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Advances in Researches on Chemical Composition and Functions ofHemerocallis Plants

更新时间:2016-07-05

Supported by Knowledge Innovation Program Funding of Institute of Food Science and Technology, Chinese Academy of Agricultural Sciences (125161015000150013), China Agriculture Research System (CARS-21), Science and Technology Project of Tibet Autonomous Region (Z2016B01N04), Beijing Food Crops Innovation Consortium(BAIC09-2017).

1 Introduction

The genus Hemerocallis L. is a kind of perennial herbaceous plants of Liliaceae. It consists of about 15 species in the world, mainly distributed in the temperate to subtropical regions of Asia and few are distributed in Europe. And there are 11 species in China. Some species of Hemerocallis are widely cultivated for medicinal, edible and ornamental application[1]. The famous dried vegetable food Hemerocalliscitrina Baroni (also known as daylily) belongs to this genus. H. citrina Baroni, as food and traditional medicine, has a history of thousands of years, and is widely cultivated in Hunan, Jiangsu, Gansu, Shaanxi, Zhejiang, Sichuan, and Hubei. The edible part of H. citrina Baroni is mainly its bud through cooking and drying process. For medical purpose, H. citrina Baroni has functions of clearing away heat and dampness, soothing the chest oppression and relieving depression, and cooling the blood and detoxification, and is mainly used for curing scanty and dark urine, jaundice, chest tightness upset, insomnia, haemorrhoids, and ulcerative carbuncle. Besides, Hemerocallis fulva (L.) L., used for medicine with its roots, has functions of clearing away heat and dampness, detoxifying and removing swell, cooling blood and stanching bleeding, is mainly used for curing jaundice, edema, turbidity, vaginal discharge, stool blood, blood in the stool, metrorrhagia, scrofula, breast pain, and breast milk stoppage, and has wide clinical application[2]. Considerable progress has been made in researches on chemical composition and functional activities of Hemerocallis plants. By now, from the roots and ground parts of these plants, many kinds of compounds have been isolated and identified, including flavonoids, anthraquinones, alkaloids, terpenoids, triterpenes and triterpenoid saponins, caffeoylquinic acid derivatives, naphthalene glycosides, steroid and steroidal saponins, phenylethanoid glycosides, and lignans. The activity studies have demonstrated that Hemerocallis plants have sedative hypnotic, antidepressant, antioxidant, anti-tumor, hepatoprotective, antibacterial and insecticidal functions[3-5]. At present, researches on Hemerocallis plants are mainly concentrated on H. fulva, H. fulva var. kwanso, H. fulva var. sempervirens, and H. longituba, few touches upon other varieties, so there is a large space for research.

二是第一大税种增值税仍将是下一步减税的主力军。在今年约4000亿元减税基础上,下一步增值税减税方向将是通过税率三档并两档来降低税率。目前增值税税率有6%、10%和16%三档,今年政府工作报告明确了增值税税率三档并为两档。但由于一些技术原因和中间环节问题尚未落地,这也有望成为下一步减税攻克的难题。专家建议,以增值税税率简并为契机将制造业税率16%分阶段降至10%,保留10%、5%两档税率,将提高减税后企业和居民的获得感。

2 Advances in researches on chemical composition

2.1 Flavonoids So far, researchers have isolated and identified 26 kinds of flavonoids from Hemerocallis plants, mainly including flavonols and glycosides, and also including a small number of flavonoids and glycosides, isoflavones and dihydroflavones. Specifically, they are quercetin (1)[6-7], quercetin 3-O-β-D-xylopyranoside (2)[7-8], isoquercitrin, quercetin 3-O-β- D-glucoside (3)[7-9], hyperoside (4)[7], rutin (5)[6-8], quercetin 3-O-α-Lrhamnopyranosyl-(1→6)-β-D-galactopyranoside (6)[8], qu-ercetin 3-O-α-L-rhamnopyranosyl-(1→6)-[α-Lrhamnopyranosyl-(1→2)]-β-D-glucopyranoside (7)[8], quercetin 3-O-{α-L-rhamno-pyranosyl-(1→6)-[α-Lrhamnopyranosyl-(1→2)]}-β-D-galactopyranoside (8)[6], kaem-pferol (9)[6], kaempferol 3-O-α-L-arabinopyranoside (10)[8], astragalin, kaempferol-3-O-β-Dglucopyranoside (11)[6,8], kaempferol 3-O-rutinoside (12)[6,8], kaempferol 3-O-{α-L-rhamnopyranosyl-(1→6) -[α-L-rhamnopyranosyl-(1→2)]}-β-Dgalactopyranoside (13)[6], isorha-mnetin-3-O-β-D-6′-acetylglucopyranoside (14)[9], sorhamnetin-3-O-β-D-6′-acetylgalactopyrano-side (15)[9], isorhamnetin 3-O-α-L-rhamnopyranosyl-(1→6)-[α-Lrhamnopyranosyl-(1→2)]-β-D-glucopyranoside (16)[8], quercetin 3,7-O-β-D-diglucopyranoside (17)[9], quercetin 3-O-α-L-rhamnopyransyl-(1→6)-β-Dglucopyranosyl-7-O-β-D-glucopyranoside (18)[9], chrysoeriol-7-O-[β-D-glucuronopyranosyl-(1→2)-(2-O-transferuloyl)-β-D-glucuronopyranoside (19)[6], chrysoe-riol 7-O-β-D-glucuronopyranosyl-(1→2)-O-β-Dglucuronopyranoside (20)[6], 6-methylluteolin (21)[10], puerarin (22)[11], 3′-methoxypuerarin (23)[11], hesperidin (24)[12], hemerocallone (25)[13], catechin (26)[14], as shown in Fig.1.

