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1.
An ionic liquid n-octylpyridinium hexafluorophosphate (OPFP) modified carbon paste electrode was developed. This ionic liquid modified carbon electrode showed better electrochemical activities compared with the traditional carbon paste electrode which employed the paraffin oil as the binder. With the electrochemically deposited bismuth film, the developed electrode exhibited well-defined and separate stripping voltammetric peaks for cadmium and lead. The linear range of the bismuth film electrode was from 1.0 μg L(-1) to 100.0 μg L(-1) for both metal ions with a deposition time of 120 s and a deposition potential of -1.2 V in pH 4.5 acetate buffer solution. The detection limit was 0.10 μg L(-1) for cadmium and 0.12 μg L(-1) for lead with a deposition time of 180 s. The electrode was also applied to determine cadmium and lead in soil sample extracts. Results suggested that the proposed electrode was sensitive, reliable and effective for the determination of trace heavy metals.  相似文献   

2.
This paper investigates the electrocatalytic oxidation of (-)-epigallocatechin gallate (EGCG), the main monomer flavanol found in green tea, with a novel ionic liquid, n-octylpyridinium hexafluorophosphate (OPFP) carbon paste electrode (CPE). Due to the natural viscosity and high conductivity of OPFP, this novel OPFP-CPE exhibited very attractive properties, such as high stability and electrochemical reactivity, low background current, and wide electrochemical window. Therefore, this electrode is a very good alternative to traditional chemically modified electrodes because the electrocatalytic effect can achieved without any further electrode modification. Comparative experiments were carried out using CPE and a glassy carbon electrode (GCE). With OPFP-CPE, highly reproducible and well-defined cyclic voltammograms were obtained for EGCG. Under optimal experimental conditions, the peak current of differential pulse voltammetry (DPV) response increased linearly with EGCG concentration over the range of 5.0 × 10(-7)-1.25 × 10(-5) M. The limit of detection (LOD) and the limit of quantification (LOQ) were 1.32 × 10(-7) and 4.35 × 10(-7) M, respectively. The method was applied to the determination of EGCG in green tea infusion samples, and the recovery of the spiked EGCG to the diluted (10-fold) tea extract was from 87.62 to 99.51%.  相似文献   

3.
The use of a laccase biosensor, under both batch and flow injection (FI) conditions, for a rapid and reliable amperometric estimation of the total content of polyphenolic compounds in wines is reported. The enzyme was immobilized by cross-linking with glutaraldehyde onto a glassy carbon electrode. Caffeic acid and gallic acid were selected as standard compounds to carry out such estimation. Experimental variables such as the enzyme loading, the applied potential, and the pH value were optimized, and different aspects regarding the operational stability of the laccase biosensor were evaluated. Using batch amperometry at -200 mV, the detection limits obtained were 2.6 x 10(-3) and 7.2 x 10(-4) mg L(-1) gallic acid and caffeic acid, respectively, which compares advantageously with previous biosensor designs. An extremely simple sample treatment consisting only of an appropriate dilution of wine sample with the supporting electrolyte solution (0.1 mol L(-1) citrate buffer of pH 5.0) was needed for the amperometric analysis of red, rosé, and white wines. Good correlations were found when the polyphenol indices obtained with the biosensor (in both the batch and FI modes) for different wine samples were plotted versus the results achieved with the classic Folin-Ciocalteu method. Application of the calibration transfer chemometric model (multiplicative fitting) allowed that the confidence intervals (for a significance level of 0.05) for the slope and intercept values of the amperometric index versus Folin-Ciocalteu index plots (r = 0.997) included the unit and zero values, respectively. This indicates that the laccase biosensor can be successfully used for the estimation of the polyphenol index in wines when compared with the Folin-Ciocalteu reference method.  相似文献   

4.
A rapid and sensitive automated method for glucose monitoring that might be employed during wine fermentation and processing was developed. A flow injection (FI) system coupled with an automated dilutor and the "redox-versatile" modified electrode were used to directly measure glucose in wine. To avoid interferences during wine analysis, different formulations of enzymatically modified carbon paste electrodes (CPE) were used and evaluated in oxidation and reduction mode. The best selectivity and sensitivity for glucose monitoring in real samples was obtained in cathodic mode at a fixed potential of 0 V versus Ag/AgCl using a CPE modified with glucose oxidase, horseradish peroxidase, and ferrocene as redox mediator. A total linear range of 0.02-50 g/L glucose was covered using this automated system and allowed the measurement of glucose in dry, medium, and sweet white or red wines without any sample pretreatment. The results showed a good correlation with the standard method, and the proposed method is very rapid, simple, and reliable and does not need skilled operators.  相似文献   

