Real-time electrochemical determination of phenolic compounds after benzene oxidation

A sensitive electrochemical sensor was successfully developed on multi-walled carbon nanotubes (MWCNT) and cobalt phthalocyanine (CoPc) modified glassy carbon electrode (GC), and used to detect byproducts formed after the electrolysis of benzene. The GC/MWCNT/CoPc electrode was applied in the detection of phenolic compounds using square wave voltammetry (SWV). The proposed sensor exhibited a sequence in the sensitivity of the tested phenols: catechol > hydroquinone > resorcinol > phenol and 1,4-benzoquinone. The detection limits for individual phenols were also calculated: catechol (15.62 mu g L-1), hydroquinone (17.91 mu g L-1), resorcinol (46.12 mu g L-1), phenol (58.83 mu g L-1) and 1,4-benzoquinone (13.75 mu g L-1). The proposed sensor was successfully applied in the determination of the total amount of phenols formed after the benzene oxidation, and the obtained results were in full agreement with those from the HPLC procedure. (C) 2012 Elsevier B.V. All rights reserved.

Phenolic compounds from Rosemary (Rosmarinus officinalis L.) attenuate oxidative stress and reduce blood cholesterol concentrations in diet-induced hypercholesterolemic rats

Abstract Background Phenolic compounds combine antioxidant and hypocholesterolemic activities and, consequently, are expected to prevent or minimize cardiometabolic risk. Methods To evaluate the effect of an aqueous extract (AQ) and non-esterified phenolic fraction (NEPF) from rosemary on oxidative stress in diet-induced hypercholesterolemia, 48 male 4-week old Wistar rats were divided into 6 groups: 1 chow diet group (C) and 5 hypercholesterolemic diet groups, with 1 receiving water (HC), 2 receiving AQ at concentrations of 7 and 140 mg/kg body weight (AQ70 and AQ140, respectively), and 2 receiving NEPF at concentrations of 7 and 14 mg/kg body weight (NEPF7 and NEPF14, respectively) by gavage for 4 weeks. Results In vitro, both AQ and NEPF had remarkable antioxidant activity in the 2,2-diphenyl-1-picrylhydrazyl (DPPH●) assay, which was similar to BHT. In vivo, the group that received AQ at 70 mg/kg body weight had lower serum total cholesterol (−39.8%), non-HDL-c (−44.4%) and thiobarbituric acid reactive substance (TBARS) levels (−37.7%) compared with the HC group. NEPF (7 and 14 mg/kg) reduced the tissue TBARS levels and increased the activity of tissular antioxidant enzymes (superoxide dismutase, catalase and glutathione peroxidase). Neither AQ nor NEPF was able to ameliorate the alterations in the hypercholesterolemic diet-induced fatty acid composition in the liver. Conclusions These data suggest that phenolic compounds from rosemary ameliorate the antioxidant defense in different tissues and attenuate oxidative stress in diet-induced hypercholesterolemic rats, whereas the serum lipid profile was improved only in rats that received the aqueous extract.

Supercritical CO2 extraction of phenolic compounds from Baccharis dracunculifolia

Extracts from Baccharis dracunculifolia leaves were obtained using the following solvents: supercritical carbon dioxide (SC-CO2), ethanol and methanol. Supercritical extraction was carried out at temperatures of 40, 50 and 60 degrees C and pressures of 20, 30 and 40 MPa. Four phenolic compounds were analysed in the extracts by high-performance liquid chromatography: 3,5-diprenyl-4-hydroxycinnamic acid (DHCA or artepillin C); 3-prenyl-4-hydroxycinnamic acid (PHCA); 4-hydroxycinnamic acid (p-coumaric acid) and 4-methoxy-3,5,7-trihydroxyflavone (kaempferide). The global extraction yields (X-0) obtained by the conventional methods with ethanol and methanol were higher than those obtained by SC-CO2. However on analysing the components of interest extracted at 60 degrees C and 40 MPa, the extraction yields of kaempferide, DHCA and PHCA were 156%, 98% and 64% higher, respectively, than in the ethanolic extracts. Only the p-coumaric acid extraction yield was better when extracted using the conventional method. (C) 2008 Elsevier B.V. All rights reserved.

