl‐(1→2)‐[β‐d ‐glucopyranosyl‐(1→3)]‐[α‐l ‐rhamnopyranosyl‐(1→6)]‐4‐O‐[(E)‐feruloyl]‐β‐d ‐glucopyranoside ( 2 ), and 2‐(3,4‐dihydroxyphenyl)ethyl β‐d ‐glucopyranosyl‐(1→3)‐{6‐O‐[(E)‐feruloyl]‐β‐d ‐glucopyranosyl‐(1→6)}‐4‐O‐[(E)‐caffeoyl]‐β‐d ‐glucopyranoside ( 3 ).     

Megastigmane Glycosides from Docynia indica and Their Anti‐inflammatory Activities

Using various chromatographic methods, three new megastigmane glycosides, docynicasides A – C ( 1  –  3 ) and ten known, (6S,9R)‐vomifoliol 9‐O‐β‐d ‐xylopyranosyl‐(1′′→6′)‐O‐β‐d ‐glucopyranoside ( 4 ), hyperin ( 5 ), quercitrin ( 6 ), quercetin 3‐α‐l ‐arabinofuranoside ( 7 ), naringenin 7‐O‐β‐d ‐glucopyranoside ( 8 ), phloridzin ( 9 ), phloretin 2′‐O‐β‐d ‐xylopyranosyl‐(1→6)‐β‐d ‐glucopyranoside ( 10 ), pinosylvin 3‐O‐β‐d ‐glucopyranoside ( 11 ), tormentic acid ( 12 ), and chlorogenic acid methyl ester ( 13 ) were isolated from the fruits of Docynia indica. Their chemical structures were elucidated by physical and chemical methods. All the isolated compounds were evaluated for the inhibitory activity on NO production in LPS‐stimulated BV2 cells. As the results, compounds 3  –  5 showed significant inhibitory activity on LPS‐stimulated NO production in BV2 cells with the IC₅₀ values ranging from 21.0 to 29.3 μm .     

Establishment of GC-MS fingerprint of fresh Houttuynia cordata

Fresh Houttuynia cordata THUNB. is a Chinese materia medica generally used in Chinese medicine therapy. It possesses the actions of clearing heat, eliminating toxins, reducing swelling, discharging pus and relieving stagnation. However, dry H. cordata has traditionally been used in clinical application instead of the fresh counterpart. In this paper, the chemical profiles of H. cordata were established using fingerprinting techniques. A modified GC-MS method was developed in the comparison of fingerprints among fresh and dry herbs of H. cordata. It was shown that the varieties, as well as relative levels of chemical components, in the fresh herb were more abundant than in the dry counterpart. Fingerprinting profiles were found to be consistent for fresh herbs acquired from various production areas, but the relative abundance of peaks were varied. Besides, the chemical components among different medicinal portions of fresh herbs were found to be inconsistent. The developed fingerprint can be successfully applied to distinguish between fresh and dry herbs, as well as determining differentiation among different medicinal portions.     

Analysis of Volatile Compounds from Different Parts of Houttuynia cordata Thunb.

Houttuynia cordata Thunb. is a medicinal and edible plant that has been commonly used in traditional Chinese medicine since ancient times. This study used headspace solid-phase microextraction (HS-SPME) and direct injection, combined with gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS), to identify the volatile compounds in H. cordata. Extraction from different parts of the plant using different extraction techniques for the identification of volatile compounds were determined. A total of 93 volatile components were analyzed in the leaves, stems, rhizomes, and whole plant samples of H. cordata. The leaves contained more (Z)-3-hexenal, β-myrcene, (Z)-β-ocimene, and (4E,6E)-allo-ocimene; the stems contained more geranyl acetate and nerolidol; and rhizomes contained more α-pinene, β-pinene, limonene, 2-undecanone, and decanoyl acetaldehyde. Among them, the essential oil extracted by HS-SPME could produce more monoterpenes, while direct injection could obtain higher contents of aliphatic ketones, terpene esters, sesquiterpenes, and was more conducive to the extraction of 2-undecanone and decanoyl acetaldehyde.     

Establishment of HPLC-DAD-MS fingerprint of fresh Houttuynia cordata

A HPLC-DAD-MS fingerprint method of fresh Houttuynia cordata THUNB. was developed basing on the consistent chromatographic features among 11 batches of authentic samples. Major chemical components including phenolic compounds, flavones and alkaloids were simultaneously analyzed. Eleven common peaks in the fingerprint were chosen and identified by comparing their UV and ESI-MS data with the authentic compounds. The unique properties of this HPLC-DAD-MS fingerprint were successfully applied to analyze and differentiate samples from different geographical origins, processing methods and various medicinal parts of H. cordata. The results showed that these variations will give rise to differences in identities and/or abundance of chemical compounds, indicating that a comprehensive quality evaluation of those major ingredients in H. cordata is critical to assess and represent its overall quality.     

Sesquiterpenoids and Their Glycosides from Gynura procumbens

Chemical investigation of the MeOH extract of the leaves of Gynura procumbens (Lour .) Merr . afforded one new sesquiterpenoid, muurol‐4‐ene‐1β,3β,10β‐triol ( 1 ), and two sesquiterpene glycosides, muurol‐4‐ene‐1β,3β,10β‐triol 3‐O‐β‐D ‐glucopyranoside ( 2 ) and muurol‐4‐ene‐1β,3β,15‐triol 3‐O‐β‐D ‐glucopyranoside ( 3 ), together with three known sesquiterpenoids. Their structures were elucidated on the basis of spectroscopic analyses and chemical methods.     

