Langmuir films of an amide extracted from Piperaceae and its interaction with phospholipids

In this work, we investigate Langmuir monolayers froth an amide extracted from dried roots of Ottonia propinqua, a native Brazilian plant believed to exhibit anesthetic and hallucinogen activities. In addition to producing monolayers from the amide itself, we probe the molecular-level action of the amide on phospholipids employed as simple membrane models. The surface pressure-molecular area (pi-A) isotherms for the amide were little affected by a number of subphase conditions. Almost no changes were observed upon varying the compression speed, spreading volume onto the surface, ions in the subphase, ionic strength and the solution solvent. However, stronger effects occurred when the subphase temperature and pH were altered, as the isotherms were shifted to larger areas with increasing temperatures and decreasing pHs. These results are discussed in terms of the molecular packing adopted by the amide at the air-water interface. In the mixed films with arachidic acid, the area per molecule varied linearly with the concentration of amide, probably due to phase separation. on the other hand, in the mixed films with dipalmitoyl phosphatidyl choline (DPPC), small amounts of the amide were sufficient to change the pi-A isotherms significantly. This points to a strong molecular-level interaction, probably between the phosphate group in the zwitterion of DPPC and the nitrogen from the amidic group. (c) 2004 Elsevier B.V. All rights reserved.

Efeito da adição de moléculas anfifílicas na formação de filmes Langmuir e Langmuir-Blodgett de derivados alquilados do politiofeno: aplicação em sensores

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Co-deposition of gold nanoparticles and metalloporphyrin using the langmuir-blodgett (LB) technique for Surface-Enhanced Raman Scattering (SERS)

The synergistic effect produced by metallic nanoparticles when incorporated into different systems empowers a research field that is growing rapidly. In addition, organometallic materials are at the center of intensive research with diverse applications such as light-emitting devices, transistors, solar cells, and sensors. The Langmuir-Blodgett (LB) technique has proven to be suitable to address challenges inherent to organic devices, since the film properties can be tuned at the molecular level. Here we report a strategy to incorporate gold nanoparticles (AuNPs) into the LB film by co-deposition in order to achieve surface-enhanced Raman scattering (SERS) of the zinc(II)-protoporphyrin (IX) dimethyl ester (ZnPPIX-DME). Prior to the LB co-deposition, the properties of the Langmuir monolayer of ZnPPIX-DME at the air-water interface, containing AuNPs in the subphase, are studied through the surface-pressure versus mean molecular area (π-A) isotherms. The ZnPPIX-DME+AuNPs π-A isotherm presented a significant shift to higher molecular area, suggesting an interaction between both ZnPPIX-DME molecules and AuNPs. Those interactions are a key factor allowing the co-deposition of both AuNPs and ZnPPIX-DME molecules onto a solid substrate, thus forming the LB film. SERS of ZnPPIX-DME was successfully attained, ensuring the spatial distribution of the AuNPs. Higher enhancement factors were found at AuNP aggregates, as a result of the intense local electromagnetic field found in the metal nanoparticle aggregates. The main vibrational bands observed in the SERS spectra suggest a physical adsorption of the ZnPPIX-DME onto the surface of AuNPs. The latter is not only in agreement with the interactions pointed out by the π-A isotherms but also suggests that this interaction is kept upon LB film co-deposition.

Filmes de Langmuir-Blodgett de nanopartículas de prata

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Propriedades luminescentes de polioxometalato contendo európio(III) correlacionadas à sua conformação em sólido estendido e em filmes auto-organizados de Langmuir e Langmuir-Blodgett

Pós-graduação em Química - IQ

Wine classification by taste sensors made from ultra-thin films and using neural networks

This paper reports on a sensor array able to distinguish tastes and used to classify red wines. The array comprises sensing units made from Langmuir-Blodgett (LB) films of conducting polymers and lipids and layer-by-layer (LBL) films from chitosan deposited onto gold interdigitated electrodes. Using impedance spectroscopy as the principle of detection, we show that distinct clusters can be identified in principal component analysis (PCA) plots for six types of red wine. Distinction can be made with regard to vintage, vineyard and brands of the red wine. Furthermore, if the data are treated with artificial neural networks (ANNs), this artificial tongue can identify wine samples stored under different conditions. This is illustrated by considering 900 wine samples, obtained with 30 measurements for each of the five bottles of the six wines, which could be recognised with 100% accuracy using the algorithms Standard Backpropagation and Backpropagation momentum in the ANNs. (C) 2003 Elsevier B.V. All rights reserved.