Leishmanicidal and cholinesterase inhibiting activities of phenolic compounds of Dimorphandra gardneriana and Platymiscium floribundum, native plants from Caatinga biome

Nos últimos anos, o Ministério da Saúde do Brasil e a Organização Mundial da Saúde tem apoiado a investigação de novas tecnologias que possam contribuir para a vigilância, novos tratamentos e controle da leishmaniose visceral no país. Assim, o objetivo deste trabalho foi isolar compostos de plantas do bioma Caatinga, e investigar a toxicidade destes compostos contra as formas promastigotas e amastigotas de Leishmania infantum chagasi, principal parasita responsável pela leishmaniose visceral na América do Sul, e avaliar a sua capacidade para inibir a enzima acetil-colinesterase (AChE). Após a exposição aos compostos em estudo, foram realizados testes utilizando a forma promastigota que expressa luciferase e ELISA in situ para medir a viabilidade das formas promastigotas e amastigota, respectivamente. O ensaio colorimétrico MTT foi realizado para determinar a toxicidade destas substâncias utilizando células monocíticas murina RAW 264.7. Todos os compostos foram testados in vitro para as sua propriedade anti-colinesterásica. Um cumarina, escoparona, foi isolada a partir de hastes de Platymiscium floribundum, e os flavonóides, rutina e quercetina, foram isolados a partir de grãos de Dimorphandra gardneriana. Estes compostos foram purificados, utilizando cromatografia em coluna gel eluída com solventes orgânicos em misturas de polaridade crescente, e identificados por análise espectral. Nos ensaios leishmanicidas, os compostos fenólicos mostraram eficácia contra as formas extracelulares promastigotas, com EC50 para escoporona de 21.4µg/mL e para quercetina e rutina 26 e 30.3µg/mL, respectivamente. Os flavonóides apresentaram resultados comparáveis à droga controle, a anfotericina B, contra as formas amastigotas com EC50 para quercetina e rutina de 10.6 e 43.3µg/mL, respectivamente. Os compostos inibiram a enzima AChE com halos de inibição variando de 0,8 a 0,6cm, indicando um possível mecanismo de ação para a atividade leishmanicida.

Stability of Carotenoids, Total Phenolics and In Vitro Antioxidant Capacity in the Thermal Processing of Orange-Fleshed Sweet Potato (Ipomoea batatas Lam.) Cultivars Grown in Brazil

Intervention strategies regarding the biofortification of orange-fleshed sweet potato, which is a rich source of carotenoids for combating vitamin A deficiency, are being developed in Brazil. This study was conducted to evaluate the concentrations of individual carotenoids, total phenolic compounds and antioxidant capacity in the roots of four biofortified sweet potato cultivars that were raw or processed by four common heat treatments. HPLC, Folin-Ciocalteu, DPPH and ABTS assays were used. All cultivars showed high levels of carotenoids in raw roots, predominantly all-trans-beta-carotene (79.1-128.5 mg.100 g(-1) DW), suggesting a high estimated vitamin A activity. The CNPH 1194 cultivar reported carotenoids values highest than those of other cultivars (p < 0.05). The total phenolic compounds varied among cultivars and heat treatments (0.96-2.05 mg.g(-1) DW). In most cases, the heat treatments resulted in a significant decrease in the carotenoids and phenolic compounds contents as well as antioxidant capacity. Processing of flour presented the greatest losses of major carotenoids and phenolics. The phenolic compounds showed more stability than carotenoids after processing. There were significant correlations between the carotenoids and phenolic compounds and the antioxidant capacity.

Enzymatic Solid-Phase Reactor Based on Silica Organofunctionalized with p-Phenylenediamine for Electrochemical Detection of Phenolic Compounds

A new biomaterial, based on silica organofunctionalized with p-phenylenediamine (p-PDA) and the enzyme peroxidase, was used in the development of an enzymatic solid-phase reactor. The analytical techniques used in the characterization showed that the organic ligand was incorporated into the silica matrix. Thus, the silica modified with p-PDA allowed the incorporation of peroxidase by the electrostatic interaction between the carboxylic groups present in the enzyme molecules and the amino groups attached to the silica. The enzymatic solid-phase reactor was used for chemical oxidation of phenols in 1, 4-benzoquinone that was then detected by chronoamperometry. The system allowed the analysis of hydroquinone with a detection limit of 83.6 nmol L-1. Thus, the new material has potential in the determination of phenolic compounds river water samples.

