Free‐radical scavenging activities of silybin and its analogues: A pulse radiolysis study

The flavonolignans (silybin and analogues) are important natural compounds with multiple biological activities operating at various cell levels. Many of these effects are connected with their radical scavenging activities. In the present study, free‐radical scavenging and antioxidant activities of four natural flavonoids, namely silybin, naringenin, naringin, and hesperetin, have been studied using nanosecond pulse radiolysis techniques. The kinetics and mechanisms of the reactions of silybin and analogues with various oxidizing radicals (such as ^?OH,N₃^?, CCl₃OO^?, SO₄^??) have been investigated. Furthermore, the transient species has been assigned and radical scavenging rate constants have also been measured. Moreover, the structure–activity relationships between chemical structures of the flavonoids and their radical scavenging activities are further analayzed by theoretical calculation. Combined our previous observation of the fast reparation of DNA damage and efficient DNA protection against radiation damage in vitro, it can be confirmed that test flavonoids are promising molecules to be used for their potential antioxidant properties. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 590–597, 2011     

4种黄酮小分子对DPPH自由基的清除作用及构效关系研究

通过紫外可见光谱测定了4种黄酮小分子芦丁、牡荆素、山奈素、金丝桃苷对DPPH自由基的清除率、稳定性及半抑制浓度(IC50),并以常用的天然抗氧化剂抗坏血酸作为对照,考察了其抗氧化效果,探讨了黄酮类化合物的抗氧化性与结构的关系。结果表明：不同的抗氧化剂清除DPPH自由基达到平衡的时间不同,芦丁所需时间最长。4种黄酮小分子及抗坏血酸均对DPPH自由基有清除效果,并存在一定的量效关系。对DPPH自由基的清除能力从大到小依次为金丝桃苷、抗坏血酸、芦丁、山奈素、牡荆素。结构分析表明,B环邻二酚羟基是黄酮类化合物抗氧化所必需的基团,其羟甲基化及A环羟基糖苷化不利于黄酮类化合物的抗氧化活性。而C环3-OH的糖苷化对抗氧化活性有利,且单糖苷优于双糖苷。     

In Vitro Studies on the Relationship Between the Antioxidant Activities of Some Berry Extracts and Their Binding Properties to Serum Albumin

The aim of this study was to investigate the possibility to use the bioactive components from cape gooseberry (Physalis peruviana), blueberry (Vaccinium corymbosum), and cranberry (Vaccinium macrocarpon) extracts as a novel source against oxidation in food supplementation. The quantitative analysis of bioactive compounds (polyphenols, flavonoids, flavanols, carotenoids, and chlorophyll) was based on radical scavenging spectrophometric assays and mass spectrometry. The total phenolic content was the highest (P?<?0.05) in water extract of blueberries (46.6?±?4.2 mg GAE/g DW). The highest antioxidant activities by 2,2-diphenyl-1-picrylhydrazyl radical scavenging assay and Cupric reducing antioxidant capacity were in water extracts of blueberries, showing 108.1?±?7.2 and 131.1?±?9.6 μMTE/g DW with correlation coefficients of 0.9918 and 0.9925, and by β-carotene linoleate assay at 80.1?±?6.6 % with correlation coefficient of 0.9909, respectively. The water extracts of berries exhibited high binding properties with human serum albumin in comparison with quercetin. In conclusion, the bioactive compounds from a relatively new source of gooseberries in comparison with blueberries and cranberries have the potential as food supplementation for human health. The antioxidant and binding activities of berries depend on their bioactive compounds.     

明日叶黄酮类化合物清除羟基自由基活性研究

为了研究明日叶黄酮类化合物对羟基自由基的清除作用,以明日叶（主要取叶片）为原料,用体积分数为65％乙醇提取明日叶总黄酮,测定其总黄酮含量.通过Fenton反应体系产生羟基自由基,利用明日叶提取液中的功能成分黄酮类化合物对羟基自由基的清除作用进行研究.结果表明：明日叶提取物总黄酮质量分数为10.18％,且黄酮类化合物对羟基自由基有较强清除效力,当提取物总黄酮浓度在0.1～1.0 mg/mL范围内,其与清除率呈正相关.明日叶中黄酮类化合物对羟基自由基有较强清除效力,作为天然抗氧化产品开发具有一定价值.     

Flavonoids from Lupinus texensis and their free radical scavenging activity

Seventeen flavonoids including one new compound were isolated from Texas bluebonnet (Lupinus texensis), the state flower of Texas. Their structures were determined by extensive nuclear magnetic resonance and high-resolution electrospray ionization mass spectrometry analyses. High-performance liquid chromatography analytic method for simultaneous determination of the 17 compounds was established and validated. Eleven isolated flavonoids were first evaluated for their free radical scavenging activity using α,α-diphenyl-β-picrylhydrazyl scavenging assay and they showed activity with EC(50) 48.6-172.5 μg mL(-1).     

