Eduardo M. Richter

Fast and direct determination of butylated hydroxyanisole in biodiesel by batch injection analysis with amperometric detection.

We report here, for the first time, application of batch injection analysis (BIA) with amperometric detection for determination of the phenolic antioxidant butylated hydroxyanisole (BHA) in biodiesel. A sample plug was directly injected onto a boron-doped diamond electrode immersed in 50% v/v hydroethanolic solution with 0.1 mol L(-1) HClO(4) using an electronic micropipette. Importantly, the only preparation step required for biodiesel analysis is dilution in the same hydroethanolic electrolyte solution. Our proposed method has several advantages for routine biodiesel analysis, including: a low relative standard deviation between injections (0.29%, n=20), high analytical frequency (120 h(-1)), adequate recovery values (93-101%) for spiked samples, satisfactory accuracy (based on comparative determinations by high-performance liquid-chromatography), and a low detection limit (100 ng of BHA per g of biodiesel). Finally, our method can be adapted for the determination of other antioxidants in biodiesel samples.

Fast simultaneous determination of BHA and TBHQ antioxidants in biodiesel by batch injection analysis using pulsed-amperometric detection

We report the first amperometric method for the simultaneous determination of butylated hydroxyanisole (BHA) and tert-butylhydroquinone (TBHQ) in biodiesel using batch-injection analysis (BIA) coupled to pulsed-amperometry. A sequence of potential pulses was selected in order to detect TBHQ and BHA separately in a single injection step at a glassy-carbon electrode. Samples were diluted in 50% v/v hydroethanolic solution with 0.1 mol L(-1) HClO(4) (supporting electrolyte) before injection using an electronic pipette. The method is highly precise (RSD<1%, n=10), fast (170 injections h(-1)), accurate (recovery between 100 and 110%), presents low detection limits (73 and 75 nmol L(-1) BHA and TBHQ, respectively), and can be easily adapted for on-site determinations.

Fast batch injection analysis system for on-site determination of ethanol in gasohol and fuel ethanol

A simple, accurate and fast (180 injections h(-1)) batch injection analysis (BIA) system with multiple-pulse amperometric detection has been developed for selective determination of ethanol in gasohol and fuel ethanol. A sample aliquot (100 μL) was directly injected onto a gold electrode immersed in 0.5 mol L(-1) NaOH solution (unique reagent). The proposed BIA method requires minimal sample manipulation and can be easily used for on-site analysis. The results obtained with the BIA method were compared to those obtained by gas-chromatography and similar results were obtained (at 95% of confidence level).

Two new electrochemical methods for fast and simultaneous determination of codeine and diclofenac.

In this paper, we present two new electrochemical methods for fast and simultaneous determination of codeine (CO) and diclofenac (DCF). The first one is based on batch injection analysis with amperometric detection (BIA-MPA) and the second one is based on capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C(4)D). The proposed BIA-MPA method is highly-precise (RSD of 1.1% and 0.9% for DCF and CO, respectively; n=10), fast (300 injections h(-1)) and has low detection limits (1.1 and 1.0 µmol L(-1) for DCF and CO, respectively). The proposed CE-C(4)D method allows the determination of CO and DFC in less than 1 min with high precision (RSD of 0.3% and 0.7% for DCF and CO, respectively; n=10) and low detection limits (11 and 21 µmol L(-1) for DCF and CO, respectively). Both proposed methods were applied to the determination of CO and DCF in pharmaceutical samples with similar results to those achieved by high-performance liquid chromatography (HPLC) at a 95% confidence level.

Compact Disks, a New Source for Gold Electrodes. Application to the Quantification of Copper by PSA

In this work we describe a versatile and very sensitive way for copper quantification by potentiometric stripping analysis using gold electrodes obtained from recordable compact disks (CDs). This new source of electrodes (CDtrodes) shown similar performance to the commercial gold electrodes with superior versatility and lower cost. Recordable CDs contains a highly pure gold film with thickness between 50 and 100 nm and superficial area of ca. 100 cm 2 . The working electrode developed was used successfully in stationary cell and many experimental parameters have been optimized. For copper, the detection limit attained was 30 ng L ˇ1 (600 s deposition time) with remarkable precision (standard deviation of 1.8 % for 20 repetitive measurements using 25m gL ˇ1 of copper with 60 s of deposition time). The gold electrode developed was used for analysis of copper in sugar cane spirits and tap water samples. The results were compared with those obtained by atomic absorption spectroscopy.

