Radical scavenging mechanism of phenol carboxylic acids: reaction of protocatechuic esters

Solvent-dependency of the antiradical reaction of protocatechuic acid (3,4-dihydroxybenzoic acid, PA) and its esters has been investigated. In aprotic solvents, methyl protocatechuate (PAMe) was readily oxidized by two molar equivalents of DPPH radical and converted to protocatechuquinone methyl ester (PQMe). On the other hand, in alcoholic solvents such as methanol, PAMe rapidly consumed five radicals in 30 min and changed to complex oxidized mixtures. A 1H-NMR analysis of the reaction mixture of PAMe and DPPH radical in methanol showed that PAMe was rapidly converted to PQMe and its 3-hemiacetal. In addition, a signal of 2-methoxy-PQMe 3-hemiacetal was also detected in the reaction mixture. The results suggested that PQMe undergoes a nucleophilic attack by the solvent alcohol molecule at the C-2 of the ring in methanol, leading to a regeneration of catechol structure, which accounts well for the higher DPPH radical scavenging activity of PAMe in alcohols than in aprotic solvents.     

A novel oxidative dimer from protocatechuic esters: contribution to the total radical scavenging ability of protocatechuic esters

A novel oxidative dimer was isolated as a major product from a reaction mixture of methyl protocatechuate and DPPH radical in methanol. Its unusual benzobicyclo[3.2.1]octane structure was elucidated by extensive spectral analysis. This result suggests that the regeneration of catechol structures by the nucleophilic addition of an alcohol molecule on o-quinones and subsequent dimerization is one of the key reactions in the high radical-scavenging activity of protocatechuic esters in an alcoholic solvent.     

Synthesis of N-hydroxycinnamoyl amide derivatives and evaluation of their anti-oxidative and anti-tyrosinase activities

Twelve N-hydroxycinnamoyl amino acid amide ethyl esters (CAES) were synthesized by using l-amino acid ethyl ester hydrochloride and corresponding cinnamic acid (ferulic acid, acetylferulic acid and caffeic acid) as raw materials in the presence of a catalytic amount of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide-hydrochloride (EDC) and 1-hydroxybenzotriene (HOBt). The 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging activities of CAES were evaluated. The anti-tyrosinase activities of N-feruloyl amino acid ethyl esters and the hydroxyl (OH) free radical scavenging activities of N-caffeoyl amino acid ethyl esters were also examined. DPPH free radical scavenging activity was shown in all CAES, of which N-caffeoyl amino acid ethyl esters demonstrated higher radical scavenging activity than N-feruloyl amide derivatives, and (E) -N-(caffeic acid)-l-glycinate ethyl ester (c₅) had the strongest ability to scavenge free radicals with an IC₅₀ value of 18.6 µM. The acetylferuloyl amino acid esters exhibited the highest tyrosinase inhibition activity among the tested amides.     

Oxidative dimer produced from a 2,3,4-trihydroxybenzoic ester

The DPPH radical-scavenging abilities of the naturally occurring phenolic acid, 2,3,4-trihydroxybenzoic acid, and its methyl ester were evaluated. Both compounds in acetonitrile scavenged as many as four radicals compared to three or fewer radical consumption in acetone or ethanol. Only the ester showed relatively high ability in methanol. Oxidation with o-chloranil in acetonitrile resulted in methyl 2,3,4-trihydroxybenzoate giving a novel benzocoumarin-type dimer, its chemical structure being confirmed by spectroscopic evidence. The formation of this dimer might partly account for the higher radical-scavenging efficiency of the ester in acetonitrile or methanol.     

Transesterification of canola oil in mixed methanol/ethanol system and use of esters as lubricity additive

Transesterification of canola oil was carried out with methanol, ethanol, and various mixtures of methanol/ethanol, keeping the molar ratio of oil to alcohol 1:6 and using KOH as a catalyst. Mixtures of alcohol increased the rate of transesterification reaction and produced methyl as well as ethyl esters. The increased rate was result of better solubility of oil in reaction mixture due to better solvent properties of ethanol than methanol and equilibrium due to methanol. With 3:3 molar ratio of methanol to ethanol {MEE (3:3)} the amount of ethyl ester formed was 50% that of methyl ester. Properties (acid value, viscosity, density) of all esters including mixed esters were within the limits of ASTM standards. Lubricities of these esters are in the order: ethyl ester>methyl ethyl ester>methyl ester.     

根皮素乙酰阿魏酸酯的合成及抗氧化活性研究

以阿魏酸和根皮素为原料,合成了三种根皮素乙酰阿魏酸酯,采用IR、1H NMR、13C NMR和HPLC-MS对其结构进行表征.并测定根皮素及其酯的还原能力、清除DPPH自由基及·OH自由基能力,结果表明根皮素乙酰阿魏酸酯的抗氧化活性显著优于根皮素.     

