Vitis vinifera L. cv Pinot noir pomace and lees as potential sources of bioactive compounds.

Food and agricultural industries generate substantial quantities of phenolic-rich by-products that could be valuable natural sources of antioxidants. The aim of this study was to identify and quantify the phenolic compounds and radical scavenging activities of two by-products (pomace and lees) from Vitis vinifera L. cv Pinot noir. We found a different distribution of phenolic classes (flavanols, flavonols, phenolic acids and stilbenes) and singular scavenging activity against free radicals (hydroxyl, superoxide and peroxyl radicals). The major class of phenolics in pomace was flavanols and in lees was flavonols, with catechin (117.9 ± 2.5 µg g(-1)) and quercetin (42.4 ± 1.2 µg g(-1)) being the most abundant individual compounds. We also found high potential on scavenging activity against superoxide radicals in pomace (80% of scavenging activity) and radical peroxyl (67% scavenging activity). These results show the possibility of using Pinot noir by-products as promising additives or as a source for the development of new products in different segments of the food and cosmetic industries.

Capillary electrophoretic methods for the screening and determination of pharmacologic adulterants in herbal-based pharmaceutical formulations.

This review aims to describe the CE methods utilized for the determination of adulterants in herbal-based formulations marketed for different therapeutic purposes. The CE methods for screening and determination of pharmacologic adulterants are reviewed on the basis of the CE techniques and their detection methods. CZE and MEKC methods coupled to optical (UV), capacitively coupled contactless conductivity, and MS detection modes are discussed and reviewed. Worldwide adulteration cases related to pharmaceutical formulations containing herbs as the main active products are presented covering all the works published in the last four decades.

Investigation of thallium as a contaminant in dietary supplements marketed for weight loss and physical fitness.

Dietary supplements are drastically growing as a category of consumer products all over the world. The abuse of supplements marketed for slimming purposes and physical fitness has been observed worldwide in recent years, which raises concerns in terms of public health. In this study, different types of dietary supplements marketed and delivered through the e-commerce were studied for the determination of thallium as a hazardous inorganic contaminant. The total content of thallium was determined by a sensitive voltammetric method after a microwave-assisted oxidative digestion of the sample. In addition, a comparative spectrometric method was applied for validation of the results in the samples. The maximum concentration found for thallium was found to be 2.89 mg kg-1, which well agree with the comparative measurement. Considering the 32 studied formulations, it can be pointed out that ∼24% of the of dietary supplements presented Tl concentrations at concentrations higher than 1 mg kg-1. The results permitted the assessment of the health risk related to thallium from contaminated samples, based on the calculation of the estimated daily intake (EDI) and the risk quotient (HQ). The highest daily intake of thallium was calculated as 82.0 µg day-1 in a protein-based supplement, which is equivalent to an EDI of 1.17 µg kg-1 day-1. This work highlights the need to develop regulations on the limits of toxic elements such as thallium in widely consumed dietary supplements, as well as an in-depth look at the adverse effects caused by this element in the human body.

Aluminum in erythropoietin formulations: lyophilized versus liquid forms.

BACKGROUND: Erythropoietin (EPO) formulations may comprise aluminum (Al) as a contaminant. Due to the toxicity of Al in chronic kidney disease patients, possible sources of Al were investigated. Since EPO formulations are stored in container-closure systems made of glass and rubber, and both contain Al, formulation ingredients may enable its leaching into the solution during shelf-life. METHODS: Individual solutions of formulation ingredients were stored in new glass vials and in contact with the rubber stopper and kept at 4 ± 2 °C. For 12 months, aliquots of each solution were collected for analysis. Fifteen commercial samples of EPO were analyzed for their Al content. Aluminum was determined by atomic absorption spectrometry. RESULTS: Glass and rubber are sources of Al for EPO formulations. Storage assay showed that citrate and phosphate (used as buffers) extracted high amounts of Al from the container/closure parts. The most important difference, however, was found when comparing liquid and lyophilized samples. While in liquid forms the Al level reached 943 µg/L, in lyophilized forms the level did not exceed 20 µg/L. The container system was also confirmed as a source of Al in reconstituted lyophilized samples. Al in reconstituted samples stored in their own vials increased 19-fold in 12 months. Lyophilized powders stored for 2 years in glass vials contained less Al than in 1 month after dissolution. CONCLUSION: The difference in the Al measured in liquid forms of EPO and in lyophilized powders suggests that the latter would be the best pharmaceutical form for CKD patients.

