An Alternative Method for the Simultaneous Determination of Copper and Lead for Quality Control of Sugar Cane Spirit using a Nanotube-Based Sensor

The development of an electroanalytical method for simultaneous determination of copper and lead ions in sugar cane spirit (cachaca) using carbon paste electrode modified with ascorbic acid and carbon nanotubes (CPE-AaCNT) is described. Squarewave voltammetry (SWV) with anodic stripping was employed, and this technique was optimized with respect to the following parameters: frequency (50 Hz), amplitude (100 mV) and scan increment (9 mV). The analytical curves were linear in the range from 0.0900 to 7.00 mg L-1 for lead and copper. The limits of detection were 48.5 and 23.9 mu g L-1 for lead and copper, respectively. The developed method was applied to the simultaneous determination of copper and lead in five commercial samples of sugar cane spirit. The results were in good agreement with those obtained by F AAS/GF AAS (flame atomic absorption spectrometry/graphite furnace atomic absorption spectrometry) and showed that CPE-AaCNT can be successfully employed in the simultaneous determination of these metals in real sugar cane spirit samples.

Development and validation of a simple and sensitive high performance liquid chromatographic method for the simultaneous determination of anastrozole, bicalutamide, tamoxifen, and their synthetic impurities

A simple and sensitive analytical method for simultaneous determination of anastrozole, bicalutamide, and tamoxifen as well as their synthetic impurities, anastrozole pentamethyl, bicalutamide 3-fluoro-isomer, and tamoxifen e-isomer, was developed and validated by using high performance liquid chromatography (HPLC). The separation was achieved on a Symmetry (R) C-8 column (100 x 4.6 mm i.d., 3.5 mu m) at room temperature (+/- 24 degrees C), with a mobile phase consisting of acetonitrile/water containing 0.18% N,N dimethyloctylamine and pH adjusted to 3.0 with orthophosphoric acid (46.5/53.5, v/v) at a flow rate of 1.0 mL min(-1) within 20 min. The detection was made at a wavelength of 270 nm by using ultraviolet (UV) detector. No interference peaks from excipients and relative retention time indicated the specificity of the method. The calibration curve showed correlation coefficients (r) > 0.99 calculated by linear regression and analysis of variance (ANOVA). The limit of detection (LOD) and limit of quantitation (LOQ), respectively, were 2.2 and 6.7 mu g mL(-1) for anastrozole, 2.61 and 8.72 mu g mL(-1) for bicalutamide, 2.0 and 6.7 mu g mL(-1) for tamoxifen, 0.06 and 0.22 mu g mL(-1) for anastrozole pentamethyl, 0.02 and 0.07 mu g mL(-1) for bicalutamide 3-fluoro-isomer, and 0.002 and 0.007 mu g mL(-1) for tamoxifen e-isomer. Intraday and interday relative standard deviations (RSDs) were <2.0% (drugs) and <10% (degradation products) as well as the comparison between two different analysts, which were calculated by f test. (C) 2012 Elsevier B.V. All rights reserved.

A new HPLC-DAD-MS/MS method for the simultaneous determination of major compounds in the crude extract of Lychnophora salicifolia Mart. (Brazilian arnicao) leaves: Application to chemical variability evaluation

Lychnophora salicifolia Mart., which occurs in the Brazilian Cerrado in the states of Bahia and Minas Gerais as well as in the southeast of the state of Goias, is the most widely distributed and also the most polymorphic species of the genus. This plant is popularly known to have anti-inflammatory and analgesic activities. In this work, we have studied the variation in terms of polar metabolites of ninety-three Lychnophora salicifolia Mart, specimens collected from different regions of the Brazilian Cerrado. Identification of the constituents of this mixture was carried out by analysis of the UV spectra and MS data after chromatographic separation. Twenty substances were identified, including chlorogenic acid derivatives, a flavonoid C-glucoside, and other sesquiterpenes. The analytical method was validated, and the reliability and credibility of the results was ensured for the purposes of this study. The concentration range required for analysis of content variability within the analyzed group of specimens was covered with appropriate values of limits of detection and quantitation, as well as satisfactory precision and recovery. A quantitative variability was observed among specimens collected from the same location, but on average they were similar from a chemical viewpoint. In relation to the study involving specimens from different locations, there were both qualitative and quantitative differences among plants collected from different regions of Brazil. Statistical analysis revealed that there is a correlation between geographical localization and polar metabolites profile for specimens collected from different locations. This is evidence that the pattern of metabolites concentration depends on the geographical distribution of the specimens. (C) 2012 Elsevier B.V. All rights reserved.

