Incorporation of a liquid crystal to enhance the luminescence properties of Langmuir-Blodgett films of OC1OC6-PPV

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

The use of Langmuir-Blodgett films of a perylene derivative and polypyrrole in the detection of trace levels of Cu2+ ions

Langmuir films of a tetracarboxylic perylene derivative and polypyrrole display condensed surface pressure isotherms that are shifted when Cu2+ ions are added to the ultrapure water subphase. These films were transferred onto interdigitated gold electrodes leading to Y-type Langmuir-Blodgett (LB) films. The electrodes modified with 5-layer LB films were immersed into a flask with ultrapure water and water containing Cu2+ ions at concentrations ranging from mM to muM. Impedance measurements indicated a distinct electrical response for the two types of films. Although the materials chosen have no specificity for ionic metals, they can be combined for detecting trace levels of Cu2+, which may be exploited in water quality monitoring. (C) 2004 Elsevier B.V. All rights reserved.

Langmuir and langmuir-blodgett films of polyfluorenes and their use in polymer light-emitting diodes

The Langmuir and Langmuir-Blodgett (LB) film properties of two polyfluorene derivatives, namely poly(2,7-9,9'-dihexylfluorene-dyil) (PDHF) and poly(9,9 dihexylfluorene-dyil-vynilene-alt-1,4-phenylene-vyninele) (PDHF-PV), are reported. Surface pressure (Pi-A) and surface potential (Delta V-A) isotherms indicated that PDHF-PV forms true monolayers at the air/water interface, but PDHF does not. LB films could be transferred onto various types of substrate for both PDHF and PDHF-PV. Only the LB films from PDHF-PV could withstand deposition of a layer of evaporated metal to form a light-emitting diode (PLED), which had typical rectifying characteristics and emitted blue light. It is inferred that the ability of the polymer to form true monomolecular layers at the air/water interface seems to be associated with the viability of the LB films in PLEDs.

Preparation, characterization and taste sensing properties of Langmuir-Blodgett Films from mixtures of polyaniline and a ruthenium complex

Langmuir-Blodgett (LB) films from a ruthenium complex, mer-[RuCl3(dppb)(py)] (dppb = PPh2(CH2)(4)PPh2; py = pyridine) (Rupy), and from mixtures with varied amounts of polyaniline (PANi) were fabricated. Molecular-level interactions between the two components are investigated by surface potential, dc conductivity and Raman spectroscopy measurements, particularly for the mixed film with 10% of Rupy. For the latter, the better miscibility led to an interaction with Rupy inducing a decrease in the conducting state of PANi, as observed in the Raman spectra and conductivity measurement. The interaction causes the final film properties to depend on the concentration of Rupy, and this was exploited to produce a sensor array made up of sensing units consisting of 11-layer LB films from pure PANi, pure Rupy and mixtures with 10 and 30% of Rupy. It is shown that the combination of only four non-specific sensing units allows one to distinguish the basic tastes detected by biological systems, viz. saltiness, sweetness, sourness and bitterness, at the muM level. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

Morphological characterization of Langmuir-Blodgett films from polyaniline and a ruthenium complex (Rupy): influence of the relative concentration of Rupy

We report on the use of dynamic scale theory and fractal analyses in a study of the growth stages of Langmuir-Blodgett (LB) films of polyaniline and a neutral biphosphinic ruthenium complex, namely mer-[ RuCl3 (dppb)(py)] (dppb = 1,4-bis(diphenylphosphine) buthane, py = pyridine), Rupy. The LB films were deposited onto indium-tin-oxide substrates and characterized with atomic force microscopy. From the granular morphology exhibited by the films one could infer growth processes inside and outside the grains. Growth outside was found to follow the Kardar-Parisi-Zhang model, with fractal dimensions of about 2.7. As one would expect, inside the grains the morphology is close to a Euclidian surface with fractal dimension of about 2.

Surface morphology and molecular organization of lignins in Langmuir-Blodgett films

Atomic force microscopy (AFM) and Fourier transform infrared spectroscopy (FTIR) are used to investigate molecular organization in Langmuir-Blodgett (LB) films of two kinds of lignins. The lignins were extracted from sugar cane bagasse using distinct extraction processes and are referred to here as ethanol lignin (EL) and saccharification lignin (SAC). AFM images show that LB films from EL have a flat surface in comparison with those from SAC. For the latter, ellipsoidal aggregates are seen oriented perpendicularly to the substrate. This result is confirmed by a combination of transmission and reflection FTIR measurements, which also point to lignin aggregates preferentially oriented perpendicularly to the substrate. For LB films from EL, on the other hand, aggregates are preferentially oriented parallel to the substrate, again consistent with the flat surface observed in AFM data. The vibrational spectroscopy data for cast films from both lignins show random molecular organization, as one should expect.