Role of medication in the level of aluminium in the blood of chronic haemodialysis patients.

BACKGROUND: Although dialysis facilities provide high-quality water, abnormal aluminium levels among patients on haemodialysis have still been reported. Since patients with chronic kidney disease are often on multiple medications, medicines may be an extra source of aluminium for them. The degree to which ingesting contaminated medication influenced the level of aluminium in the patients' blood was investigated. METHODS: All medications consumed by a group of patients on regular dialysis treatment were analysed and the total aluminium ingested by each patient was calculated. At the same time, the patients' blood was collected and aluminium was measured. The analyses were carried out by atomic absorption spectrometry. RESULTS: For all drugs consumed, the amount of aluminium ingested versus the blood aluminium level presented no correlation. Since a high level of contamination was presented by injectable iron, insulin and erythropoietin (EPO), another group of patients that received a reduced amount of oral medication was selected. Among them, eight did not receive any injectable drug, five received only EPO and seven injectable iron, EPO and insulin. With these restricted groups, it was possible to show that the injectable administration of contaminated medication increased the Al level in the patients' blood, mainly in relation to iron formulations. CONCLUSION: Among the medications investigated, the injectables are the most significant source of aluminium for patients with renal insufficiency. This extra aluminium intake is reflected in higher aluminium levels in the patients' blood.

Performance of polymeric materials for solid phase extraction prior to chromatographic analysis.

Synthetic polymeric materials such as polyethylene and polyurethane (PU) were compared to conventional adsorbents for solid phase extraction for cleaning up biological samples. Efficiency in eliminating proteins and other components usually present in biological samples, such as serum, urine, and tissues extracts, was evaluated. The assays consisted of measuring the remaining protein content in serum and tissue homogenates (liver) and collecting the spectra in the UV region for urine samples. Since the analysis of many endogenous and exogenous species in these matrices usually involves chromatographic separation, the efficiency of the clean-up procedures was also evaluated by injecting cleaned samples into a C-18 chromatographic column with UV detection. Among the investigated polymers, polytetrafluorethylene, high density polyethylene (HDPE) and ultra-high molecular weight polyethylene (UHMWPE) presented the best performance in retaining serum proteins. Proteic components of the liver homogenate were completely retained on polyurethane and polybutadiene (PB). Urine samples were cleaned by crossing columns of polytetrafluorethylene, ultra-high molecular weight polyethylene, high density polyethylene, polyurethane, and polyethylene co-butyl acrylate co-anhydride maleic (PEco), since the spectra collected after column percolation presented no peaks in the region between 190 and 390 nm. SPE cartridges showed different behavior, but along the lines of their usual performance; neither serum proteins nor urine components were retained on the phases and the liver components, though partially retained, were not desorbed with either water or methanol washes, with the exception of SAX. Chromatograms of samples cleaned with high density polyethylene showed that polymeric materials can be satisfactorily used as adsorbent for biological matrix components.

Detection and determination of undeclared synthetic caffeine in weight loss formulations using HPLC-DAD and UHPLC-MS/MS.