Fig.1 Chemical structure of compounds 1-26

2.2 Anthraquinones Robert H. isolated 14 kinds of anthraquinones from roots of Hemerocallis L., H. fulva var. kwanso, and H. citrina Baroni, including kwanzoquinone A (27)[10], kwanzoquinone B (28)[10], kwanzoquinone E (29)[10], kwanzoquinone F (30)[10], rhein (31)[13], kwanzoquinone G (32)[10], 2-hydroxychrysophanol (33)[10], kwanzoquinone C (34)[10], kwanzoquinone D (35)[10],chrysophanol (36)[13], 2-methoxy-obtusifolin (37)[13], obtusifolin (38)[13], aloe-emodin (39)[13], hemerocal (40)[15], as shown in Fig.2.

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Fig.2 Chemical structure of compounds 27-40

2.8 Steroid and steroidal saponins The isolated and identified steroid and steroidal saponins include 25 (R) -spirostan-4-ene-3,12-dione (88)[20], 24S-hydroxy-neotokorogenin 1-O-a-L-arabinopyranosyl24-O-β-D-glucopyranoside (89)[22], isorhodeasapogenin3-O-β-D- glucopyranosyl-(1→3)-[β-D-xylopyranosyl-(1→2)]-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside (90)[22], as shown in Fig.8.

Fig.3 Chemical structure of compounds 41-54

2.6 Caffeoylquinic acid derivatives The isolated and identified caffeoylquinic acid derivatives include: chlorogenic acid (71)[6,21], chlorogenic acid methyl ester (72)[6], 4-O-caffeoylquinic acid (4-O-caffeoylquinic acid, (73)[6,21], 4-O-caffeoylquinic acid n-butylester (74)[6], 5-O-caffeoyl quinine (5-O-caffeoylquinic acid, (75)[6,21], 3-O-p-coumaroylquinic acid (76)[21] 4-Op-coumaroylquinic acid (77)[21], 5-Op-coumaroylquinic acid (78)[21], 3-O-feruloylquinic acid 3-O-feruloylquinic acid (79)[21], 4-O-feruloylquinic acid (80)[21], 5-O-feruloylquinic acid -O-feruloylquinic acid (81)[21], 5-caffeoylquinic acid 4-hydroxyphenethylammonium salt (82)[17], and 5-caffeoylquinic ammonium salt (83)[17], as shown in Fig.6.

当满载速度为12knots、满载状态时,育明轮在艏倾和较大的艉倾下都会使船舶的静水阻力增加,在一定的艉倾状态下可以降低船舶阻力,当吃水差为-0.2米时,船舶的阻力最小,相比于平吃水时阻力可减少4.79%。

According to CompendiumofMateriaMedica, Hemerocallis flowers are sweet in taste, cool in nature, have functions of clearing away heat and dampness, alleviating depression, cooling the blood and removing toxins, and are mainly used for treating scanty and dark urine, jaundice, chest distress, insomnia, hemorrhoids and hematochezia, and carbuncle. Due to its benefit for chest diaphragm, soothing five internal organs (heart, liver, spleen, lungs and kidneys), making people happy and free from all anxieties, it is also named "no anxiety grass". The flowers mentioned include three colors, red, yellow and purple. Through investigation, H. citrina, H. fulva, H. plicata, H. lilio-asphodelus, and H. minor can be used as drugs. Modern studies indicate that Hemerocallis plants have sedative hypnotic, antidepressant, antioxidant, anti-tumor, hepatoprotective, antibacterial and insecticidal functions, which are consistent with records of CompendiumofMateriaMedica.

