Multilayered Nanostructures Integrated with Emerging Technologies

Surface and interface functionalization are crucial steps to introduce new functionalities in numerous applications, as faster dynamics occur on surfaces rather than bulk. Within this context, the layer-by-layer (LbL) technique is a versatile methodology to controllably form organized nanostructures from the spontaneous adsorption of charged molecules. It enables the assembly of multilayered LbL films on virtually any surface using non-covalent molecular interactions, allowing the nanoengineering of interfaces and creation of multifunctional systems with distinct building blocks (polymers, clays, metal nanoparticles, enzymes, organic macromolecules, etc.). Several applications require thin films on electrodes for sensing/biosensing, and here we explore LbL films deposited on interdigitated electrodes (IDEs) that were 3D-printed using the fusing deposition modeling (FDM) technique. IDEs covered with LbL films can be used to form multisensory systems employed in the analysis of complex liquids transforming raw data into specific patterns easily recognized by computational and statistical methods. We extend the FDM 3D-printing methodology to simplify the manufacturing of electrodes and microchannels, thus integrating an e-tongue system in a microfluidic device. Moreover, the continuous flow within microchannels contributes to faster and more accurate analysis, reducing the amount of sample, waste, and costs

Water at interfaces and its influence on the electrical properties of adsorbed films

This paper discusses water at interfaces with emphasis on the electrical properties of adsorbed films. Two issues are addressed, namely adsorption of organic molecules at the air/water interface in Langmuir monolayers and the influence of adsorbed water on the electrical properties of nanostructured organic films deposited onto solid substrates. In Langmuir monolayers the focus will be on the interaction of the adsorbed molecules with the underlying water, particularly with regard to the surface potential and lateral conductance of the monolayers. It will be shown that these electrical measurements are extremely sensitive to small changes in the subphase, including trace amounts of impurities. Phase transitions due to structuring of the monolayer will be discussed at the light of theoretical models that deal with proton transfer along the monolayers. Attempts will be made to connect the interpretation at the molecular level with experimental findings from techniques such as Brewster angle microscopy and fluorescence microscopy, which provide information at the mesoscopic or microscopic scale. The gradient of the dielectric constant for water at the monolayer interface is inferred from modeling the monolayer surface potential in terms of the dipole moments of the molecules. For deposited films, the discussion will be centered on the electrical properties of nanostructured films produced with either the Langmuir-Blodgett (LB) or the layer-by-layer (LBL) methods. The strong effects from adsorbed water will be presented, with mention to sensor applications where the extreme sensitivity of the electrical properties to water is exploited and to doping of a conducting polymer induced by X-ray irradiation.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

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

On the distinct molecular architectures of dipping- and spray-LbL films containing lipid vesicles

FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPCONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESThe introduction of spraying procedures to fabricate layer-by-layer (LbL) films has brought new possibilities for the control of molecular architectures and for making the LbL technique compliant with industrial processes. In this study we show that significantly distinct architectures are produced for dipping and spray-LbL films of the same components, which included DODAB/DPPG vesicles. The films differed notably in their thickness and stratified nature. The electrical response of the two types of films to aqueous solutions containing erythrosin was also different. With multidimensional projections we showed that the impedance for the DODAB/DPPG spray-LbL film is more sensitive to changes in concentration, being therefore more promising as sensing units. Furthermore, with surface-enhanced Raman scattering (SERS) we could ascribe the high sensitivity of the LbL films to adsorption of erythrosin.The introduction of spraying procedures to fabricate layer-by-layer (LbL) films has brought new possibilities for the control of molecular architectures and for making the LbL technique compliant with industrial processes. In this study we show that significantly distinct architectures are produced for dipping and spray-LbL films of the same components, which included DODAB/DPPG vesicles. The films differed notably in their thickness and stratified nature. The electrical response of the two types of films to aqueous solutions containing etythrosin was also different. With multidimensional projections we showed that the impedance for the DODAB/DPPG spray-LbL film is more sensitive to changes in concentration, being therefore more promising as sensing units. Furthermore, with surface-enhanced Raman scattering (SEES) we could ascribe the high sensitivity of the LbL films to adsorption of elythrosin.41363371FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPCONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPCONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESSem informaçãoSem informaçãoSem informaçã