Caffeine is present in products marketed for weight loss, with the purpose of increasing thermogenesis and lipid metabolism. The dosage declared by the product manufacturer, or even its presence, is not always correctly described on the label. This work aimed to investigate the undeclared synthetic caffeine in weight loss formulations by a high-performance liquid chromatography with diode array detection (HPLC-DAD) method. From one hundred products purchased through Brazilian e-commerce, seventeen contained caffeine, either naturally or synthetically added to formulation. The caffeine-containing samples were confirmed by an ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method, and adulteration was clearly proven in five products. The content highest caffeine contained 448.8 mg per dose. Other irregularities were also found; nevertheless, the most serious was the addition of synthetic drugs without asking the consumers. Additional drugs expose the consumer to more possible side-effects as well as deleterious drug interactions. Intentional adulteration with any unlabeled substance is typically motivated by a desire to increase or alter the claimed effect of the marketed product to gain a commercial advantage.

Presence of Polycyclic Aromatic Hydrocarbons in Rubber Packaging Materials and in Parenteral Formulations Stored in Bottles With Rubber Stoppers.

BACKGROUND: Rubber closures are the primary packaging material for sterile preparations intended for repeated use. Important features of rubber closures are achieved after additives are added to the elastomeric material that compounds the rubber. Among these additives is carbon black. Because of its origin, carbon black may contain polycyclic aromatic hydrocarbons (PAHs). The U.S. Environmental Protection Agency has identified 16 priority PAHs on the basis of concerns that they cause or might cause cancer in animals and humans. Regulatory agencies impose carbon black purity specifications based on limits for total PAHs (0.5 mg/kg) and benzo[a]pyrene (5 µg/kg) or benzo[a]pyrene only (250 µg/kg). PAHs in rubber packaging used for pharmaceutical formulations and in parenteral products stored in containers with rubber stoppers were investigated. METHODS: To this end, the method proposed by the National Institute for Occupational Safety and Health-based on high-performance liquid chromatography with ultraviolet and fluorescence detection-was adapted to determine the levels of PAHs in rubber stoppers (gray and red) and in lipid emulsions and amino acid solutions stored in bottles with rubber stoppers. RESULTS: The rubber materials were shown to contain 12 PAHs, in concentrations ranging from 0.25-3.31 µg/g. Only 1 of 18 samples (11 amino acid solutions and 7 lipid emulsions) was uncontaminated. The most prevalent contaminants were pyrene, benzo[a]pyrene, and fluoranthene. The total PAH concentrations in the samples ranged from 0.11-5.96 µg/mL. CONCLUSION: Components of parenteral nutrition may be contaminated with PAHs, and rubber stoppers represent a potential source of these contaminants.

Liquid chromatographic determination of caffeine and adrenergic stimulants in food supplements sold in Brazilian e-commerce for weight loss and physical fitness.

Methyl-xanthines and adrenergic stimulants, such as caffeine and synephrine, are commonly added to food supplements due to their stimulating and thermogenic effects. In addition, the abusive consumption of food supplements with ergogenic and aesthetic purposes has been observed worldwide. This work describes the study of caffeine, p-synephrine, hordenine, octopamine, tyramine, ephedrine and salicin as stimulants in dietary supplements marketed in Brazil for weight loss and physical fitness claims. A total of 94 different products were acquired from 30 Brazilian websites. Thus, the sampling of marketed supplements was performed in virtual commerce (e-commerce) with claims of weight loss, appetite reduction, fat burning and metabolism acceleration. The developed analytical method involved the separation of the stimulants by HPLC with diode array detection (HPLC-DAD) by using a gradient elution of flow rate (0.7-2.5 ml min(-1)) and mobile phase composition (0.1% H3PO4/methanol). The validated method was applied to the study of 46 dietary supplements. Caffeine, p-synephrine and ephedrine were found to be present as stimulants in 52% of the studied samples marketed as encapsulated or bulk forms. Caffeine was found to be present in concentrations that represent doses from 25.0 to 1476.7 mg day(-1). Synephrine was found in concentrations that represent doses from 59.1 to 127.0 mg day(-1). Ephedrine was found to be associated with caffeine in one formulation at a concentration representing a 26.1 mg day(-1) dosage.