5.
Phenolics from grapes and wines can play a role against oxidation and development of atherosclerosis. Levels of phenolics, major catechins [(+)-catechin, (-)-epicatechin, procyanidin dimers B1, B2, B3, and B4], phenolic acids (gallic acid and caffeic acid), caftaric acid, malvidin-3-glucoside, peonidin-3-glucoside, and cyanidin-3-glucoside were quantified by HPLC with UV detection for 54 French varietal commercial wines taken from southern France to study the antioxidant capacity and the daily dietary intake of these compounds for the French population. The highest antioxidant capacity was obtained with red wines and ranged from 12.8 mmol/L (Grenache) to 25.2 mmol/L (Pinot Noir). For white wines, Chardonnay enriched in phenolics by special wine-making was found to have an antioxidant capacity of 13.8 mmol/L, comparable to red wine values. For red wines classified by vintages (1996-1999) antioxidant capacities were approximately 20 mmol/L and then decreased to 13.4 mmol/L for vintages 1995-1991. Sweet white wines have 1.7 times more antioxidant capacity (3.2 mmol/L) than dry white wines (1.91 mmol/L). On the basis of a still significant French wine consumption of 180 mL/day/person, the current daily intake of catechins (monomers and dimers B1, B2, B3, and B4) averaged 5 (dry white wine), 4.36 (sweet white wines), 7.70 (rosé wines), 31.98 (red wines), and 66.94 (dry white wine enriched in phenolic) mg/day/resident for the French population. Red wine, and particularly Pinot Noir, Egiodola, Syrah, Cabernet Sauvignon, and Merlot varieties, or Chardonnay enriched in phenolics during wine-making for white varieties contribute to a very significant catechin dietary intake.  相似文献   

6.
This work describes the method for total antioxidant capacity (TAC) and/or total content of phenolics (TCP) analysis in wines using microdialysis online-coupled with amperometric detection using a carbon microfiber working electrode. The system was tested on 10 selected wine samples, and the results were compared with total reactive antioxidant potential (TRAP), oxygen radical absorbance capacity (ORAC), and chemiluminescent determination of total antioxidant capacity (CL-TAC) methods using Trolox and catechin as standards. Microdialysis online-coupled with amperometric detection gives similar results to the widely used cyclic voltammetry methodology and closely correlates with ORAC and TRAP. The problem of electrode fouling is overcome by the introduction of an electrochemical cleaning step (1-2 min at the potential of 0 V vs Ag/AgCl). Such a procedure is sufficient to fully regenerate the electrode response for both red and white wine samples as well as catechin/Trolox standards. The appropriate size of microdialysis probes enables easy automation of the electrochemical TAC/TCP measurement using 96-well microtitration plates.  相似文献   

7.
The thermal modification kinetics of a commercial grape seed extract (GSE) was investigated. A GSE was exposed to 60, 90, and 120 °C for 5, 10, 15, 30, 45, and 60 min. The antioxidant activity (AA) and the absorbance at 420 nm (A(420)) were measured. (+)-Catechin, (-)-epicatechin, procyanidins B1 and B2, and gallic acid were identified and measured. After the thermal treatments, the AA did not show a significant difference (p > 0.05) and both procyanidins and gallic acid increased as well as A(420). (+)-Catechin and (-)-epicatechin decreased. To obtain the activation energy (E(a)) of the changes, a modified Weibull and a combined zero- and first-order model were compared, both followed by the Arrhenius equation. The Weibull model was more accurate. The E(a) values for browning and (+)-catechin, (-)-epicatechin, gallic acid, and procyanidins B1 and B2 were 170, 286, 42, 102, 249, and 95 kJ/mol, respectively. The results were valid at a confident level of 95%.  相似文献   

8.
A simultaneous determination of trans-resveratrol, (-)-epicatechin, and (+)-catechin in red wine by capillary electrophoresis with electrochemical detection (CE-ED) is reported. The effects of the potential of the working electrode, pH and concentration of running buffer, separation voltage, and injection time on CE-ED were investigated. Under the optimum conditions, the analytes could be separated in a 100 mmol/L borate buffer (pH 9.2) within 20 min. A 300 microm diameter carbon disk electrode has a good response at +0.85 V (vs SCE) for all analytes. The response was linear over 3 orders of magnitude with detection limit (S/N = 3) ranging from 2 x 10(-7) to 5 x 10(-7) g/mL for all analytes. This method has been used for the determination of these analytes in red wine without enrichment, and the assay result was satisfactory.  相似文献   