Photoinduced birefringence at low temperatures in Langmuir-Blodgett films of azobenzene-functionalized copolymers

The temperature dependence has been investigated for the photoinduced birefringence in Langmuir-Blodgett (LB) films from the azocopolymer 4-[N- ethyl -N-(2-hydroxyethyl)] amino-2'-chloro-4'-nitroazobenzene (MMA-DR13) mixed with cadmium stearate. The buildup and relaxation of the birefringence in the range from 20 to 296 K were fitted with a Kohlrausch-Williams-Watts (KWW) function, with a beta-value of 0.78-0.98 for the build-up and 0.18-0.27 for the decay. This is consistent with a distribution of time constants for the kinetics of the birefringence processes. The maximum birefringence increased with increasing temperature up to 120 K because the free volume fluctuation also increased with temperature. Above 120 K, the birefringence decreased with temperature as thermal diffusion dominates. In the latter range of temperature, an Arrhenius behavior is inferred for both build-up and decay of birefringence. In each case two activation energies were obtained: 0.8 and 5 kJ/mol for the build-up and 10 and 30 kJ/mol for the decay. The energies for the build-up are much lower than those associated with motion of the polymer chain, which means that the dynamics is governed by the orientation of the chromophores. For the decay, local motion of lateral groups of the polymer chains becomes important as the activation energies are within the range of gamma-relaxation energies. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Fabrication of phytic acid sensor based on mixed phytase-lipid Langmuir-Blodgett films

This paper reports the surface activity of phytase at the air-water interface, its interaction with lipid monolayers, and the construction of a new phytic acid biosensor on the basis of the Langmuir-Blodgett (LB) technique. Phytase was inserted in the subphase solution of dipalmitoylphosphatidylglycerol (DPPG) Langmuir monolayers, and its incorporation to the air-water interface was monitored with surface pressure measurements. Phytase was able to incorporate into DPPG monolayers even at high surface pressures, ca. 30 mN/m, under controlled ionic strength, pH, and temperature. Mixed Langmuir monolayers of phytase and DPPG were characterized by surface pressure-area and surface potential-area isotherms, and the presence of the enzyme provided an expansion in the monolayers ( when compared to the pure lipid at the interface). The enzyme incorporation also led to significant changes in the equilibrium surface compressibility (in-plane elasticity), especially in liquid-expanded and liquid-condensed regions. The dynamic surface elasticity for phytase-containing interfaces was investigated using harmonic oscillation and axisymmetric drop shape analysis. The insertion of the enzyme at DPPG monolayers caused an increase in the dynamic surface elasticity at 30 mN m(-1), indicating a strong interaction between the enzyme and lipid molecules at a high-surface packing. Langmuir-Blodgett (LB) films containing 35 layers of mixed phytase-DPPG were characterized by ultraviolet-visible and fluorescence spectroscopy and crystal quartz microbalance nanogravimetry. The ability in detecting phytic acid was studied with voltammetric measurements.

Spectroscopic and electrochemical characterization of polyaniline and a ruthenium complex, mer-[RuCl3(dppb)(py)], in the form of Langmuir-Blodgett films

Langmuir monolayers and Langmuir-Blodgett (LB) films have been produced from polyaniline and a biphosphinic ruthenium complex, referred to as Rupy. Strong, repulsive interaction between the two components led to a nonlinear change in area per molecule and surface potential with the concentration of Rupy in the mixed film. Molecular interaction was also denoted in the spectroscopic and electrochemical properties of the Y-type LB transferred films. The Raman spectra of mixed PANI-Rupy films indicated that the degree of oxidation of PANI increased linearly with the concentration of Ropy. With PANI being increasingly oxidized by presence of Rupy, the electroactivity of the mixed films decreased with the amount of Rupy, to become undetectable when the mixed LB film is 501 mol in Rupy. The presence of Rupy caused the electrical properties of the mixed LB films to be less sensitive to environmental changes. The electrical capacitance of a mixed film changed only by 15% when the sample was taken from vacuum to air, whereas the change was 215% for a pure PANI LB film.

Langmuir-Blodgett films incorporating an ionic europium complex

Langmuir-Blodgett (LB) technique is a powerful tool to fabricate ultrathin films with highly ordered structures and controllable molecular array for efficient energy and electron transfer, allowing the construction of devices at molecular level. One method to obtain LB films consists in the mixture of classical film-forming molecules, for example Stearic Acid (SA) and functional metal complex. In this work NH(4)[Eu(bmdm)(4)], where the organic ligand bmdm is (butyl methoxy-dibenzoyl-methane) or (1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione) was used to build up Langmuir and LB films. Langmuir isotherms were obtained from (i) NH(4)[Eu(bmdm)(4)] complex and (ii) NH(4)[Eu(bmdm)(4)]/SA (1:1). Results indicated that (i) form multilayer structure; however the surface pressure was insufficient to obtain LB films, and (ii) can easily reproduce and build LB films. The dependence of number of layers in the UV absorption spectra suggest that the complex did not hydrolyze or show decomposition, UV spectral differences observed between the solution and the LB film indicate that the complex has a highly ordered arrangement in the film and the complex has an interaction with SA. Excitation spectra confirm a ligand-europium energy transfer mechanism. The transition lines of Eu(3+) ion were observed in emission spectra of all films, the photoluminescence spectra indicate a fluorescence enhanced effect with the number of LB layers. (C) 2009 Elsevier B.V. All rights reserved.

Optical, electrical, and thermochromic properties of polyazothiophene Langmuir-Blodgett films

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

Optically anisotropic and photoconducting Langmuir-Blodgett films of neat poly(3-hexylthiophene)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Preparation and characterization of Langmuir-Blodgett films of 16-membered azobenzocrown ether with naphthalene residue

Langmuir and Langmuir-Blodgett films of 16-membered azobenzocrown ether with naphthalene residue were prepared and characterized. The Langmuir monolayers were successfully transferred to form LB films onto solid substrates. The films deposited onto ITO electrodes were also used as electrodes in cyclic voltammetry and the results showed that the films had a distinct response to metal ions. (C) 2009 Elsevier B.V. All rights reserved.

Detection of catechol using mixed Langmuir-Blodgett films of a phospholipid and phthalocyanines as voltammetric sensors

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

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.