Estudo e desenvolvimento de sensores biomiméticos baseados em materiais carbonáceos modificados com ftalocianinacobalto (II) para detecção amperométrica de metribuzin

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Desenvolvimento de sistem biomimético para análise de 3,5,6-Tricloro-2-piridinol, o principal metabólito do clorpirifós

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Sensores de filmes finos para avaliação de etanol combustível

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Propriedades multifuncionais do CaCu3Ti4O12: estudo dos mecanismos e suas aplicações

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Desenvolvimento de sensores descartáveis de ouro nanoestruturado modificados com complexo metálico visando detecção in situ de corantes semipermanentes de cabelo

Pós-graduação em Química - IQ

An investigation into the influence of zinc precursor on the microstructural, photoluminescence, and gas-sensing properties of ZnO nanoparticles

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Development and application of a screen-printed electrode modified with MWCNT for the electrocatalytic detection of thiram

Interest in the electronic properties of carbon nanotubes has increased in recent years. These materials can be used in the development of electrochemical sensors for the measurement and monitoring of analytes of environmental interest, such as pharmaceuticals, dyes, and pesticides. This work describes the use of homemade screen-printed electrodes modified with multi-walled carbon nanotubes (MWCNT) for the electrochemical detection of the fungicide thiram. The electrochemical characteristics of the proposed system were evaluated using cyclic voltammetry, with investigation of the electrochemical behavior of the sensor in the presence of the analyte, and estimation of electrochemical parameters including the diffusion coefficient, electron transfer coefficient (α), and number of electrons transferred in the catalytic electro-oxidation. The sensor response was optimized using amperometry. The best sensor performance was obtained in 0.1 mol L-1 phosphate buffer solution at pH 8.0, where a detection limit of 7.9 x 10-6 mol L-1 was achieved. Finally, in order to improve the sensitivity of the sensor, square wave voltammetry (SWV) was used for thiram quantification, instead of amperometry. Using SWV, a response range for thiram from 9.9 x 10-6 to 9.1 x 10-5 mol L-1 was obtained, with a sensitivity of 30948 µA mol L-1, and limits of detection and quantification of 1.6 x 10-6 and 5.4 x 10-6 mol L-1, respectively. The applicability of this efficient new alternative methodology for thiram detection was demonstrated using analyses of enriched soil samples.

Sensores eletroquímicos à base de nanomateriais carbonáceos e catalisadores biomiméticos para determinação de tetraciclina em diferentes tipos de amostras

Pós-graduação em Química - IQ

Multi-walled carbon nanotubes modified screen-printed electrodes for cisplatin detection

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Advanced schemes for surface plasmon resonance and plasmon-enhanced fluorescence biosensors

Advanced optical biosensor platforms exploiting long range surface plasmons (LRSPs) and responsive N-isopropylacrylamide (NIPAAm) hydrogel binding matrix for the detection of protein and bacterial pathogen analytes were carried out. LRSPs are optical waves that originate from coupling of surface plasmons on the opposite sites of a thin metallic film embedded between two dielectrics with similar refractive indices. LRSPs exhibit orders of magnitude lower damping and more extended profile of field compared to regular surface plasmons (SPs). Their excitation is accompanied with narrow resonance and provides stronger enhancement of electromagnetic field intensity that can advance the sensitivity of surface plasmon resonance (SPR) and surface plasmon-enhanced fluorescence spectroscopy (SPFS) biosensors. Firstly, we investigated thin gold layers deposited on fluoropolymer surface for the excitation of LRSPs. The study indicates that the morphological, optical and electrical properties of gold film can be changed by the surface energy of fluoropolymer and affect the performance of a SPFS biosensor. A photo-crosslinkable NIPAAm hydrogel was grafted to the sensor surface in order to serve as a binding matrix. It was modified with bio-recognition elements (BREs) via amine coupling chemistry and offered the advantage of large binding capacity, stimuli responsive properties and good biocompatibility. Through experimental observations supported by numerical simulations describing diffusion mass transfer and affinity binding of target molecules in the hydrogel, the hydrogel binding matrix thickness, concentration of BREs and the profile of the probing evanescent field was optimized. Hydrogel with a up to micrometer thickness was shown to support additional hydrogel optical waveguide (HOW) mode which was employed for probing affinity binding events in the gel by means of refractometric and fluorescence measurements. These schemes allow to reach limits of detection (LODs) at picomolar and femtomolar levels, respectively. Besides hydrogel based experiments for detection of molecular analytes, long range surface plasmon-enhanced fluorescence spectroscopy (LRSP-FS) was employed for detection of bacterial pathogens. The influence of capture efficiency of bacteria on surfaces and the profile of the probing field on sensor response were investigated. The potential of LRSP-FS with extended evanescent field is demonstrated for detection of pathogenic E. coli O157:H7 on sandwich immunoassays . LOD as low as 6 cfu mL-1 with a detection time of 40 minutes was achieved.rn

