Magno Aparecido Gonçalves Trindade

Detection of bisphenol a on a screen-printed carbon electrode in CTAB micellar medium.

This work illustrates the effect of cetyltrimethylammonium bromide (CTAB) as an antifouling and pre-concentrating agent for electroanalytical measurement of bisphenol A (BPA) on a screen-printed carbon electrode. The calibration graphs are obtained for BPA from 1.0 × 10−6 to 1.0 × 10−5 mol L−1 in B-R buffer pH 8.0 with addition of CTAB in a ratio of [CTAB]/[BPA] 2:1 and the limit of detection was 5.1 × 10−8 mol L−1. Nonylphenol can be also monitored by SWV at a potential 170 mV more positive than bisphenol A in B-R buffer pH 11.0 in the presence of CTAB. The method was successfully applied for BPA determination in river water and sewage without any pretreatment of the samples.

Polarographic determination of sunscreen agents in cosmetic products in micellar media

This paper introduces a simple, fast and reliable electroanalytical method for differential-pulse polarography based on electrochemical reduction at a dropping mercury electrode. The method was validated for the determination of 2-ethylhexyl-4-methoxycinnamate (EHMC) alone and in association with 4-methylbenzylidene camphor (MBC) or 2-hydroxy-4-methoxybenzophenone (BENZ-3) in samples of commercial cosmetic preparations. The supporting electrolyte that provided the best-defined and most intense peak current for EHMC determination was Britton-Robinson buffer (pH 4.0) in the presence of a cationic surfactant. Under optimized conditions, EHMC exhibited one single peak of reduction at -1.49 V versus Ag/AgCl. A limit of detection of 3.76 x 10(-8)mol L(-1) and a limit of quantitation of 1.25 x 10(-7) mol L(-1) were found for the pure EHMC standard. A good average recovery rate was reached for all the samples analyzed.

Cathodic Stripping Voltammetry Determination of Ceftiofur Antibiotic in Formulations and Bovine Serum

Abstract A sensitive and reliable stripping voltammetry method was developed to determine the presence of Ceftiofur antibiotic drug. This method is based on the adsorptive accumulation of the drug at a hanging mercury drop electrode and then the initiation of a negative sweep that yielded well‐defined cathodic peaks at −0.65 V (1 C) and −1.00 V (2 C) vs. Ag/AgCl reference electrode. To achieve high sensitivity, various experimental and instrumental variables were investigated such as supporting electrolyte, pH, accumulation time and potential, drug concentration, scan rate, convection rate, and working electrode area. The monitored adsorptive current of peak 1 C was directly proportional to the concentration of Ceftiofur; it shows a linear response in the range from 0.50×10−8 to 8.00×10−8 mol L−1 (correlation coefficient=0.998); and the limit of detection is 6.00×10−10 mol L−1 at an accumulation time of 300 s. The applicability of this approach was illustrated by the determination of Ceftiofur in pharmaceutical preparations and bovine serum.

Baseline-Corrected Second-Order Derivative Electroanalysis Combined With Ultrasound-Assisted Liquid-Liquid Microextraction: Simultaneous Quantification of Fluoroquinolones at Low Levels.

A baseline-corrected second-order derivative procedure and a miniaturized sample preparation based on low-density solvent and ultrasound-assisted liquid-liquid microextraction (LDS-UA-LLME) was combined to provide the simultaneous electroanalysis of three fluoroquinolones (FQ) as emerging contaminants (ECs). The enhanced mathematical processing provided the best separation with an accurate measurement of the overlapping peaks during the simultaneous electro-oxidation of target FQs that were directly dropped on the surface of carbon nanofiber-modified screen-printed electrodes. The adapted LDS-UA-LLME protocol was the key step involved in the sample preparation, which preconcentrate target analytes from diluted tap water samples with an enrichment factor of around 80×, allowing their quantification at trace levels. This combined feature demonstrated the unique application of an electroanalytical technique for the simultaneous electroanalysis of three FQs in spiked tap water samples, with recovery values remarkably close to 100%.

Determinação de corantes marcadores do tipo azo e antraquinona em combustíveis por cromatografia líquida com detecção eletroquímica

An analytical method based on high-performance liquid chromatography with electrochemical detection has been developed and applied to the determination of Solvent blue 14 (SA-14) and Solvent red 24 (SV-24) in fuel samples. The dyes were better separated on C18 column, using a mobile phase composed of acetonitrile and ammonium acetate (90:10, v/v). Detection was carried out at an oxidation potential of +0.85V. The detector response was linear at concentration range of 7.50×10-8 - 1.50×10-6 mol L-1 (r = 0.997) for SA-14 and SV-24, respectively. The method was used to quantify these dyes in fuels samples with satisfactory accuracy and precision.

