Wilney de Jesus Rodrigues Santos

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)%.

Synthesis and application of a peroxidase-like molecularly imprinted polymer based on hemin for selective determination of serotonin in blood serum

This work reports the preparation of a molecularly imprinted polymer (MIP) for selective catalytic detection of serotonin (5-hydroxytryptamine, 5-HT). The process is based on the synthesis of polymers with hemin introduced as the catalytic center to mimic the active site of peroxidase. The copolymer MIP, containing artificial recognition sites for 5-HT, has been prepared by bulk polymerization using methacrylic acid (MAA) and hemin as the functional monomers, and ethylene glycol dimethacrylate (EGDMA) as the cross-linker. For the determination of 5-HT, a flow injection analysis system coupled to an amperometric detector was optimized using multivariate analysis. The effects of different parameters, such as pH, buffer flow rate, buffer nature, peroxide concentration and sample volume were evaluated. After optimizing the experimental conditions, a linear response range from 1.0 up to 1000.0 micromolL(-1) was obtained with a sensitivity of 0.4nA/ micromolL(-1). The detection limit was found to be 0.30 micromolL(-1), while the precision values (n=6) evaluated by relative standard deviation (R.S.D.) were, respectively, 1.3 and 1.7% for solutions of 50 and 750 micromolL(-1) of 5-HT. No interference was observed by structurally similar compounds (including epinephrine, dopamine and norepinephrine), thus validating the good performance of the imprinted polymer. The method was applied for the determination of 5-HT in spiked blood serum samples.

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)%.

Novel electrochemical sensor for the selective recognition of chlorogenic acid

In this study, a novel sensitive molecularly imprinted electrochemical sensor was constructed for the selective detection of chlorogenic acid (CGA) by deposition of a molecularly imprinted siloxane (MIS) film, prepared by sol-gel process, onto Au bare electrode surface. Initially, a (3-mercaptopropyl)siloxane layer (MSL) was formed on the Au bare surface, followed by a siloxane layer obtained from the acid-catalyzed hydrolysis/condensation of a solution constituted by tetraethoxysilane (TEOS), phenyltriethoxysilane (PTEOS), 3-(aminopropyl)trimethoxysilane (APTMS) and CGA, as a molecular template. After the GCA extraction the MIS imprinted film was electrochemically characterized using differential pulse voltammetry (DPV). The MIS/Au sensor was tested in a solution of the CGA template and other similar molecules. This electrode displayed excellent selectivity towards CGA when compared with structurally similar molecules. Under optimized experimental conditions, the peak current response of the sensor for CGA was linear from 5.0 × 10(-7)mol L(-1) to 1.4 × 10(-5)mol L(-1), and the detection limit was 1.48 × 10(-7)mol L(-1). The MIS/Au sensor was successfully applied for the determination of CGA in coffee and tea samples.

Speciation of Sb(III) and Sb(V) in meglumine antimoniate pharmaceutical formulations by PSA using carbon nanotube electrode.

A new and simple electroanalytical method for speciation of Sb(III) and Sb(V) in pharmaceutical formulation by potentiometric stripping analysis (PSA) using a multiwall carbon nanotube paste electrode was developed. All instrumental and chemical parameters influencing the performance of the method were carefully assessed and optimized. Trivalent antimony was determined in acid medium (pH 3.6) under the optimized condition (deposition potential of -0.7 V, deposition time of 180 s, ionic strength of 0.3M and oxidant mercury concentration of 10 mg l(-1)). Total antimony was determined after quantitative reduction of Sb(V) with l-cysteine (1.5%, w/v) and its concentration was calculated from difference between the total antimony and Sb(III). The developed method provided two distinct linear calibration one ranging from 10 up to 50 microg l(-1) and other from 100 up to 800 microg l(-1) with respective correlation coefficient of 0.9978 and 0.9993, presenting a detection limit of 6.2 microg l(-1). Repeatability for the six independent samples expressed in terms of relative standard deviation was found to be 3.01 and 1.39% for 40.0 and 300.0 microg l(-1) antimony concentration, respectively. Results on the effect of foreign substances [Al(III), Mg(II), Fe(III), Cd(II), Zn(II) and meglumine] on analytical signal of antimony showed no interference even using high content of foreign ions in the analyte:interferent ratio up to 1:100. The proposed method was successfully applied for the speciation of Sb(III) and Sb(V) in pharmaceutical formulation and the accuracy was assessed from addition and recovery tests as well as comparing with graphite furnace atomic absorption spectrometry (GF AAS) technique used as reference analytical method.

