Nanostructured films employed as sensing units in an electronic tongue system

Nanostructured films of lignin (macromolecule extracted from sugar cane bagasse), polypyrrole (conducting polymer) and bis butylimido perylene (organic dye) were used in the detection of trace levels of fluorine (from H2SiF6), chlorine (from NaCIO), Pb+2, Cu+2, and Cd+2 in aqueous solutions. Langmuir monolayers on ultrapure water were characterised by surface pressure-mean molecular area (II-A) isotherms. Langmuir-Blodgett (LB) films were transferred onto gold interdigitated electrodes and used as individual sensing units of an electronic tongue system. Impedance spectroscopy measurements were taken with the sensor immersed into aqueous solutions containing the ions described above in different molar concentrations. Fourier transform infrared absorption (FTIR) was employed to identify possible interactions between the LB films and the analytes in solution, and no significant changes could be observed in the FTIR spectra of BuPTCD and Ppy. Therefore, the results for lignin point to an interaction involving the electronic cloud of the phenyl groups with the metallic ions.

Lignin from sugar cane bagasse: Extraction, fabrication of nanostructured films, and application

Four lignin samples were extracted from sugar cane bagasse using four different alcohols (methanol, ethanol, n-propanol, and 1-butanol) via the organosolv-CO2 supercritical pulping process. Langmuir films were characterized by surface pressure vs mean molecular area (Pi-A) isotherms to exploit information at the molecular level carrying out stability tests, cycles of compression/expansion (hysteresis), subphase temperature variations, and metallic ions dissolved into the water subphase at different concentrations. Briefly, it was observed that these lignins are relatively stable on the water surface when compared to those obtained via different extraction processes. Besides, the Pi-A isotherms are shifted to smaller molecular areas at higher subphase temperatures and to larger molecular areas when the metallic ions are dissolved into the subphase. The results are related to the formation of stable aggregates (domains) onto the water subphase by these lignins, as shown in the Pi-A isotherms. It was found as well that the most stable lignin monolayer onto the water subphase is that extracted with 1-butanol. Homogeneous Langmuir-Blodgett (LB) films of this lignin could be produced as confirmed by UV-vis absorption spectroscopy and the cumulative transfer parameter. In addition, FTIR analysis showed that this lignin LB film is structured in a way that the phenyl groups are organized preferentially parallel to the substrate surface. Further, these LB films were deposited onto gold interdigitated electrodes and ITO and applied in studies involving the detection of Cd+2 ions in aqueous solutions at low concentration levels throughimpedance spectroscopy and electrochemical measurements. FTIR spectroscopy was carried out before and after soaking the thin films into Cd+2 aqueous solutions, revealing a possible physical interaction between the lignin phenyl groups and the heavy metal ions. The importance of using nanostructured systems is demonstrated as well by comparing both LB and cast films.

Nanostructured films of perylene derivatives: High performance materials for taste sensor applications

Four perylene derivatives (PTCD) have been used as transducing materials in taste sensors fabricated with nanostructured Langmuir-Blodgett (LB) films deposited onto interdigitated gold electrodes. The Langmuir monolayers of PTCDs display considerable collapse pressures, with areas per molecule indicative of an edge-on or head-on arrangement for the molecules at the air/water interface. The sensing units for the electronic tongue were produced from 5-layer LB films of the four PTCDs, whose electrical response was characterized with impedance spectroscopy. The distinct responses of the PTCDs, attributed to differences in their molecular structures, allowed one to obtain a finger printing system that was able to distinguish tastes (salty, sweet, bitter and sour) at 1 μM concentrations, which, in some cases, are three orders of magnitude below the human threshold. Using Principal Component Analysis (PCA) data analysis, the electronic tongue also detected trace amounts of a pesticide and could distinguish among samples of ultrapure, distilled and tap water, and two brands of mineral water. © 2004 by American Scientific Publishers. All rights reserved.