Simultaneous determination of dextromethorphan, dextrorphan and doxylamine in human plasma by HPLC coupled to electrospray ionization tandem mass spectrometry: Application to a pharmacokinetic study

In the present study, a fast, sensitive and robust method to quantify dextromethorphan, dextrorphan and doxylamine in human plasma using deuterated internal standards (IS) is described. The analytes and the IS were extracted from plasma by a liquid-liquid extraction (LLE) using diethyl-ether/hexane (80/20, v/v). Extracted samples were analyzed by high performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). Chromatographic separation was performed by pumping the mobile phase (acetonitrile/water/formic acid (90/9/1, v/v/v) during 4.0 min at a flow-rate of 1.5 mL min(-1) into a Phenomenex Gemini (R) C18, 5 mu m analytical column (150 x 4.6 mm id.). The calibration curve was linear over the range from 0.2 to 200 ng mL(-1) for dextromethorphan and doxylamine and 0.05 to 10 ng mL(-1) for dextrorphan. The intra-batch precision and accuracy (%CV) of the method ranged from 2.5 to 9.5%, and 88.9 to 105.1%, respectively. Method inter-batch precision (%CV) and accuracy ranged from 6.7 to 10.3%, and 92.2 to 107.1%, respectively. The run-time was for 4 min. The analytical procedure herein described was used to assess the pharmacokinetics of dextromethorphan, dextrorphan and doxylamine in healthy volunteers after a single oral dose of a formulation containing 30 mg of dextromethorphan hydrobromide and 12.5 mg of doxylamine succinate. The method has high sensitivity, specificity and allows high throughput analysis required for a pharmacokinetic study. (C) 2012 Elsevier B.V. All rights reserved.

An alternative method for the simultaneous determination of copper and lead for quality control of sugar cane spirit using a nanotube-based sensor

The development of an electroanalytical method for simultaneous determination of copper and lead ions in sugar cane spirit (cachaça) using carbon paste electrode modified with ascorbic acid and carbon nanotubes (CPE-AaCNT) is described. Squarewave voltammetry (SWV) with anodic stripping was employed, and this technique was optimized with respect to the following parameters: frequency (50 Hz), amplitude (100 mV) and scan increment (9 mV). The analytical curves were linear in the range from 0.0900 to 7.00 mg L- 1 for lead and copper. The limits of detection were 48.5 and 23.9 µg L- 1 for lead and copper, respectively. The developed method was applied to the simultaneous determination of copper and lead in five commercial samples of sugar cane spirit. The results were in good agreement with those obtained by F AAS/GF AAS (flame atomic absorption spectrometry/graphite furnace atomic absorption spectrometry) and showed that CPE-AaCNT can be successfully employed in the simultaneous determination of these metals in real sugar cane spirit samples.

Sensitive and fast determination of Sudan dyes in chilli powder by partial-filling micellar electrokinetic chromatography-tandem mass spectrometry

A fast and sensitive method for the simultaneous determination of Sudan dyes (I, II, III, and IV) in food samples was developed for the first time using partial filling micellar electrokinectic chromatography-mass spectrometry (MEKC-MS). The use of MEKC was essential to achieve the separation of these neutral analytes, while the partial filling technique was necessary to avoid the contamination of the ion source with non-volatile micelles. MEKC separation and MS detection conditions were optimized in order to achieve a fast, efficient, and sensitive separation of the four dyes. Filling 25% of the capillary with an MEKC solution containing 40 mM ammonium bicarbonate, 25 mM SDS, and 32.5% (v/v) acetonitrile, a baseline separation of the four azo-dyes was obtained in 10 min. Tandem MS was investigated in order to improve the sensitivity and selectivity of the analysis. Limits of detection (LOD) values 5, 8, 15, and 29 times better were obtained for Sudan III, I, II, and IV, respectively, using partial filling MEKC-MS/MS instead of partial filling MEKC-MS. Under optimized conditions, LOD from 0.05 to 0.2 mu g/mL were obtained. The suitability of the developed method was demonstrated through the fast and sensitive determination of Sudan I, II, III, and IV in spiked chilli powder samples. This determination could not be achieved by MEKC-UV due to the existence of several interfering compounds from the matrix.

From Sample Processing to Quantification: A Full Electrochemical Approach for Neutral Analyte Derivatization, Capillary Electrophoresis Separation, and Contactless Conductivity Detection

A thin-layer electrochemical flow cell coupled to capillary electrophoresis with contactless conductivity detection (EC-CE-(CD)-D-4) was applied for the first time to the derivatization and quantification of neutral species using aliphatic alcohols as model compounds. The simultaneous electrooxidation of four alcohols (ethanol, 1-propanol, 1-butanol, and 1-pentanol) to the corresponding carboxylates was carried out on a platinum working electrode in acid medium. The derivatization step required 1 min at 1.6 V vs. Ag/AgCl under stopped flow conditions, which was preceded by a 10 s activation at 0 V. The solution close to the electrode surface was then hydrodynamically injected into the capillary, and a 2.5 min electrophoretic separation was carried out. The fully automated flow system operated at a frequency of 12 analyses per hour. Simultaneous determination of the four alcohols presented detection limits of about 5 x 10(-5) mol As a practical application with a complex matrix, ethanol concentrations were determined in diluted pale lager beer and in nonalcoholic beer. No statistically significant difference was observed between the EC-CE-(CD)-D-4 and gas chromatography with flame ionization detection (GC-FID) results for these samples. The derivatization efficiency remained constant over several hours of continuous operation with lager beer samples (n = 40).