CHEMICAL CONSTITUENTS FROM RED ALGAE Bostrychia radicans (Rhodomelaceae): NEW AMIDES AND PHENOLIC COMPOUNDS

This study describes the isolation and structural determination of two amides, isolated for the first time: N,4-dihydroxy-N-(2'-hydroxyethyl)-benzamide (0.019%) and N, 4-dihydroxy-N-(2'-hydroxyethyl)-benzeneacetamide (0.023%). These amides, produced by the red macroalgae Bostrychia radicans, had their structures assigned by NMR spectral data and MS analyses. In addition, this chemical study led to the isolation of cholesterol, heptadecane, squalene, trans-phytol, neophytadiene, tetradecanoic and hexadecanoic acids, methyl hexadecanoate and methyl 9-octadecenoate, 4-(methoxymethyl)-phenol, 4-hydroxybenzaldehyde, methyl 4-hydroxybenzeneacetate, methyl 2-hydroxy-3-(4-hydroxyphenyl)-propanoate, hydroquinone, methyl 4-hydroxymandelate, methyl 4-hydroxybenzoate, 4-hydroxybenzeneacetic acid and (4-hydroxyphenyl)-oxo-acetaldehyde. This is the first report concerning these compounds in B. radicans, contributing by illustrating the chemical diversity within the Rhodomelaceae family.

LC-DAD/ESI-MS/MS study of phenolic compounds in ash (Fraxinus excelsior L. and F. americana L.) heartwood. Effect of toasting intensity at cooperage

The phenolic composition of heartwood extracts from Fraxinus excelsior L. and F. americana L., both before and after toasting in cooperage, was studied using LC-DAD/ESI-MS/MS. Low-molecular weight (LMW) phenolic compounds, secoiridoids, phenylethanoid glycosides, dilignols and oligolignols compounds were detected, and 48 were identified, or tentatively characterized, on the basis of their retention time, UV/Vis and MS spectra, and MS fragmentation patterns. Some LMW phenolic compounds like protocatechuic acid and aldehyde, hydroxytyrosol and tyrosol, were unlike to those for oak wood, while ellagic and gallic acid were not found. The toasting of wood resulted in a progressive increase in lignin degradation products with regard to toasting intensity. The levels of some of these compounds in medium-toasted ash woods were much higher than those normally detected in toasted oak, highlighting vanillin levels, thus a more pronounced vanilla character can be expected when using toasted ash wood in the aging wines. Moreover, in seasoned wood, we found a great variety of phenolic compounds which had not been found in oak wood, especially oleuropein, ligstroside and olivil, along with verbascoside and isoverbascoside in F. excelsior, and oleoside in F. americana. Toasting mainly provoked their degradation, thus in medium-toasted wood, only four of them were detected. This resulted in a minor differentiation between toasted ash and oak woods. The absence of tannins in ash wood, which are very important in oak wood, is another peculiar characteristic that should be taken into account when considering its use in cooperage. Copyright (C) 2012 John Wiley & Sons, Ltd.

Chemical constituents from red algae Bostrychia radicans (Rhodomelaceae): new amides and phenolic compounds

This study describes the isolation and structural determination of two amides, isolated for the first time: N,4-dihydroxy-N-(2'-hydroxyethyl)-benzamide (0.019%) and N,4-dihydroxy-N-(2'-hydroxyethyl)-benzeneacetamide (0.023%). These amides, produced by the red macroalgae Bostrychia radicans, had their structures assigned by NMR spectral data and MS analyses. In addition, this chemical study led to the isolation of cholesterol, heptadecane, squalene, trans-phytol, neophytadiene, tetradecanoic and hexadecanoic acids, methyl hexadecanoate and methyl 9-octadecenoate, 4-(methoxymethyl)-phenol, 4-hydroxybenzaldehyde, methyl 4-hydroxybenzeneacetate, methyl 2-hydroxy-3-(4-hydroxyphenyl)-propanoate, hydroquinone, methyl 4-hydroxymandelate, methyl 4-hydroxybenzoate, 4-hydroxybenzeneacetic acid and (4-hydroxyphenyl)-oxo-acetaldehyde. This is the first report concerning these compounds in B. radicans, contributing by illustrating the chemical diversity within the Rhodomelaceae family.