Evaluation of free radical scavenging activity of Butea monosperma Lam

In the present study, ethyl acetate, butanol and aqueous fractions derived from total methanol extract of Butea monosperma flowers were evaluated for radical scavenging activities using different in vitro models like reducing power assay, scavenging of 2,2 diphenyl-1-picrylhydrazyl (DPPH) radical, nitric oxide radical, superoxide anion radical, hydroxyl radical and inhibition of erythrocyte hemolysis using 2, 2' azo-bis (amidinopropane) dihydrochloride (AAPH). Methanol extract along with its ethyl acetate and butanol fractions showed potent free radical scavenging activity, whereas aqueous fraction was found to be devoid of any radical scavenging properties. The observed activity could be due to the higher phenolic content in the extracts (16.1, 25.29, and 17.74% w/w in methanol extract, ethyl acetate and butanol fractions respectively). HPTLC fingerprint profile of the ethyl acetate and butanol fractions were developed which would serve as reference standard for quality control of the extracts.     

DPPH radical scavengers from dried leaves of oregano (Origanum vulgare)

1,1-Dipehnyl-2-picrylhydrazyl (DPPH) radical scavenging activities were found in the extract of dried leaves of oregano (Origanum vulgare). The water-soluble active ingredients were isolated, and their structures were determined to be 4'-O-beta-D-glucopyranosyl-3',4'-dihydroxybenzyl protocatechuate and 4'-O-beta-D-glucopyranosyl-3',4'-dihydroxybenzyl 4-O-methylprotocatechuate by (1)H-, (13)C-NMR, DEPT, HMQC, and HMBC spectral analyses, and by NOE experiments. The DPPH radical scavenging activities of these compounds were compared with those of rutin, quercetin and rosmarinic acid at a concentration of 2 x 10(-5) M. The scavenging activity of 4'-O-beta-D-glucopyranosyl-3',4'-dihydroxybenzyl protocatechuate was almost the same as that of quercetin and rosmarinic acid, but that of 4'-O-beta-D-glucopyranosyl-3',4'-dihydroxybennzyl 4-O-methylprotocatechuate was less than that of quercetin, rosmarinic acid and 4'-O-beta-D-glucopyranosyl-3',4'-dihydroxybenzyl protocatechuate. The amount of 4'-O-beta-D-glucopyranosyl-3',4'-dihydroxybenzyl protocatechuate was estimated to be 3.8 mg/1 g of dried leaves by an HPLC analysis.     

The antioxidative activity of traditional Japanese herbs

The objective of this research was to examine the radical scavenging activity of traditional Japanese herbs. Samples used in the experiments were gennoshoko (Geranium nepalense var. thunbergii), yomogi (Artemisia vulgaris var.indica), senburi (Swertia japonica), iwa-tobacco (Conandron ramondioides), sarunokoshikake (Elfvingia applanata), kanzo (Glycyrrhiza uralensis Fisch) and matatabi (Actinidia polygama). The water-soluble components of the herbs were extracted in boiling water, and the volatile oil was extracted by a distillation apparatus or steeping in some organic solvents such as petroleum ether and ethyl ether. The radical scavenging activity was determined by the decrease of free radicals of DPPH detected by both colorimetric assay and HPLC method at 517 nm. The extracts of gennoshoko, yomogi and iwa-tobacco showed remarkable radical scavenging activity. The volatile oil of yomogi obtained by distillation or steeping in organic solvents had especially strong antioxidative activity.     

Antioxidant Activities of Some Extracts of Thymus zygis

The antioxidant activities of methanol and ethyl ether extracts obtained from Thymus zygis, collected during the flowering or non-flowering period, were evaluated and compared. To investigate this potential, extracts were tested on their capacity to react with diphenyl-picrylhydrazyl (DPPH) in a homogeneous medium, and to inhibit Fe²⁺/ascorbate-induced membrane lipid peroxidation, as estimated by the formation of thiobar-bituric acid-reactive substances (TBARS). Although methanol extracts reduce DPPH radicals more efficiently than ethyl ether extracts, suggesting a potent radical scavenger activity, the ethyl ether extracts were found to be most active in inhibiting lipid peroxidation in sarcoplasmic reticulum (SR) membranes. In addition, both extracts present peroxyl and superoxide radical scavenging activities. Peroxyl radicals were generated by the water soluble 2, 2A-azobis(2-amidinopropane) dihydrochloride (AAPH) azoinitiator, and the scavenging activities of the extracts were measured by the inhibition of cis-parinaric acid (PnA) fluorescence decay in SR. Superoxide radicals were generated either by an enzymatic or a non-enzymatic system, and the scavenger ability was evaluated by the inhibition of nitrob-lue tetrazolium reduction. Methanolic extracts are more potent as scavengers of peroxyl and super oxide radicals than the ethyl ether extracts. Apparently, there is a relationship between antioxidant potency and the total phenolic groups content in each extract.     