Fig.4 Chemical structure of compounds 55-61

2.5 Triterpenes and glycosides The isolated and identified triterpenes and glycosides include 3-Oxo-lanosta-8, 24-diene-21-carboxylic acid (62)[20], 3β-hydroxy lanosta-8, 24- diene-21-carboxylic acid (63)[20], 3α-Hydroxanthost-8,24-diene-21-carboxylic acid (64)[20], 3α-acetyl-11-oxo-12-uvraene-24-carboxylic acid (66)[20], β-boswellic acid (67)[20], 11α-hydroxy-3-hexanoyl-β-boswellic acid (68)[20], HN saponin F (69)[11], (3β, 4α)-3, 23-Dihydroxyolean-12-en-28-oic acid -3-O-β-D-glucopyran- (1-3) -α-L-arabinopyranosyl-28-O-β-D - glucopyranosyl ester (70)[11], as shown in Fig.5.

Fig.5 Chemical structure of compounds 62-70

2.4 Terpenoids By now, researchers have isolated and identified 7 kinds of terpenoids from Hemerocallis plants, including hemerocallal A (55)[19], emottene (56)[19], hemerocalloside (57)[19], roseoside (58)[9], phlomuroside (59)[9], sweroside (60)[11], and loganin (61)[11], as shown in Fig.4.

Fig.6 Chemical structure of compounds 71-83

Lin etal.[30] studied the anti-depressant effect of ethanol extract of Hemerocallis and its typical flavonoid rutin. The results showed that in both the short-term and long-term experiments, the extracts and rutin significantly reduced the immobility time of mice in the forced swimming test and increased the concentrations of serotonin, norepinephrine and dopamine. The anti-depressant effect of Hemerocallis may be highly correlated with serotonin system. In addition, rutin may play a very important role in the process of Hemerocallis exerting its anti-depressant effect.

Fig.7 Chemical structure of compounds 84-87

2.3 Alkaloids By now, scholars have isolated and identified 14 kinds of alkaloids, including kwansonine A (41)[16], kwansonine B (42)[16], kwansonine C (43)[17], longitubanine B (44)[16,18], oxypinnatanine A (45)[17], longitubanine A (46)[8,16,18], oxypinnatanine (47)[18], pinnatanine (48)[16,18], 1′,2′,3′,4′-tetrahydro-5′-deoxypinnatanine (49)[9], adenosine (50)[6], guanosine (51)[6], lycoperodine-1 (52)[6], fulvanine A (53)[17], adenosine (54)[9], as shown in Fig.3.

2.10 Lignans The isolated and identified lignans include picraquassioside C(94)[11] and lariciresinol (95)[9], as shown in Fig.9.

Fig.8 Chemical structure of compounds 88-90

2.9 Phenylethanoid glycosides The isolated and identified phenylethanoid glycosides include phenethylβ-D-glucopyranoside (91)[8], salidroside (92)[17], and icariside D2(93)[17], as shown in Fig.9.

Fig.9 Chemical structure of compounds 91-95

由图1可知,位于面层和基层间的测点1的竖向应力及应变水平较高,随着结构厚度增加,测点2及测点3的应力和应变水平降低,降低趋势呈现近似直线,说明超厚宽幅水泥稳定碎石基层各结构层间的黏结力较强,结构整体性较好。

2.11 Other types of compounds Apart from the above compounds, there are other types components: orcinolβ-D-glucopyranoside (96)[8], phloretin 2′-O-β-Dglucopyranoside (97)[8], phloretin 2′-O-β-Dxylopyranosyl-(1→6)-β-D-glucopyranoside (98)[8], 7-hydroxynaphthalide-β-D-glucopyranoside (99)[11], 7-hydroxynaphthalide (100)[20], (3S,4S)-3,4-dihydroxy-3-ethyldihydrofuran-2-one (101)[18], p-dibenzoate (102)[23], gallic acid (103)[14], fulvanol (104)[24], as shown in Fig.10.