Glyphosate has low toxicity to citrus plants growing in the field

Gravena, R., Filho, R. V., Alves, P. L. C. A., Mazzafera, P. and Gravena, A. R. 2012. Glyphosate has low toxicity to citrus plants growing in the field. Can. J. Plant Sci. 92: 119-127. There has been controversy over whether glyphosate used for weed management in citrus fields causes significant toxicity to citrus plants. Glyphosate may be toxic to non-target plants exposed to accidental application or drift. This work evaluated glyphosate toxicity in plants of Valencia citrus (Citrus sinensis. L. Osbeck) grafted onto 'Rangpur lime' (Citrus limonia L. Osbeck) and citrumelo 'Swingle' (Poncirus trifoliata (L.) Raf x Citrus paradisi Mad) by trunk- or foliar-directed herbicide applications under field conditions. In the first experiment, glyphosate was sprayed at rates of 0, 90, 180, 260, 540, 1080 and 2160 g a.e. ha(-1) directly on the trunk to a height of 5 cm above the grafting region. In the second experiment, glyphosate was sprayed on the plant canopies at rates of 0, 0.036, 0.36, 3.6, 36, 360 and 720 g a.e. ha(-1). There was no visual damage caused by glyphosate applied directly to the trunk, but the plants were affected by glyphosate sprayed directly on the canopies at rates over 360 g a.e. ha(-1). The main symptom was observed in the new shoots formed after the application, indicating an effect on meristems. Little or no effect was observed in mature leaves. Eight days after application the levels of shikimate, total free amino acids and total phenolic compounds were unaffected. All plants affected by glyphosate recovered between 6 and 12 mo after the treatments. Therefore, despite some transient symptoms Valencia citrus grafted onto 'Rangpur lime' and citrumelo 'Swingle' were tolerant to glyphosate.

The correlation between the phenolic composition and biological activities of two varieties of Brazilian propolis (G6 and G12)

Biological assays that have been performed on different types of Brazilian propolis have shown that type 6 propolis (G6) has a strong antimicrobial activity and a low flavonoid content. This study aimed to evaluate the correlation between the phenolic composition and the biological activities displayed by propol is G6 from the state of Bahia and green propol is, also known as type 12 (G12). The values of the flavonoids and the total phenolics in propol is G6 were different than those in propolis G12. Although the G12 variety presented greater antioxidant activity, propolis G6 proved to have greater antimicrobial and cytotoxic activities. The results showed that the phenolic compounds may not be the only compounds responsible for the biological activity. More detailed studies of the chemical composition and an assessment or the biological activity are required to establish the quality of propolis.

Modified CUPRAC spectrophotometric quantification of total polyphenol content in beer samples using Cu(II)/neocuproine complexes

Cu(II)/neocuproine (2,9-dimethyl-1,10-phenanthroline) complexes were utilized for spectrophotometric determination of total polyphenol content in beers. This procedure is based on the reduction of Cu(II) by polyphenols in hydroethanolic medium (pH 7.0) in the presence of neocuproine, yielding Cu(I)/complexes with maximum absorption at 454 nm. The sensitivity of the proposed method was compared with the AOAC method using tannic and gallic acid as standards. The average apparent molar absorptivity, in L cm(-1) mol(-1), of tannic acid (3.50 +/- 0.20) x 10(5) and gallic acid (5.12 +/- 0.21) x 10(4), was twice as high for the proposed method. A lower limit of detection (LOD) (2.9 x 10(-1) mg L-1) was found when tannic acid was used in the proposed method. Additionally, less interference from the most common additives in beers was noticed. Total content of polyphenols was analyzed in 17 Brazilian samples. Results ranged from 35.5 to 556 mg L-1 of tannic acid, with higher values for recovery rates (45.4-118%, mean 85.0%) than for gallic acid. Although tannic acid is a mixture of polygalloyl glucoses, the total polyphenol content found in the samples suggests that tannic acid should be used as a standard. This is the first attempt to use this particular copper complex to quantify total polyphenol content in beer samples. (C) 2012 Elsevier Inc. All rights reserved.

Antioxidant, anti-acetylcholinesterase and cytotoxic activities of ethanol extracts of peel, pulp and seeds of exotic Brazilian fruits Antioxidant, anti-acetylcholinesterase and cytotoxic activities in fruits

Ethanol extracts of powdered genipap (Genipa americana L), umbu (Spondia tuberosa A.) and siriguela (Spondia purpurea L) prepared from separate pulp, seeds and peel were investigated for their (i) antioxidant capacity, which was evaluated by various known methods; (ii) acetylcholinesterase (AChE) inhibitory activity; and (iii) cytotoxic effect on corneal epithelial cells of sheep. The highest values of total phenolic content were obtained with peel and seed extracts. Siriguela and umbu (seeds and peel) extracts displayed the highest antioxidant activities. Lipid peroxidation assays using mimetic biomembranes and mouse liver homogenates indicated that genipap pulp is a promising antioxidant. The investigation of phenols and organic acid contents revealed the presence of quercetin, citric and quinic acids, chlorogenic acid derivatives, among others, in several extracts, with the highest amount found in siriguela seeds. Genipap pulp and siriguela seed ethanol extracts presented an AChE inhibition zone similar to that of the positive control, carbachol. AChE inhibition assay with chlorogenic acid, one of the main constituents of siriguela seeds, revealed that this acid showed activity similar to that of the control physostigmine. These data suggest that these extracts are potentially important antioxidant supplements for the everyday human diet, pharmaceutical and cosmetic industries. (C) 2012 Elsevier Ltd. All rights reserved.

Anti-Atherogenic Effects of a Phenol-Rich Fraction from Brazilian Red Wine (Vitis labrusca L.) in Hypercholesterolemic Low-Density Lipoprotein Receptor Knockout Mice

Moderate wine intake (i.e., 1-2 glasses of wine a day) is associated with a reduced risk of morbidity and mortality from cardiovascular disease. The aim of this study was to evaluate the anti-atherosclerotic effects of a nonalcoholic ethyl acetate fraction (EAF) from a South Brazilian red wine obtained from Vitis labrusca grapes. Experiments were carried out on low-density lipoprotein (LDL) receptor knockout (LDLr-/-) mice, which were subjected to a hypercholesterolemic diet and treated with doses of EAF (3, 10, and 30 mg/kg) for 12 weeks. At the end of the treatment, the level of plasma lipids, the vascular reactivity, and the atherosclerotic lesions were evaluated. Our results demonstrated that the treatment with EAF at 3 mg/kg significantly decreased total cholesterol, triglycerides, and LDL plus very low-density lipoprotein levels compared with control hypercholesterolemic mice. The treatment of mice with EAF at 3 mg/kg also preserved the vasodilatation induced by acetylcholine on isolated thoracic aorta from hypercholesterolemic LDLr-/- mice. This result is in agreement with the degree of lipid deposit on arteries. Taken together, the results show for the first time that the lowest concentration of an EAF obtained from a red wine produced in southern Brazil significantly reduced the progression of atherosclerosis in mice.

Gamma Radiation Effects on Peanut Skin Antioxidants

Peanut skin, which is removed in the peanut blanching process, is rich in bioactive compounds with antioxidant properties. The aims of this study were to measure bioactive compounds in peanut skins and evaluate the effect of gamma radiation on their antioxidant activity. Peanut skin samples were treated with 0.0, 5.0, 7.5, or 10.0 kGy gamma rays. Total phenolics, condensed tannins, total flavonoids, and antioxidant activity were evaluated. Extracts obtained from the peanut skins were added to refined-bleached-deodorized (RBD) soybean oil. The oxidative stability of the oil samples was determined using the Oil Stability Index method and compared to a control and synthetic antioxidants (100 mg/kg BHT and 200 mg/kg TBHQ). Gamma radiation changed total phenolic content, total condensed tannins, total flavonoid content, and the antioxidant activity. All extracts, gamma irradiated or not, presented increasing induction period (h), measured by the Oil Stability Index method, when compared with the control. Antioxidant activity of the peanut skins was higher than BHT. The present study confirmed that gamma radiation did not affect the peanut skin extracts' antioxidative properties when added to soybean oil.