Flavio Santos Damos

Amperometric sensor for nitrite using a glassy carbon electrode modified with alternating layers of iron(III) tetra-(N-methyl-4-pyridyl)-porphyrin and cobalt(II) tetrasulfonated phthalocyanine.

The development of a highly sensitive amperometric sensor for nitrite using a glassy carbon electrode modified with alternated layers of iron(III) tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and cobalt(II) tetrasulfonated phthalocyanine (CoTSPc) is described. The modified electrode showed an excellent catalytic activity and stability for the nitrite oxidation decreasing the peak potentials about 200mV toward less positive values and presenting much higher peak currents than those obtained on the bare GC electrode. A linear response range of 0.2-8.6mumoll(-1), with a sensitivity of 0.37muAlmumol(-1) and detection limit of 0.04mumoll(-1) were obtained with this sensor. The repeatability of the proposed sensor, evaluated in term of relative standard deviation, was verified to be 1.4% for 10 measurements of 0.2mumoll(-1) nitrite solution. Interference caused by common ions has been investigated in simulated mixtures containing high concentration level of interfering ions and the sensor was found to be tolerant against these ions. The developed sensor was applied for the nitrite determination in water samples and the results were in agreement with those obtained by a comparative method described in the literature. The average recovery for these samples was 100.1 (+/-0.7)%.

Voltammetric determination of 4-nitrophenol at a lithium tetracyanoethylenide (LiTCNE) modified glassy carbon electrode

The reduction of 4-nitrophenol (4-NP) has been carried out on a modified glassy carbon electrode using cyclic and differential pulse voltammetry (DPV). The sensor was prepared by modifying the electrode with lithium tetracyanoethylenide (LiTCNE) and poly-l-lysine (PLL) film. With this modified electrode 4-NP was reduced at -0.7V versus SCE. The sensor presented better performance in 0.1moll(-1) acetate buffer at pH4.0. The other experimental parameters, such as concentration of LiTCNE and PLL, pulse amplitude and scan rate were optimized. Under optimized operational conditions, a linear response range from 27 up to 23200nmoll(-1) was obtained with a sensitivity of 3.057nAlnmol(-1)cm(-2). The detection limit for 4-NP determination was 7.5nmoll(-1). The proposed sensor presented good repeatability, evaluated in term of relative standard deviation (R.S.D.=4.4%) for n=10 and was applied for 4-NP determination in water samples. The average recovery for these samples was 103.0 (+/- 0.7)%.

Amperometric sensor for nitrite based on copper tetrasulphonated phthalocyanine immobilized with poly-L-lysine film.

In this work, an amperometric sensor for nitrite detection based on a glassy carbon electrode modified with copper tetrasulphonated phthalocyanine immobilized by polycationic poly-L-lysine film is presented. The modified electrode showed an excellent catalytic activity toward nitrite oxidation. A linear response range from 0.12 up to 12.20 micromol L(-1) was obtained with a sensitivity of 0.83 microA L micromol(-1). The detection limit for nitrite was 36 nmol L(-1). The repeatability of the proposed sensor, evaluated in terms of relative standard deviation, was 1% for 10 measurements of 10 micromol L(-1) nitrite solution. Finally, the developed sensor was applied for nitrite determination in water samples and the results were in agreement to the comparative method. The average recovery for the samples was 101 (+/-4)%.

Iron(III) tetra-(N-methyl-4-pyridyl)-porphyrin as a biomimetic catalyst of horseradish peroxidase on the electrode surface: An amperometric sensor for phenolic compound determinations

The use of iron(III) tetra-(N-methyl-4-pyridyl) porphyrin (FeIIIT4MpyP) and histidine (His) in the construction of an amperometric sensor for phenolic compound determinations is reported, based on horseradish peroxidase (HRP) chemistry. The sensor was prepared by modifying a glassy carbon electrode with Nafion membrane doped with FeIIIT4MpyP and His, in a mass ratio of 1:2. The sensor presented its best performance at 50 mV vs. SCE in 0.1 mol l(-1) succinate buffer (pH = 4.0) containing 125 micromol l(-1) H2O2. Under optimized operational conditions, a linear response range from 0.6 to 6.0 micromol l(-1) was obtained with a sensitivity of 61 nA cm(-2) micromol l(-1). The detection limit for catechol determination was 0.35 micromol l(-1). The response time was less than 0.5 s. The proposed sensor presented stable responses for 100 successive determinations, while satisfactory responses were observed even after 200 measurements. The repeatability, evaluated in terms of relative standard deviation, was 4% for n = 7. The signal responses for other phenolic compounds, including those of environmental and clinical interest, were also investigated.

Development of a label-free immunosensor based on surface plasmon resonance technique for the detection of anti-Leishmania infantum antibodies in canine serum.

In this work, a surface plasmon resonance (SPR) immunosensor was developed using an 11-mercaptoundecanoic acid (11-MUA) modified gold SPR sensor chip for the detection of anti-Leishmania infantum antibodies. The soluble antigens of L. infantum were securely immobilized on an SPR gold disk by an 11-MUA self-assembled monolayer. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SECM) techniques were employed in the characterization of the antigen immobilization. After the immunosensor construction, canine serum positive for visceral leishmaniasis was added to its surface and showed significant variation in the SPR angle, indicating excellent sensitivity of the technique for antigen-antibody interaction detection. Moreover, the addition of negative serum was accompanied by a smaller response, demonstrating that the immunosensor shows good specificity against anti-L. infantum antibodies. Therefore, this work demonstrates the successful development of an SPR sensor for anti-L. infantum antibodies detection in short time, showing a great perspective as a sensing system of visceral leishmaniasis in endemic regions.