Electrocatalytic activity of 4-nitrophthalonitrile-modified electrode for the l-glutathione detection

The present work describes the substantial electrocatalytic activity of (NC)2C6H3-NHOH/(NC)2C6H3-NO redox couple-modified electrode toward the low voltage detection of l-glutathione (GSH), in neutral medium, at an applied potential of 0.4V versus Ag/AgCl. After optimizing the operational conditions, the sensor provided a linear response range for GSH from 8.0 up to 83.0 micromol L(-1) with sensitivity, detection and quantification limits of 54nA L micromol(-1), 2.7 micromol L(-1) and 8.0 micromol L(-1), respectively. The proposed sensor presented higher sensitivity when compared to other modified electrodes described in the literature and showed a stable response for at least 100 successive determinations. The repeatability of the measurements with the same sensor and different sensors, evaluated in terms of relative standard deviation, were 4.1 and 5.0%, respectively, for n=10. The developed sensor was applied for GSH determination in yeast extract and the results were statistically the same with those obtained by the comparative method described in the literature at a confidence level of 95%.

Electrochemical investigations of the reaction mechanism and kinetics between NADH and redox-active (NC)2C6H3-NHOH/(NC)2C6H3-NO from 4-nitrophthalonitrile-(NC)2C6H3-NO2-modified electrode.

A simple and sensitive method for the electrocatalytic detection of NADH on a carbon paste electrode modified with a redox-active (NC)(2)C(6)H(3)-NO/(NC)(2)C(6)H(3)-NHOH (NOPH/NHOHPH) electrogenerated in situ from 4-nitrophthalonitrile (4-NPHN) is presented. The electrode modified with 4-NPHN showed an efficient electrocatalytic activity towards the oxidation of NADH with activation overpotential of 0.12V vs. Ag/AgCl. The formation of an intermediate charge transfer complex is proposed for the charge transfer reaction between NADH and the 4-NPHN-resulting system. The second-order rate constant for electrocatalytic oxidation of NADH, kappa(obs), and the apparent Michaelis-Menten constant K(M), at pH 7.0 were evaluated with rotating disk electrode (RDE) experiments, giving 1.0 x 10(4)mol(-1)Ls(-1) and 2.7 x 10(-5)mol L(-1), respectively. Employing the Koutecky-Levich approach indicated that the NADH oxidation reaction involves two electrons. The sensor provided a linear response range for NADH from 0.8 up to 8.5 micromol L(-1) with sensitivity, detection, quantification limits and time response of 0.50 microA L micromol(-1), 0.25micromol L(-1), 0.82 micromol L(-1) and 0.1s, respectively. The repeatability of the measurements with the same sensor and different sensors, evaluated in terms of relative standard deviation, were 4.1 and 5.0%, respectively, for n=10.

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.

Application of a nanostructured platform and imprinted sol-gel film for determination of chlorogenic acid in food samples.

Chlorogenic acid (CGA) is a polyphenol derivative that widely exists in higher plants like fruits, vegetables, black teas, and some traditional Chinese medicines. In this work, we have proposed a sensitive and selective electrochemical sensor for detection of CGA. The sensor was based on a glassy carbon electrode (GCE) modified with a functional platform by grafting vinyltrimethoxysilane (VTMS) in multi-walled carbon nanotubes (MWCNTs) and covered by a molecularly imprinted siloxane (MIS) film prepared using the sol-gel process. The VTMS was grafted onto the surface of the MWCNTs via in situ free radical polymerization. The MIS was obtained from the acid-catalyzed hydrolysis/condensation of a solution consisting of tetraethoxysilane (TEOS), phenyltriethoxysilane (PTEOS), (3-aminopropyl)trimethoxysilane (APTMS), and CGA as a template molecule. The modification procedure was evaluated by differential pulse voltammetry (DPV) and scanning electron microscopy (SEM). Under optimized operational conditions, a linear response was obtained covering a concentration ranging from 0.08μmolL(-1) to 500μmolL(-1) with a detection limit (LOD) of 0.032μmolL(-1). The proposed sensor was applied to CGA determination in coffee, tomato, and apple samples with recoveries ranging from 99.3% to 108.6%, showing a promising potential application in food samples. Additionally, the imprinted sensor showed a significantly higher affinity for target CGA than the non-imprinted siloxane (NIS) sensor.