Surface-enhanced resonance Raman scattering: Single-molecule detection in a Langmuir-Blodgett monolayer

Surface-enhanced resonance Raman scattering (SERRS) is used for single-molecule detection from spatially resolved 1-mum(2) sections of a Langmuir-Blodgett (LB) monolayer deposited onto a Ag film. The target molecule, his (benzimidazo) thioperylene (BZP), is dispersed in an arachidic acid monomolecular layer containing one BZP molecule per mum(2) which is also the probing area of the Raman microscope. For concentrated samples (attomole quantities in the field of view), average SERRS, surface-enhanced fluorescence (SEF), and Raman imaging, including line mapping and global images at different temperatures, were recorded. Single-molecule SERRS spectra, obtained using an LB monolayer, present changes in bandwidth and relative intensities, highlighting the properties of single-molecule SERRS that are lost in average SERRS measurements of mixed LB monolayers obtained at the same temperatures. Also, the dilute system phenomenon of blinking is discussed with regard to results obtained from LB monolayers. The dilution process used in the single-molecule LB SERRS work is independently supported by fluorescence results obtained from very dilute solutions with monomer concentrations down to 10(-12) M.

Monomolecular films of cholesterol oxidase and S-Layer proteins

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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

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

Surface morphology and optical characterization of OC1 OC6-PPV films

We report optical and morphological properties of poly(2-methoxy-5-hexyloxy-p-phenylenevinylene) (OC1OC6-PPV) films processed by casting, spin-coating (SC) and Langmuir-Blodgett (LB) techniques. The absorption spectra are practically the same, with an absorption maximum at approximately at 500 nm. For the photoluminescence (PL) spectra at low temperature (T=10K), a small but significant difference was noted in the cast film, in comparison with the LB and SC films. The zero-phonon transition shifted from 609 nm for the LB film to 615 and 621 nm for the SC and cast films, respectively. At room temperature, the PL spectra are similar for all films, and blue shifted by ca. 25 nm in comparison with the spectra at low temperature due to thermal disorder. Using atomic force microscopy (AFM) we inferred that the distinctive behavior of the cast film, probably associated with structural defects, is related to the large thickness of this film. The surface roughness, which was surprisingly higher for the LB film, apparently played no role in the emission properties of OC1OC6-PPV films.

Soliton model for proton conductivity in Langmuir films

A soliton model for proton conductivity in Langmuir films is presented. The model contains three real scalar fields describing the hydrogen involved in the conduction, the hydrophilic head of the Langmuir film, and the water. Soliton solutions that describe proton motion along the hydrogen bonds are found. Under compression of the film, the distance between the minima of the proton potential and the strength of the hydrogen bonds between the film molecule and the water are changed. Such changes increase the probability of soliton creation. The model. presented allows proton conductivity data in Langmuir films to be explained. (C) 2001 Published by Elsevier B.V. B.V.

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.

The influence of preparation method of OC1OC6-PPV films on the photo-oxidation process

Poly(p-phenylene vinylene) (PPV) derivatives are well known for their applications in polymer light emitting diodes (PLEDs). PPV derivatives are highly susceptible to photo-oxidation though, which is mainly caused by the scission of the vinyl double bond on the polymer backbone. In this work, we show that Langmuir-Blodgett (LB) films are less degraded than cast films of a PPV derivative (OC1OC6-PPV). Both films had similar thickness (similar to 50 nm) to allow for a more realistic comparison. Degradation was monitored with UV-vis and FTIR spectroscopies. The results indicated that cast films were completely degraded in ca. 400 min, while LB took longer time, i.e. about four times the values for the cast films. The differences can be attributed to the more compact morphology in the LB than in the cast films. With a compact morphology the diffusion of oxygen in the LB film is hampered and this causes a delay in the degradation process. (c) 2006 Elsevier Ltd. All rights reserved.

Interaction of small amounts of bovine serum albumin with phospholipid monolayers investigated by surface pressure and atomic force microscopy

The influence of small amounts of bovine serum albumin (BSA) (nM concentration) on the lateral organization of phospholipid monolayers at the air-water interface and transferred onto solid substrates as one-layer Langmuir-Blodgett (LB) films was investigated. The kinetics of adsorption of BSA onto the phospholipid monolayers was monitored with surface pressure isotherms in a Langmuir trough, for the zwitterionic dipalmitoylphosphatidyl ethanolamine (N,N-dimethyl-PE) and the anionic dimyristoylphosphatidic acid (DMPA). A monolayer of N,N-dimethyl-PE or DMPA incorporating BSA was transferred onto a solid substrate using the Langmuir-Blodgett technique. Atomic force microscopy (AFM) images of one-layer LB films displayed protein-phospholipid domains, whose morphology was characterized using dynamic scaling theories to calculate roughness exponents. For DMPA-BSA films the surface is characteristic of self-affine fractals, which may be described with the Kardar-Parisi-Zhang (KPZ) equation. on the other hand, for N,N-dimethyl-PE-BSA films, the results indicate a relatively flat surface within the globule. The height profile and the number and size of globules varied with the type of phospholipid. The overall results, from kinetics of adsorption on Langmuir monolayers and surface morphology in LB films, could be interpreted in terms of the higher affinity of BSA to the anionic DMPA than to the zwitterionic N,N-dimethyl-PE. Furthermore, the effects from such small amounts of BSA in the monolayer point to a cooperative response of DMPA and N,N-dimethyl-PE monolayers to the protein. (c) 2005 Elsevier B.V. All rights reserved.

Layer-by-Layer Technique as a New Approach to Produce Nanostructured Films Containing Phospholipids as Transducers in Sensing Applications

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