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Given the importance of identifying the presence of biomarkers of human diseases in DNA samples, the main objective of this work was to investigate, for the first time, the electro-catalytic oxidation of 7-methyl-guanine (7-mGua) and 5-methyl-cytosine (5-mCyt) on a boron doped diamond electrode pre-treated cathodically (red-BDDE), using differential pulse voltammetry (DPV) and cyclic voltammetry (CV). The anodic peak potentials of 7-mGua and 5-mCyt by DPV were at E = 1.04 V and E = 1.37 V at pH = 4.5, indicating excellent peak separation of approximately 330 mV between species. Using DPV, experimental conditions such as supporting electrolyte, pH and influence of interferents were also investigated to develop a sensitive and selective method for individual and simultaneous quantification of these biomarkers. The analytical curves for the simultaneous quantification of 7-mGua and 5-mCyt in the acid medium (pH = 4.5) were: concentration range of 0.50-5.00 µmol L-1 (r = 0.999), detection limit of 0.27 µmol L-1 for 7-mGua; from 3.00 to 25.00 µmol L-1 (r = 0.998), with a detection limit of 1.69 µmol L-1 for 5-mCyt. A new DP voltammetric method for the simultaneous detection and quantification of biomarkers 7-mGua and 5-mCyt using a red-BDDE is proposed.
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5-Metilcitosina , Boro , Humanos , Oxidación-Reducción , Electrodos , GuaninaRESUMEN
The present study reports, for the first time, the development and application of a highly efficient method based on digital imaging analysis for the simultaneous determination of Cu2+ and furfural in cachaça samples using a two-phase system and chemometrics tools. Furfural reacts with aniline in an acidic medium to form a Schiff base, which exhibits a pink color. On the other hand, Cu2+ reacts with cuprizone in a basic medium to form a blue complex. The two reactions were performed on a porcelain plate, and a smartphone was used to capture the colorimetric images. Partial least squares (PLS) regression was used to construct the prediction models for Cu2+ and furfural contents in cachaça samples. After finding the best PLS models, the ordered predictor selection (OPS) analysis was performed in order to select the most predictive variables. The method developed was found to be effective in estimating the amounts of Cu2+ and furfural in cachaça samples, with a mean absolute error of 0.2 mg L-1 for the Cu2+ model, and 0.3 mg per 100 mL of anhydrous alcohol for the furfural model. The method proposed in this study is simple and straightforward; it does not require complex technical knowledge and can be used by the producers themselves in the cachaça manufacturing process.
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The present work describes a laboratory-on-a-drone (Lab-on-a-Drone) developed to perform in situ detection of contaminants in environmental water samples. Toward this goal, the system was mounted on an unmanned aerial vehicle (UAV) (drone) and remotely controlled via Wi-Fi to acquire a water sample, perform the electrochemical detection step, and then send the voltammetry data to a smartphone. This Lab-on-a-Drone system was also able to recharge its battery using a solar cell, greatly increasing the autonomy of the system, even in the absence of a power line. As a proof of concept, the Lab-on-a-Drone was employed for the detection of Pb2+ in environmental waters, using a simple electrochemical cell containing a miniaturized screen-printed boron-doped diamond electrode (SP-BDDE) as a working electrode, an Ag/AgCl as a reference electrode, and a graphite ink as a counter electrode. For quantification purposes, analytical curves were constructed covering a concentration range from 1.0 µg L-1 (4.83 nmol L-1) to 80.0 µg L-1 (386.10 nmol L-1), featuring a detection limit of 0.062 µg L-1 (0.30 nmol L-1). The Lab-on-a-Drone was applied to monitor a water reservoir in the Metropolitan Region of Recife, Brazil. To evaluate its performance regarding accuracy and precision, a reference method based on inductively coupled plasma optical emission spectrometry (ICP-OES) was applied, and the results obtained by both methods showed no statistical differences (t-test at 95% confidence level, n = 3). These results represent the first demonstration of the capabilities of an adapted UAV for the quantification of electroactive environmental contaminant using voltammetry, with real-time data transmission. Thus, the Lab-on-a-Drone makes it possible to reach difficult-to-access environmental reserves and to monitor potentially polluting activity in distant water bodies. Thus, this tool can be used by governments and non-profit organizations to monitor environmental waters using fast, low-cost, process autonomy with accurate and precise data useful to decision making.
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For the first time, a method is proposed for colorimetric determination of reducing sugars in cachaça employing digital image and a smartphone as detector. The method was based on the reduction of Cu(II) to Cu(I) by sugars and followed by the formation of a colored Cu(I)-Neocuproine complex. A calibration curve was linear from 0.1 to 15 g L-1 for glucose and fructose with limits of detection of 0.012 g L-1 and 0.010 g L-1, respectively. It was observed that the non-aged cachaças, known for having inferior flavors and aromas, had a reducing sugar content three times higher than the aged cachaças, once a common practice among producers is to add sugar to adjust sensory deficits in the final product. Furthermore, the method is simple, does not require complex technical knowledge and it could be used as a tool to check possible fraud, adulteration or non-compliance to the law.
