Nanoscale processing of polyaniline and phthalocyanines for sensing applications

Nanostructured polyaniline-modified electrodes were fabricated via the electrostatic layer-by-layer (LbL) technique where polyaniline (PANI) was assembled with one of three tetrasulfonated metallic phthalocyanines, viz. iron (FeTsPc), nickel (NiTsPc) and copper (CuTsPc). The multilayer formation was monitored via UV-vis spectroscopy by measuring the increase in the 800 run absorption band due to PANI. Infrared spectroscopy in the transmission mode suggested specific interactions between PANI and the phthalocyanines, such as those between SO3- groups from the phthalocyanines and the protonated NH group from PANI. The films were employed to detect dopamine (DA) using cyclic voltammetry. In the presence of dopamine the PANI-based LbL films showed additional redox peaks at ca. 230 and 190 mV the oxidation peak increased linearly with the concentration of DA in the electrolytic solution. Films comprising PANI/FeTsPc were able to distinguish between DA and ascorbic acid (AA), which acts as a natural interferent in biological fluids. (c) 2005 Elsevier B.V. All rights reserved.

Unusual interactions binding iron tetrasulfonated phthalocyanine and poly(allylamine hydrochloride) in layer-by-layer films

Molecular-level interactions are found to bind iron tetrasulfonated phthalocyanine (FeTsPc) and the polyelectrolyte poly(allylamine hydrochloride) (PAH) in electroactive layer-by-layer (LBL) films. These interactions have been identified by comparing Fourier transform infrared (FTIR) and Raman spectroscopy data from bulk samples of FeTsPc and PAH with those from FeTsPc/PAH LBL films. of particular importance were the SO3- -NH3 interactions that we believe to bind PAH and FeTsPc and the interactions between unprotonated amine groups of PAH and the coordinating metal of the phthalocyanine. The multilayer formation was monitored via UV-vis spectroscopy by measuring the increase in the Q band of FeTsPc at 676 nm. Film thickness estimated with profilometry was ca. I I Angstrom per bilayer for films adsorbed on glass. Reflection absorption infrared spectroscopy (RAIRS) revealed an anisotropy in the LBL film adsorbed on gold with FeTsPc molecules oriented perpendicularly to the substrate plane. Cyclic voltammograms showed reproducible pairs of oxidation-reduction peaks at 1.07 and 0.81 V, respectively, for a 50-bilayer PAH/FeTsPc film at 50 mV/s (vs Ag/Ag+). The peak shape and current dependence on the scan rate suggest that the process is a diffusion controlled charge transport. In the presence of dopamine, the electroactivity of FeTsPc/PAH LBL films vanishes due to a passivation effect. Dopamine activity is not detected either because the interaction between Fe atoms and NH2 groups prevents dopamine molecules from coordinating with the Fe atoms.

Morphology characterization of layer-by-layer films from PAH/MA-co-DR13: the role of film thickness

We report on the use of dynamic scale theory and fractal analyses in the Study of distinct growth stages of layer-by-layer (LBL) films of poly(allylamine hydrochloride) (PAH) and a side-chain-substituted azobenzene copolymer (Ma-co-DR13). The LBL films were adsorbed oil glass substrates and characterized with atomic force microscopy with the Ma-co-DR13 at the top layer. The ganular morphology exhibited by the films allowed the observation of the growth process inside and outside the grains. The growth outside the grains was found to follow the Kardar-Parisi-Zhang model, with fractal dimensions of ca. 2.6. One could expect that inside the grains the morphology would be close to a Euclidian surface with fractal dimension of ca. 2 for any growth stage. The latter, however, was observed only for thicker films containing more than 10 bilayers. For thinner films the morphology was well described by a self-affine fractal. Such dependence of the growth behavior with the film thickness is associated with a more complete coverage of adsorption sites in thicker films due to diffusion of polymer molecules. (c) 2004 Elsevier B.V. All rights reserved.

Photoinduced phenomena in layer-by-layer films of poly(allylamine hydrochloride) and Brilliant Yellow azodye

The nanoscale interactions between adjacent layers of layer-by-layer (LBL) films from poly(allylamine hydrochloride) (PAH) and azodye Brilliant Yellow (BY) have been investigated, with the films employed for optical storage and the formation of surface-relief gratings. Using Fourier transform infrared spectroscopy, we identified interactions involving SO3- groups from BY and NH3+ groups from PAH. These electrostatic interactions were responsible for the slow kinetics of writing in the optical storage experiments, due to a tendency to hinder photoisomerization and the subsequent reorientation of the azochromophores. The photoinduced birefringence did not saturate after one hour of exposure to the writing laser, whereas in azopolymer films, saturation is normally reached within a few minutes. on the other hand, the presence of such interactions prevented thermal relaxation of the chromophores after the writing laser was switched off, leading to a very stable written pattern. Moreover, the nanoscale interactions promoted mass transport for photoinscription of surface-relief gratings on PAH/BY LBL films, with the azochromophores being able to drag the inert PAH chains when undergoing the trans-cis-trans photoisomerization cycles. A low level of chromophore degradation was involved in the SRG photoinscription, which was confirmed with micro-Raman and fluorescence spectroscopies.