桦褐孔菌提取物抗氧化活性研究

以乙酸乙酯和甲醇为提取剂,采用索氏提取法,剩余残渣采用热水浸提,最终得到桦褐孔菌不同极性提取物,对其DPPH自由基、羟基自由基及超氧阴离子自由基清除活性作用进行了研究,确定桦褐孔菌的抗氧化能力,为深入研究和开发桦褐孔菌功能性食品奠定理论基础。实验结果表明桦褐孔菌具有较好的抗氧化活性,其中乙酸乙酯提取物的DPPH自由基清除率、羟基自由基清除率和超氧阴离子自由基清除率均高于其他两组分及BHT,桦褐孔菌提取物有望成为功能性食品组分中合成抗氧化剂的天然替代品。     

河南产景天三七抗氧化活性研究

用清除二苯代苦味酰基(DPPH)自由基、2,2′-连氨-(3-乙基苯并噻唑啉-6-磺酸)二氨盐(ABTS)自由基和铁离子还原/抗氧化能力(FRAP)测定法对洛阳和信阳产景天三七(Sedum aizoon)体外总抗氧化活性进行评价,并与阳性对照丁基羟基茴香醚(BHA)、没食子酸丙酯(PG)和二丁基羟基甲苯(BHT)比较。发现洛阳和信阳景天三七有较好的体外抗氧化活性。洛阳和信阳产乙酸乙酯部位活性最强,正丁醇部位活性次之。在6个提取部位中,信阳产景天三七乙酸乙酯部位活性最强,其清除DPPH、ABTS自由基能力强于阳性对照BHA和BHT,还原Fe3+的能力大于阳性对照BHT,洛阳产景天三七乙酸乙酯部位和正丁醇部位活性次之。     

Antioxidant Activities of Some Extracts of Thymus zygis

The antioxidant activities of methanol and ethyl ether extracts obtained from Thymus zygis, collected during the flowering or non-flowering period, were evaluated and compared. To investigate this potential, extracts were tested on their capacity to react with diphenyl-picrylhydrazyl (DPPH) in a homogeneous medium, and to inhibit Fe²⁺/ascorbate-induced membrane lipid peroxidation, as estimated by the formation of thiobar-bituric acid-reactive substances (TBARS). Although methanol extracts reduce DPPH radicals more efficiently than ethyl ether extracts, suggesting a potent radical scavenger activity, the ethyl ether extracts were found to be most active in inhibiting lipid peroxidation in sarcoplasmic reticulum (SR) membranes. In addition, both extracts present peroxyl and superoxide radical scavenging activities. Peroxyl radicals were generated by the water soluble 2, 2A-azobis(2-amidinopropane) dihydrochloride (AAPH) azoinitiator, and the scavenging activities of the extracts were measured by the inhibition of cis-parinaric acid (PnA) fluorescence decay in SR. Superoxide radicals were generated either by an enzymatic or a non-enzymatic system, and the scavenger ability was evaluated by the inhibition of nitrob-lue tetrazolium reduction. Methanolic extracts are more potent as scavengers of peroxyl and super oxide radicals than the ethyl ether extracts. Apparently, there is a relationship between antioxidant potency and the total phenolic groups content in each extract.     

拟细羽束梗孢发酵菌丝体中自由基清除活性成分分析

用二苯基苦基苯肼(DPPH)自由基法,首次对拟细羽束梗孢(Isaria gracilioides RCEF3 279)菌丝体的不同溶剂提取物进行了自由基清除活性的定性定量分析,发现其甲醇提取物具有较强的清除自由基活性,当菌丝浓度为10 g/L时,其甲醇提取物的自由基清除率达到了92.4％±0.3％.DPPH自显影-薄层...     

一株地衣内生真菌Daldinia childiae的化学成分

本研究对分离自星点梅衣属地衣Punctelia sp.的一株内生真菌蔡氏轮层炭壳菌Daldinia childiae进行大米固体发酵培养,乙酸乙酯萃取发酵产物,采用硅胶柱色谱法、重结晶等方法分离纯化次生代谢产物,结合核磁共振波谱与质谱技术对单体化合物进行结构解析,运用DPPH法测定化合物的自由基清除能力.结果分离得到8...     

