马蔺根的化学成分研究

从鸢尾科植物马蔺根70%乙醇提取液中分离鉴定了11个已知化合物,分别为:5,7,3'-三羟基-4'-甲氧基黄酮(5,7,3'-Trihydroxy-4'-methoxyflavone,1),3、6、7-四羟基口山酮-2-C-β-D-葡萄糖(mangiferin,2),5-羟基-7,4'-二甲氧基黄酮-6-C-β-D-葡萄糖-2-O-L-鼠李糖(embinin,3),1-β-D-arabinofuranosyluracil(4),hyperolactone B(5),香草酸(6),2-methyl-propyl-β-D-ucopyranoside(7),decanoic acid(8),4-methylpentanoic acid(9),胡萝卜苷(10),β-谷甾醇(11).其中化合物1、4、5、7、8、9为首次从该植物中分离得到.     

Biotransformation of sinesetin by the larvae of the common cutworm (Spodoptera litura)

Biotransformation of sinesetin (1) by larvae of Spodoptera litura was investigated. Compound 1 was converted to a new flavonoid, (+)-5,7,3',4'-tetramethoxyflavone-6-O-beta-D-glucoside (4), and two known flavones, 4'-hydroxy-5,6,7,3'-tetramethoxyflavone (2) and 6-hydroxy-5,7,3',4'-tetramethoxyflavone (3). These structures were established by IR, HR-EI-MS, HR-FAB-MS, 1D NMR, and 2D NMR spectral studies. The results indicate that the metabolic reaction of compound 1 by larvae of S. litura proceeded along two pathways; the main pathway is demethylation at the C-6 position followed by glucosylation, and the minor pathway is demethylation at the C-4' position.     

New Flavonoid Glycosides from Arnicae Flos DAB 91

Five flavonoid glycosides were identified from flowers of Arnica montana, ten from A. CHAMISSONIS subsp. FOLIOSA var. INCANA. The structures were established on the basis of acid hydrolysis and spectral data (UV, NMR, MS) as the 7-beta-glucosides of pectolinarigenin, apigenin, and chrysoeriol; luteolin 3'- O-beta-glucoside; the 3-beta-glucuronides of kaempferol, isorhamnetin, and 6-methoxykaempferol; the 3,7-di-beta-glucosides of quercetin and patuletin; the 3-beta-glucosides of betuletol and quercetagetin 6,3',4'-trimethyl ether; and the 7-[6'- O-(2-methylbutyryl)]=glucosides of luteolin and eupafolin. The latter four are new natural compounds. Differences between these two ARNICA species are discussed.     

中间锦鸡儿黄酮类成分的研究

目的研究中间锦鸡儿的化学成分。方法用溶剂法、色谱法分离化学成分，用波谱法鉴定其结构。结果从中间锦鸡儿中分离得到10个黄酮类化合物，分别鉴定为5,7,4′-三羟基-3,3′-二甲氧基黄酮(1)，3,5,7,8,4′-五羟基-3′-甲氧基黄酮(2),槲皮素(3),柠檬黄酮醇(4),槲皮素-3-甲醚(5)，2(S)-7,3′,5′-三羟基二氢黄酮(6)，5,7,3′,4′-四羟基-3,8-二甲氧基黄酮(7),紫铆查尔酮（8）,甘草素（9）和5,7,4′-三羟基-3,8二甲氧基黄酮（10）。结论化合物6为新化合物，其余皆首次从中间锦鸡儿中分离得到。     

Screening for Protozoocidal Activity of Spanish Plants

Crude extracts of Spanish plants (60 representing 12 species from 7 families) have been screened for antiparasitic activity against Leishmania infantum and Trichomonas vaginalis. 30% of the extracts showed activity against one of the parasites and 15% of the extracts were active against both tests organisms. The most promising extracts originate from plants used in traditional medicine, such as Inula montana L. (Asteraceae), Bupleurum rigidum L. (Apiaceae) and Scrophularia scorodonia L. (Scrophulariaceae).     

Two Flavonoid Glycosides from Cassia occidentalis Pods

From the ethanolic extract of the pods of CASSIA OCCIDENTALIS, two flavonoid glycosides namely 3,5,3',4'-tetrahydroxy-7-methoxyflavone 3- O-(2'-rhamnosyl glucoside) and 5,7,4'-trihydroxy-3,6,3'-trimethoxy-flavone 7- O-(2'-rhamnosyl glucoside) have been isolated and their structures characterised. Both these aglycones (1, 2) are known but their glycosides are being reported for the first time.     