Estudo da interação da natamicina com membranas fosfolipídicas incorporadas de esteróis

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Vibrational spectroscopy for probing molecular-level interactions in organic films mimicking biointerfaces

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Synergistic electrocatalytic effect of nanostructured mixed films formed by functionalised gold nanoparticles and bisphthalocyanines

A synergistic electrocatalytic effect was observed in sensors where two electrocatalytic materials (functionalized gold nanoparticles and lutetium bisphthalocyanine) were co-deposited using the Langmuir-Blodgett technique. Films were prepared using a novel method where water soluble functionalised gold nanoparticles [(11-mercaptoundecyl)tetra(ethylene glycol)] (SAuNPs) were inserted in floating films of lutetium bisphthalocyanine (LuPc2) and dimethyldioctadecylammonium bromide (DODAB) as the amphiphilic matrix. The formation of stable and homogeneous mixed films was confirmed by pi-A isotherms, BAM, UV-vis and Raman spectroscopy, as well as by SEM and TEM microscopy. The synergistic effect towards hydroquinone of the electrodes modified with LuPc2:DODAB/SAuNP was characterised by an increase in the intensity of the redox peaks and a reduction of the overpotential. This synergistic electrocatalytic effect arose from the interaction between the SAuNPs and the phthalocyanines that occur in the Langmuir-Blodgett films and from the high surface area provided by the nanostructured films. The sensitivity increased with the amount of LuPc2 and SAuNPs inserted in the films and limits of detection in the range of 10(-7) mol L-1 were attained. (C) 2014 Elsevier B.V. All rights reserved.

Sprayed films of europium complexes toward light conversion devices

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Structural and Electrochemical Properties of Lutetium Bis-Octachloro-Phthalocyaninate Nanostructured Films. Application as Voltammetric Sensors

Thin films of the bis[2,3,9,10,16,17,23,24-octachlorophthalocyaninate] lutetium(III) complex (LuPc2Cl32) have been prepared by the Langmuir-Blodgett and the Langmuir-Schaefer (LS) techniques. The influence of the chlorine substituents in the structure of the films and in their spectroscopic, electrochemical and sensing properties has been evaluated. The pi-A isotherms exhibit a monolayer stability greater than the observed in the unsubstituted analogue (LuPc2), being easily transferred to solid substrates, also in contrast to LuPc2. The LB and LS films present a linear growth forming stratified layers, monitored by UV-VIS absorption spectroscopy. The latter also revealed the presence of LuPc2Cl32 in the form of monomers and aggregates in both films. The FTIR data showed that the LuPc2Cl32 molecules present a non-preferential arrangement in both films. Monolayers of LB and LS were deposited onto 6 nm Ag island films to record surface-enhanced resonance Raman scattering (SERRS), leading to enhancement factors close to 2 x 10(3). Finally, LB and LS films deposited onto ITO glass have been successfully used as voltammetric sensors for the detection of catechol. The improved electroactivity of the LB and LS films has been confirmed by the reduction of the overpotential of the oxidation of catechol. The enhancement of the electrocatalytic effect observed in LB and LS films is the result of the nanostructured arrangement of the surface which increases the number of active sites. The sensors show a limit of detection in the range of 10(-5) mol/L.

Supramolecular arrangements of an organometallic forming nanostructured films

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Estudo de interação entre um hormônio estrógeno e modelos simples de membrana biológica

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Coeficientes de difusão de metais em materiais não convencionais (agarose e acetato de celulose) usados na técnica de difusão em filmes finos por gradientes de concentração

The DGT technique allows one to measure quantitatively free and labile metal species in aquatic systems. Nevertheless, for this approach, knowledge is required of the diffusion coefficients of the analytes in a diffusive layer. In this study, the diffusion coefficients of Hg(II), As(III), Mn(II), Mg(II), Cu(II), Cd(II) were determined in agarose gel and those of Ba(II), Cd(II), Cu(II), Mg(II), Mn(II) e Zn(II) in cellulose acetate membranes. These materials presented good performance and the reported results can be used as a data base for further DGT studies.