9.
A previous study showed β-glucan with low molecular weight (MW, 1.56×10(5) g/mol) bound more bile acid and produced greater amounts of short-chain fatty acids (SCFA) than did β-glucan with high MW (Mn=6.87×10(5) g/mol). In the current study, β-glucan extracted from oat flour was fractionated into six different MW levels (high MW, 7.09×10(5); low level 1 (L1), 3.48×10(5); L2, 2.42×10(5); L3, 1.61×10(5); L4, 0.87×10(5); and L5, 0.46×10(5) g/mol) and evaluated to find the optimum MW affecting in vitro bile acid binding and fermentation. The β-glucan fractions with 2.42×10(5)-1.61×10(5) g/mol (L2 and L3) bound the greatest amounts of bile acid. After 24 h of fermentation, no differences were found in total SCFA formation among L1, L2, L3, and L4 fractions; however, the high MW and L5 MW fractions produced lower amounts of total SCFA. Thus, the optimum MW of β-glucan to affect both hypocholesterolemic and antitumorigenic in vitro effects was in the range of 2.42×10(5)-1.61×10(5) g/mol. This MW range also was the most water-soluble among the MWs evaluated.  相似文献   

10.
Regeneration of β-carotene from the β-carotene radical cation by the 4'-propylpuerarin anion (second-order rate constant=1.5×10(9) L mol(-1) s(-1) in methanol/chloroform=1:9 (v/v) solution at 25 °C as determined by laser flash photolysis) was found to be marginally slower than regeneration by the 7-propylpuerarin anion (2.3×10(9) L mol(-1) s(-1)), in agreement with the 7-propylpuerarin anion being more reducing (E'=0.56 V vs NHE) than the 4'-propylpuerarin anion (E'=1.01 V vs NHE). The potentials were calculated from E°=1.12 and 1.44 V (vs NHE) as determined by cyclic voltametry in aqueous solution and pKa=9.51 and 7.23 obtained previously for 7-propylpuerarin and 4'-propylpuerarin, respectively. The less reducing but more acidic 4'-propylpuerarin showed less antioxidant activity in liposome of pH 7.4, but more significant antioxidant synergism with β-carotene than the more reducing but less acidic 7-propylpuerarin for oxidation initiated in the liposome lipid phase. Electrostatic effects are concluded to be important in the regeneration of β-carotene from the radical cation in the water/lipid interface because approximately 50% of 4'-propylpuerarin is present as the anion, whereas only 0.5% of 7-propylpuerarin is present as the anion. In contrast, penetration of the undissociated phenolic group into the lipid phase, more significant for 7-propylpuerarin than for 4'-propylpuerarin according to the calculated water/lipid partition coefficients, becomes important for the chain-breaking action in lipid oxidation of the puerarin derivatives as models for (iso)flavonoids and their glycosides.  相似文献   

11.
An integrated amperometric gluconic acid biosensor constructed using a gold electrode (AuE) modified with a self-assembled monolayer (SAM) of 3-mercaptopropionic acid (MPA) on which gluconate dehydrogenase (GADH, 0.84 U) and the mediator tetrathiafulvalene (TTF, 1.5 micromol) were coimmobilized by covering the electrode surface with a dialysis membrane is reported. The working conditions selected were Eapp=+0.15 V and 25+/-1 degrees C. The useful lifetime of one single TTF-GADH-MPA-AuE was surprisingly long. After 53 days of continuous use, the biosensor exhibited 86% of the original sensitivity. A linear calibration plot was obtained for gluconic acid over the 6.0x10(-7) to 2.0x10(-5) M concentration range, with a limit of detection of 1.9x10(-7) M. The effect of potential interferents (glucose, fructose, galactose, arabinose, and tartaric, citric, malic, ascorbic, gallic, and caffeic acids) on the biosensor response was evaluated. The behavior of the biosensor in a flow-injection system in connection with amperometric detection was tested. The analytical usefulness of the biosensor was evaluated by determining gluconic acid in wine and must samples, and the results obtained were validated by comparison with those provided by using a commercial enzyme test kit.  相似文献   

