Energy Transfer in Nanostructured Films Containing Poly(p-phenylene vinylene) and Acceptor Species

The combination of luminescent polymers and suitable energy-accepting materials may lead to a molecular-level control of luminescence in nanostructured films. In this study, the properties of layer-by-layer (LbL) films of polyp-phenylene vinylene) (PPV) were investigated with steady-state and time-resolved fluorescence spectroscopies, where fluorescence quenching was controlled by interposing inert polyelectrolyte layers between the PPV donor and acceptor layers made with either Congo Red (CR) or nickel tetrasulfonated phthalocyanine (NiTsPc). The dynamics of the excited state of PPV was affected by the energy-accepting layers, thus confirming the presence of resonant energy transfer mechanisms. Owing to the layered structured of both energy donor and acceptor units, energy transfer varied with the distance between layers, r, according to 1/r(n) with n = 2 or 3, rather than with 1/r(6) predicted by the Forster theory for interacting point dipoles.

Photoluminescent behavior of SrZrO(3)/SrTiO(3) multilayer thin films

A detailed investigation was made into the origin of photoluminescence in an alternate multilayer system of SrZrO(3) (SZO) and SrTiO(3) (STO) thin films. XRD and room-temperature PL studies revealed a high consistency with respect to improved crystallization at elevated temperatures. The photoluminescence behaviour of SZO/STO multilayered system consists in the superposition of independent photoluminescence emissions of both STO and SZO films. Based on the present results and on previous experimental and theoretical data, we propose that the origin of the photoluminescence emission results from structural disorder generated by the presence of distortions in the ideal constituent clusters of these materials. (c) 2009 Elsevier B.V. All rights reserved.

Using phospholipid Langmuir and Langmuir-Blodgett films as matrix for urease immobilization

The immobilization of enzymes in organized two-dimensional matrices is a key requirement for many biotechnological applications. In this paper, we used the Langmuir-Blodgett (LB) technique to obtain controlled architectures of urease immobilized in solid supports, whose physicochemical properties were investigated in detail. Urease molecules were adsorbed at the air-water interface and incorporated into Langmuir monolayers of the phospholipid dipalmitoyl phosphatidyl glycerol (DPPG). Incorporation of urease made DPPG monolayers more flexible and caused the reduction of the equilibrium and dynamic elasticity of the film. Urease and DPPG-urease mixed monolayers could be transferred onto solid substrates, forming LB films. A close packing arrangement of urease was obtained, especially in the mixed LB films, which was inferred with nanogravimetry and electrochemistry measurements. From the blocking effect of the LB films deposited onto indium tin oxide (ITO) substrates, the electrochemical properties of the LB films pointed to a charge transport controlled by the lipid architecture. (c) 2007 Elsevier Inc. All rights reserved.

Physical Vapor Deposited Thin Films of Lignins Extracted from Sugar Cane Bagasse: Morphology, Electrical Properties, and Sensing Applications

The concern related to the environmental degradation and to the exhaustion of natural resources has induced the research on biodegradable materials obtained from renewable sources, which involves fundamental properties and general application. In this context, we have fabricated thin films of lignins, which were extracted from sugar cane bagasse via modified organosolv process using ethanol as organic solvent. The films were made using the vacuum thermal evaporation technique (PVD, physical vapor deposition) grown up to 120 nm. The main objective was to explore basic properties such as electrical and surface morphology and the sensing performance of these lignins as transducers. The PVD film growth was monitored via ultraviolet-visible (UV-vis) absorption spectroscopy and quartz crystal microbalance, revealing a linear relationship between absorbance and film thickness. The 120 nm lignin PVD film morphology presented small aggregates spread all over the film surface on the nanometer scale (atomic force microscopy, AFM) and homogeneous on the micrometer scale (optical microscopy). The PVD films were deposited onto Au interdigitated electrode (IDE) for both electrical characterization and sensing experiments. In the case of electrical characterization, current versus voltage (I vs V) dc measurements were carried out for the Au IDE coated with 120 nm lignin PVD film, leading to a conductivity of 3.6 x 10(-10) S/m. Using impedance spectroscopy, also for the Au IDE coated with the 120 nm lignin PVD film, dielectric constant of 8.0, tan delta of 3.9 x 10(-3)) and conductivity of 1.75 x 10(-9) S/m were calculated at 1 kHz. As a proof-of-principle, the application of these lignins as transducers in sensing devices was monitored by both impedance spectroscopy (capacitance vs frequency) and I versus time dc measurements toward aniline vapor (saturated atmosphere). The electrical responses showed that the sensing units are sensible to aniline vapor with the process being reversible. AFM images conducted directly onto the sensing units (Au IDE coated with 120 nm lignin PVD film) before and after the sensing experiments showed a decrease in the PVD film roughness from 5.8 to 3.2 nm after exposing to aniline.