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Bebidas Alcohólicas/análisis , Análisis de los Alimentos/instrumentación , Análisis de los Alimentos/métodos , Teléfono Inteligente , Azúcares/análisis , Colorimetría/instrumentación , Colorimetría/métodos , Cobre/química , Diseño de Equipo , Contaminación de Alimentos/análisis , Fructosa/análisis , Glucosa/análisis , Fenantrolinas/química , SaccharumRESUMEN
Aqueous extract of macerated Vochysia rufa stem bark has been commonly used in the treatment of diabetes. Therefore, we evaluated the antihyperglycemic and antioxidant effects of an extract of V. rufa on the pancreata of streptozotocin (STZ)-induced diabetic rats. Animals received one of the following treatments daily by oral gavage: water (diabetic-control), V. rufa extract (diabetic-V. rufa), or glibenclamide (diabetic-GBD). Total antioxidant capacity; levels of thiobarbituric acid reactive substances, reduced glutathione, and sulfhydryls; and superoxide dismutase, catalase, and glutathione peroxidase (GPx) activities were measured in the pancreas. Biochemical analysis of serum total cholesterol and fractions, triglycerides, creatinine, urea, acid uric, ALP, γ-GT, AST, and ALT was performed, and pancreatic ß-cells positive for insulin were evaluated by immunohistochemistry. Rats treated with extract exhibited a decrease in fasting blood glucose compared with levels in diabetic control rats. GPx activity and sulfhydryl levels were significantly lower in diabetic-V. rufa rats compared with those of diabetic-control rats. V. rufa extract acted to normalize the biochemical alterations found in diabetic rats (diabetic-controls), as demonstrated by increases in urea, HDL, ALP, AST, and ALT. Reduction in blood glucose was independent of an increase in insulin. The V. rufa extract was found to be composed of free sugars (inositol, galactose, glucose, mannose, sucrose, arabinose, and ribose) as the main metabolites. Thus, aqueous extract of the stem bark of V. rufa is capable of reducing blood glucose, resulting in an antioxidant effect on the pancreatic tissue of STZ-diabetic rats.
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Antioxidantes/farmacología , Diabetes Mellitus Experimental/metabolismo , Magnoliopsida , Estrés Oxidativo/efectos de los fármacos , Páncreas/efectos de los fármacos , Fitoterapia , Extractos Vegetales/farmacología , Animales , Glucemia , Peso Corporal/efectos de los fármacos , Catalasa/metabolismo , Glutatión/metabolismo , Masculino , Páncreas/metabolismo , Ratas , Ratas Wistar , Superóxido Dismutasa/metabolismo , Sustancias Reactivas al Ácido Tiobarbitúrico/metabolismoRESUMEN
Hemiesters of carbonic acid can be freely formed in aqueous media containing HCO3(-)/CO2 and mono- or poly-hydroxy compounds. Herein, (13)C NMR spectroscopy was used to identify isomers formed in aqueous solutions of glycerol (a prototype compound) and seven carbohydrates, as well as to estimate the equilibrium constant of formation (Keq). Although both isomers are formed, glycerol 1-carbonate corresponds to 90% of the product. While fructose and ribose form an indistinct mixture of isomers, the anomers of d-glucopyranose 6-carbonate correspond to 74% of the eight isomers of glucose carbonate that were detected. The values of Keq for the disaccharides sucrose (4.3) and maltose (4.2) are about twice the values for the monosaccharides glucose (2.0) and fructose (2.3). Ribose (Keq = 0.89)-the only sugar without a significant concentration of a species containing a -CH2OH group in an aqueous solution-resulted in the smallest Keq. On the basis of the Keq value and the concentrations of HCO3(-) and glucose in blood, one can anticipate a concentration of 2-4 µmol L(-1) for glucose 6-carbonate, which corresponds to ca. of 10% of its phosphate counterpart (glucose 6-phosphate).
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Carbohidratos/química , Ácido Carbónico/química , Ésteres/síntesis química , Espectroscopía de Resonancia Magnética con Carbono-13/métodos , Ésteres/química , Glicerol/química , Isomerismo , Estructura Molecular , Agua/químicaRESUMEN
In order to reduce the sample consumption and waste generation for electrochemical purposes, a screen-printed electrode (SPE) used for electrodeposition of bismuth film (SPE-BiFE) and a thermostated electrochemical flow cell (EFC) were developed. The SPE-BiFE with the EFC was employed to determine Cd(2+) and Pb(2+) ions in natural, wastewater and tap water samples by square-wave anodic stripping voltammetry (SWASV). For this, the flow-batch analysis (FBA) approach based on solenoid micro-pumps and three-way valves was developed to carry out a fully automated procedure with temperature control. Furthermore, the FBA and the SWASV parameters were optimized, on line simultaneous determination of Cd(2+) and Pb(2+) ions was performed and two analytical curves were linearly acquired in the concentration ranges from 6.30 to 75.6µg L(-1) and from 3.20 to 38.4µg L(-1), respectively. Moreover, limits of detection of 0.60µg L(-1) and 0.10µg L(-1) for Cd(2+) and Pb(2+), respectively, were obtained. Studies of precision for the same SPE-BiFE and repeatability for five built SPE-BiFE were carried out for Cd(2+) and Pb(2+) ion measurements and RSD of 4.1% and 2.9% (n=3) with repeatabilities (n=5) of 6.5% and 8.0% were respectively obtained for both analytes. Besides, a low consumption of 700µL of reagents and a sampling frequency of 13h(-1) were acquired. Simplicity, fast response, accuracy, high portability, robustness and suitability for in loco analyses are the main features of the proposed electroanalytical method.