12.
A Chardonnay white wine enriched in polyphenols was obtained by modification of winemaking and characterized by its enrichment in total polyphenolic content (1346 mg/L as compared to 316 mg/L for traditional Chardonnay) and in various individual polyphenols (catechin, epicatechin, procyanidins dimers B1-B4, gallic acid, cafeic acid, and caftaric acid), as determined from HPLC coupled to a diode array detector. The polyphenols-enriched white wine (W) or its ethanol-free derivative (EFW) was then administered by gavage (10 mL/kg, twice a day) for 6 weeks to rats that have been rendered diabetic by a single iv injection of streptozotocin (55 mg/kg). Treatments had no effect on the symptoms associated with hyperglycemia. However, while a reduction in plasma antioxidant capacity was associated with the diabetic state, administration of W or EFW restored plasma antioxidant capacities to a level not significantly different from that of nondiabetic control animals. In addition, the effect of both treatments was manifested by the enlargement of mesenteric arteries, as determined by quantitative histomorphometry. In summary, our study indicates that white wine, when enriched in polyphenols, is able to induce ethanol-independent in vivo effects in a model of insulin-deficient diabetes characterized by a major oxidative stress.  相似文献   

13.
Extracts from Murta leaves are used by Chilean natives for their benefits on health and cosmetic properties, which are mainly due to the presence of polyphenolic compounds. Extraction of such compounds is strongly influenced by several variables, the effects of which are studied in this work; the antioxidant power of the resulting extracts was measured by two different methods [2,2-diphenyl-1-picrylhydrazyl (DPPH) and thiobarbituric acid reactive substances (TBARS)]. On the whole, maximum values of polyphenolic yields and antiradical power (DPPH method) were attained at 50 degrees C (from 25 to 50 degrees C) and a solvent-to-solid ratio (v/w) of 15:1 (15:1-25:1). The solvents assayed were ethanol, methanol, and water. The highest polyphenolic yield values (2.6% expressed as gallic acid) were reached with methanol, whereas maximum EC50 was attained by the ethanol extract (0.121 mol gallic acid/mol DPPH). Contact time was shown to have only a slight influence in alcoholic extraction, while in water a remarkable effect of increasing contact times (30-90 min) was observed. Just water was the solvent that offered the best result when the antioxidant power was measured by the TBARS method. High-performance liquid chromatography-mass spectrometry analysis revealed the presence of polyphenols, basically flavonols and flavanols, sometimes glycosilated; myricetin and quercetin glycosides were detected in all extracts, whereas epicatechin was present in alcoholic extracts and gallic acid was only present in water.  相似文献   

14.
Phenolic antioxidants are ranked by reducing strength and characterized for reversibility using cyclic voltammetry at a glassy carbon electrode. Phenolics with an ortho-diphenol group show a first oxidation peak close to 400 mV (vs. Ag/AgCl) in a model wine solution (12% ethanol, 0.033 M tartaric acid, adjusted to pH 3.6), with a linear concentration dependence below 0.01 mM. Dilution of white wines 10x, and red wines 400x, gave first oxidation peak currents in the 1.5 to 2.2 microA range and 1.9 to 3.4 microC of charge passed by 500 mV, producing values for the concentrations of phenolic antioxidants with low oxidation potentials in the wines. Further peaks in the cyclic voltammograms of the diluted wines correspond to classes of phenolics with higher oxidation potentials, providing a qualitative assessment of wine phenolics based on reducing strength.  相似文献   

15.
16.
The relationship among antioxidant activity, based on the electron-spin resonance determination of the reduction of Fremy's radical, vasodilation activity, and phenolic content was investigated in 16 red wines. The wines were selected to provide a range of origins, grape varieties, and vinification methods. Sensitive and selective HPLC methods were used for the analysis of the major phenolics in red wine: free and conjugated myricetin, quercetin, kaempferol, and isorhamnetin; (+)-catechin, (-)-epicatechin, gallic acid, p-coumaric acid, caffeic acid, caftaric acid, trans-resveratrol, cis-resveratrol, and trans-resveratrol glucoside. Total anthocyanins were measured using a colorimetric assay. The total phenolic content of the wines was determined according to the Folin-Ciocalteu colorimetric assay and also by the cumulative measurements obtained by HPLC. The 16 wines exhibited a wide range in the values of all parameters investigated. However, the total phenol contents, measured both by HPLC and colorimetrically, correlated very strongly with the antioxidant activity and vasodilation activity. In addition, the antioxidant activity was associated with gallic acid, total resveratrol, and total catechin. In contrast, only the total anthocyanins were correlated with vasodilation activity. The results demonstrate that the different phenolic profiles of wines can produce varying antioxidant and vasodilatant activities, which opens up the possibility that some red wines may provide enhanced health benefits for the consumer.  相似文献   