鱼腥草中黄酮类成分的高效液相色谱指纹图谱分析

采用均匀实验设计和信息理论评价方法,建立了鱼腥草中黄酮类成分的高效液相色谱(HPLC)指纹图谱的分析方法。采用建立的方法和本研究室提出的指纹图谱评价软件,对同样种植条件下10个批次的鱼腥草指纹图谱进行了相似性评价,相似度均大于0.90;同时测定了芦丁、槲皮甙和槲皮素3个成分在10批鱼腥草药材中的含量分别为0.25%～0.34%、0.27%～0.37%、0.012%～0.016%。另外对不同采收季节和不同部位的鱼腥草药材中的黄酮类成分进行了指纹图谱的测定、主成分分析以及成分含量测定,结果表明,不同季节、不同部位的鱼腥草中黄酮类化合物的指纹图谱及成分含量存在较大的差异,且药用部位的差异大于采收季节的差异。该方法为规范鱼腥草中黄酮类成分在制药和用药的实际应用提供了一些可靠的基础信息。     

Arylethyl (= Phenylethanoid) Glycosides and Oligosaccharide from the Stem of Cistanche tubulosa

Three new analogues of the arylethyl (= phenylethanoid) glycoside echinacoside ( 5 ), namely cistantubulosides A ( 1 ), B₁/B₂ ( 2a / 2b ), and C₁/C₂ ( 3a / 3b ), and one new oligosaccharide, cistantubulose A₁/A₂ ( 4a / 4b ), were isolated from the stems of Cistanche tubulosa (Schenk ) R. Wight , together with five known compounds, i.e., campneoside I, campneoside II ( 6 ), echinacoside ( 5 ), tubuloside, and cistanoside F. Among the compounds isolated, 2a / 2b, 3a / 3b, 4a / 4b , campneoside I, campneoside II ( 6 ), and cistanoside F each consisted of a pair of epimers. The structures of the new compounds were elucidated on the basis of spectral data.     

Houttuynoids A-E, anti-herpes simplex virus active flavonoids with novel skeletons from Houttuynia cordata

Houttuynoids A-E (1-5), a new type of flavonoid with houttuynin tethered to hyperoside, and their presumed biosynthetic precursor hyperoside (6) were isolated from the whole plant of Houttuynia cordata. Their structures were elucidated by analysis of 1D and 2D NMR. A hypothetical biogenetic pathway for houttuynoids A-E was proposed. Compounds 1-5 exhibited potent anti-HSV (herpes simplex viruses) activity.     

黔产市售鱼腥草中重金属含量分析及膳食风险评估

为研究黔产市售鱼腥草中铅、镉、铬、砷4种重金属的含量水平及其膳食健康风险水平。以贵州贵阳(GY)、遵义(ZY)、铜仁(TR)、安顺(AS)、毕节(BJ)、六盘水(LPS)、黔东南(QDN)、黔西南(QXN)、黔南(QN)等9个市(州)市售鱼腥草为研究对象,利用微波消解处理样品,采用电感耦合等离子体质谱(ICP-MS)法同时测定样品中的4种重金属含量,利用单因子污染指数法、内梅罗综合污染指数法对重金属的污染程度进行评价,利用目标危害系数法进行膳食风险评估。结果显示,鱼腥草中Pb含量为0.084～0.12 mg/kg, Cd含量为0.041～0.068 mg/kg, Cr含量为0.076～0.43 mg/kg, As含量为0.074～0.14 mg/kg。TR、QDN、ZY市售鱼腥草Pb的单项污染指数均大于1,9个市(州)市售鱼腥草Cd、Cr、As的单项污染指数均小于1。不同市(州)市售鱼腥草的内梅罗综合污染指数大小次序为1>TR>QDN>ZY>AS>GY>BJ>QXN>0.7≥QN>LPS。单一重金属的膳食健康风险指数(THQ)总体上...     

鱼腥草中3种有效成分含量的测定

建立鱼腥草不同品种、不同部位绿原酸、芸香苷和槲皮素的测定方法. 以90% EtOH为溶剂, 采用索氏提取器提取, 利用HPLC测定3种活性成分的含量. 采用DiamonsilTMC18 (4.6 mm×150 mm, 5 μm)为色谱柱, 流动相分别为0.06 mol/L V(NaH2PO4)∶V(MeOH)＝7.3∶2.7、 V(MeOH)∶V(H2O)∶V(HAc)＝48∶50∶2, 流速为1 mL/min, 绿原酸检测波长为326 nm, 芸香苷和槲皮素为254 nm. 绿原酸、芸香苷、槲皮素的线性范围分别为4.6～30.7 μg/mL、 0.30～7.5 μg/mL、 0.034～0.85 μg/mL, 平均回收率和RSD分别为99.3%、 1.0%, 98.9%、 1.6%, 98.7%、 0.7%. 该方法可用于鱼腥草原料选择和制剂质量的控制.     

保留指数结合准确质量测定对鱼腥草挥发性成分的定性分析

采用顶空-气相色谱-四极质谱法和顶空-气相色谱-飞行时间质谱法对鱼腥草挥发性成分进行检测,运用保留指数结合准确质量测定,分别从鱼腥草茎和叶中鉴定出49、39种挥发性组分,并采用峰面积归一化法测定各组分的相对含量。鱼腥草茎和叶中的挥发性成分差别较大。鱼腥草茎以α-蒎烯(12.24%)、β-蒎烯(22.42%)、月桂烯(11.98%)、乙酸冰片酯(10.97%)、甲基正壬酮(10.83%)为主要成分,而鱼腥草叶则以月桂烯(39.48%)、(Z)-β-罗勒烯(26.52%)、癸醛(10.35%)、桧烯(4.43%)、甲基正壬酮(2.44%)为主。结合保留指数和准确质量测定能显著提高质谱定性的准确性,有利于解决质谱检索时定性不确定的问题。