Conservação pós-colheita de frutos de pimentão sob diferentes condições de armazenamento e filmes

Este trabalho teve como objetivo avaliar diferentes temperaturas e coberturas na conservação de frutos de pimentão 'Magali-R'. No primeiro experimento, avaliou-se o uso de filme de PVC ou cera, e os frutos foram armazenados a 20ºC e 66%UR, e no segundo experimento associou-se o filme de PVC e cera, com armazenamento a 22°C (67% UR); 12ºC (90% UR) e 5ºC (87% UR). Acompanhou-se a evolução da qualidade dos frutos avaliando-se a massa fresca, a aparência, o aparecimento de podridões e os teores de sólidos solúveis, acidez titulável e ácido ascórbico. A proteção dos pimentões com cera ou filme de PVC foi favorável à manutenção da aparência e da massa fresca, e protegeu-os contra podridões, sem prejuízos aos teores de sólidos solúveis, acidez titulável e ácido ascórbico, com aumento significativo na vida útil para até 33 dias com o armazenamento a 5°C.

Aditivos de formulação na formação de filmes isolados de etilcelulose. estudos físico-químicos e morfológicos

Formulation Additives on Formation of Films isolated from Ethylcellulose. Physicochemical and Morphological Studies. In this work were developed free films from Surelease (R), additives alpha-GOS (alfa-glucooligosaccharide) and/or Tween (R) 80 in aqueous solution. It was obtained by Teflon plates casting process. The free films were characterized by thermal analysis (DSC and TGA), infrared spectroscopy (FTIR-ATR) and scanning electron microscopy (SEM). DSC and TO analysis showed that the additives do not influenced in the thermal stability of Surelease (R) films. SEM analysis observed homogeneous morphological characteristics and phase detachment absence. FTIR-ATR spectra were used to confirm the physical mixture between the components of films.

Study of the interaction between cardiolipin bilayers and methylene blue in polymer-based Layer-by-Layer and Langmuir films applied as membrane mimetic systems

An increase of the reports involving mimetic systems has been observed. Briefly, these systems use biological phospholipids to exploit specific interactions between membrane-models and drugs. Here, the Layer-by-Layer (LbL) and Langmuir techniques were used to investigate the interaction between cardiolipin (CLP-negative phospholipid) and a cationic-like drug methylene blue (MB). Supported by a cationic polyelectrolyte (PAH), LbL films containing PAH/(CLP + MB) and PAH/(CLP + MB + AgNP) were grown up to 14 bilayers. The optical microscopy analysis revealed a decrease of the CLP vesicle sizes in the presence of MB as a possible consequence of the MB action onto the mechanical properties of the CLP membrane. From FTIR spectra, changes mainly related to peak position and band intensity and shape were observed in the spectra from PAH/CLP when in the presence of MB. The latter supports that the interactions between the phosphate and amine charged groups from CLP and PAH, respectively, established during the LbL film fabrication, besides the CLP hydrocarbon environment, are influenced by the presence of MB. Using the micro-Raman technique, a chemical mapping was build based on MB spectrum by resonance Raman scattering (RRS) and surface-enhanced resonance Raman scattering (SERRS). The later phenomenon was activated by Ag nanoparticles (AgNPs) trapped within the LbL film allowing collecting spectra for a single bilayer of PAH/(CLP + MB + AgNP). A rough estimation showed a SERRS amplification of 10(3) in comparison to RRS spectra. As a complementary approach, Langmuir films of CLP in the presence of co-spread MB were investigated through surface pressure vs mean molecular area (pi-A) isotherms. The results showed that for concentrations of MB below 100 mol%, the drug is expelled to water subphase for high values of surface pressure (condensed phase). For concentration at 100% and higher, the MB keeps bound to CLP floating monolayer. (C) 2010 Elsevier B.V. All rights reserved.

Construção de um sistema de caracterização das propriedades de transporte de filmes finos pelo efeito Hall

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)