Development of multifunctional coatings deposited on polymers based sensors for biomedical applications

Tese de Doutoramento (Programa Doutoral em Engenharia de Materiais)

Development of Electrochemical and Fluorescent Sensors

Chemical sensors have growing interest in the determination of food additives, which are creating toxicity and may cause serious health concern, drugs and metal ions. A chemical sensor can be defined as a device that transforms chemical information, ranging from the concentration of a specific sample component to total composition analysis, into an analytically useful signal. The chemical information may be generated from a chemical reaction of the analyte or from a physical property of the system investigated. Two main steps involved in the functioning of a chemical sensor are recognition and transduction. Chemical sensors employ specific transduction techniques to yield analyte information. The most widely used techniques employed in chemical sensors are optical absorption, luminescence, redox potential etc. According to the operating principle of the transducer, chemical sensors may be classified as electrochemical sensors, optical sensors, mass sensitive sensors, heat sensitive sensors etc. Electrochemical sensors are devices that transform the effect of the electrochemical interaction between analyte and electrode into a useful signal. They are very widespread as they use simple instrumentation, very good sensitivity with wide linear concentration ranges, rapid analysis time and simultaneous determination of several analytes. These include voltammetric, potentiometric and amperometric sensors. Fluorescence sensing of chemical and biochemical analytes is an active area of research. Any phenomenon that results in a change of fluorescence intensity, anisotropy or lifetime can be used for sensing. The fluorophores are mixed with the analyte solution and excited at its corresponding wavelength. The change in fluorescence intensity (enhancement or quenching) is directly related to the concentration of the analyte. Fluorescence quenching refers to any process that decreases the fluorescence intensity of a sample. A variety of molecular rearrangements, energy transfer, ground-state complex formation and collisional quenching. Generally, fluorescence quenching can occur by two different mechanisms, dynamic quenching and static quenching. The thesis presents the development of voltammetric and fluorescent sensors for the analysis of pharmaceuticals, food additives metal ions. The developed sensors were successfully applied for the determination of analytes in real samples. Chemical sensors have multidisciplinary applications. The development and application of voltammetric and optical sensors continue to be an exciting and expanding area of research in analytical chemistry. The synthesis of biocompatible fluorophores and their use in clinical analysis, and the development of disposable sensors for clinical analysis is still a challenging task. The ability to make sensitive and selective measurements and the requirement of less expensive equipment make electrochemical and fluorescence based sensors attractive.

Confinement effects and why carbon nanotube bundles can work as gas sensors

Carbon nanotubes have been at the forefront of nanotechnology, leading not only to a better understanding of the basic properties of charge transport in one dimensional materials, but also to the perspective of a variety of possible applications, including highly sensitive sensors. Practical issues, however, have led to the use of bundles of nanotubes in devices, instead of isolated single nanotubes. From a theoretical perspective, the understanding of charge transport in such bundles, and how it is affected by the adsorption of molecules, has been very limited, one of the reasons being the sheer size of the calculations. A frequent option has been the extrapolation of knowledge gained from single tubes to the properties of bundles. In the present work we show that such procedure is not correct, and that there are qualitative differences in the effects caused by molecules on the charge transport in bundles versus isolated nanotubes. Using a combination of density functional theory and recursive Green's function techniques we show that the adsorption of molecules randomly distributed onto the walls of carbon nanotube bundles leads to changes in the charge density and consequently to significant alterations in the conductance even in pristine tubes. We show that this effect is driven by confinement which is not present in isolated nanotubes. Furthermore, a low concentration of dopants randomly adsorbed along a two-hundred nm long bundle drives a change in the transport regime; from ballistic to diffusive, which can account for the high sensitivity to different molecules.

Relationship between surface segregation and rapid propane electrical response in Cd-doped SnO2 nanornaterials

Controlling the surface properties of nanoparticles using ionic dopants prone to be surface segregated has emerged as an interesting tool for obtaining highly selective and sensitive sensors. In this work, the surface segregation of Cd cations on SnO2 nanopowders prepared by the Pechini`s method was studied by infrared spectroscopy, X-ray diffraction, and specific surface area analysis. We observed that the surface chemistry modifications caused by the surface segregation of Cd and the large specific surface area were closely responsible for a rapid and regular electrical response of 5 mol% Cd-doped SnO2 films to 100 ppm propane and NO, diluted in dry air at relatively low temperature (100 degrees C). (c) 2008 Elsevier B.V. All rights reserved.