Sulfur speciation by capillary zone electrophoresis. Determination of dithionite and its decomposition products sulfite, sulfate and thiosulfate in commercial bleaching agents.

In this paper, a capillary zone electrophoretic (CZE) method was developed for the separation of the sulfur species dithionite (S2O4(2-)), sulfite (SO3(2-)), sulfate (SO4(2-)) and thiosulfate (S2O3(2-)). A carrier electrolyte (pH 7.0) containing 1.5 mmol L(-1) pyromellitic (PM) acid, 10 mmol L(-1) Tris(hydroxymethyl)-aminomethane (Tris), 0.5 mmol L(-1) diethylenetriamine (DETA) and 0.1% (v/v) formaldehyde (as stabilizer for S2O4(2-) and SO3(2-)) allowed the determination of the sulfur anions after 9 min CZE separation with indirect UV detection at 214 nm. The addition of 0.1% (v/v) formaldehyde to the sample solution stabilizes dithionite and sulfite as HOCH2SO2- and HOCH2SO3- anions. The procedure was applied for the determination of dithionite and its decomposition products sulfite, sulfate and thiosulfate in commercial formulations of bleaching agents. Dithionite was found to be the major component of the commercial formulations in concentrations between 30.80 and 33.30% (w/w). As anticipated, sulfite, sulfate and thiosulfate were found to be present as decomposition or by-products in the commercial formulations at concentrations of 14.30-14.80, 5.20-5.70 and 0.30-0.40% (w/w), respectively. The results were found to be in good agreement with those of polarographic and spectrophotometric determinations.

Comparison of ultrafiltration and solid phase extraction for the separation of free and protein-bound serum copper for the Wilson's disease diagnosis.

BACKGROUND: The determination of the ratio free/protein-bound serum copper along with urinary copper can be used as a preliminary test for the Wilson's Disease diagnosis. In this work, the determination of these copper fractions in serum samples was carried out in two different ways; after separation of the copper bound to proteins from the free fraction by a column for protein adsorption and by ultrafiltration. As proteins can be adsorbed onto plastic polymeric surfaces, polyethylene (PE) with different molecular weights in powder form was investigated for protein adsorption. A small column was adapted in a flow system to carry out a solid-phase extraction (SPE) on-line. Preliminary experiments defined conditions for protein retention and elution and column saturation. Good performance was achieved using Mg(NO3)2 solution as carrier and methanol as eluent. The presence of proteins in both fraction (column effluent and eluate) was checked by the Coomassie Brilliant Blue test. Copper was measured by graphite furnace atomic absorption spectrometry. The measurement in the column effluent furnished the free-fraction of copper while the copper measured in the eluate the bound-fraction. The method was compared with ultrafiltration (20 kDa), measuring the free-copper in the ultrafiltrate. For the determination of protein-bound copper, the copper found in the ultrafitrate was discounted from the total copper measured in the sample. RESULTS: Serum samples of 10 individuals were analyzed by both methods with good agreement of the results. The regression plots, obtained by analysing the samples by both methods, presented r2 and slope of 0.97 and 0.96 for free copper and 1.00 and 1.00 for bound copper, respectively. Protein-bound copper (PB) concentrations ranged from 74 to 2074 microg/l and free-copper (F) from 22 to 54 microg/l. The ratio F/PB, calculated from SPE data, was 29.7% for one individual, with Wilson Disease well-characterized, and ranged from 1.2% to 5.2% for the others. CONCLUSION: The SPE method performed well in terms of accuracy and precision, and showed good agreement with the UF. Advantages of SPE are small sample volume (50 microl), separation carried out in 10 min, and the use of the same column for several analyses.

High-performance liquid chromatographic analysis of biogenic amines in pharmaceutical products containing Citrus aurantium.