Impact of High-Pressure Processing on Antioxidant Activity during Storage of Fruits and Fruit Products: A Review

Fruits and fruit products are an essential part of the human diet. Their health benefits are directly related to their content of valuable bioactive compounds, such as polyphenols, anthocyanins, or vitamins. Heat treatments allow the production of stable and safe products; however, their sensory quality and chemical composition are subject to significant negative changes. The use of emerging non-thermal technologies, such as HPP (High Pressure Processing), has the potential to inactivate the microbial load while exerting minimal effects on the nutritional and organoleptic properties of food products. HPP is an adequate alternative to heat treatments and simultaneously achieves the purposes of preservation and maintenance of freshness characteristics and health benefits of the final products. However, compounds responsible for antioxidant activity can be significantly affected during treatment and storage of HPP-processed products. Therefore, this article reviews the effect of HPP treatment and subsequent storage on the antioxidant activity (oxygen radical absorbance capacity (ORAC) assay), 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging capacity assay, ferric reducing antioxidant power (FRAP) assay, 2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical scavenging capacity assay or Trolox equivalent antioxidant capacity (TEAC) assay), and on the total phenolic, flavonoid, carotenoid, anthocyanin and vitamin contents of fruits and different processed fruit-based products.     

Rapid screening,separation, and detection of hydroxyl radical scavengers from total flavonoids of Ginkgo biloba leaves by chromatography combined with molecular devices

Hydroxyl radicals are the most reactive free radical of human body, a strong contributor to tissue damage. In this study, liquid chromatography coupled to electrospray ionization mass spectrometry was applied to screen and identify hydroxyl radical scavengers from the total flavonoids of Ginkgo biloba leaves, and high‐performance counter current chromatography was used to separate and isolate the active compounds. Furthermore, molecular devices were used to determine hydroxyl radical scavenging activities of the obtained hydroxyl radical scavengers and other flavonoids from G. biloba leaves. As a result, six compounds were screened as hydroxyl radical scavengers, but only three flavonoids, namely, rutin, cosmos glycosides and apigenin‐7‐O‐Glu‐4’‐O‐Rha, were isolated successfully from total flavonoids by high‐performance counter current chromatography. The purities of the three obtained compounds were over 90%, respectively, as determined by liquid chromatography. Molecular devices with 96‐well microplates evaluation indicated that the 50% scavenging concentration values of screened compounds were lower than that of other flavonoids, they performed greater hydroxyl radical scavenging activity, and the evaluation effects were consistent with the liquid chromatography with mass spectrometry screening results. Therefore, chromatography combined with molecular devices is a feasible and an efficient method for systematic screening, identification, isolation, and evaluation of bioactive components in mixture of botanical medicines.     

黄酮类化合物抗氧化活性的构效关系研究

自由基具有强烈的氧化能力,研究寻找自由基清除剂越来越引起人们的重视。本文对已有实验报道的10种黄酮的结构进行了几何优化,并进行了电子结构计算,以实验测定的黄酮类化合物清除对苯半醌自由基能力的高低,即清除率数据为因变量,以量化计算得到的电子结构指数为自变量,用相关分析和逐步回归方法加以讨论,从理论上对实验结果进行了较为圆满的解释,并得出了较为合理的定量构效关系(QSAR)方程,为设计高活性抗氧化性黄酮类化合物提供了理论参考。     

Antioxidant, electrochemical, thermal, antimicrobial and alkane oxidation properties of tridentate Schiff base ligands and their metal complexes

In this study, two Schiff base ligands (HL(1) and HL(2)) and their Cu(II), Co(II), Ni(II), Pd(II) and Ru(III) metal complexes were synthesized and characterized by the analytical and spectroscopic methods. Alkane oxidation activities of the metal complexes were studied on cyclohexane as substrate. The ligands and their metal complexes were evaluated for their antimicrobial activity against Corynebacterium xerosis, Bacillus brevis, Bacillus megaterium, Bacillus cereus, Mycobacterium smegmatis, Staphylococcus aureus, Micrococcus luteus and Enterococcus faecalis (as gram-positive bacteria) and Pseudomonas aeruginosa, Klebsiella pneumoniae, Escherichia coli, Yersinia enterocolitica, Klebsiella fragilis, Saccharomyces cerevisiae, and Candida albicans (as gram-negative bacteria). The antioxidant properties of the Schiff base ligands were evaluated in a series of in vitro tests: 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging and reducing power activity of superoxide anion radical generated non-enzymatic systems. Electrochemical and thermal properties of the compounds were investigated.     