Aryleneethynylene Trimers Bearing Calix[4]arenes: synthesis, optical properties and self-assembling studies

New homoditopic bis-calix[4]arene-carbazole conjugates, armed with hydrophilic carboxylic acid functions at their lower rims, are disclosed. Evidence for their self-association in solution was gathered from solvatochromic and thermochromic studies, as well as from gel-permeation chromatography analysis. Their ability to function as highly sensitive sensors toward polar electron-deficient aromatic compounds is demonstrated.

Label-free Detection of Microcystin-LR in Waters Using Real-Time Potentiometric Biosensors Based on Single-Walled Carbon Nanotubes Imprinted Polymers

Microcystin-LR (MC-LR) is a dangerous toxin found in environmental waters, quantified by high performance liquid chromatography and/or enzyme-linked immunosorbent assays. Quick, low cost and on-site analysis is thus required to ensure human safety and wide screening programs. This work proposes label-free potentiometric sensors made of solid-contact electrodes coated with a surface imprinted polymer on the surface of Multi-Walled Carbon NanoTubes (CNTs) incorporated in a polyvinyl chloride membrane. The imprinting effect was checked by using non-imprinted materials. The MC-LR sensitive sensors were evaluated, characterized and applied successfully in spiked environmental waters. The presented method offered the advantages of low cost, portability, easy operation and suitability for adaptation to flow methods.

Competence foresight: linking the identification of HR competences and competence management alignment with business strategy

The objective of this study was to increase understanding of the link between the identification of required HR competences and competence management alignment with business strategy in a Finnish, global company employing over 8,000 people and about 100 HR professionals. This aim was approached by analyzing the data collected in focus group interviews using a grounded theory method and in parallel reviewing the literature of strategic human resource management, competence-based strategic management, strategy and foresight. The literature on competence management in different contexts dismisses in-depth discussions on the foresight process and individuals are often forgotten in strategic frameworks. However, corporate foresight helps in the detection of emerging opportunities for innovations and in the implementation of strategy. The empirical findings indicate a lack of strategic leadership and an alignment with HR and business. Accordingly, the most important HR competence areas identified were the need for increasing business understanding and enabling change. As a result, the study provided a holistic model for competence foresight, which introduces HR professionals as strategic change agents in the role of organizational futurists at the heart of the company: facilitating competence foresight and competence development on individual as well as organizational levels, resulting in an agile organization with increased business understanding, sensitive sensors and adaptive actions to enable change.

Dendrimer-assisted immobilization of alcohol dehydrogenase in nanostructured films for biosensing: Ethanol detection using electrical capacitance measurements

The selective determination of alcohol molecules either in aqueous solutions or in vapor phase is of great importance for several technological areas. In the last years, a number of researchers have reported the fabrication of highly sensitive sensors for ethanol detection, based upon specific enzymatic reactions occurring at the surface of enzyme-containing electrodes. In this study, the enzyme alcohol dehydrogenase (ADH) was immobilized in a layer-by-layer fashion onto Au-interdigitated electrodes (IDEs), in conjunction with layers of PAMAM dendrimers. The immobilization process was followed in Teal time using quartz crystal microbalance (QCM), indicating that an average mass of 52.1 ng of ADH was adsorbed at each deposition step. Detection was carried out using a novel strategy entirely based upon electrical capacitance measurements, through which ethanol could be detected at concentrations of 1 part per million by volume (ppmv). (C) 2007 Elsevier B.V. All rights reserved.

A disposable chitosan-modified carbon fiber electrode for dengue virus envelope protein detection

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Laser stimulated light reflection for TeO2-WO 3-Bi2O3 thin films with incorporated Si nanoparticles

A novel method of preparation of the Si nanoparticles (NPs) incorporated in tellurite TeO2-WO3-Bi2O3 (TWB) thin films is proposed. This mew method applies RF magnetron sputtering technique at room temperature. The incorporation of Si NP was confirmed by transmission electron microscopy (TEM); isolated Si NPs with diameters of around 6 nm are observed. Energy dispersive X-ray spectroscopy (EDS) was performed during TEM analysis in order to confirm the presence of Si NP and also the other elements of the thin film. The thin films are explored with respect to the photoinduced changes of the reflectivity within the 400-65 nm spectra range using a 10 ns pulsed Nd:YAG with power densities varying up to 400 MW/cm2 and beam diameter within the 3-5 mm range. The observed processes are analyzed within a framework of trapping level conceptions for the Si NP. The possible application of the discovered materials as optical sensitive sensors is proposed. © 2013 Elsevier B.V.