Functional dna nanostructures for in vitro biosensing in live cells

DNA is a fascinating biomolecule that is well known for its genetic role in living systems. The emerging area of DNA nanotechnology provides an alternative view that exploits unparallel self-assembly ability of DNA molecules for material use of DNA. Although many reports exist on the results of DNA self-assembling systems, still few of them focus on the in vitro study about the function of such DNA nanostructures in live cells. Due to this, there are still a limited research about the in vitro functionality of such designs. To address an aspect of this issue, we have designed, synthesized and characterized two multifunctional fluorescencent nanobiosensors by DNA self-assembling. Each structure was designed and implemented to be introduced in live cells in order to give information on their functioning in real-time. Computational tools were used in order to design a graphic model of two new DNA motifs and also to obtain the specific sequences to all the ssDNA molecules. By thermal self-assembly techniques we have successfully synthesized the structure and corroborate their formation by the PAGE technique. In addition, we have established the conditions to characterize their structural conformation change when they perform their sensor response. The sensing behavior was also accomplished by fluorescence spectroscopy techniques; FRET evaluation and fluorescence microscopy imaging. Providing the evidence about their adequate sensing performance outside and inside the cells detected in real-time. In a preliminary evaluation we have tried to show the in vitro functionality of our structures in different cancer cell lines with the ability to perform local sensing responses. Our findings suggest that DNA sensor nanostructures could serve as a platform to exploit further therapeutic achievements in live cells.

Optical bistable devices as sensing elements

The nonlinear optical properties of many materials and devices have been the main object of research as potential candidates for sensing in different places. Just one of these properties has been, in most of the cases, the basis for the sensing operation. As a consequence, just one parameter can be detected. In this paper, although just one property will be employed too, we will show the possibility to sense different parameters with just one type of sensor. The way adopted in this work is the use of the optical bistability obtained from different photonic structures. Because this optical bistability has a strong dependence on many different parameters the possibility to sense different inputs appears. In our case, we will report the use of some non-linear optical devices, mainly Semiconductor Optical Amplifiers, as sensing elements. Because their outputs depend on many parameters, as the incident light wavelength, polarization, intensity and direction, applied voltage and feedback characteristics, they can be employed to detect, at the same time, different type of signals. This is because the way these different signals affect to the sensor response is very different too and appears under a different set of characteristics.

Modified hydrogel matrices in fibre optic sensors

Common problems encountered in clinical sensing are those of non-biocompatibility, and slow response time of the device. The latter, also applying to chemical sensors, is possibly due to a lack of understanding of polymer support or membrane properties and hence failure to optimise membranes chosen for specific sensor applications. Hydrogels can be described as polymers which swell in water. In addition to this, the presence of water in the polymer matrix offers some control of biocompatibility. They thus provide a medium through which rapid transport of a sensed species to an incorporated reagent could occur. This work considers the feasibility of such a system, leading to the design and construction of an optical sensor test bed. The development of suitable membrane systems and of suitable coating techniques in order to apply them to the fibre optics is described. Initial results obtained from hydrogel coatings implied that the refractive index change in the polymer matrix, due to a change in water content with pH is the major factor contributing to the sensor response. However the presence of the colourimetric reagent was also altering the output signal obtained. An analysis of factors contributing to the overall response, such as colour change and membrane composition were made on both the test bed, via optical response, and on whole membranes via measurement of water content change. The investigation of coatings with low equilibrium water contents, of less than 10% was carried out and in fact a clearer signal response from the test bed was noted. Again these membranes were suprisingly responding via refractive index change, with the reagent playing a primary role in obtaining a sensible or non-random response, although not in a colourimetric fashion. A photographic study of these coatings revealed some clues as to the physical nature of these coatings and hence partially explained this phenomenon. A study of the transport properties of the most successful membrane, on a coated wire electrode and also on the fibre optic test bed, in a series of test environments, indicated that the reagent was possibly acting as an ion exchanger and hence having a major influence on transport and therefore sensor characteristics.