Antiradical, chelating and antioxidant activities of hydroxamic acids and hydroxyureas

Reactive oxygen species, along with reactive nitrogen species, may play an important role in the pathogenesis and progress of many diseases, including cancer, diabetes and sickle cell disease. It has been postulated that hydroxyurea, one of the main treatments in sickle cell disease, achieves its activity partly also through its antioxidant properties. A series of hydroxyurea derivatives of L- and D-amino acid amides and cycloalkyl-N-aryl-hydroxamic acids was synthesized and investigated for their radical scavenging activity, chelating properties and antioxidant activity. All the compounds showed exceptional antiradical activities. For example, free radical scavenging activities of investigated hydroxyureas were higher than the activity of standard antioxidant, butylated hydroxyanisole (BHA). Moreover, most of the investigated hydroxamic acids were stronger Fe2? ion chelators than quercetin. In addition, the investigated compounds, especially hydroxamic acids, were proven to be excellent antioxidants. They were as effective as BHA in inhibiting β-carotene-linoleic acid coupled oxidation. It is reasonable to assume that the antioxidant activity of the investigated compounds could contribute to their previously proven biological properties as cytostatic and antiviral agents.     

Phenolic Building Blocks for the Assembly of Functional Materials

Phenolic materials have long been known for their use in inks, wood coatings, and leather tanning. However, there has recently been a renewed interest in engineering advanced materials from phenolic building blocks. The intrinsic properties of phenolic compounds, such as metal chelation, hydrogen bonding, pH responsiveness, redox potentials, radical scavenging, polymerization, and light absorbance, have made them a distinct class of structural motifs for the synthesis of functional materials. Materials prepared from phenolic compounds often retain many of these useful properties with synergistic effects in applications ranging from catalysis to biomedicine. This Review provides an overview of the diverse functional materials that can be prepared from natural and synthetic phenolic building blocks, as well as their applications.     

In vivo anti-inflammatory and in vitro antioxidant activities of Moroccan medicinal plants

Five ethanol extracts of wild plants from the Casablanca region (Morocco) used in local traditional medicine for the treatment of inflammatory diseases were evaluated for their in vivo topical anti-inflammatory activity (inhibition of carrageenan-induced ear edema in mice) and in vitro antioxidant and antiradical properties (inhibition of linoleic acid oxidation, DPPH radical scavenging). All the extracts showed an anti-inflammatory effect: 300 microg/cm2 provoked edema reductions ranging from 22 to 28%. All the extracts also exerted radical scavenging and/or antioxidant properties, the most active plant being Mentha pulegium L. (Lamiaceae), which contained the highest amount of phenolics (339 mg/g), and flavonoids (16.7 mg/g).     

Antiradical activity of dioxolane derivatives

1,3-Benzodioxoles synthesized by condensation of 3,6-di-tert-butylbenzene-1,2-diol with carbonyl compounds showed antiradical activity due to their ability to undergo one-electron oxidation with formation of stable radical cations. On this basis, the antiknock effect of their structural analogs, 1,3-dioxolanes derived from vicinal diols, was interpreted in terms of oxidation of these compounds with active radicals generated from fuel hydrocarbons to produce more stable radical or radical ion species, depending on the fuel composition. The formation of radical species was detected in model oxidation reactions of 2,2-dimethyl-1,3-dioxolane and 2,2-dimethyl-1,3-dioxolan-4-ylmethanol with radicals generated by photolysis of iron(III) chloride and benzoyl peroxide.     

Phenolic compounds in Brassica vegetables

Phenolic compounds are a large group of phytochemicals widespread in the plant kingdom. Depending on their structure they can be classified into simple phenols, phenolic acids, hydroxycinnamic acid derivatives and flavonoids. Phenolic compounds have received considerable attention for being potentially protective factors against cancer and heart diseases, in part because of their potent antioxidative properties and their ubiquity in a wide range of commonly consumed foods of plant origin. The Brassicaceae family includes a wide range of horticultural crops, some of them with economic significance and extensively used in the diet throughout the world. The phenolic composition of Brassica vegetables has been recently investigated and, nowadays, the profile of different Brassica species is well established. Here, we review the significance of phenolic compounds as a source of beneficial compounds for human health and the influence of environmental conditions and processing mechanisms on the phenolic composition of Brassica vegetables.     

Synthesis,conformational analysis and free radical scavenging activity of some new spiropyranoquinolinones

A series of novel spiroadamantyl- and spirocyclical substituted pyranoquinolin-2-ones were synthesized and the conformation of the pyran ring was investigated. The free radical scavenging activity of the synthesized compounds was determined by their interaction with the stable free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH). All compounds tested scavenged the DPPH radical and among them derivatives possessing extended conjugation showed the highest activity.     