半枝莲黄酮类化学成分分析

目的 分析半枝莲黄酮类化学成分。方法 采用硅胶、Sephadex LH-20等多种色谱方法,依据波谱数据对其结构进行分析和鉴定。结果 半枝莲中共分离了12个化合物,分别为圣草酚、野黄芩素、三裂鼠尾草素、黄芩苷、芹菜素、汉黄芩素、4''-羟基汉黄芩素、木犀草素、4'',5-二羟基-3'',5'',6,7-四甲氧基黄酮、柚皮素、7-羟基-5,8,2''-三甲氧基黄烷酮、大波斯菊苷。结论 分离得到的化合物类型均为黄酮苷元和苷类化合物,可为半枝莲的黄酮成分分析提供一定的科学依据。     

兔毛蒿有效成分的研究

从兔毛蒿Filifolium sibiricum(L)Kitam中分离出三个黄酮类化合物。晶Ⅰ为-新二氢黄酮,命名为兔毛蒿素(Filifolin);晶Ⅱ为北美圣草素(Eriodictyol);晶Ⅲ为万寿菊黄素3,6-二甲醚(3,6-dimethoxyquercetag:tin)。三者对金葡菌等革兰氏阳性菌有不同程度的抑制作用。     

白杨素衍生物的合成和晶体结构及与DNA的作用

以白杨素为先导化合物经羟甲基化反应合成中间体5,7-二羟基-6,8-二羟甲基黄酮(1)，进而合成了5,7-二羟基-6,8-二(甲氧基甲基)黄酮(2)，5,7-二羟基-6,8-二(乙氧基甲基)黄酮(3)，5,7-二羟基-6,8-二(丁氧基甲基)黄酮(4)，5,7-二羟基-6,8-二(戊氧基甲基)黄酮(5)和5-羟基-7-甲氧基-6,8-二(乙氧基甲基)黄酮(6)；采用IR，¹H NMR，¹³C NMR和元素分析对1～6进行了表征，同时用X-射线单晶衍射法对6进行了晶体结构测定。利用荧光法分别对1～4与CT-DNA的作用进行了研究，根据Stern-Volmer方程，它们对EB-DNA体系的荧光猝灭常数分别为k_q1=9.71×10³ L·mol^-1，k_q2=2.25×10⁴L·mol^-1，k_q3=1.03×10⁴L·mol^-1和k_q4=7.96×10³ L·mol^-1。1～4与白杨素相比，对DNA更具亲和力，为开发更有效的黄酮类化合物提供了实验依据。     

Polyoxygenated flavones; Synthesis,cytotoxicities and antitumor activity against ICR mice carrying S-180 cells

Fifty two flavones were synthesized from polyoxygenated dibenzoylmethanes which were obtained by a modified Baker-Venkataraman rearrangement, of 2-benzoyl oxyacetophenones. The following flavones among then showed good cytotoxic activities against L1210 and HL-60 cells; 2′-benzyloxy-5-methoxyflavone [ED₅₀(L1210)=4.9 μg/ml) ED₅₀(HL-60)=3.1 μg/ml] 2′-benzyloxy-5,7-dimethoxyflavone (8.2 μg/ml, 5.0 μg/ml), 2′-benzyloxy-5,7,8-trimethoxyflavone (5.9 μg/ml, 11.0 μg/ml), 2′-hydroxy-5,7-dimethoxyflavone (8.3 μg/ml 4.9 μg/ml) 2′-hydroxy-5-methoxyflavone (4.2 μg/ml, 2.7 μg/ml), 2′-hydroxy-5,7,8-trimethoxyflavone (9.8 μg/ml, 6.2 μg/ml), 2′-benzyloxy-5-hydroxyflavone (5.2 μg/ml, 3.6 μg/ml), and 5,2′-dihydroxyflavone (5.1 μg/ml, 4.0 μg/ml). Presence of 5-methoxy group potentiated the cytotoxic activity, while the existence of 7-methoxy group decreased the activity. 5-Hydroxy or methoxy, activates 4-carbonyl group, while 7-methoxy group deactivates the carbonyl group. From these observation it was concluded that the activation of carbonyl group at C-4 of a flavone is important for the enhancement of the cytotoxic activity. The presence of both 5-hydroxy and 2′-benzyloxy- or 2′-hydroxy group enhanced the antitumor activity; 2′-benzyloxy-5-hydroxy-7-methoxyflavone (T/C=144%), 5,2′-dihydroxy-7-methoxyflavone (T/C=132%), and 5,2′-dihydroxy-6,7,8,6′ tetramethoxyflavone (T/C=172%). 2′-Hexanoylation of 5,2′-dihydroxy-flavones did not improve the antitumor activity; 2′-hexanoyloxy-5-hydroxy-7-methoxyflavone showed T/C=132%, about the same as that of 5,2′-dihydroxy-7-methoxyflavone (T/C=130%)     

Final report on the safety assessment of Arnica montana extract and Arnica montana

Arnica Montana Extract is an extract of dried flowerheads of the plant, Arnica montana. Arnica Montana is a generic term used to describe a plant material derived from the dried flowers, roots, or rhizomes of A. montana. Common names for A. montana include leopard's bane, mountain tobacco, mountain snuff, and wolf's bane. Two techniques for preparing Arnica Montana Extract are hydroalcoholic maceration and gentle disintegration in soybean oil. Propylene glycol and butylene glycol extractions were also reported. The composition of these extracts can include fatty acids, especially palmitic, linoleic, myristic, and linolenic acids, essential oil, triterpenic alcohols, sesquiterpene lactones, sugars, phytosterols, phenol acids, tannins, choline, inulin, phulin, arnicin, flavonoids, carotenoids, coumarins, and heavy metals. The components present in these extracts are dependent on where the plant is grown. Arnica Montana Extract was reported to be used in almost 100 cosmetic formulations across a wide range of product types, whereas Arnica Montana was reported only once. Extractions of Arnica Montana were tested and found not toxic in acute toxicity tests in rabbits, mice, and rats; they were not irritating, sensitizing, or phototoxic to mouse or guinea pig skin; and they did not produce significant ocular irritation. In an Ames test, an extract of A. montana was mutagenic, possibly related to the flavenoid content of the extract. No carcinogenicity or reproductive/developmental toxicity data were available. Clinical tests of extractions failed to elicit irritation or sensitization, yet Arnica dermatitis, a delayed type IV allergy, is reported in individuals who handle arnica flowers and may be caused by sesquiterpene lactones found in the flowers. Ingestion of A. montana-containing products has induced severe gastroenteritis, nervousness, accelerated heart rate, muscular weakness, and death. Absent any basis for concluding that data on one member of a botanical ingredient group can be extrapolated to another in the group, or to the same ingredient extracted differently, these data were not considered sufficient to assess the safety of these ingredients. Additional data needs include current concentration of use data; function in cosmetics; ultraviolet (UV) absorption data-if absorption occurs in the UVA or UVB range, photosensitization data are needed; gross pathology and histopathology in skin and other major organ systems associated with repeated dermal exposures; dermal reproductive/developmental toxicity data; inhalation toxicity data, especially addressing the concentration, amount delivered, and particle size; and genotoxicity testing in a mammalian system; if positive, a 2-year dermal carcinogenicity assay performed using National Toxicology Program (NTP) methods is needed. Until these data are available, it is concluded that the available data are insufficient to support the safety of these ingredients in cosmetic formulations.     

Studies on the constituents of roots of Scutellaria planipes

From the roots of Scutellaria planipes (L.), three new flavonoids, 5,7,3',6'-tetrahydroxy-6,8,2'-trimethoxyflavone, (2 R,3 R)-3,5,7,2',5'-pentahydroxyflavanone and 7,2'-dihydroxy-5-methoxyflavone were isolated, together with ten known flavonoids, skullcapflavone I, wogonin, baicalein, norwogonin, viscidulin III, 5,7,2',6'-tetrahydroxy-flavone, 3,5,7,2',6'-pentahydroxyflavone, wogonin 7- O-beta- D-glucuronide, baicalin, baicalein 7- O-beta- D-glucopyranoside, and three phenethyl alcohol glycosides, acteoside, martynoside, and jionoside D. The structures were elucidated by spectroscopic methods.     