Fibre-grating sensors for the measurement of physiological pulsations

Mechanical physiological pulsations are movements of a body surface incited by the movements of muscles in organs inside the body. Here we demonstrate the use of long-period grating sensors in the detection of cardio-vascular pulsations (CVP), in particular apex and carotid pulsations. To calibrate the sensors, we use a mechanical tool designed specifically to measure the sensor response to a localized perturbation at different grating curvatures as working points. From the data we infer the amplitude of the CVP. Together with the electrophysiological signals, the CVP signals obtained from the sensors can provide significant information on heart function which is inaccessible to the electrocardiogram. The low cost and easy handling of the fibre sensors increase their prospects to become the sensors of choice for novel diagnostic devices. © 2013 The Royal Swedish Academy of Sciences.

Improving the stability of an oxime based electrochemical microsensor for organo-phosphate vapor detection

A micro gas sensor has been developed by our group for the detection of organo-phosphate vapors using an aqueous oxime solution. The analyte diffuses from the high flow rate gas stream through a porous membrane to the low flow rate aqueous phase. It reacts with the oxime PBO (1-Phenyl-1,2,3,-butanetrione 2-oxime) to produce cyanide ions, which are then detected electrochemically from the change in solution potential. Previous work on this oxime based electrochemistry indicated that the optimal buffer pH for the aqueous solution was approximately 10. A basic environment is needed for the oxime anion to form and the detection reaction to take place. At this specific pH, the potential response of the sensor to an analyte (such as acetic anhydride) is maximized. However, sensor response slowly decreases as the aqueous oxime solution ages, by as much as 80% in first 24 hours. The decrease in sensor response is due to cyanide which is produced during the oxime degradation process, as evidenced by the cyanide selective electrode. Solid phase micro-extraction carried out on the oxime solution found several other possible degradation products, including acetic acid, N-hydroxy benzamide, benzoic acid, benzoyl cyanide, 1-Phenyl 1,3-butadione, 2-isonitrosoacetophenone and an imine derived from the oxime. It was concluded that degradation occurred through nucleophilic attack by a hydroxide or oxime anion to produce cyanide, as well as a nitrogen atom rearrangement similar to Beckmann rearrangement. The stability of the oxime in organic solvents is most likely due to the lack of water, and specifically hydroxide ions. The reaction between oxime and organo-phosphate to produce cyanide ions requires hydroxide ions, and therefore pure organic solvents are not compatible with the current micro-sensor electrochemistry. By combining a concentrated organic oxime solution with the basic aqueous buffer just prior to being used in the detection process, oxime degradation can be avoided while preserving the original electrochemical detection scheme. Based on beaker cell experiments with selective cyanide sensitive electrodes, ethanol was chosen as the best organic solvent due to its stabilizing effect on the oxime, minimal interference with the aqueous electrochemistry, and compatibility with the current microsensor material (PMMA). Further studies showed that ethanol had a small effect on micro-sensor performance by reducing the rate of cyanide production and decreasing the overall response time. To avoid incomplete mixing of the aqueous and organic solutions, they were pre-mixed externally at a 10:1 ratio, respectively. To adapt the microsensor design to allow for mixing to take place within the device, a small serpentine channel component was fabricated with the same dimensions and material as the original sensor. This allowed for seamless integration of the microsensor with the serpentine mixing channel. Mixing in the serpentine microchannel takes place via diffusion. Both detector potential response and diffusional mixing improve with increased liquid residence time, and thus decreased liquid flowrate. Micromixer performance was studies at a 10:1 aqueous buffer to organic solution flow rate ratio, for a total rate of 5.5 μL/min. It was found that the sensor response utilizing the integrated micromixer was nearly identical to the response when the solutions were premixed and fed at the same rate.