A reverse-phase (RP)-HPLC method is reported for determining L-tyrosine, p-octopamine, synephrine, tyramine and hordenine as chemical markers of the species Citrus aurantium in raw material, dry extracts and phytotherapeutic herbal formulations. Using RP-HPLC with diode array detection (DAD) and gradient elution, the amines were determined in 12 different products from different Brazilian states labelled as containing C. aurantium. The presence of the amines was confirmed by mass spectrometry using electrospray ionisation (ESI-MS/MS). This RP-HPLC method allowed the separation of the amines from complex mixtures containing caffeine, ephedrine, salicin and other raw materials (e.g. Garcinia camboja, Phaseolus vulgaris, Caralluma fimbriata, Cassia nomane, Ephedra sp. and Cordia ecalyculata). The method proved useful and selective for inspecting herbal medicines containing p-synephrine and structural analogues. The herbal products analysed had a p-synephrine content ranging from 0.005 to 4.0% (w/w).

Triterpene 3ß, 6ß, 16ß trihidroxilup-20(29)-ene protects against excitability and oxidative damage induced by pentylenetetrazol: the role of Na(+),K(+)-ATPase activity.

Administration of the compound triterpene 3ß, 6ß, 16ß-trihidroxilup-20(29)-ene (TTHL) resulted in antinociceptive activity in several pain models in mice. Because pain and epilepsy have common mechanisms, and several anticonvulsants are clinically used to treat painful disorders, we investigated the anticonvulsant potential of TTHL. Behavioral and electrographic recordings revealed that pretreatment with TTHL (30 mg/kg; i.g.) increased the latencies to the first clonic seizure to the tonic-clonic and reduced the duration of the generalized seizures induced by the GABA(A) receptor antagonist PTZ (80 g; i.p.). The TTHL pretreatment also protected against PTZ-induced deleterious effects, as characterized by protein carbonylation, lipid peroxidation, [(3)H] glutamate uptake and the inhibition of Na(+),K(+)-ATPase (subunits α(1) and α(2)/α(3)). Although TTHL did not exhibit DPPH, ABTS radical scavenging activity per se and does not alter the binding of [(3)H]flunitrazepam to the benzodiazepinic site of the GABA(A) receptor, this compound was effective in preventing behavioral and EEG seizures, as well as the inhibition of Na(+),K(+)-ATPase induced by ouabain. These results suggest that the protection against PTZ-induced seizures elicited by TTHL is due to Na(+),K(+)-ATPase activity maintenance. In fact, experiments in homogenates of the cerebral cortex revealed that PTZ (10 mM) reduced Na(+),K(+)-ATPase activity and that previous incubation with TTHL (10 µM) protected against this inhibition. Collectively, these data indicate that the protection exerted by TTHL in this model of convulsion is not related to antioxidant activity or GABAergic activity. However, these results demonstrated that the effective protection of Na(+),K(+)-ATPase elicited by this compound protects against the damage due to neuronal excitability and oxidation that is induced by PTZ.

Aqueous extract of pecan nut shell (Carya illinoensis [Wangenh.] K. Koch) exerts protection against oxidative damage induced by cyclophosphamide in rat testis.

This study investigated the protective effect of pecan nut (Carya illinoensis) shell aqueous extract (AE) on the oxidative and morphological status of rat testis treated with cyclophosphamide (CP). Wistar rats received water or AE (5%) ad libitum for 37 days. On day 30, half of each group received a single intraperitoneal administration of vehicle or CP 200 mg/kg. After 7 days, the animals were killed and their testis removed. Rats treated with CP presented reduced levels of lactate dehydrogenase, vitamin C, and gluthatione, as well as decreased catalase activity, increased lipid peroxidation levels and superoxide dismutase activity, no alteration in carbonyl protein levels, and a loss of morphological testicular integrity. In contrast, cotreatment with pecan shell AE totally prevented the decrease of lactate dehydrogenase and vitamin C levels and catalase activity and partially prevented the depletion of gluthatione levels. Moreover, it totally prevented the increase in superoxide dismutase activity and lipid peroxidation levels and maintained testicular integrity. These findings show the protective role of pecan shell AE in CP-induced testicular toxicity. The use of this phytotherapy may be considered to minimize deleterious effects related to this chemotherapy.

