Preparation, structure, and properties of three-dimensional ordered alpha-Fe2O3 nanoparticulate film

alpha-Fe2O3 nanoparticulate films could be formed on the surface of alpha-Fe2O3 hydrosol after aging of the hydrosol or by compressing of the nanoparticles on the sol surface, in. which a three-dimensional ordered structure was constructed by the Langmuir-Blodgett; technique and colloid chemical methods. The structure of the LB film was characterized by AFM, TEM, XPS, and UV-vis spectra and small-angle X-ray diffraction. Gas-sensing measurement shows that the LB film has good sensitivity to alcohols at room temperature,

Molecular orientation of copper phthalocyanine derivative ins copper phthalocyanine-Fe2O3 nanoparticles alternating LB films

Copper phthalocyanine-Fe2O3 nanoparticles alternating thin films were fabricated by Langmuir-Blodgett technique. Molecular orientation of [4-(4'-benzyloxy phenyl sulfonyl)phenoxy]-tris-4-(2,4-di-t-phenoxy) phthalocyanine copper (II) in its alternating LB films, deposited at different conditions,was studied by polarized UV-Vis spectra. The tilt extent of the copper phthalocyanine molecule omits LB films increases with the surface pressure of the subphase increasing on the same subphase, or with Fe2O3 concentration decreasing at the same pressure. The orientation of the copper phthalocyanine derivative is important for the gas-sensing properties. The bigger the tilt extent of the phthalocyanine molecule is, the greater the sensitivity of the film is.

Preparation and characterization of doped polyaniline films

Stable monolayer of the polyaniline doped with camphor sulfonic acid at the air-water interface has been obtained, of which multilayers have been successfully deposited by Langmuir-Blodgett technique onto CaF2 substrate. The limiting mean molecular area and collapse pressure are found to be 0.294 nm(2) and 41 mN/m, respectively. The multilayers were characterized by IR and W-Vis-NIR spectroscopies. X-ray small-angle diffraction data show that the multilayer was periodic layer structure with the layer spacing of 1.60 nm. The comparisons are also made with characterization of the casting film. (C) 1999 Elsevier Science S.A. 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.

Monomolecular films of cholesterol oxidase and S-Layer proteins

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Ultrathin films of lignins as a potential transducer in sensing applications involving heavy metal ions

Lignins extracted from sugar cane bagasse using different alcohols in the organosolv-CO(2) supercritical pulping process have been applied in the fabrication of ultrathin films through the Langmuir-Blodgett technique. Langmuir films were characterized by surface pressure versus mean molecular area (Pi-A) isotherms to exploit the sensitivity of nanostructured lignin films to metallic ions (Cu(2+), Cd(2+) and Pb(2+)). The Pi-A isotherms were shifted to larger molecular areas when heavy metal ions are present into the subphase, which might be related to electrostatic repulsions between metallic ions entrapped within the lignin molecular structure. Taking the advantage of metal incorporation, Langmuir monolayers were transferred onto solid substrates forming Langmuir-Blodgett (LB) films to be used as a transducer in an "electronic tongue" system to detect Cu(2+) in aqueous solution below threshold standard established by the Brazilian regulation. Both techniques impedance spectroscopy and electrochemistry have been used in these experiments. Complementary, Fourier transform infrared (FTIR) spectroscopy recorded for LB films before and after soaking into Cu(2+) aqueous solution revealed an interaction between the lignin phenyl groups and the metallic ion. (C) 2007 Elsevier B.V.. All rights reserved.

Polyaniline mixed LB films exposed to X-rays

X-ray irradiation is shown to affect electronic properties of polyaniline (PANi) in composite Langmuir-Blodgett (LB) films of PANi and cadmium stearate, in a similar way to acid doping. The time it takes for the shift in the UV-vis spectra, characteristic of PANi doping, increases linearly with the film thickness, thus indicating a surface-controlled process. The humidity of the environment under which the films are irradiated is also of extreme importance. No shin is observed under vacuum or under dry atmospheres of N-2, O-2 and Ar. For humid environments the time for the shift decreases with increasing relative humidity.

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)

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.

Structure formation of amphiphilic molecules at the air,water interface and after film transfer

One of the basic concepts of molecular self-assembly is that the morphology of the aggregate is directly related to the structure and interaction of the aggregating molecules. This is not only true for the aggregation in bulk solution, but also for the formation of Langmuir films at the air/water interface. Thus, molecules at the interface do not necessarily form flat monomolecular films but can also aggregate into multilayers or surface micelles. In this context, various novel synthetic molecules were investigated in terms of their morphology at the air/water interface and in transferred films. rnFirst, the self-assembly of semifluorinated alkanes and their molecular orientation at the air/water interface and in transferred films was studied employing scanning force microscopy (SFM) and Kelvin potential force microscopy. Here it was found, that the investigated semifluorinated alkanes aggregate to form circular surface micelles with a diameter of 30 nm, which are constituted of smaller muffin-shaped subunits with a diameter of 10 nm. A further result is that the introduction of an aromatic core into the molecular structure leads to the formation of elongated surface micelles and thus implements a directionality to the self-assembly. rnSecond, the self-assembly of two different amphiphilic hybrid materials containing a short single stranded desoxyribonucleic acid (DNA) sequence was investigated at the air/water interface. The first molecule was a single stranded DNA (11mer) molecule with two hydrophobically modified 5-(dodec-1-ynyl)uracil nucleobases at the terminal 5'-end of the oligonucleotide sequence. Isotherm measurements revealed the formation of semi-stable films at the air/water interface. SFM imaging of films transferred via Langmuir-Blodgett technique supported this finding and indicated mono-, bi- and multilayer formation, according to the surface pressure applied upon transfer. Within these films, the hydrophilic DNA sequence was oriented towards air covering 95% of the substrate.rnSimilar results were obtained with a second type of amphiphile, a DNA block copolymer. Furthermore, the potential to perform molecular recognition experiments at the air/water interface with these DNA hybrid materials was evaluated.rnThird, polyglycerol ester molecules (PGE), which are known to form very stable foams, were studies. Aim was to elucidate the molecular structure of PGE molecules at the air/water interface in order to comprehend the foam stabilization mechanism. Several model systems mimicking the air/water interface of a PGE foam and methods for a noninvasive transfer were tested and characterized by SFM. It could be shown, that PGE stabilizes the air/water interface of a foam bubble by formation of multiple surfactant layers. Additionally, a new transfer technique, the bubble film transfer was established and characterized by high speed camera imaging.The results demonstrate the diversity of structures, which can be formed by amphiphilic molecules at the air/water interface and after film transfer, as well as the impact of the chemical structure on the aggregate morphology.