Dissolved oxygen amperometric sensor based on layer-by-layer assembly using host–guest supramolecular interactions

The development of a simple, efficient and sensitive sensor for dissolved oxygen is proposed using the host-guest binding of a supramolecular complex at a host surface by combining a self-assembled monolayer (SAM) of mono-(6-deoxy-6-mercapto)-beta-cyclodextrin (betaCDSH), iron (III) tetra-(N-methyl-4-pyridyl)-porphyrin (FeTMPyP) and cyclodextrin-functionalized gold nanoparticles (CDAuNP). The supramolecular modified electrode showed excellent catalytic activity for oxygen reduction. The reduction potential of oxygen was shifted about 200 mV toward less negative values with this modified electrode, presenting a peak current much higher than those observed on a bare gold electrode. Cyclic voltammetry and rotating disk electrode (RDE) experiments indicated that the oxygen reduction reaction involves probably 4-electrons with a rate constant (k(obs)) of 7 x 10(4) mol(-1) Ls(-1). A linear response range from 0.2 up to 6.5 mg L(-1), with a sensitivity of 5.5 microA L mg(-1) (or 77.5 microA cm(-2) L mg(-1)) and a detection limit of 0.02 mg L(-1) was obtained with this sensor. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation was 3.0% for 10 measurements of a solution of 6.5 mg L(-1) oxygen.

A highly sensitive amperometric sensor for oxygen based on iron(II) tetrasulfonated phthalocyanine and iron(III) tetra-(N-methyl-pyridyl)-porphyrin multilayers

The development of a highly sensitive sensor for oxygen is proposed using a glassy carbon (GC) electrode modified with alternated layers of iron(II) tetrasulfonated phthalocyanine (FeTsPc) and iron(III) tetra-(N-methyl-pyridyl)-porphyrin (FeT4MPyP). The modified electrode showed excellent catalytic activity for the oxygen reduction. The reduction potential of the oxygen was shifted about 330 mV toward less negative values with this modified electrode, presenting a peak current much higher than those observed on a bare GC electrode. Cyclic voltammetry and rotating disk electrode (RDE) experiments indicated that the oxygen reduction reaction involves 4 electrons with a heterogenous rate constant (k(obs)) of 3x10(5) mol(-1) L s(-1). A linear response range from 0.2 up to 6.4 mg L(-1), with a sensitivity of 4.12 microA L mg(-1) (or 20.65 microA cm(-2) L mg(-1)) and a detection limit of 0.06 mg L(-1) were obtained with this sensor. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation (R.S.D.) was 2.0% for 10 measurements of a solution of 6.4 mg L(-1) oxygen. The sensor was applied to determine oxygen in pond and tap water samples showing to be a promising tool for this purpose.

Aplicações de QCM, EIS e SPR na investigação de superfícies e interfaces para o desenvolvimento de (bio)sensores

The use of the quartz crystal microbalance process, electrochemical impedance spectroscopy and surface plasmon resonance for characterizing thin films and monitoring interfaces is presented. The theorical aspects of QCM, EIS and SPR are introduced and the main application areas are outlined. Future prospects of the combined applications of QCM, EIS and SPR methods in the studies of interfacial processes at surfaces are also discussed.

Development of a sensor for L-Dopa based on Co(DMG)2ClPy/multi-walled carbon nanotubes composite immobilized on basal plane pyrolytic graphite electrode

L-Dopa is the immediate precursor of the neurotransmitter dopamine, being the most widely prescribed drug in the treatment of Parkinsons disease. A sensitive and selective method is presented for the voltammetric determination of L-Dopa in pharmaceutical formulations using a basal plane pyrolytic graphite (BPPG) electrode modified with chloro(pyridine)bis(dimethylglyoximato)cobalt(III) (Co(DMG)(2)ClPy) absorbed in a multi-walled carbon nanotube (MWCNT). Scanning Electron Microscopy and Fourier Transform Infrared Spectroscopy were used to characterize the materials. The electrocatalytical oxidation of L-Dopa using the Co(DMG)(2)ClPy/MWCNT/BPPG electrode was investigated by cyclic voltammetry and square wave voltammetry. The parameters that influence the electrode response (the amount of Co(DMG)(2)ClPy and of MWCNT, buffer solution, buffer concentration, buffer pH, frequency and potential pulse amplitude) were investigated. Voltammetric peak currents showed a linear response for L-Dopa concentration in the range of 3 to 100 μM, with a sensitivity of 4.43 μAcm(-2)/μM and a detection limit of 0.86 μM. The related standard deviation for 10 determinations of 50 μM L-Dopa was 1.6%. The results obtained for L-Dopa determination in pharmaceutical formulations (tablets) were in agreement with the compared official method. The sensor was successfully applied for L-Dopa selective determination in pharmaceutical formulations.

Manganese phthalocyanine as a biomimetic electrocatalyst for phenols in the development of an amperometric sensor

The construction of an amperometric sensor for phenolic compounds using a carbon paste electrode modified with manganese phthalocyanine and histidine is reported. Under optimized conditions, at 0 mV vs Ag/AgCl in 0.1 mol dm-3 phosphate buffer solutions (pH 7.0) containing 250 µmol dm-3 H2O2, a linear response for catechol from 20 up to 130 µmol dm-3 was obtained with a sensitivity of 0.56 (± 0.02) µA dm3 µmol-1 cm-2. The detection limit was 1.1 µmol dm-3 and the response time was 2 s. The sensor presented stable response during 40 successive determinations. The repeatability, evaluated in terms of relative standard deviation, was 3.6% for n = 5 and [catechol] = 10 µmol dm-3. The sensor responses for other phenolic compounds were also investigated in details. Finally, the applicability of the sensor was tested in a pharmaceutical containing dopamine and the results compared favorably with those obtained with the official method.