Influência do grau de hidrólise do poli(vinil álcool) nas propriedades físicas de filmes à base de blendas de gelatina e poli(vinil álcool) plastificados com glicerol

O objetivo deste trabalho foi o estudo do efeito do Grau de Hidrólise (GH) do poli(vinil álcool) (PVA) nas propriedades dos filmes à base de blendas de gelatina suína e PVA com dois GH. Os filmes foram produzidos com soluções com 2 g de macromoléculas/100 g de solução, contendo 23,1 g de PVA.100 g-1 de macromoléculas e 25 g de glicerol/100 g de macromoléculas. As propriedades mecânicas e térmicas, cor, opacidade, umidade e solubilidade, além de espectros de infravermelho com transformada de Fourier (FTIR) dos filmes, foram estudadas. As soluções foram analisadas por reometria dinâmica. Os filmes produzidos com o PVA de menor GH foram mais higroscópicos e mais solúveis. Mas o tipo de PVA não afetou a cor, afetando a opacidade e o brilho dos filmes. O PVA com maior GH proporcionou filmes mais resistentes, e o PVA de menor GH produziu filmes mais resistentes à tração, embora menos deformáveis na perfuração. O GH do PVA não afetou a temperatura de transição vítrea dos filmes, determinada na primeira varredura, mas a afetou na segunda varredura. Os resultados das análises de FTIR corroborraram com esses resultados. As propriedades viscoelásticas das soluções não foram afetadas pelo GH do PVA, muito possivelmente por se tratar de soluções diluídas.

Análise comportamental de recém-nascidos pré-termos incluídos em um programa de estimulação tátil-cinestésica durante a internação hospitalar

OBJETIVO: Avaliar o efeito da estimulação tátil-cinestésica na evolução do padrão comportamental e clínico de recém-nascidos pré-termos (RNPT) durante o período de internação hospitalar. MÉTODOS: Trinta e dois RNPT, com peso ao nascimento inferior a 2.500 gramas, clinicamente estáveis e destituídos de asfixia perinatal importante foram divididos em 16 bebês do grupo controle (GC) e 16 do experimental (GE). Foram coletados dados da evolução clínica a partir dos registros hospitalares e da avaliação comportamental por meio de filmagens semanais de oito minutos, desde a inclusão do RNPT na amostra até a alta hospitalar. RESULTADOS: Tendência a redução do tempo de internação hospitalar, aumento do ganho de peso diário e predominância de comportamentos auto-organizados (respiração regular, estado de alerta, tônus equilibrado, posturas mistas, movimentação coordenada, movimentos de mão na face, sucção, preensão, apoio) para os RNPT do GE. A análise comparativa das idades pós-conceptuais divididas em intervalos (I - 31 a 33 semanas 6/7; II - 34 a 36 semanas 6/7; e III - 37 a 39 semanas 6/7) ressaltou, no aspecto motor, um tônus equilibrado e movimentação voluntária coordenada para os três períodos, maior permanência em posturas mistas (intervalo I) ou em flexão (intervalo II) e a obtenção de respiração mais regular na faixa etária I do GE. CONCLUSÃO: Destaque da estimulação tátil-cinestésica como método de intervenção durante o período de internação hospitalar, contribuindo para a auto-organização e regulação comportamental de RNPT. Artigo registrado no Australian New Zealand Clinical Trials Registry (ANZCTR) sob o número ACTRN12610000133033.

Time resolved emission spectroscopy of poly(2,5-dicyano-p-phenylene-vinylene) films

Films of poly (2,5-dicyano-p-phenylene vinylene), DCNPPV, were obtained by electrochemical synthesis over gold thin layer (20 nm) transparent electrode deposited on a glass plate. The DCNPPV films of 4 µm thickness were produced by electropolymerization process of α,α,α',α'-tetrabromo-2-5-dicyano-p-xilene at different applied potentials (-0.15, -0.25, -0.40, -0.60, -0.80, and -1.0 V) using 0.1 mol L-1 of tetraethylammonium bromide in acetonitrile as the supporting electrolyte. The emission decays have three exponential components: a fast component in the picosecond range (200-400 ps), and two other of about one and five nanoseconds at 293 K. The fluorescence quenching process seems to occur by exciton trapping in a low-energy site and quenching by residual bromine monomer attached at the end of the polymer chain. However, the electrochemical synthesis generates entrapped bromide or ion pairs during the growth step of the film which also contributes to the deactivation. The change of the electrolyte from bromide to perchlorate reduces significantly this additional quenching effect by allowing ion exchange of formed bromide with the nonquenching perchloride anion.

Characterization of thiol-functionalised silica films deposited on electrode surfaces

Thiol-functionalised silica films were deposited on various electrode surfaces (gold, platinum, glassy carbon) by spin-coating sol-gel mixtures in the presence of a surfactant template. Film formation occurred by evaporation induced self-assembly (EISA) involving the hydrolysis and (co)condensation of silane and organosilane precursors on the electrode surface. The characterization of such material was performed by IR spectroscopy, thermogravimetry (TG), elemental analysis (EA), atomic force microscopy (AFM), scanning electron microscopy (SEM) and cyclic voltammetry (CV).

Electronic conduction and electrocatalysis by supramolecular tetraruthenated copper porphyrazine films

A new tetraruthenated copper(II)-tetra(3,4-pyridyl)porphyrazine species, [CuTRPyPz]4+, has been synthesized and fully characterized by means of analytical, spectroscopic and electrochemical techniques. This À-conjugated system contrasts with the related meso-tetrapyridylporphyrins by exhibiting strong electronic interaction between the coordinated peripheral complexes and the central ring. Based on favorable À-stacking and electrostatic interactions, layer-by-layer assembled films were successfully generated from the appropriate combination of [CuTRPyPz]4+ with copper(II)-tetrasulfonated phtalocyanine, [CuTSPc]4-. Their conducting and electrocatalytic properties were investigated by means of impedance spectroscopy and rotating disc voltammetry, exhibiting metallic behavior near the Ru(III/II) redox potential, as well as enhanced catalytic activity for the oxidation of nitrite and sulphite ions.

Nanostructured thin films obtained by electrodeposition over a colloidal crystal template: applications in electrochemical devices

Colloidal particles have been used to template the electrosynthesis of several materials, such as semiconductors, metals and alloys. The method allows good control over the thickness of the resulting material by choosing the appropriate charge applied to the system, and it is able to produce high density deposited materials without shrinkage. These materials are a true model of the template structure and, due to the high surface areas obtained, are very promising for use in electrochemical applications. In the present work, the assembly of monodisperse polystyrene templates was conduced over gold, platinum and glassy carbon substrates in order to show the electrodeposition of an oxide, a conducting polymer and a hybrid inorganic-organic material with applications in the supercapacitor and sensor fields. The performances of the resulting nanostructured films have been compared with the analogue bulk material and the results achieved are depicted in this paper.

Spectroscopic characterization and investigation of the dynamic of charge compensation process of supramolecular films derived from tetra-2-pyridyl-1,4-pyrazine ligand

This work describes the infrared spectroscopy characterization and the charge compensation dynamics in supramolecular film FeTPPZFeCN derived from tetra-2-pyridyl-1,4-pyrazine (TPPZ) with hexacyanoferrate, as well as the hybrid film formed by FeTPPZFeCN and polypyrrole (PPy). For supramolecular film, it was found that anion flux is greater in a K+ containing solution than in Li+ solution, which seems to be due to the larger crystalline ionic radius of K+. The electroneutralization process is discussed in terms of electrostatic interactions between cations and metallic centers in the hosting matrix. The nature of the charge compensation process differs from others modified electrodes based on Prussian blue films, where only cations such as K+ participate in the electroneutralization process. In the case of FeTPPZFeCN/PPy hybrid film, the magnitude of the anions’s flux is also dependent on the identity of the anion of the supporting electrolyte.

Storage effect on the acceptability of snacks made of pure amaranth and blends of amaranth and corn or chickpea

Snacks made by extrusion cooking of pure amaranth flour or mixtures of 80 per cent amaranth flour and 20 per centcorn grits or chickpea flour were developed to replace the traditional commercial ones with improved nutritional and functional quality. Pure amaranth snacks and the blended ones were flavored with salty and sweet flavors and evaluated for acceptability using a 9-point hedonic scale. The good acceptance observed for either salty or sweet flavored snacks indicated that they have characteristics to compete with similar commercial products. Acceptability of salty snacks increased with storage time at room temperature in BOPP (polypropylene bi-guided) packs whereas slightly decreased for the sweet ones. This type of storage proved to be very efficient for the conservation of the salty product and also suitable for the sweet ones

Near-infrared third-order nonlinearity of PbO-GeO(2) films containing Cu and Cu(2)O nanoparticles

We report measurements of the nonlinear (NL) refractive index n(2) of lead-germanium films (LGFs) containing Cu and Cu(2)O nanoparticles (NPs). The thermally managed eclipse Z-scan technique with 150 fs pulses from a laser operating at 800 nm was used. The NL refractive index measured, n(2)=6.3x10(-12) cm(2)/W has electronic origin and the NL absorption coefficient alpha(2) is smaller than 660 cm/GW. The figure of merit n(2)/lambda alpha(2) is enhanced by more than two orders of magnitude in comparison with the result for the LGFs without the copper based NPs. (C) 2008 American Institute of Physics.

Homeotropic surface anchoring and the layer-thinning transition in free-standing films

In this work, we investigate the interplay between surface anchoring and finite-size effects on the smectic-isotropic transition in free-standing smectic films. Using an extended McMillan model, we study how a homeotropic anchoring stabilizes the smectic order above the bulk transition temperature. In particular, we determine how the transition temperature depends on the surface ordering and film thickness. We identify a characteristic anchoring for which the transition temperature does not depend on the film thickness. For strong surface ordering, we found that the thickness dependence of the transition temperature can be well represented by a power-law relation. The power-law exponent exhibits a weak dependence on the range of film thicknesses, as well as on the molecular alkyl tail length. Our results reproduce the main experimental findings concerning the layer-thinning transitions in free-standing smectic films.