Chromatography and atomic absorption spectrometry for the assessment of heavy metal distribution among amino acids used in parenteral nutrition formulations-studies with cadmium and lead.

The distribution of Cd (II) and Pb (II) among amino acids in parenteral nutrition formulations was investigated by coupling ion-chromatography (HPLC/IC) and electrothermal atomic absorption spectrometry. The methodology was based on ion-exchange separation and fluorimetric amino acid detection after post-column derivatization. Cd (II) and Pb (II) were assayed in 500-µL fractions of the column effluent. The distribution of Cd (II) and Pb (II) in alanine (Ala), aspartic acid (Asp), glutamic acid (Glu), glycine (Gly), histidine (His), methionine (Met), phenylalanine (Phe), serine (Ser), and threonine (Thr) were analyzed by monitoring changes in the concentration of free amino acids by HPLC/IC. The results indicated that Cd (II) and Pb (II) were distributed according to the following trend: Gly-Cd > Gly-Pb > Ala-Cd > Ala-Pb > His-Cd ∼ His-Pb > Thr-Cd > Thr-Pb > Phe-Cd ∼ Phe-Pb ∼ Asp-Cd ∼ Asp-Pb ∼ Met-Cd ∼ Met-Pb ∼ Glu-Cd ∼ Glu-Pb > Ser-Cd ∼ Ser-Pb. The effects of amino acid concentration and stability constants of amino acid-metal complexes are discussed.

Evidence for aluminum-binding erythropoietin by size-exclusion chromatography coupled to electrothermal absorption atomic spectrometry.

Erythropoietin (EPO) is a glycoprotein that stimulates erythropoiesis and is clinically used for treating anemia during chronic renal failure and for anemia in preterm infants. EPO formulations usually have elevated rates of contamination due to aluminum (Al), which is toxic to both types of patients. Size-exclusion chromatography (SEC) coupled with graphite furnace atomic absorption spectrometry (GF AAS) was employed to separate proteins and to quantify the amount of aluminum present in the elution volume corresponding to EPO and, therefore, to evaluate possible binding. Because EPO formulations contain human serum albumin (HSA), a chromatographic method was optimized for the separation of these proteins. Subsequent to the chromatographic separation, 1-mL fractions of the column effluent were collected, and the Al content in these aliquots was measured by GF AAS. EPO and HSA samples were incubated with Al for 4h at 4°C and 37°C as well as for 16 h at 4°C and 37°C. Afterwards, they were injected into the chromatographic system. These samples were also submitted to ultrafiltration (10 and 50 kDa membranes), and Al was measured in the ultrafiltrates. The results showed that Al was present in the eluent volume corresponding to the EPO peak but not in the HSA peak in the chromatograms. Temperature strengthened the interaction because the Al present in the EPO fraction was 3 times higher at 37°C compared to 4°C. Thirty-eight percent of the Al present in a 2.4 µg/mL EPO standard solution, and approximately 50% of the Al in formulation samples containing approximately 11 µg/mL EPO and either citrate or phosphate, were non-ultrafiltrable, which suggests that EPO is an effective Al acceptor in vitro.

Presence of synthetic pharmaceuticals as adulterants in slimming phytotherapeutic formulations and their analytical determination.

Obesity that is associated with a high consumption of slimming substances is considered a public health problem around the world. In this context, the increasing consumption of phytotherapeutic formulations as alternative obesity treatments has revealed the presence of synthetic pharmaceuticals as adulterants. The illegally added adulterants are frequently anorexic, anxiolytic, and antidepressant pharmaceuticals. This review aims to describe the analytical methodologies utilized for the determination of adulterants in slimming phytotherapeutic formulations. Furthermore, this review describes some important adulteration cases, which occurred mainly in Europe, Asia, Brazil, and the USA.

