Rodrigo A.A. Munoz

Highly sensitive electrochemical detection of trace liquid peroxide explosives at a Prussian-blue ‘artificial-peroxidase’ modified electrode

A highly sensitive electrochemical assay of the peroxide-based explosives triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD) at a Prussian-blue (PB) modified electrode is reported. The method involves photochemical degradation of the peroxide explosives and a low potential (0.0 V) electrocatalytic amperometric sensing of the generated hydrogen peroxide at the PB transducer and offers nanomolar detection limits following a short (15 s) irradiation times. The electrochemical sensing protocol should facilitate rapid field screening of peroxide explosives.

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.

Combination of ultrasonic extraction and stripping analysis : An effective and reliable way for the determination of Cu and Pb in lubricating oils

The determination of metals in lubricating oil has been used as an important way to prevent components failures, to provide environmental information and in some cases, to identify adulteration. In this work, an effective and simple procedure is proposed for Cu and Pb determination in lubricating oils. An ultrasonic bath was employed for extraction of these elements from oil samples in a mixture 1:1 (v/v) of concentrated HCl and H(2)O(2). A very efficient extraction of Cu and Pb (approximately 100%) was attained after 30 min of ultrasound, allowing the simultaneous determination of both metals using square-wave anodic stripping voltammetry at thin-film gold electrodes. The extraction procedure was performed in 4 mL polypropylene closed vessels and dozens of samples could be treated simultaneously in the same ultrasonic bath. The regions of the ultrasonic bath, where the maximum efficiency of extraction was attained were evaluated. Over the optimized region, 30 samples can be treated simultaneously. Used lubricating oils from automotive engines were analyzed by using the optimized extraction procedure.

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.

Gold electrodes from compact discs modified with platinum for amperometric determination of ascorbic acid in pharmaceutical formulations

A simple, rapid and precise amperometric method has been developed for quantification of ascorbic acid (AA) in pharmaceutical formulations using flow-injection analysis (FIA). A slice of recordable compact disc (CD) modified by electrodeposition of platinum was employed as the working electrode. The proposed flow system allows determinations in the 1 mumol l(-1) of the analyte and enables 90 determinations per h, employing only 150-mul sample. The method permits the direct quantification of ascorbic acid in many pharmaceutical products, avoiding cumbersome processes as previous separations, solvent extraction or sample filtration. This new procedure was applied to commercial pharmaceutical tablets and the results obtained were identical than the ones obtained by the classical iodometric method. The calibration plots for freshly prepared ascorbic acid standards were highly linear in the concentration range of 1-10 mumol l(-1) with a relative standard deviation (R.S.D.) <1%. For all real samples studied, the deviations were situated between 0.5 and 8.7%.

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.