αα'-trehalose 6,6'-dibehenate in non-phospholipid-based liposomes enables direct interaction with trehalose, offering stability during freeze-drying

Trehalose is a well known protector of biostructures like liposomes and proteins during freeze-drying, but still today there is a big debate regarding its mechanism of action. In previous experiments we have shown that trehalose is able to protect a non-phospholipid-based liposomal adjuvant (designated CAF01) composed of the cationic dimethyldioctadecylammonium (DDA) and trehalose 6,6-dibehenate (TDB) during freeze-drying [D. Christensen, C. Foged, I. Rosenkrands, H.M. Nielsen, P. Andersen, E.M. Agger, Trehalose preserves DDA/TDB liposomes and their adjuvant effect during freeze-drying, Biochim. Biophys. Acta, Biomembr. 1768 (2007) 2120-2129]. Furthermore it was seen that TDB is required for the stabilizing effect of trehalose. Herein, we show using the Langmuir-Blodgett technique that a high concentration of TDB present at the water-lipid interface results in a surface pressure around 67 mN/m as compared to that of pure DDA which is approximately 47 mN/m in the compressed state. This indicates that the attractive forces between the trehalose head group of TDB and water are greater than those between the quaternary ammonium head group of DDA and water. Furthermore, addition of trehalose to a DDA monolayer containing small amounts of TDB also increases the surface pressure, which is not observed in the absence of TDB. This suggests that even small amounts of trehalose groups on TDB present at the water-lipid interface associate free trehalose to the liposome surface, presumably by hydrogen bonding between the trehalose head groups of TDB and the free trehalose molecules. Hence, for CAF01 the TDB component not only stabilizes the cationic liposomes and enhances the immune response but also facilitates the cryo-/lyoprotection by trehalose through direct interaction with the head group of TDB. Furthermore the results indicate that direct interaction with liposome surfaces is necessary for trehalose to enable protection during freeze-drying.

Immobilization of lutetium bisphthalocyanine in nanostructured biomimetic sensors using the LbL technique for phenol detection

This study describes the development of amperometric sensors based on poly(allylamine hydrochloride) (PAH) and lutetium bisphthalocyanine (LuPc(2)) films assembled using the Layer-by-Layer (LbL) technique. The films have been used as modified electrodes for catechol quantification. Electrochemical measurements have been employed to investigate the catalytic properties of the LuPc(2) immobilized in the LbL films. By chronoamperometry, the sensors present excellent sensitivity (20 nA mu M(-1)) in a wide linear range (R(2) = 0.994) up to 900 mu M and limit of detection (s/n = 3) of 37.5 x 10(-8) M for catechol. The sensors have good reproducibility and can be used at least for ten times. The work potential is +0.3 V vs. saturated calomel electrode (SCE). In voltammetry measurements, the calibration curve shows a good linearity (R(2) = 0.992) in the range of catechol up to 500 mu M with a sensitivity of 90 nA mu M(-1) and LD of 8 mu M. (C) 2011 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)

Formation of thin luminescent Eu3+-LB films by in situ coordination with 2,3,5,6-tetra(2 '-pyridyl)pyrazine and 1-octadecanol in pure and mixed Langmuir monolayers

The in situ complexation between 2,3,5,6-tetra(2-pyridyl)pyrazine (tppz) molecules and europium ions at the air-liquid interface by means of mixed 1-octadecanol Langmuir films is reported. These films were transferred to solid supports by means of the Langmuir-Blodgett (LB) technique. The EDS maps attested the homogeneity of the LB films as well as the presence of the europium ions. The mixed alcohol/tppz LB film contained a larger amount of europium ions as compared to the pure octadecanol LB film. This work reports the production of a thin luminescent Eu3+ film containing europium ions using only alcohol molecules as ligands an unexpected result, since it is well known that there is an occurrence of non-radiative deactivation of excited europium by hydroxyl groups. Europium ion multiple binding sites were detected from lifetime decay measurements of these films in the presence of tppz molecules. (C) 2012 Elsevier B.V. All rights reserved.

Study of singlet excited state absorption spectrum of lutetium bisphthalocyanine using the femtosecond Z-scan technique

In this study we investigate the singlet excited state absorption of lutetium bisphthalocyanine (LuPc2) over a wide spectral range. It was observed distinct nonlinear absorption behaviors; saturable (SA) and reverse saturable absorption (RSA). The RSA effect was observed below 640 and above 680 nm, while SA occurs around the Q-band region, located around 660 nm. To describe the main singlet-singlet transitions, we employed the rate equation model considering the simplified three-energy level diagram. Our results reveal a ratio between excited and ground state absorption smaller than 0.05 at the Q-band region, and of approximately 4 for the other regions. (C) 2012 Elsevier B.V. All rights reserved.