火绒草黄酮类成分的分离与结构鉴定

目的对火绒草的化学成分进行研究,为进一步开发利用该植物资源提供依据。方法采用反复正相硅胶、反相ODS、Sephadex LH-20等柱色谱以及高效液相色谱法等手段进行分离纯化,并通过理化性质与光谱分析鉴定化合物的结构。结果从火绒草体积分数为70%的乙醇溶液提取物中分离鉴定了9个黄酮类化合物,分别为槲皮素-3-O-β-D-吡喃葡萄糖苷(quercetin-3'-O-β-D-gluco-pyranoside,1)、槲皮素-3'-O-β-D-葡萄糖苷(quercetin-3'-O-β-D-glucopyranoside,2)、5,7,3',4'-tetra-hydroxy-3-methoxyflavone(3)、5,7,3',4'-tetrahydroxy-3-methoxyflavonol-3'-O-β-D-glucopyranoside(4)、山柰酚(kaempferol5,)、山柰酚-3-O-β-D-吡喃葡萄糖苷(kaempferol-3-O-β-D-glucopyranoside6,)、3-甲基-山柰酚(3-methyl-kaempferol,7)、3-甲醚-山柰黄素-7-O-β-D-吡喃葡萄糖苷(3-methylether-kaempferol-7-O-β-D-glucoside,8)、木犀草素-3'-O-β-D-葡萄糖苷(luteolin-3'-O-β-D-glucoside9,)。结论化合物2-57、8、为首次从火绒草属植物中分离得到。     

Rapid characterization of 96 chemical constituents in Citri Reticulatae Folium (leaves of ‘Fuju’) using HPLC-DAD-ESI-MSn

In order to systematically investigate the chemical constituents of Citri Reticulatae Folium (leaves of ‘Fuju’), an analytical method that included high-performance liquid chromatography, diode array detection, electrospray ionization, and ion-trap time-of-flight mass spectrometry (HPLC-DAD-ESI-MSⁿ) was used to separate and identify the individual chemical components of Citri Reticulatae Folium. As a result, 96 compounds were tentatively identified in this study: including 31 phenolic acids, 4 flavonoid aglycones, 6 flavonoid mono-O-glycosides, 10 flavonoid-O-diglycosides, 5 flavonoid mono-C-glycosides, 5 flavonoid di-C-glycosides, 6 flavonoid O,C-glycosides, 5 (3-hydroxy-3-methylglutaryl) glycosyl flavonoids, 1 flavan-3-ol,and 2 alkaloids. In addition, 21 polymethoxy flavonoids (PMFs) were identified in this paper. Among these compounds, 52 compounds, which were previouslyfound in other Citrus plants, have been identified for the first time in Citri Reticulatae Folium. 15 compounds have not been previously found in theCitrusgenus were identified. Moreover, 9 potentially new compounds have also been detected in this paper. This is the first report of the full characterization of chemical components of Citri Reticulatae Folium (leaves of ‘Fuju’) by HPLC-DAD-ESI-MSⁿ.     

Permeation of bioactive constituents from Arnica montana preparations through human skin in-vitro

This study investigated and characterised transdermal permeation of bioactive agents from a topically applied Arnica montana tincture. Permeation experiments conducted over 48 h used polydimethylsiloxane (silastic) and human epidermal membranes mounted in Franz-type diffusion cells with a methanol-water (50:50 v/v) receptor fluid. A commercially available tincture of A. montana L. derived from dried Spanish flower heads was a donor solution. Further donor solutions prepared from this stock tincture concentrated the tincture constituents 1, 2 and 10 fold and its sesquiterpene lactones 10 fold. Permeants were assayed using a high-performance liquid chromatography method. Five components permeated through silastic membranes providing peaks with relative retention factors to an internal standard (santonin) of 0.28, 1.18, 1.45, 1.98 and 2.76, respectively. No permeant was detected within 12 h of applying the Arnica tincture onto human epidermal membranes. However, after 12 h, the first two of these components were detected. These were shown by Zimmermann reagent reaction to be sesquiterpene lactones and liquid chromatography/diode array detection/mass spectrometry indicated that these two permeants were 11,13-dihydrohelenalin (DH) analogues (methacrylate and tiglate esters). The same two components were also detected within 3 h of topical application of the 10-fold concentrated tincture and the concentrated sesquiterpene lactone extract.     