Hydroxyethyl curdlan as a novel water soluble derivative: Synthesis,characterization, and antioxidant capacity

In this study, hydroxyethyl curdlans (HeCDs) with different molecular weights were successfully fabricated. The structure and properties of the synthesized HeCDs were measured by FTIR, ¹³C nuclear magnetic resonance (NMR), and Raman spectroscopy and compared with curdlan. The degree of crystallinity of HeCDs was measured with X-ray diffractometry (XRD). Differential scanning calorimetry and thermogravimetric analysis were performed to determine thermal properties of HeCs. Solubility of HeCDs was tested in water, common organic solvents, and NaOH solution. Antioxidant activities of HeCs were investigated using various in vitro assay systems. The HeCDs exhibited a dose-dependent free radical scavenging activity as shown by their DPPH radical, ABTS radical and superoxide anion radical inhibition, and ferrous chelating ability and reducing power. The improved water solubility property and antioxidant activity of these curdlan derivatives could have a wide range of applications, particularly its use as an antioxidant in food, food packaging, biomedical, and pharmaceutical industries.     

Synthesis and DPPH radical scavenging activity of prenylated phenol derivatives

The synthesis of twenty six prenylated phenols derivatives is reported. These compounds were obtained under mild conditions via Electrophilic Aromatic Substitution (EAS) coupling reactions between phenol derivatives containing electron-donor subtituents and 3-methyl-2-buten-1-ol using BF(3)×OEt(2). Dialkylations were also produced with this method. The formation of a chroman ring by intramolecular cyclization between a sp2 carbon from the prenyl group with the hydroxyl substituent in the ortho position occurred with some phenols. All the synthesized compounds were evaluated as antioxidants according to a DPPH radical scavenging activity assay. IC(50) values of five synthesized compounds indicated they were as good antioxidants as Trolox?.     

Synthesis,characterization, and biological evaluation of indole aldehydes containing N-benzyl moiety

Abstract

The present study describes the synthesis, characterization and biological evaluation of N-benzyl indole aldehydes. The biological activities of the newly synthesized compounds were examined by investigating their antioxidant and anti-inflammatory activities. The potential of these compounds as an antioxidant was determined by 2,2-diphenylpicrylhydrazyl, Nitric oxide, Superoxide, peroxide radical scavenging methods. We found that aldehydes 4a, 4b, 4c, and 4e and shows promising in vitro DPPH scavenging antioxidant activity while aldehyde 4b and 4e show good in vitro anti-inflammatory activity.     

Key role of chemical hardness to compare 2,2-diphenyl-1-picrylhydrazyl radical scavenging power of flavone and flavonol O-glycoside and C-glycoside derivatives

The antioxidant activities of flavonoids and their glycosides were measured with the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH radical, DPPH(·)) scavenging method. The results show that free hydroxyl flavonoids are not necessarily more active than O-glycoside. Quercetin and kaempferol showed higher activity than apigenin. The C- and O-glycosides of flavonoids generally showed higher radical scavenging activity than aglycones; however, kaempferol C3-O-glycoside (astragalin) showed higher activity than kaempferol. In the radical scavenging activity of flavonoids, it was expected that OH substitutions at C3 and C5 and catechol substitution at C2 of B ring and intramolecular hydrogen bonding between OH at C5 and ketone at C3 would increase the activity; however, the reasons have yet to be clarified. We here show that the radical scavenging activities of flavonoids are controlled by their absolute hardness (η) and absolute electronegativity (χ) as a electronic state. Kaempferol and quercetin provide high radical scavenging activity since (i) OH substitutions at C3 and C5 strikingly decrease η of flavones, (ii) OH substitutions at C3 and C7 decrease χ and η of flavones, and (iii) phenol or o-catechol substitution at C2 of B ring decrease χ of flavones. The coordinate r(χ,?η) as the electron state must be small to increase the radical scavenging activity of flavonoids. The results show that chemically soft kaempferol and quercetin have higher DPPH radical scavenging activity than chemically hard genistein and daidzein.     

HPLC-ESI-MS/MS analysis of phenolics and in vitro antioxidant activity of Epilobium angustifolium L.

The aerial parts of Epilobium plants are widely used as folk medicine and food around the world. The present study was aimed to investigate the antioxidant activities and active chemical constituents from Epilobium angustifolium L. The results revealed that the EtOAc extract, rich in phenolic compounds and flavonoids (16.81 ± 0.67 g GAE/100 g extract and 4.95 ± 0.21 g QE/100 g extract, respectively), possessed significantly antioxidant activities in reducing power, DPPH radical scavenging activity, ABTS radical scavenging activity and highly in inhibiting lipid peroxidation activity. Simultaneously, active fractions F to H from EtOAc extracts showing potent in vitro antioxidant activities also contained high content of total phenolic and flavonoid. Twenty-eight compounds were identified as phenolic compounds and flavonoids by LC-MS/MS. The results illustrate that the E. angustifolium L., which is rich in phenolics, could be used as a natural resource of antioxidant ingredient.