Photo-oxidation of polyphenylenevinylene chains in Langmuir-Blodgett and cast films

Poly(p-phenylene vinylene) (PPV) derivatives are well known for their applications in polymer light emitting diodes (PLEDs). These derivatives are highly susceptible to photooxidation 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 (∼50 nm) to allow for a more realistic comparison. Photodegradation experiments were carried out by illuminating the films with white light from a halogen lamp (50W, 12 V), placed at a fixed dstance from the sample. The decay was monitored by UV-Vis and FTIR spectroscopies. The results showed that cast films are completely degraded in ca. 300 min, while LB took longer times, ca. 1000 min, i.e. 3 times the values for the cast films. The degradation process occurs in at least two stages, the rates of which were calculated assuming that the reaction follows a first order kinetics. The characteristic times for the first stage were 3.6×10-2 and 1.3×10-3 min-1 for cast and LB films, respectively. For the second stage the characteristic times were 5.6×10-2 and 5.0×10 -3 min-1. 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.

Polymer light emitting devices with Langmuir Blodgett (LB) films of a polyfluorene derivative

Polyfluorenes are promising materials for the emitting layer of polymer light emitting devices (PLEDs) with blue emission. In this work, we report on PLEDs fabricated with Langmuir-Blodgett (LB) films of a polyfluorene derivative, namely poly(9,9-di-hexylfluorenediyl vinylene-alt-1,4-phenylenevinylene) (PDHF-PV). Y-type LB films were transferred onto ITO substrates at a surface pressure of 35 mN m-1 and with dipping speed of 3 mm min -1. A thin aluminum layer was evaporated on top of the LB film, thus yielding a sandwich structure (ITO/PDHF-PV(LB)/Al). Current-voltage (I vs V) measurements indicate that the device displays a classical behavior of a rectifying diode. The threshold value is approximately 5 V, and the onset for visible light emission occurs at ca. 10 V. From the a.c. electrical responses we infer that the active layer has a typical behavior of PLEDs where the real component of ac conductivity obeys a power-law with the frequency. Cole-Cole plots (Im(Z) vs. Re(Z)) for the device exhibit a series of semicircles, the diameter of which decreases with increasing forward bias. This PLED structure is modeled by a parallel resistance and capacitance combination, representing the dominant mechanisms of charge transport and polarization in the organic layer, in series with a resistance representing the ITO contact. Overall, the results presented here demonstrate the feasibility of LEDs made with LB films of PDHF-PV.

SERS mapping in langmuir-blodgett films and single-molecule detection

Plasmon-enhanced spectroscopic techniques have expanded single-molecule detection (SMD) and are revolutionizing areas such as bio-imaging and single-cell manipulation. Surface-enhanced (resonance) Raman scattering (SERS or SERRS) combines high sensitivity with molecularfingerprint information at the single-molecule level. Spectra originating from single-molecule SERS experiments are rare events, which occur only if a single molecule is located in a hot-spot zone. In this spot, the molecule is selectively exposed to a significant enhancement associated with a high, local electromagnetic field in the plasmonic substrate. Here, we report an SMD study with an electrostatic approach in which a Langmuir film of a phospholipid with anionic polar head groups (PO 4 -) was doped with cationic methylene blue (MB), creating a homogeneous, two-dimensional distribution of dyes in the monolayer. The number of dyes in the probed area of the Langmuir-Blodgett (LB) film coating the Ag nanostructures established a regime in which single-molecule events were observed, with the identification based on direct matching of the observed spectrum at each point of the mapping with a reference spectrum for the MB molecule. In addition, advanced fitting techniques were tested with the data obtained from micro-Raman mapping, thus achieving real-time processing to extract the MB single-molecule spectra. © 2013 Society for Applied Spectroscopy.

Filmes nanoestruturados de fosfolipídios como sistemas miméticos de membrana biológica para aplicação em sensores via sers e espectroscopia de impedância

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

Adsorção de copolímeros tribloco de óxido de etileno e óxido de propileno na interface líquido-ar

Pós-graduação em Química - IQ

Complexos aniônicos contendo európio ou gandolínio e beta-dicetonas aplicados aos estudos foto e/ou eletroluminescentes de sólidos e filmes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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)

Estudo da interação da natamicina com membranas fosfolipídicas incorporadas de esteróis

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Nanostructured screen-printed electrodes modified with self-assembled monolayers for determination of metronidazole in different matrices

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

Deconstructing the DGAT1 enzyme: Binding sites and substrate interactions

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

Hybridization effects on the out-of-plane electron tunneling properties of monolayers: is h-BN more conductive than graphene?

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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.

Aplicabilidade das equações isotermas de Freundlich e Langmuir na interação biossortiva de corantes têxteis com Saccharomyces cerevisiae liofilizada

This paper presents a study of the applicability of adsorption isotherms, known as Langmuir and Freundlich isotherm, between the biosorptive interaction of yeast lyophilized Saccharomyces cerevisiae and textile dyes. To that end, we prepared stock solutions of the textile dyes Direct Red 23 and Direct Red 75 in the concentration of 1.000μg/mL and a yeast suspension at 2,5%. We did experiments for two cases, firstly for the case that we have a fix concentration of yeast at 0,500mg/mL and an variable concentration of dye range from40, 50, 60, 80 and 100μg/mL, then for the case that we fixed the concentration of dye at 100μg/mL and the yeast concentration was variable range from 0,250, 0,500, 0,750, 1,000, 1,250mg/mL. For the dye Direct Red 23 we did analysis in the pH 2,5, 4,5 and 6,5; for the Direct Red 75, we just did for the pH 2,5. We leave the dye solution in contact with the yeast for 2 hours at a constant temperature of 30°C and then centrifuged and analyzed the sample in a spectrophotometer and finally made and analysis of parameters for the removal and study of the isotherms. After the biosorption, was observed that for the Direct Red 23 in the pH 2,5 was needed 1,407mg/mL of yeast for total removal, while for the pH 4,5 was needed 8,806mg/mL and in pH 6,5 was 9,286mg/mL; for the Direct Red 75 in pH 2,5 was needed 1,337mg/mL. This difference can be explain by the adsorption isotherms, was observed that in the case when the yeast was fix when we had in a acid pH the behavior of the system was compatible with the Langmuir isotherm, and thus, an monolayer pattern. And that when we decrease the acidity of the medium the system became more compatible with a Freundlich isotherm, and thus, a multilayer pattern; for the case that the yeast was variable this is not much evident, however for the pH 2,5 she became compatible with a Langmuir isotherm... (Complete abstract click electronic access below)

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

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