ZnO-ZnS QDs interfacial heterostructure for drug and food delivery application: enhancement of the binding affinities of flavonoid aglycones to bovine serum albumin

Zero-dimensional nanostructures are green nanomaterials that have recently attracted increasing attention. However, very little information is available on whether or not these heterostructures affect drug transport in blood. In current work, flavonoid aglycones were studied for their affinities for bovine serum albumin (BSA) in the presence and absence of zinc oxide-zinc sulfide quantum dots (ZnO-ZnS QDs) in vitro. The fluorescence intensity of BSA decreased remarkably with increasing concentration of ZnO-ZnS QDs, resulting in an obvious red-shift of the maximum emission of BSA from 340 to 348 nm. The magnitudes of binding constants in the presence of QDs ranged from 10(4) to 10(6) L/mol, and the number of binding sites per BSA molecule (n) was determined as 1.12 ± 0.17. Although ZnO-ZnS QDs significantly increased the affinities for BSA of myricetin, luteolin, gallocatechin gallate, tectorigenin, and formononetin, they barely affected the binding affinities of flavone, (-)-epicatechin gallate, and quercetin. FROM THE CLINICAL EDITOR: Serum albumins are major transport proteins in blood that reversibly bind fatty acids, amino acids, drugs, and inorganic ions, which interactions have important effects on the distribution, free concentration, and metabolism of drugs in blood. In this research nine flavonoid aglycones were studied for their affinities for bovine serum albumin (BSA). Interestingly it was found that presence of ZnO-ZnS QDs significantly increased the affinities of BSA for several of these aglycones.     

Note Flavonoid Aglycones From Ballota saxatilis Subsp. saxatilis

From the aerial parts of Ballota saxatilis subsp. saxatilis, the three flavone aglycones 6 hydroxy apigenol 7,4'-dimethyl ether (ladanein) (1), kaempferol 3,7,4'-trimethyl ether (2), and quercetin 3,7,3',4'-tetramethyl ether (retusin) (3), have been isolated and identified.     

Flavonoid aglycones and phytosterols from the Erigeron acris L. herb

Four flavonoid aglycones (apigenin, kaempferol, luteolin, quercetin) were isolated from methanolic extract from the herb of Erigemn acris L. (Asteraceae). In this extract five phytosterols (campesterol, chondrillasterol, stigmast-7-en-3-ol(5alpha,3alpha), stigmasterol and spinasterone) were also identified.     

Immunostimulating action of polysaccharides (heteroglycans) from higher plants

From the water or alcaline-water extracts of Echinacea purpurea (L.) Moench. and -angustifolia DC., Eupatorium cannabium L. and -perfoliatum L., Chamomilla recutita L. Rauscher, Calendula officinalis L., Baptisia tinctoria (L.) R. B., Achyrocline satureioides DC., Arnica montana L., Sabal serrulata Roem. et Schult., and Eleutherococcus (Acanthopanax) senticosus Maxim. polysaccharide fractions with molecular weights in the range of 25 000 to 500 000 and higher have been isolated, which, according to the granulocytes- and carbon clearance tests, showed significant immunostimulating activities. The isolated compounds belong to the group of watersoluble, acidic branched-chain heteroglycans. Their immunostimulating activity is compared and discussed with respect to other polysaccharides of biological activity.     

Skin penetration studies of Arnica preparations and of their sesquiterpene lactones

Alcoholic preparations of Arnica montana are widely used for the topical treatment of various inflammatory diseases. Sesquiterpene lactones (SLs) are mainly responsible for their anti-inflammatory activity. Here we have studied the penetration kinetics of Arnica tinctures prepared from dried Arnica flowers originating from different chemotypes as well as of their respective dominating SLs, helenalin isobutyrate and 11alpha,13-dihydrohelenalin acetate. Some alcoholic preparations of fresh Arnica flowers and an Arnica fresh plant gel were also included in the study. We used the stripping method with adhesive tape and pig skin as a model and determined the quantity of SLs in the stripped layers of the stratum corneum (SC). Thus, we observed the penetration into and permeation through this uppermost part of the skin. Whereas isolated SLs permeate through the SC only in a very small amount, permeation of SLs was much higher when they were present in the tinctures. Furthermore, differences of permeation were observed between helenalin and dihydrohelenalin derivatives. Permeation through the SC could be determined for the tested Arnica preparations of fresh Arnica flowers with two preparations showing the best penetration behaviour of all the tested substances. Moreover, the effects of incubation time as well as of repeated applications were investigated with one preparation. Altogether, this study shows that a sufficient amount of SLs might permeate the skin barrier by using Arnica preparations to exert anti-inflammatory effects and that the topical use of plant preparations may be advantageous compared to the isolated compounds.