Highly sensitive biological and chemical sensors based on reversible fluorescence quenching in a conjugated polymer

The fluorescence of a polyanionic conjugated polymer can be quenched by extremely low concentrations of cationic electron acceptors in aqueous solutions. We report a greater than million-fold amplification of the sensitivity to fluorescence quenching compared with corresponding “molecular excited states.” Using a combination of steady-state and ultrafast spectroscopy, we have established that the dramatic quenching results from weak complex formation [polymer(−)/quencher(+)], followed by ultrafast electron transfer from excitations on the entire polymer chain to the quencher, with a time constant of 650 fs. Because of the weak complex formation, the quenching can be selectively reversed by using a quencher-recognition diad. We have constructed such a diad and demonstrate that the fluorescence is fully recovered on binding between the recognition site and a specific analyte protein. In both solutions and thin films, this reversible fluorescence quenching provides the basis for a new class of highly sensitive biological and chemical sensors.

Highly sensitive temperature and strain sensors based on all-fiber 45°-TFG Lyot filter

We demonstrate highly sensitive temperature and strain sensors based on an all-fiber Lyot filter structure, which is formed by concatenating two 45°-TFGs (tilted fiber gratings) with a PM fiber cavity. The experiment results show the all-fiber 45°-TFG Lyot filter has very high sensitivity to strain and temperature. The 45°-TFG Lyot filters of two different cavity lengths (18cm and 40 cm) have been evaluated for temperature sensing by heating a section of the cavity from 10°C to 50°C. The experiment results have shown remarkably high temperature sensitivities of 0.616nm/°C for 18cm and 0.31nm/°C for 40cm long cavity filter, respectively. The 18cm long cavity filter has been subjected to strain variations up to around 550μ ε and the filter has exhibited strain sensitivities of 0.02499nm/μ ε and 0.012nm/μ ε for two straining situations, where its cavity middle section of 18cm and 9cm were stretched, respectively. © 2012 SPIE.

Highly sensitive type IA fiber Bragg gratings as sensors in radiation environments

Type IA fiber gratings have unusual physical properties compared with other grating types. We compare with performance characteristics of Type IA and Type I Bragg gratings exposed to the effects of Co60 gamma-irradiation. A Bragg peak shift of 190 pm was observed for Type IA gratings written in Fibercore PS-1250/1500 photosensitive fiber at a radiation dose of 116 kGy. This is the largest wavelength shift recorded to date under radiation exposure. The Type IA and Type I gratings show different kinetics under radiation and during post-radiation annealing; this can be exploited for the design of a grating based dosimetry system. © 2012 SPIE.

Functionalized macrocyclic compounds: potential sensors of small molecules and ions

The potential applications of macrocycles in chemistry and at its interfaces with biology and physics continue to emerge, one of which is as receptors for small molecules and ions. This review illustrates these applications with examples from the last ten years employing complexation as the binding mechanism; some of the systems presented have already found real-world sensor applications. In any case, the challenges remain to design more selective and sensitive receptors for guests.

Piezoresistive sensors for force mapping of hip-prostheses

The success of artificial prosthetic replacements depends on the fixation of the artificial prosthetic component after being implanted in the thighbone. The materials for fixation are subject to mechanical stresses, which originate permanent deformations, incipient cracks and even fatigue fractures. This work shows the possibility of monitoring the mechanical stress over time in prosthesis. In this way, highly sensitive silicon thin-film piezoresistive sensors were developed attached to prosthesis and their results compared with commercial strain gauge sensors. Mechanical stress-strain experiments were performed in compressive mode, during 10,000 cycles. Experimental data was acquired at mechanical vibration frequencies of 0.5 Hz, 1 Hz and 5 Hz, and sent to a computer by means of a wireless link. The results show that there is a decrease in sensitivity of the thin-film silicon piezoresistive sensors when they are attached to the prosthesis, but this decrease does not compromise its monitoring performance. The sensitivity, compared to that of commercial strain gauges, is much larger due to their higher gauge factors (-23.5), when compared to the GFs of commercial sensors (2).