Rafael R. Cunha

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.

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.

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.

Simultaneous determination of diclofenac and its common counter-ions in less than 1 minute using capillary electrophoresis with contactless conductivity detection.

This paper presents a method for fast and simultaneous determination of diclofenac (DCF) and its common counter‐ions (potassium, sodium, and diethylammonium) using CE with capacitively coupled contactless conductivity detection (CE‐C4D). On the basis of a single electropherogram (about 50 s), the proposed method allows the determination of the stoichiometry, absolute quantification and evaluation of the degradation degree of the active pharmaceutical ingredient (DCF). A linear working range from 100 to 500 μmol/L was obtained for all analytes in an equimolar TRIS/TAPS (10 mmol/L) solution as the background electrolyte as well as adequate LOD (7, 6, 7, and 10 μmol/L for K+, Na+, diethylammonium, and DCF, respectively). The proposed method was applied to the analysis of pharmaceutical formulations (tablets and spray form) with similar results to those achieved by HPLC (DCF) or flame photometry (K and Na) at a 95% confidence level.

Ultra-fast determination of caffeine, dipyrone, and acetylsalicylic acid by capillary electrophoresis with capacitively coupled contactless conductivity detection and identification of degradation products.

Capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C(4)D) was used for fast, simultaneous determination of dipyrone (DIP), caffeine (CAF), and acetylsalicylic acid (ASA). In the same run and in less than 1min, the degradation products from DIP and ASA were also detected. In addition, the usage of the CE-C(4)D system allowed, for the first time, the detection of methylamine as a degradation product of DIP. Capillary electrophoresis with electrospray mass spectrometry experiments were carried out in order to confirm the formation of methylamine. The limits of detection by CE-C(4)D were 5, 5, and 6μmolL(-1) for CAF, DIP, and ASA, respectively. The proposed method was applied to the analysis of these compounds in pharmaceutical formulations with similar results to those achieved by HPLC (p<0.05).

Determinação simultânea de ácido ascórbico e ácido acetilsalicílico usando análise por injeção em fluxo com detecção amperométrica pulsada

A simple flow system with multiple pulse amperometric detection using a single working electrode is proposed for simultaneous determination of ascorbic (AA) and acetylsalicylic (AAS) acids in pharmaceutical formulations. The procedure is based on application of two potential pulses: 0.90 V/50 ms: oxidation and determination of AA without the interference of AAS; 1.35 V/50 ms: oxidation of both compounds and quantification of AAS by current subtraction using a correction factor. Sampling rate was estimated as 125 injections per hour and the limits of detection were 0.17 and 0.16 µmol L-1 for AA and AAS, respectively. Results for commercial samples agreed with those obtained using HPLC.

Combining C4D and MS as a dual detection approach for capillary electrophoresis

The hyphenation of two detectors in combination with separation techniques is a powerful tool to enhance the analytical information. In this work, we present for the first time the coupling of two important detectors for capillary electrophoresis (CE), namely capacitively coupled contactless conductivity detection (C4D) and electrospray ionization time‐of‐flight mass spectrometry (ESI‐TOF‐MS). The elaborated experimental protocol took into account the requirements of separation aspects and the compatibility with both detectors. ESI‐TOF‐MS requires background electrolytes (BGE) containing only volatile components such as ammonium acetate or formate. These, however, exhibit a rather high conductivity, which is disadvantageous for C4D. Thus, the selection of the BGE in an appropriate concentration was undertaken for the determination of various phenolic compounds serving as a model system. The chosen BGE was a 10 mM ammonium acetate/ammonia buffer with a pH of 9. This BGE was a compromise concerning the detection performance of both detectors. The LODs for m‐cresol, m‐ and p‐nitrophenol, and 2,4‐dinitrophenol were 3.1 μM (C4D), 0.8 μM (MS), 0.8 μM (MS), and 1.5 μM (MS), respectively. Moreover, the overall separation efficiency was excellent illustrating that detector‐induced band broadening can be neglected in the CE‐C4D/MS system. The analytical characteristics for the determination of phenolic compounds show the suitability of this dual detection approach and demonstrate the complementary use of C4D and MS detection.

Determinação rápida de hidroquinona usando análise por injeção em batelada (BIA) com detecção amperométrica

A fast analytical method for determination of hydroquinone in pharmaceutical formulations employing batch injection analysis (BIA) with amperometric detection using a boron-doped diamond electrode is described. The supporting electrolyte was a 0.1 mol L-1 H2SO4 solution (the single reagent used for analysis). The method showed good repeatability (RSD of 0.45%, n=20), wide linear range (from 10 to 2000 µmol L-1, R=0.9999), low detection limit (0.016 µmol L-1) and satisfactory recovery values (91-96%). Accuracy of the method was evaluated by comparative analyses using high-performance liquid-chromatography. The ability to replace the electronic pipette by disposable syringes (injection procedure) in BIA systems was also shown.

Electrochemical Oxidation of Chlorhexidine and its Amperometric Determination by Flow-Injection Analysis

HClO 4 solution at a glassy-carbon electrode. The mechanism of the electrochemical oxidation of chlorhexidine is pH-dependent and involves a single-electron transfer possibly via radical cation formation. The FIA parameters were optimized and a detection limit of 0.3 µmol L -1 was obtained. The proposed method was applied in mouth rinses and skin disinfectants samples and compared with high-performance liquid chromatography.