17.
Typical components of the Mediterranean diet, such as olive oil and red wine, contain high concentrations of complex phenols, which have been suggested to have an important antioxidant role. The aim of the present work was to determine the inhibitory potency of compounds such as oleuropein, hydroxytyrosol, and other structurally related compounds, such as gallic acid, toward reactive oxygen species generation and free radical scavenging ability. The potency of these compounds was also examined with respect to protecting in vitro low-density lipoprotein oxidation. These studies indicate that complex phenols, such as hydroxytyrosol, and gallic acid both inhibit free radical generation and act as free radical scavengers. The use of three different approaches to determine antioxidant potency demonstrates that activity in one test does not necessarily correlate with activity in another. It was also demonstrated that the presence of two phenolic groups is not always associated with antioxidant activity.  相似文献   

18.
Hexagonal mesoporous silica modified with carboxylic acid (SiAc) has been obtained by reaction between chloroacetic acid and 3-aminopropyltrimethoxysilane, which was immobilized on porous material by a sol-gel process in the presence of an n-dodecylamine template. SiAc was characterized by TG, FT-IR, (29)Si NMR, (13)C NMR, SEM, surface charge density, surface area and porous diameter, which proved that the carboxylic group was chemically bonded to an inorganic structure, and the material presented a nanometric structure with spheres <50 nm and porous diameter of 10 nm. Herbicides 2,4-D and picloram were anchored on SiAc porous gel to produce the materials named SiD and SiPi, respectively. The controlled release of picloram from the SiAc was less than that of 2,4-D. After 26 days of releasing, 4.43 × 10(-5) mol L(-1) of picloram was delivered by SiPi, and 5.0 × 10(-5) L(-1) was released from the SiD in 30 days.  相似文献   

19.
Glutathione was assessed individually, and in combination with ascorbic acid, for its ability to act as an antioxidant with respect to color development in an oxidizing model white wine system. Glutathione was utilized at concentrations normally found in wine (30 mg/L), as well as at concentrations 20-fold higher (860 mg/L), the latter to afford ascorbic acid (500 mg/L) to glutathione ratios of 1:1. The model wine systems were stored at 45 °C without sulfur dioxide and at saturated oxygen levels, thereby in conditions highly conducive to oxidation. Under these conditions the results demonstrated the higher concentration of glutathione could initially provide protection against oxidative coloration, but eventually induced color formation. In the period during which glutathione offered a protective effect, the production of xanthylium cation pigment precursors and o-quinone-derived phenolic compounds was limited. When glutathione induced coloration, polymeric pigments were formed, but these were different from those found in model wine solutions without glutathione. In the presence of ascorbic acid, high concentrations of glutathione were able to delay the decay in ascorbic acid and inhibit the reaction of ascorbic acid degradation products with the wine flavanol compound (+)-catechin. However, on depletion, the glutathione again induced the production of a range of different polymeric pigments. These results highlight new mechanisms through which glutathione can offer both protection and spoilage during the oxidative coloration of a model wine.  相似文献   

20.
Tomato (Lycopersicon esculentum Mill.), one of the most important crops worldwide, contains different classes of substances with antioxidant properties such as carotenoids, vitamin C, and phenolics. A method based on capillary electrophoresis with electrochemical detection has been developed to analyze ascorbic acid and phenolics in the peel, pulp, and seeds of tomatoes. Operating in a wall-jet configuration, a 300 microm diameter carbon disk electrode was used as the working electrode, which exhibits a good response at +0.90 V (vs saturated calomel electrode) for the analytes. Under optimum conditions, the analytes were baseline separated within 20 min in a 50 mmol/L borate buffer (pH 8.7). Notably, excellent linearity was obtained over 3 orders of magnitude with detection limits (S/N=3) ranging from 1x10(-8) to 2x10(-7) g/mL for all analytes. This proposed method has been successfully applied to monitor the content of ascorbic acid and phenolics in real samples, and the assay results were satisfactory.  相似文献   

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