Fig.10 Chemical structure of compounds 96-104

3 Advances in researches of activity ofHemerocallis plants

通过KBr压片,使用美国Nicolet公司Nicolet 6700智能型傅立叶变换红外分光光度计分别对酰胺丙基二甲基叔胺盐酸盐和芥酸酰胺丙基甜菜碱结构进行表征,见图1、2。

3.1 Sedative and hypnotic activity Since the 1990s, when clinically using H. citrina to treat the hepatitis, it accidentally found that H. citrina also has significant sedative and hypnotic effects. Through comparative study, it found that its function is better than conventional application of the sleeping pills (such as Diazepam Tablet and Yangxue Anshen Capsule), and it is safer and more reliable due to the same source for drug and food. Later, scholars further confirmed the sedative and hypnotic effects of Hemerocallis plants. The ethanol extract of Hemerocallis plants could significantly prolong the slow wave sleep (SWS) and paradoxical sleep. The decrease of autonomic activity in rats may be due to the decrease of the concentration of noradrenaline, dopamine and serotonin in cerebral cortex and brain stem[25-26].

3.2 Antidepressive activity Yi’s team undertook an intensive study on the antidepressant function and mechanism of H. citrina. In 2012, the team[27] reported the antidepressant effect of H. citrina extract and confirmed the possible antidepressant effects of 5-HT1A and 5-HT2 receptors), norepinephrine (α1-, α2- and β-adrenergic receptors) and dopamine (D2 receptor) systems as well as elevated serotonin, norepinephrine and dopamine levels in the brain of mice. In the same year, it also confirmed[28] that the antidepressant function may be connected with BDNFTrkB mediated signaling in the frontal cortex and hippocampus. In 2014, it discovered that[29] the anti-inflammatory effect of H. citrina extract may play a crucial role in its anti-depressant process and may be related to the repair and improvement of monoamine neurotrophic factor system. Du etal.[12] found that the antidepressant effect of H. citrina is associated with the flavonoids, especially rutin (5) and hesperidin (24).

2.7 Naphthalene glycosides The isolated and identified naphthalene glycosides include: dianellin (84)[10], 5-hydroxydianellin (85)[10], stelladerol (86)[8], hemerocallin (87)[13], as shown in Fig.7.

3.3 Antioxidant activity Bor etal.[31] found that the aqueous extract of H. citrina had a significant inhibitory effect on lipopolysaccharide-induced inhibition of NO production in macrophages, which may be related to the decline of inducible nitric oxide synthase (iNOS). Que etal.[14] proved that Hemerocallis extract had significant antioxidant activity, ethanol extract was more effective than aqueous extract. Polyphenols such as rutin (5), catechin (26) and gallic acid (103) may be related to its antioxidant activity. The caeic acid derivatives isolated by Lin etal.[6] from Hemerocallis have strong free radical scavenging activity. From H. cv. Stella de Oro, Robert etal.[8] isolated and obtained stelladerol (86).

3.4 Anti-tumor activity Anthraquinones from the roots of the genus Hemerocallis have a significant anti-tumor activity[32]. Rhein exerts its anti-tumor effect through cell cycle arrest, induction of apoptosis, and control of metastasis[33]. Aloe-emodin has a wide anti-tumor activity on leukemia, glioma, pharyngeal cancer, liver cancer, stomach cancer and breast cancer and other tumors, and it can play the anti-tumor role through inducing apoptosis, anti-metastasis, and other ways[34].

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3.5 Hepatoprotective activity Shen Nan etal.[34] discussed the improvement function of total flavonoids in Hemerocallis flower to liver fibrosis of rats. The results showed that the total flavonoids of Hemerocallis flower (25, 50 mg/kg) could reduce the alanine transaminase (ALT), aspartate aminotransferase (AST), r-Glutamyl transpeptidase (GT), and alkaline phosphatase (ALP) in serum, increase the superoxide dismutase (SOD) and reduce the malondialdehyde (MAD), reduce the content and expression of TGF-β1, reduce Procollagen type I N-terminal propeptide (PINP) content in liver tissue, and improve the pathological changes of liver tissue.

3.6 Antibacterial insecticide activity Robert etal.[10] found that the anthraquinones 2-hydroxychrysophanol and kwanzoquinones A isolated from Hemerocallis fulva var. kwanso have certain insecticide effect on schistosoma. Components of anthraquinones such as emodin, rhein, aloe-emodin have certain antibacterial effect[3]. Hemerocallis plants are widely distributed in China, the resources are rich, especially H. citrina as a vegetable has been widely cultivated. Chemical components of Hemerocallis plants are various, and structural type is rich, and Hemerocallis plants have a variety of significant functional activities, so it is worth further study.

References

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