A new method for the simultaneous determination of 1,4-benzodiazepines and amfepramone as adulterants in phytotherapeutic formulations by voltammetry.

The use of synthetic pharmaceuticals in phytotherapeutics can be defined as an illegal practice, since these compounds are normally present as non-declared compounds in the phytotherapeutical formulations. This work aims to show the development of an analytical method based on adsorptive cathodic stripping voltammetry (AdCSV) for the simultaneous determination of 1,4-benzodiazepines and amfepramone. The developed method was used to measure seven benzodiazepines (clonazepam, flurazepam, alprazolam, midazolam, medazepam, chlordiazepoxide, and diazepam) and amfepramone in slimming formulations that have been commercialized in Brazil. This method permits the screening of adulterant classes in a single voltammetric run by using a hanging mercury drop electrode as a working electrode and Ringer buffer (pH 10.0) as a supporting electrolyte. Recovery values ranging from 92.0% to 117.0% demonstrate the reliability of the method in the determination of adulterants in real samples. Among the 12 samples studied by the proposed method, 4 were demonstrated to be adulterated by 1,4-benzodiazepines.

Nanostructured Systems Containing Rutin: In Vitro Antioxidant Activity and Photostability Studies.

The improvement of the rutin photostability and its prolonged in vitro antioxidant activity were studied by means of its association with nanostructured aqueous dispersions. Rutin-loaded nanocapsules and rutin-loaded nanoemulsion showed mean particle size of 124.30 ± 2.06 and 124.17 ± 1.79, respectively, polydispersity index below 0.20, negative zeta potential, and encapsulation efficiency close to 100%. The in vitro antioxidant activity was evaluated by the formation of free radical ·OH after the exposure of hydrogen peroxide to a UV irradiation system. Rutin-loaded nanostructures showed lower rutin decay rates [(6.1 ± 0.6) 10(-3) and (5.1 ± 0.4) 10(-3) for nanocapsules and nanoemulsion, respectively] compared to the ethanolic solution [(35.0 ± 3.7) 10(-3) min(-1)] and exposed solution [(40.1 ± 1.7) 10(-3) min(-1)] as well as compared to exposed nanostructured dispersions [(19.5 ± 0.5) 10(-3) and (26.6 ± 2.6) 10(-3), for nanocapsules and nanoemulsion, respectively]. The presence of the polymeric layer in nanocapsules was fundamental to obtain a prolonged antioxidant activity, even if the mathematical modeling of the in vitro release profiles showed high adsorption of rutin to the particle/droplet surface for both formulations. Rutin-loaded nanostructures represent alternatives to the development of innovative nanomedicines.

Voltammetric determination of Se(IV) and Se(VI) in saline samples--studies with seawater, hydrothermal and hemodialysis fluids.

Determination of Se(IV) and Se(VI) in high saline media was investigated by cathodic stripping voltammetry (CSV). The voltammetric method was applied to assay selenium in seawater, hydrothermal and hemodialysis fluids. The influence of ionic strength on selenium determination is discussed. The CSV method was based on the co-electrodeposition of Se(IV) with Cu(II) ions and Se(VI) determined by difference after sample UV-irradiation for photolytic selenium reduction. UV-irradiation was also used as sample pre-treatment for organic matter decomposition. Detection limit of 0.030 microg L(-1) (240 s deposition time) and relative standard deviation (RSD) of 6.19% (n=5) for 5.0 microg L(-1) of Se(IV) were calculated. Linear calibration range for selenium was observed from 1.0 to 100.0 microg L(-1). Concerning the pre-treatment step, best results were obtained by using 60 min UV-irradiation interval in H(2)O(2)/HCl medium. Se(VI) was reduced to the Se(IV) electroactive species with recoveries between 91.7% and 112.9%. Interferents were also investigated.