Adsorption processes in layer-by-layer films of poly(o-methoxyaniline): the role of aggregation

In this work we investigate the effect from the solution concentration on aggregation in layer-by-layer (LBL) films of poly(omethoxyaniline) (POMA) alternated with poly(vinyl sulfonic acid). Films are adsorbed on hydrophilized glass substrates and characterized with UV-Vis spectroscopy and atomic force microscopy. The formation of aggregates is favored in more concentrated solutions, leading to an increase in the diameter of the domains. This is caused by stronger polymer-polymer interactions under high concentrations. The size of POMA aggregates in solution is estimated to be larger than in LBL films, which is surprising because one should expect aggregates from solution to coalesce into larger aggregates in the deposited films. This unexpected result may be explained by a swelling effect of aggregates in the aqueous POMA solutions, consistent with other reports in the literature which consider the aggregates in solution to be made up of smaller aggregates. Upon adsorption on a solid substrate to form the LBL film, a molecular reorganization probably takes place, resulting in smaller aggregates. It is also found that the size distribution of the POMA domains in the LBL films is determined by the concentration of the solution. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Deposition of controlled thickness ultrathin SnO2 : Sb films by spin-coating

The technological interest in transparent conductive oxide films (TCOs) has motivated several works in processing techniques, in order to obtain adequate routes to application. In this way, this work describes a new route to obtain antimony-doped tin oxide (ATO) films, based in colloidal dispersions of oxide nanocrystals. The nanoparticles were obtained by a hydrolisis method, using SnCl2 and SbCl3 in ethanolic solutions. The residual halides were removed by dyalisis, obtaining a limpid and transparent colloidal suspension. By this, the method offers the advantage of producing ultrathin films without organic contaminants. This route was employed to produce films with 5, 10, 14, and 18 mol% Sb doping, with thickness ranging from 40 to 70 nm. The physical characterization of the samples showed a uniform layer deposition, resulting in good packing density and high transmittance. A preliminar electrical study confirmed the low electrical resistivity even in the ultrathin films, in such level similar of reported data. The method described is similar in some aspects to layer-by-layer (LbL) techniques, allowing fine control of thickness and interesting properties for ultrathin films, however, with low cost when compared to similar routes.

Immobilization of humic acid in nanostructured layer-by-layer films for sensing applications

Humic acids (HAs), naturally occurring biomacromolecules, were incorporated into nanostructured polymeric films using the layer-by-layer (LbL) technique, in which HA layers were alternated with layers of poly(allylamine hydrochloride) (PAH). Atomic force microscopy (AFM) revealed very smooth films, with mean roughness varying from 0.89 to 1.19 nm for films containing 5 and 15 PAH/HA bilayers, respectively. The films displayed electroactivity, with the presence of only one reduction peak at ca. 0.675 V (vs Ag/AgCl). Such a well-defined electroactivity allowed the films to be used as highly sensitive pesticide sensors, with detection of pentachlorophenol (PCP) in solutions at concentrations as low as 10(-9) mol L(-1).

Molecular engineering strategies to control photo-induced birefringence and surface-relief gratings on layer-by-layer films from an azopolymer

The interactions governing adsorption of layer-by-layer (LBL) films from an azopolymer, PS-119(R), and poly(allylamine hydrochloride) (PAH) have been controlled by modifying the pH of the solutions used to form the films. The thickness per bilayer was varied by one order of magnitude, from 10 to 240 A, as the pH changed from 4 to 10. Thick layers were formed at higher pHs because in this case the PAH is only partially charged adopting a loopy conformation. This change in molecular conformation caused the kinetics of isomerization and mass transport to be much slower than at lower pHs. The writing time defined as the time to achieve 50% of maximum birefringence dropped from 110 to 18 min for films prepared from solutions with pH 10 and pH 4, respectively. This decrease is probably due to the higher free volume for isomerization in the films prepared at lower pHs, in which PAH molecules are less coiled than at higher pHs. For the same reason, the rate of inscription of surface-relief gratings with an interference pattern of p-polarized light was also much slower at higher pHs. (C) 2003 Elsevier B.V. All rights reserved.