Alternative Multifunctional Additives for Biodiesel Stabilization: Perspectives for More Efficiency and More Cost-Effectiveness

In this chapter, we address the current technologies to cover the alternative blends composed by multifunctional antioxidants—sometimes called secondary antioxidants—used to overcome the problems of degradation and provide more stability to the biodiesel which is derived from different raw materials. To this end, some valuable works with notable studies of conventional antioxidants, and sometimes synergetic binary/ternary blends and their applications, were briefly reviewed. However, the chapter attempts to cover only an overview of the recent advances in the field of multifunctional alternative additives, which provide a more efficient stabilization of the biodiesel. Also, its activities allow lowering the concentration of additives into biodiesel while maintaining their required specification. Furthermore, the chapter brings some aspects of the chemistry behind the multifunctional activities, focusing on the key benefits that afford in their multifunctional properties. Lastly, considering the vast scale in which the biofuel can be processed, we also show that the target additives improve the performance of conventional antioxidants more cost-effectively.

Sample preparation combined with electroanalysis to improve simultaneous determination of antibiotics in animal derived food samples

A procedure based on liquid-liquid extraction (LLE) and phase separation using magnetically stirred salt-induced high-temperature liquid-liquid extraction (PS-MSSI-HT-LLE) was developed to extract and pre-concentrate ciprofloxacin (CIPRO) and enrofloxacin (ENRO) from animal food samples before electroanalysis. Firstly, simple LLE was used to extract the fluoroquinolones (FQs) from animal food samples, in which dilution was performed to reduce interference effects to below a tolerable threshold. Then, adapted PS-MSSI-HT-LLE protocols allowed re-extraction and further pre-concentration of target analytes in the diluted acid samples for simultaneous electrochemical quantification at low concentration levels. To improve the peak separation, in simultaneous detection, a baseline-corrected second-order derivative approach was processed. These approaches allowed quantification of target FQs from animal food samples spiked at levels of 0.80 to 2.00 µmol L-1 in chicken meat, with recovery values always higher than 80.5%, as well as in milk samples spiked at 4.00 µmol L-1, with recovery values close to 70.0%.

Alternative binary blends and their synergistic effect on stability of soybean biodiesel

The primary antioxidant tert-butylhydroquinone (TBHQ) and an alternative additive, named 1,4-bis(ethylamino)-9,10-anthraquinone, were mixed to yield a potent blend able to be used in the field of biodiesel preservation. Physicochemical parameters such as peroxide value, total acid number, density and induction period were used to evaluate the effectiveness of the combination in stabilising soybean biodiesel during the accelerate storage period of degradation. The induction period values were also used to calculate the occurrence of synergistic effect, and it was observed a high percentage of synergism for the combined additives. The results showed that the presence of target alternative additive also enables lower the concentration of the primary antioxidant (TBHQ) in the blend. The cost-effective comparison was evaluated, and it was verified that the final cost of biodiesel can also be lowered, since the amount of additives (in the blend) required to meet the biodiesel specifications was reduced between 70 and 88%.

Fluorescence Spectroscopy Applied to Monitoring Biodiesel Degradation: Correlation with Acid Value and UV Absorption Analyses

The techniques used to monitor the quality of the biodiesel are intensely discussed in the literature, partly because of the different oil sources and their intrinsic physicochemical characteristics. This study aimed to monitor the thermal degradation of the fatty acid methyl esters of Sesamum indicum L. and Raphanus sativus L. biodiesels (SILB and RSLB, resp.). The results showed that both biodiesels present a high content of unsaturated fatty acids, ∼84% (SILB) and ∼90% (RSLB). The SILB had a high content of polyunsaturated linoleic fatty acid (18  :  2), about 49%, and the oleic monounsaturated (18  :  1), ∼34%. On the other hand, RSLB presented a considerable content of linolenic fatty acid (18  :  3), ∼11%. The biodiesel samples were thermal degraded at 110°C for 48 hours, and acid value, UV absorption, and fluorescence spectroscopy analysis were carried out. The results revealed that both absorption and fluorescence presented a correlation with acid value as a function of degradation time by monitoring absorptions at 232 and 270 nm as well as the emission at 424 nm. Although the obtained correlation is not completely linear, a direct correlation was observed in both cases, revealing that both properties can be potentially used for monitoring the biodiesel degradation.

New Electrochemical Flow-Cell Configuration Integrated into a Three-Dimensional Microfluidic Platform: Improving Analytical Application in the Presence of Air Bubbles

A newly configured electrochemical flow cell to be used for (end-channel) amperometric detection in a microfluidic device is presented. The design was assembled to place the reference electrode in a separated compartment, isolated from the flow in the microchannel, while the working and counter electrodes remain in direct contact with both compartments. Moreover, a three-dimensional coil-shaped microfluidic device was fabricated using a nonconventional protocol. Both devices working in association enabled us to solve the drawback caused by the discrete injection when the automatic micropipette was used. The high performance of the proposed electrochemical flow cell was demonstrated after in situ modifying the surface of the platinum working electrode with surfactant (e.g., using Tween 20 at 0.10%). As the reference electrode remained out of contact with the flowing solution, there was no trouble by air bubble formation (generated by accidental insertion or by presence of surfactants) throughout the measurements. This device was characterized regarding its analytical performance by evaluating the amperometric detection of acetaminophen, enabling determination from 6.60 to 66.0 μmol L-1. This issue is important since at high concentration (e.g., as assessed in clinical analysis) the acetaminophen is known to passivate the working electrode surfaces by electrogenerated products, impairing the accuracy of the electrochemical measurements.