Capillary electrophoretic enantioselective determination of zopiclone and its impurities

A capillary electrophoretic enantioselective method with UV detection was developed and validated for the simultaneous quantification of zopiclone enantiomers and its impurities, zopiclone-N-oxide enantiomers, and 2-amino-5-chloropyridine, in tablets. The analytes were extracted from the tablets using ACN and were separated in an uncoated fused-silica capillary (50 mu m, 42 cm effective length, 50 cm total length) using 80 mM sodium phosphate buffer pH 2.5 and 5 mM carboxymethyl-beta-cyclodextrin as running buffer. The analytes and the internal standard (trimethoprim) were detected at 305 and 200 nm, respectively. A voltage of 27 kV was applied and the capillary temperature was maintained at 25 degrees C. All enantiomers were analyzed within 8 min and linear calibration curves over the concentration range of 0.40.8 mg mL-1 for each zopiclone enantiomer, 0.81.6 mu g mL-1 for 2-amino-5-chloropyridine and 0.40.8 mu g mL-1 for each zopiclone-N-oxide enantiomer were obtained. The coefficients of correlation obtained for the linear curves were greater than 0.99. The intra-day and inter-day accuracy and precision were lower than 2% for all analytes. This validated method was employed to study the degradation and racemization of zopiclone under stress conditions. This application demonstrated the importance of a stability-indicating assay method for this drug.

Platinum nanoparticles incorporated in silsesquioxane for use in LbL films for the simultaneous detection of dopamine and ascorbic acid

We describe the preparation of platinum nanoparticles (PtNPs) using the 3-n-propylpyridinium silsesquioxane chloride (SiPy+Cl-) as a nanoreactor and stabilizer. The formation of PtNPs was monitored by UV-Vis spectroscopy by measuring the decrease in the intensity of the band at 375 nm, which is attributed to the electronic absorption of PtCl62- ions. TEM images of Pt-SiPy+Cl- nanohybrid indicated an average size of 3-40 nm for PtNPs. The Pt-SiPy+Cl- was used as a polycation in the preparation of layer-by-layer films (LbL) on a glass substrate coated with fluorine-doped tin oxide (FTO) alternating with the polyanion poly(vinyl sulfonic acid) (PVS). The films were electrochemically tested in sulfuric acid to confirm the deposition of Pt-SiPy+Cl- onto the LbL films, observing the adsorption and desorption of hydrogen (E-pa = 0.1 V) and by the redox process of formation for PtO with E-pa = 1.3 V and E-pc = 0.65 V. FTIR and Raman spectra confirmed the presence of the PVS and Pt-SiPy+Cl- in the LbL films. A linear increase in the absorbance in the UV-Vis spectra of the Pt-SiPy+Cl- at 258 nm (pi -> pi* transition of the pyridine groups) with a number of Pt-SiPy+Cl-/PVS or PVS/SiPy+Cl- bilayers (R = 0.992) was observed. These LbL films were tested for the determination of dopamine (DA) in the presence of ascorbic acid (AA) with a detection limit (DL) on the order of 2.6 x 10(-6) mol L-1 and a quantification limit (QL) of 8.6 x 10(-6) mol L-1. The films exhibited a good repeatability and reproducibility, providing a potential difference of 550 mV for the oxidation of DA with AA interferent.

Maximal exercise test is a useful method for physical capacity and oxygen consumption determination in streptozotocin-diabetic rats

Abstract Background The aim of the present study was to investigate the relationship between speed during maximum exercise test (ET) and oxygen consumption (VO2) in control and STZ-diabetic rats, in order to provide a useful method to determine exercise capacity and prescription in researches involving STZ-diabetic rats. Methods Male Wistar rats were divided into two groups: control (CG, n = 10) and diabetic (DG, n = 8). The animals were submitted to ET on treadmill with simultaneous gas analysis through open respirometry system. ET and VO2 were assessed 60 days after diabetes induction (STZ, 50 mg/Kg). Results VO2 maximum was reduced in STZ-diabetic rats (72.5 ± 1 mL/Kg/min-1) compared to CG rats (81.1 ± 1 mL/Kg/min-1). There were positive correlations between ET speed and VO2 (r = 0.87 for CG and r = 0.8 for DG), as well as between ET speed and VO2 reserve (r = 0.77 for CG and r = 0.7 for DG). Positive correlations were also obtained between measured VO2 and VO2 predicted values (r = 0.81 for CG and r = 0.75 for DG) by linear regression equations to CG (VO2 = 1.54 * ET speed + 52.34) and DG (VO2 = 1.16 * ET speed + 51.99). Moreover, we observed that 60% of ET speed corresponded to 72 and 75% of VO2 reserve for CG and DG, respectively. The maximum ET speed was also correlated with VO2 maximum for both groups (CG: r = 0.7 and DG: r = 0.7). Conclusion These results suggest that: a) VO2 and VO2 reserve can be estimated using linear regression equations obtained from correlations with ET speed for each studied group; b) exercise training can be prescribed based on ET in control and diabetic-STZ rats; c) physical capacity can be determined by ET. Therefore, ET, which involves a relatively simple methodology and low cost, can be used as an indicator of cardio-respiratory capacity in future studies that investigate the physiological effect of acute or chronic exercise in control and STZ-diabetic male rats.