Direct amperometric determination of tert-butylhydroquinone in biodiesel

The direct amperometric determination of tert-butylhydroquinone (TBHQ) in biodiesel at an unmodified glassy carbon electrode is reported. A biodiesel aliquot was added into an electrochemical cell containing a 75% (v/v) ethanol-water solution under stirring (with final concentration of 50 mmol L(-1) HClO(4)). The amperometric method involved the continuous application of three sequential potential pulses to the working electrode (700 mV for 300 ms, 0 mV for 100 ms and -50 mV for 1s). TBHQ was continuously monitored at the first (direct oxidation) and optionally at the second (reduction) potential pulse while the third potential pulse was applied for cleaning of the electrode surface. For comparison, the samples were also analyzed by high-performance liquid-chromatography and a good agreement between the results was verified. Recovery values for spiked samples were between 90% and 95% and the reproducibility of the proposed method was around 5% (n=5). The proposed method can be easily adapted for on-site analysis.

Simultaneous determination of caffeine, paracetamol, and ibuprofen in pharmaceutical formulations by high‐performance liquid chromatography with UV detection and by capillary electrophoresis with conductivity detection

Paracetamol, caffeine and ibuprofen are found in over-the-counter pharmaceutical formulations. In this work, we propose two new methods for simultaneous determination of paracetamol, caffeine and ibuprofen in pharmaceutical formulations. One method is based on high-performance liquid chromatography with diode-array detection and the other on capillary electrophoresis with capacitively coupled contactless conductivity detection. The separation by high-performance liquid chromatography with diode-array detection was achieved on a C18 column (250×4.6 mm(2), 5 μm) with a gradient mobile phase comprising 20-100% acetonitrile in 40 mmol L(-1) phosphate buffer pH 7.0. The separation by capillary electrophoresis with capacitively coupled contactless conductivity detection was achieved on a fused-silica capillary (40 cm length, 50 μm i.d.) using 10 mmol L(-1) 3,4-dimethoxycinnamate and 10 mmol L(-1) β-alanine with pH adjustment to 10.4 with lithium hydroxide as background electrolyte. The determination of all three pharmaceuticals was carried out in 9.6 min by liquid chromatography and in 2.2 min by capillary electrophoresis. Detection limits for caffeine, paracetamol and ibuprofen were 4.4, 0.7, and 3.4 μmol L(-1) by liquid chromatography and 39, 32, and 49 μmol L(-1) by capillary electrophoresis, respectively. Recovery values for spiked samples were between 92-107% for both proposed methods.

On-site fuel electroanalysis: Determination of lead, copper and mercury in fuel bioethanol by anodic stripping voltammetry using screen-printed gold electrodes

The potential application of commercial screen-printed gold electrodes (SPGEs) for the trace determination of lead, copper, and mercury in fuel bioethanol is demonstrated. Samples were simply diluted in 0.067 mol L(-1) HCl solution prior to square-wave anodic stripping voltammetry (SWASV) measurements recorded with a portable potentiostat. The proposed method presented a low detection limit (<2 μg L(-1)) for a 240 s deposition time, linear range between 5 and 300 μg L(-1), and adequate recovery values (96-104%) for spiked samples. This analytical method shows great promise for on-site trace metal determination in fuel bioethanol once there is no requirement for sample treatment or electrode modification.

Fast determination of naproxen in pharmaceutical formulations by batch injection analysis with pulsed amperometric detection

A novel and fast electroanalytical method for naproxen determination in pharmaceutical formulations using batch injection analysis (BIA) with pulsed amperometric detection is described. Bare glassy carbon electrode was used as working electrode and 0.05 mol L-1 phosphate buffer solution as supporting electrolyte. The amperometric method involved the continuous application of two sequential potential pulses to the working electrode in order to detect naproxen by its electrochemical oxidation (+1.5 V for 200 ms) and to clean the electrode surface from adsorption products (+1.0 V for 100 ms), avoiding electrode contamination. The proposed method has several advantages for routine analysis, including: a low relative standard deviation between injections (3.0%, n = 10), high analytical frequency (90 h-1), satisfactory accuracy (based on comparative determinations by spectrofluorimetry) and low limit of detection (0.3 µmol L-1).

Determination of Inorganic Ions in Ethanol Fuel by Capillary Electrophoresis

The control of the content of inorganic ions in vehicular fuels plays an important role in the engine maintenance. A novel and versatile methodology to carry out rapid analysis of ions in ethanol is presented. Capillary electrophoresis was used to quantify cations (sodium, potassium, calcium, magnesium, and ammonium) and anions (sulfate, chloride, and nitrate). The injection of the sample directly in the capillary shows some lack of repeatability of the results. The prior evaporation of the ethanol, followed by a re-suspension of the residual material, leads to reliable results. The detection limits of the eight ions range between 0.06 and 0.18 mg L-1. Lower detection limits could be attained by increasing the injection time and/or the injection pressure.