Exploiting Cascade Reactions in Bienzyme Layer-by-Layer Films

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

Diffusion-controlled growth of aggregates in layer-by-layer films of poly(o-methoxyaniline)

The adsorption process in layer-by-layer (LBL) films of poly(o-methoxyaniline) alternated with poly(vinyl sulfonic acid) is explained using the Avrami equation. This equation was used due to its mathematical simplicity and adequate description of experimental data in real polymer systems. The Avrami parameters are a convenient means to represent empirical data of crystallization, and if microscopic knowledge is available these parameters can also be associated with adsorption mechanisms. The growth of spherulites in the LBL films was studied as a function of time using atomic force microscopy and the data were used to estimate the number and radii of aggregates, from which the Avrami parameters were determined. We find that the adsorption mechanism may correspond to a tri dimensional, diffusion-controlled growth, with increasing nucleation rate, consistent with results from kinetics of adsorption.

Nanostructured films from phthalocyanine and carbon nanotubes: Surface morphology and electrical characterization

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Mechanisms of surface-relief gratings formation in layer-by-layer films from azodyes

Surface-relief gratings are photoinscribed on ionically adsorbed layer-by-layer (LBL) films of an azodye, Brilliant Yellow (BY), which was layered alternately with a polyelectrolyte. Photoinscription is performed by impinging an interference pattern of p- or s-polarized laser light with moderate intensity onto the LBL film, which is unlikely to cause thermal effects. Large-scale mass transport occurs due to the force associated with the field gradient of the light pattern. The ionic interactions between adjacent layers appear to provide the means for the chromophores to drag the polymer chains upon photoizomerization. LBL films were produced from two different polyelectrolytes and under two distinct pH values leading to markedly different film properties especially concerning photodegradation. Exposure to the laser light, for instance, leads to higher photodegradation in the poly(dimethyl diallylammonium chloride)/BY system, in comparison to the poly(allylamine hydrochloride)/BY films. Mass transport in the latter case is predominantly light-driven, which is consistent with the higher amplitude of modulation for p-polarized light (70 nm) compared to that caused by s-polarized light (18 nm). © 2003 Elsevier Ltd. All rights reserved.

Electrooptic proprieties of layer-by-layer films of a azobenzene containing copolymer

The methacrylic copolymer functionalized with the azo chromophore 4-[N-ethyl-N-(2-hydroxiethyl)]-amino-2′-chloro-4-nitroazobenzene (MMADR13), in its polyelectrolyte form, can be used to fabricate thin films by the layer-by-layer (LbL) technique just if one alternates this anionic polyelectrolyte with a cationic polyelectrolyte such as poly(allylamine hydrochloride) (PAH). Since PAH does not present any particular optical functionality, the main final film feature will came from the side chain DR13 azo-chromophore group due to its large nonlinear optical properties and photoisomerization capabilities. This work reports the electrooptic activity of MMADR13/DR13 LBL films, which arises from the high hiperpolarizability about the azo side chain group.

Use of hemoglobin as alternative to peroxidases in cholesterol amperometric biosensors

Sophisticated molecular architectures can be produced with the layer-by-layer (LbL) method, which may combine distinct materials on the same film. In this study, we take advantage of this capability to produce cholesterol amperometric biosensors from LbL films containing hemoglobin (Hb) and cholesterol oxidase in addition to the polyelectrolytes poly(allylamine hydrochloride) (PAH) and poly(ethylene imine) (PEI). Following an optimization procedure, we found that an LbL film deposited onto ITO substrates, with the architecture ITO(PEI/Hb)5(PEI/COx)10, yielded a sensitivity of 93.4 μA μmol L-1 cm-2 for cholesterol incorporated into phospholipid liposomes, comparable to state-of-the-art biosensors. Hb acted as efficient electron mediator and did not suffer interference from phospholipids. Significantly, cholesterol could also be detected in real samples from chicken egg yolk, with no effects from potential interferents, including phospholipids. Taken together these results demonstrate the possible fabrication of low cost, easy-to-use cholesterol amperometric biosensors, whose sensitivity can be enhanced by further optimizing the molecular architectures of the LbL films. © 2012 Elsevier B.V.

Immunosensor based on immobilization of antigenic peptide NS5A-1 from HCV and silk fibroin in nanostructured films

The peptide NS5A-1 (PPLLESWKDPDYVPPWHG), derived from hepatitis C virus (HCV) NS5A protein, was immobilized into layer-by-layer (LbL) silk fibroin (SF) films. Deposition was monitored by UV-vis absorption measurements at each bilayer deposited. The interaction SF/peptide film induced secondary structure in NS5A-1 as indicated by fluorescence and circular dichroism (CD) measurements. Voltammetric sensor (SF/NS5A-1) properties were observed when the composite film was tested in the presence of anti-HCV. The peptide-silk fibroin interaction studied here showed new architectures for immunosensors based on antigenic peptides and SF as a suitable immobilization matrix. © 2013 American Chemical Society.