Structure-radical scavenging activity relationships of phenolic compounds from traditional Chinese medicinal plants

Traditional Chinese medicinal plants associated with anticancer contain a wide variety of natural phenolic compounds with various structural features and possessing widely differing antioxidant activity. The structure-radical scavenging activity relationships of a large number of representative phenolic compounds (e.g., flavanols, flavonols, chalcones, flavones, flavanones, isoflavones, tannins, stilbenes, curcuminoids, phenolic acids, coumarins, lignans, and quinones) identified in the traditional Chinese medicinal plants were evaluated using the improved ABTS*+ and DPPH methods. Different categories of tested phenolics showed significant mean differences in radical scavenging activity. Tannins demonstrated the strongest activity, while most quinones, isoflavones, and lignans tested showed the weakest activity. This study confirmed that the number and position of hydroxyl groups and the related glycosylation and other substitutions largely determined radical scavenging activity of the tested phenolic compounds. The differences in radical scavenging activity were attributed to structural differences in hydroxylation, glycosylation and methoxylation. The ortho-dihydroxy groups were the most important structural feature of high activity for all tested phenolic compounds. Other structural features played a modified role in enhancing or reducing the activity. Within each class of phenolic compounds, the structure-activity relationship was elucidated and discussed. This study reveals the structure-activity relationships of a large series of representative natural phenolic compounds more systematically and fully than previous work. Structure-radical scavenging activity relationships of some natural phenolics identified in the medicinal plants were evaluated for the first time.     

Comparative analysis of bioactive phenolic compounds composition from 26 medicinal plants

Bioactive phenolic compounds are powerful antioxidants in traditionally used medicinal and industrial crop plants and have attracted increased interest in the last years in their application and role in non-destructive methodology for pre-screening analysis of some stress factors. In this study the qualitative target was linked with future possible applications of received data for improving non-destructive methodology as well as for improving existing knowledge regarding antioxidant content in some plant species. Comparative analysis of total phenolics, flavonoid contents, phenolic acid composition, and antioxidant activity in known east central Europe medicinal and industrial crop plants of 26 species of families Asteraceae, Rosaceae and Lamiaceae was done. Among the investigated leaf extracts the highest total phenolic, total flavonoid contents and antioxidant activity have been seen for Stachys byzantine L. (Lamiaceae), Calendula officinalis L. (Asteraceae) and for Potentilla recta L. (Rosaceae). The highest syringic acid content has been found in the leaf extracts of plant family Asteraceae – in the range from 0.782 to 5.078 mg g^?1 DW. The representative’s family Rosaceae has a higher content of p-anisic acid in the range 0.334–3.442 mg g^?1DW compared to the leaf extracts of families Lamiaceae and Asteraceae. The comparative study showed significant differences of content of phenolic acids in the leaf extracts of different representative’s families Rosaceae, Asteraceae and Lamiaceae. We suggest that the presence of some phenolic acids can be used as a possible marker for family botanical specifications of representative families Asteraceae and Rosaceae. It was supposed that some pharmacological effects can be connected with the analyzed data.     

Molecular perspective and anticancer activity of medicinal plants

To evaluate phytochemical constituents from the methanolic extracts of medicinal plants Aloe castellorum and Aloe pseudorubroviolacea. The cytotoxic activity of Aloe castellorum and Aloe pseudorubroviolacea leaf extracts against Human colon cancer cell line (HCT-116) was also assessed. The two medicinal plant extracts having significant cytotoxic activity, meanwhile the methanolic extract of Aloe castellorum shows higher cytotoxic activity than Aloe pseudorubroviolacea extract. The Aloe castellorum shows remarkable activity against respective cell line than control. The characteristic chemical constituents of Aloe castellorum and Aloe pseudorubroviolacea leaf extracts were recognized from Gas chromatography and Mass spectrometry (GC–MS) technique. The molecular docking studies also support the cytotoxic activity.     

Antioxidant properties and phenolic profiling by UPLC-QTOF-MS of Ajwah,Safawy and Sukkari cultivars of date palm

Date palm (P. dactylifera) plays a vital role in ethnomedicinal practices in several parts of the world. There are over 2000 cultivars of date palm that differ in chemical composition and extent of bioactivity. The present study was undertaken to comparatively evaluate the antioxidant potential of three cultivars of date palm (Ajwah, Safawy and Sukkari) from Saudi Arabia and analyze their phenolic constituents in order to draw a rationale for their activity. Antioxidant activities of the date cultivars were evaluated by different quantitative methods including 2,2-diphenyl-1-picrylhydrazyl (DPPH) and hydroxyl radical scavenging assay, total antioxidant capacity, reducing power, total phenolic (TPC), flavonoid (TFC) and tannin content (TTC), while qualitative phenolic composition was determined using ultra performance liquid chromatography coupled to quadropole time of flight mass spectrometry (UPLC-QTOF-MS). All the three date extracts showed good DPPH radical scavenging (IC₅₀ 103–177 μg/mL) and hydroxyl radical scavenging (IC₅₀ 1.1–1.55 mg/mL) activity and total antioxidant capacity (IC₅₀ 87–192 μg/mL). The reducing power was also comparable to that of ascorbic acid, used as standard in above experiments. All the three samples contain significant amount of major antioxidant components (phenolic, flavonoid and tannin) that successfully correlates with the results of radical scavenging assays. UPLC-QTOF-MS revealed a total of 22 compounds in these date cultivars classified into common phenolics, flavonoids, sterols and phytoestrogens. Significant variation in the degree of antioxidant activity of these three date cultivars can be attributed to the difference in the content and composition of phenolic compounds.     

Phenolcarboxylic acids from medicinal herbs exert anticancer effects through disruption of COX-2 activity

Integrated research of herbs and formulas characterized by functions of promoting blood circulation and removing blood stasis is one of the most active fields in traditional Chinese medicine. This paper strives to demonstrate the roles of a homologous series of phenolcarboxylic acids from these medicinal herbs in cancer treatment via targeting cyclooxygenase-2 (COX-2), a well-recognized mediator in tumorigenesis. We selected thirteen typical phenolcarboxylic acids (benzoic acid derivatives, cinnamic acid derivatives and their dehydration-condensation products), and found gallic acid, caffeic acid, danshensu, rosmarinic acid and salvianolic acid B showed 50% inhibitory effects on hCOX-2 activity and A549 cells proliferation. 2D-quantitative method was introduced to describe the potential structural features that contributed to certain bioactivities. We also found these compounds underwent responsible hydrogen bonding to Arg120 and Ser353 in COX-2 active site residues. We further extensively focused on danshensu [d-(+)-β-(3,4-dihydoxy-phenylalanine)] or DSS, which exerted COX-2 dependent anticancer manner. Both genetic and pharmacological inhibition of COX-2 could enhance the ability of DSS inhibiting A549 cells growth. Additionally, COX-2/PGE₂/ERK signaling axis was essential for the anticancer effect of DSS. Furthermore, combined treatment with DSS and celecoxib could produce stronger anticancer effects in experimental lung metastasis of A549 cells in vivo. All these findings indicated that phenolcarboxylic acids might possess anticancer effects through jointly targeting COX-2 activity in cancer cells and provided strong evidence in cancer prevention and therapy for the herbs characterized by blood-activating and stasis-resolving functions in clinic.     

Study of interactions between phenolic compounds and H2O2 or Cu(II) ions in B14 Chinese hamster cells

The antioxidant and prooxidant effects of tannic, ellagic and gallic acids (1-60 microM) in the presence of hydrogen peroxide (40 and 100 microM) or copper ions (50 microM) on B14 Chinese hamster cells were examined. The fluorescence probe DCFH-DA (dichlorofluorescein-diacetate) was used to analyse the levels of reactive oxygen species. This method showed the reduction in oxidation of DCF (dichlorofluorescein). It indicates that antioxidant capacity of tested polyhenols is decreased in the presence of hydrogen peroxide or copper ions. Spectrophotometric assay with Ellman's reagent was used to determine SH-groups. The experimental results revealed the oxidative modification of proteins after exposure to polyphenols at concentrations above 15 microM. Additional incubation with H2O2 or Cu(2+) ions showed the prooxidant activity of tested complexes also for polyphenols used at a concentration of 1 microM. Fluorescence method with Hoechst 33258/propidium iodide dyes was used to study apoptotic and necrotic cell death. The obtained data demonstrated that polyphenols alone, as well as in the presence of hydrogen peroxide or copper ions, can induce DNA fragmentation.     

Assessment of polyphenolic compounds,in vitro antioxidant and anti-inflammation properties of Securidaca longepedunculata root barks

The present study was carried out to evaluate the antioxidant activities of the root bark extract of Securidaca longepedunculata. This plant material is commonly used in folk medicine in several parts in the world. The bark extracts of S. longepedunculata were evaluated for their total phenols, flavonoids, anthocyanins, tannins content and total antioxidant capacity. The compounds were identified and quantified both by RP-HPLC and UV spectrophotometer; the antioxidant capacity was assessed by ABTS and DPPH tests and expressed as IC₅₀. The total phenolic compounds determinate was 9.86 mg gallic acid equivalents/g dw, the total flavonoid contents was 5.85 mg catechin equivalents/g dw, the total anthocyanin contents was 0.032 mg cyanidin-3-glycosyl equivalents/g dw and the condensed tannins content were 1.03 mg catechin equivalents/g dw. The major compound identified using RP-HPLC was quercetin (0.98 mg/ml). The IC₅₀ value reached 5.5 μg/ml, revealing that the root barks of S. longepedunculata have a very high antioxidant and anti-inflammation properties.     

Distribution patterns and industry planning of commonly used traditional Chinese medicinal plants in China

Medicinal plants are the primary material basis for disease prevention and treatment in traditional Chinese medicine (TCM). The conservation and sustainable utilization of these medicinal plants is critical for the development of the TCM industry. However, wild medicinal plant resources have sharply declined in recent decades. To ameliorate the shortage of medicinal plant resources, it is essential to explore the development potential of the TCM industry in different geographical regions. For this purpose, we examined the spatial distribution of commonly used medicinal plants in China, the number of Chinese medicinal material markets, and the number of TCM decoction piece enterprises. Specifically, multispecies superimposition analysis and Thiessen polygons were used to reveal the optimal range for planting bulk medicinal plants and the ideal regions for building Chinese medicinal material markets, respectively. Furthermore, we quantitatively analyzed mismatches between the spatial distribution of commonly used medicinal plant richness, Chinese medicinal material markets, and TCM decoction piece enterprises. We found that the areas suitable for growing commonly used medicinal plants in China were mainly distributed in Hengduan Mountain, Nanling Mountain, Wuling Mountain, and Daba Mountain areas. The Thiessen polygon network based on Chinese medicinal material market localities showed there are currently fewer markets in southwestern, northwestern, and northeastern China than in central and southern China. TCM decoction piece enterprises are concentrated in a few provinces, such as Hebei and Jiangxi. We found that the distribution of commonly used medicinal plants, Chinese medicinal material markets and TCM decoction piece enterprises are mismatched in Henan, Shaanxi, Hunan, Hubei, Zhejiang, Fujian, Chongqing, and Xizang. We recommend strengthening development of the TCM industry in Henan, Hunan, Zhejiang, Shaanxi, Hubei, Chongqing, Fujian, and Xizang; building more Chinese medicinal material markets in southwestern, northwestern, and northeastern China; and establishing medicinal plant nurseries in resource-rich provinces to better protect and domesticate local medicinal plants.     

Antioxidant activity of mycosporine-like amino acids isolated from three red macroalgae and one marine lichen

Several standard in vitro assays were performed in order to determine the potential antioxidant capabilities of purified aqueous extracts of the mycosporine-like amino acids (MAAs), porphyra-334 plus shinorine (P-334 + SH), isolated from the red alga Porphyra rosengurttii, asterina-330 plus palythine (AS-330 + PNE), from the red alga Gelidium corneum, shinorine (SH), from the red alga Ahnfeltiopsis devoniensis, and mycosporine -glycine (M-Gly), isolated from the marine lichen Lichina pygmaea. The scavenging potential of hydrosoluble radicals (ABTS⁺ decolorization method), the antioxidant activity in lipid medium (β-carotene/ linoleate bleaching method) and the scavenging capacity of superoxide radicals (pyrogallol autooxidation assay) were evaluated. In terms of scavenging of hydrosoluble radicals, the antioxidant activity of all MAAs studied was dose-dependent and it increased with the alkalinity of the medium (pH 6 to 8.5). M-Gly presented the highest activity in all pH tested; at pH 8.5 its IC₅₀ was 8-fold that of L-ascorbic acid (L-ASC) followed by AS-330 + PNE while P-334 + SH and SH showed scarce activity of scavenging of hydrosoluble free radicals. AS-330 + PNE showed high activity for inhibition of β-carotene oxidation relative to vitamin E and superoxide radical scavenging whilst the activity of P-334 +SH and SH were moderate. According to these results, the potential of MAAs in photoprotection can be considered high due to a double function: (1) UV chemical screening with high efficiency for UVB and UVA regions of the solar spectrum, and (2) their antioxidant capacity.     

一株高抗氧化活性内生真菌的分子鉴定及产酚酸类物质研究

【目的】以疏花水柏枝(Myricaria laxiflora)淹水前根部分离到的内生真菌SG17为研究对象,为明确其抗氧化能力及可能的物质基础,对其进行生物学鉴定、抗氧化能力分析及产酚酸类物质研究。【方法】对该菌nr DNA的内转录间隔区进行测序;应用总抗氧化试剂盒,以维生素C为阳性对照,测定其抗氧化能力;采用高效液相色谱(HPLC)和薄层色谱(TLC)探讨其发酵液中的酚酸类化合物。【结果】SG17具有很高的抗氧化活性,其发酵液粗提物的抗氧化活性达到同浓度抗坏血酸的31.86%,分子和形态鉴定表明SG17是一株烟曲霉(Aspergillus fumigatus)。其发酵产物中酚酸类物质含量丰富,HPLC能检测到含有没食子酸,且通过HPLC和TLC分析还发现一种光学性质与绿原酸极为相似的类似物。【结论】内生真菌烟曲霉SG17发酵液的抗氧化能力远高于国际报道水平,是一种具有潜在开发价值的抗氧化剂资源。     

Anti-inflammatory and antioxidant activity of a medicinal tincture from Pedilanthus tithymaloides

Pedilanthus tithymaloides (L.) Poit. (Euphorbiaceae) is a low tropical American shrub with a reported wide range of healing properties such as emetic, anti-inflammatory, antibiotic, antiseptic, antihemorrhagic, antiviral, antitumoral, and abortive. In the present study, a tincture from P. tithymaloides collected in Cuba was evaluated for its in vivo anti-inflammatory activity, using the rat paw oedema assay, and for its in vitro scavenging effects on reactive oxygen species (ROS) (HO*, O2*-, HOCl, ROO* and H2O2), reactive nitrogen species (RNS) (ONOO- and *NO), and DPPH* radical. The protein, free amino acid, and phenolic contents of the tincture were also determined. Pertaining to the anti-inflammatory activity, the intraperitoneal administration of the tincture inhibited carrageenan-induced rat paw oedema, whereas in the scavenging assays the tincture showed to be effective against all the assayed ROS and RNS, specially for HO* (IC50 = 345+/-77 microg/mL), O2*- (IC50 = 143+/-7 microg/mL), HOCl (IC50 = 113+/-20 microg/mL), ONOO- (IC50 = 44+/-3 microg/mL), and *NO (IC50 = 54+/-4 microg/mL), but displayed weak activity in the DPPH* assay. The protein content of the tincture was 0.70%, and twenty free amino acids were identified and quantified. The content of total phenolics was 17.4+/-0.15 mg of gallic acid equivalents (GAE)/g dry material. These results provide scientific support for the empirical use of P. tithymaloides tincture as an anti-inflammatory medicine.     

Antioxidant activity and phenolic profile of pistachio (Pistacia vera L., variety Bronte) seeds and skins

Pistachio (Pistacia vera L.; Anacardiaceae) is native of aride zones of Central and West Asia and distributed throughout the Mediterranean basin. In Italy, a pistachio cultivar of high quality is typical of Bronte (Sicily), an area around the Etna volcano, where the lava land and climate allow the production of a nut with intense green colour and aromatic taste, very appreciated in international markets. Pistachio nuts are a rich source of phenolic compounds, and have recently been ranked among the first 50 food products highest in antioxidant potential. Pistachio nuts are often used after removing the skin, which thus represents a significant by-product of pistachio industrial processing. The present study was carried out to better characterize the phenolic composition and the antioxidant activity of Bronte pistachios, with the particular aim to evaluate the differences between pistachio seeds and skins. The total content of phenolic compounds in pistachios was shown to be significantly higher in skins than in seeds. By HPLC analysis, gallic acid, catechin, eriodictyol-7-O-glucoside, naringenin-7-O-neohesperidoside, quercetin-3-O-rutinoside and eriodictyol were found both in pistachio seeds than in skins; furthermore, genistein-7-O-glucoside, genistein, daidzein and apigenin appeared to be present only in pistachio seeds, while epicatechin, quercetin, naringenin, luteolin, kaempferol, cyanidin-3-O-galactoside and cyanidin-3-O-glucoside are contained only in pistachio skins. The antioxidant activity of pistachio seeds and skins were determined by means of four different assays (DPPH assay, Folin-Ciocalteau colorimetric method and TEAC assay, SOD-mimetic assay). As expected on the basis of the chemical analyses, pistachio skins have shown to possess a better activity with respect to seeds in all tests. The excellent antioxidant activity of pistachio skins can be explained by its higher content of antioxidant phenolic compounds. By HPLC-TLC analysis, gallic acid, catechin, cyanidin-3-O-galactoside, eriodictyol-7-O-glucoside and epicatechin appeared to be responsible for the antioxidant activity of pistachio skin, together with other unidentified compounds. In conclusion, our work has contributed to clarify some particular characteristics of Bronte pistachios and the specific antioxidant power of pistachio skins. Introduction of pistachios in daily diet may be of undoubted utility to protect human health and well-being against cancer, inflammatory diseases, cardiovascular pathologies and, more generally, pathological conditions related to free radical overproduction. On the other hand, pistachio skins could be successfully employed in food, cosmetic and pharmaceutical industry.     

Seasonal dynamics of allelopathically significant phenolic compounds in globally successful invader Conyza canadensis L. plants and associated sandy soil

The seasonal dynamics of total phenolics and phenolic acids in the stems of the global invader Conyza canadensis, from March (young plants in the form of rosettes) to September (fruit abscission and the beginning of plant decline), and in sandy soil were monitored monthly in non-native areas. The highest amount of total free phenolics was found in its tissues (31,000 μg g⁻¹) during the flowering and fruiting time (August). Bound phenolics peaked (up to 8443 μg g⁻¹) during shoot elongation and intensive plant growth (May–June) and in September. In the stems, bound phenolic acids (p-coumaric, ferulic, p-hydroxybenzoic, vanillic and syringic) have a maximum twice, in May and in August, with ferulic acid predominating (up to 951.6 μg g⁻¹). Free phenolic acids in the plant's tissue peaked in May (plant elongation). In the soil under C. canadensis, the amount of bound phenolics decreased between March and June, before increasing up to the full bloom phase of the plants (August). The amount of bound phenolic acids was several times greater than that of free ones, with maximum values in August. C. canadensis is a highly important source of phenolics in the ruderal phytocoenosis in new areas. In order to better explain the mechanisms of the spread and domination of invasive plants in non-native areas, in which allelopathy plays a decisive role, it is necessary to measure the production of allelochemicals in tissue and their accumulation in soil at the shortest possible intervals and link this with the phases of plant development.     

Production of amino acids by Azotobacter vinelandii and Azotobacter chroococcum with phenolic compounds as sole carbon source under diazotrophic and adiazotrophic conditions

Summary. Azotobacter vinelandii strain ATCC 12837 and Azotobacter chroococcum strain H23 (CECT4435) were tested to grow in N-free or NH₄Cl amended chemically defined media, with protocatechuic acid or sodium p-hydroxybenzoate as sole carbon (C) sources at a concentration of 2 mmol/L. Both substrates supported grow at similar rates than bacteria grown in control media amended with 2 mmol/L sodium succinate as C source. The two strains produced aspartic acid, serine, glutamic acid, glycine, hystidine, threonine, arginine, alanine, proline, cysteine, tyrosine, valine, methionine, lysine, isoleucine, leucine and phenylalanine after 72 h of growth in chemically defined media with 2 mmol/L of phenolic compounds or sodium succinate as sole C source amended or unamended with 0.1% (w/v) NH₄Cl. Qualitative and quantitative production of all amino acids was not affected by the use of different C and N substrates.     

18种中草药提取物对褐飞虱和甜菜夜蛾的杀虫活性分析

为了筛选对农产品和环境安全、对害虫高效的植物源杀虫剂,分别采用喷雾法和饲毒法,测定了18种中草药的3种溶剂（水、乙醇、石油醚）提取物对褐飞虱Nilaparvata lugens Stål的触杀活性和对甜菜夜蛾Spodoptera exigua Hübner的胃毒作用。结果表明,各种提取物（0.8 g/mL）对甜菜夜蛾的胃毒作用不明显,校正死亡率最高为33.33%;但对褐飞虱的杀虫活性较高,其中百部、黄柏、榧子、生山栀、鹤虱、木香的乙醇或石油醚提取物,对褐飞虱3龄若虫的24 h校正死亡率均在80%以上,其石油乙醚提取物的LC50值依次为：0.0826,0.0455,0.0145,0.0047,0.0038,0.0033 g/mL。采用系统溶剂法分析发现,木香和鹤虱的主要杀虫活性成分均在氯仿萃取物中,表明其杀虫成分易溶于较弱极性溶剂中。进一步通过活性追踪法,对鹤虱提取物的柱层析各流分的活性检测表明,其杀虫活性成分的Rf值为0.5556~0.5926。该研究为进一步纯化新型植物源杀虫物质并确定其分子结构,从而开发其应用前景及发现新的杀虫活性先导化合物奠定了基础。