库克诺你果汁提取物体外清除自由基及抗氧化活性研究

本文对诺你果汁多糖、乙醇溶出物和乙酸乙酯萃取物体外对超氧阴离子(O2·)、羟自由基(·OH)、DPPH和脂质过氧化(LPO)的抑制作用进行了研究。超氧阴离子(O2·)由邻苯三酚自氧化产生;羟自由基(·OH)由Fenton反应产生;利用Fe2 诱发卵黄脂蛋白产生丙二醛(MDA),TBA法测定。所有测定均为分光光度法。结果表明,与已知抗氧化剂L抗坏血酸相比,乙醇溶出物和乙酸乙酯萃取物均有明显的捕捉自由基和抗氧化能力,而多糖捕捉自由基和抗氧化能力很低,且对O2·没有抑制作用,反而会增加其生成速度。     

Production of Cold-Flow Quality Biodiesel from High-Acidity On-Edible Oils—Esterification and Transesterification of Macauba (<Emphasis Type="Italic">Acrocomia aculeata</Emphasis>) Oil Using Various Alcohols

Biodiesel is an alternative fuel that has been used for partial or total substitution of diesel to reduce its environmental impacts. Prior studies on this topic have focused on the quest for better synthesis process, new catalysts and low-cost non-food and raw materials to improve the economic and sustainable production as well as product quality. In this study, acidic oil from macauba, a palm tree native to South America that has no food uses, was converted into biodiesel. The esterification and transesterification reactions were performed with methanol, ethanol and isobutanol with the goal of improving the cold properties of the biodiesel. The isobutyl ester exhibited the lowest freezing point temperature but underperformed outside of international specifications for kinematic viscosity; it also exhibited a low ester content. The methyl and ethyl esters were within the specifications of the international standards for ester content, density, kinematic viscosity and sulphur content. The ethyl ester produced from macauba oil displayed better properties in cold conditions than methyl and isobutyl esters studied here, with a cold filter plugging point of 0 °C. Its onset crystallisation temperature was reduced from ?5.96 to ?13.41 °C when subjected to fractional crystallisation. The ethyl ester exhibited the best lubricity value among the other esters studied.     

In vitro antioxidant activity of banana (Musa spp. ABB cv. Pisang Awak)

The methanolic extract of Musa ABB cv Pisang Awak was investigated for the polyphenolic contents and antioxidant activity. The total phenol and flavonoid contents of the fruit extract were found to be 120 mg gallic acid equivalents (GAE) and 440 mg quercetin equivalents (QE)/100 g of sample dry weight, respectively. The antioxidant activity of the Pisang Awak methanol extract (PAME) (20-500 microg/ml) was determined using 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical scavenging activity, reducing capacity, 2-2'-azinobis-3-ethylbenzothiozoline-6-sulfonic acid (ABTS) radical cation decolourization and hydroxyl radical scavenging capacity (OH*). The EC50 values of DPPH, ABTS and OH* activities of the PAME and butylated hydroxy toluene (BHT) were found to be 65 and 9 microg/ml, 29 and 6 microg/ml, 36 and 42 microg/ml respectively. The reducing capacity increased with increasing concentration (31.5-1000 mg/ml) of the fruit extract and the activity was comparable with the standard BHT. The high performance thin layer chromatography (HPTLC) analysis of the extract revealed the presence of polyphenols. The strong and positive correlations were obtained between total phenol/flavonoid contents (R2 = 0.693-1.0) and free radical scavenging ability was attributed to the polyphenols as the major antioxidants.     

DPPH radical scavenging reaction of hydroxy- and methoxychalcones

The DPPH radical scavenging activity of 2',4',6'-trihydroxy- and 2'-hydroxy-4',6'-dimethoxychalcones carrying a 2,3- and 3,4-dihydroxylated, and 3,4,5-trihydroxylated B-ring was evaluated in alcoholic and non-alcoholic solvents. All test compounds scavenged more than two equivalent of radicals by a possible conversion to the corresponding B-ring quinones and in most cases subsequently underwent cyclization to aurones and flavanones, these being identified in the reaction solutions by an in situ NMR analysis. Interestingly, the reaction between 2',3,4-trihydroxy-4',6'-dimethoxychalcone and the DPPH radical was significantly affected by the solvent used, which might be accounted for by the difference in readiness for cyclization to an aurone.     

Nucleophilic addition of glycine esters to Gd@C82

The first investigation of nucleophilic addition of glycine esters to Gd@C₈₂ is reported and hydroxyl was found to compete with glycine esters in the reaction. The multiple adducts containing either mere glycine esters or both glycine esters and hydroxyl group were identified by MALDI TOF mass spectrometry and characterized with UV-Vis-NIR spectrometry. Because glycine ethyl ester is more soluble than glycine methyl ester in alcohol and toluene, as many as eight glycine ethyl ester groups can be added to the metallofullerene cage while the maximal number for glycine methyl ester groups is only four.