Simplified fabrication of integrated microfluidic devices using fused deposition modeling 3D printing

FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPCONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESMicrofluidic devices based on polydimethylsiloxane shown a plethora of experimental possibilities due to good transparency, flexibility and ability to adhere reversibly and irreversibly to distinct materials. Though PDMS is a milestone in microfluidic developments, its cost and handling directed the field to search for new options. 3D printing technology nowadays starts a revolution offering materials and possibilities that can contribute positively to current methodologies. Here we explored the fused deposition modeling 3D printing technique to obtain integrated, transparent and sealed microchannels made with polylactic acid, a cheap alternative material to set up microfluidic systems. Using a home-made 3D printer, devices could be assembled in a simplified process, enabling the integration of different materials such as paper, glass, wire and polymers within the microchannel. To demonstrate the efficacy of this approach, a 3D-printed electronic tongue sensor was built, enabling the distinction of basic tastes below the human threshold. (C) 2016 Elsevier B.V. All rights reserved.Microfluidic devices based on polydimethylsiloxane shown a plethora of experimental possibilities due to good transparency, flexibility and ability to adhere reversibly and irreversibly to distinct materials. Though PDMS is a milestone in microfluidic developments, its cost and handling directed the field to search for new options. 3D printing technology nowadays starts a revolution offering materials and possibilities that can contribute positively to current methodologies. Here we explored the fused deposition modeling 3D printing technique to obtain integrated, transparent and sealed microchannels made with polylactic acid, a cheap alternative material to set up microfluidic systems. Using a home-made 3D printer, devices could be assembled in a simplified process, enabling the integration of different materials such as paper, glass, wire and polymers within the microchannel. To demonstrate the efficacy of this approach, a 3D-printed electronic tongue sensor was built, enabling the distinction of basic tastes below the human threshold.2423540FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPCONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPCONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPES2014/03691-7Sem informaçãoSem informaçã

Ultra-Thin Films of Reduced Graphene Oxide (RGO) Nanoplatelets Functionalized with Different Organic Materials

This work aims the functionalization of reduced graphene oxide nanoplatelets with chitosan (G-chitosan) and also with poly(styrenesulfonic acid) (GPSS), thus forming stable, dispersed aqueous solutions. G-chitosan and GPSS solutions allowed the layer-by-layer (LbL) film formation with glucose oxidase (GOx), establishing multilayered nanostructures with elevated control in thickness and morphology. The graphene nanoplatelets were characterized by UV-vis and FTIR spectroscopies, resulting in good adherence and linear deposition of the graphene nanoplatelets with GOx in the LbL structures.Cyclic voltammetry shows an enlargement in the current intensity with increasing number of deposited LbL layers, possibly owing to the formation of conducting paths by the graphene nanoplatelets in the tailored multilayer nanomaterial forme

Immobilization of cholesterol oxidase in LbL films and detection of cholesterol using ac measurements

The preserved activity of immobilized biomolecules in layer-by-layer (LbL) films can be exploited in various applications. including biosensing. In this study, cholesterol oxidase (COX) layers were alternated with layers of poly(allylamine hydrochloride) (PAH) in LbL films whose morphology was investigated with atomic force microscopy (AFM). The adsorption kinetics of COX layers comprised two regimes, a fast, first-order kinetics process followed by a slow process fitted with a Johnson-Mehl-Avrami (JMA) function. with exponent similar to 2 characteristic of aggregates growing as disks. The concept based on the use of sensor arrays to increase sensitivity, widely employed in electronic tongues, was extended to biosensing with impedance spectroscopy measurements. Using three sensing units, made of LbL films of PAH/COX and PAHIPVS (polyvinyl sulfonic acid) and a bare gold interdigitated electrode, we were able to detect cholesterol in aqueous solutions down to the 10(-6) M level. This high sensitivity is attributed to the molecular-recognition interaction between COX and cholesterol, and opens the way for clinical tests to be made with low cost. fast experimental procedures. (C) 2008 Published by Elsevier B.V.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)FAPESPConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)CNPqCAPES (Brazil)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES