Femtosecond laser induced synthesis of Au nanoparticles mediated by chitosan.

This paper reports the synthesis of Au nanoparticles by 30-fs pulses irradiation of a sample containing HAuCl4 and chitosan, a biopolymer used as reducing agent and stabilizer. We observed that it is a multi-photon induced process, with a threshold irradiance of 3.8 × 10(11) W/cm2 at 790 nm. By transmission electron microscopy we observed nanoparticles from 8 to 50 nm with distinct shapes. Infrared spectroscopy indicated that the reduction of gold and consequent production of nanoparticles is related to the fs-pulse induced oxidation of hydroxyl to carbonyl groups in chitosan.

Transitions in the orientational order of liquid crystals induced by periodic patterned substrates.

The orientational order of liquid crystals (LCs) induced by periodic patterned substrates has been investigated with cells coated by azopolymer films that could be photoaligned in a controlled way. Two regimes were observed depending on the period of the patterns: (i) above 3.0 microm the LC follows the direction imposed by the patterned substrate since the energy stored in the surface potential minimizes the elastic energy of the LC medium. (ii) For periods smaller than 1.0 microm a homogeneous in-plane state was induced and the LC did not follow the orientation imposed by the surface. This in-plane transition could be explained qualitatively by a theoretical model based on the competition between the Frank-Oseen elastic energy and the phenomenological surface potential. The results also suggest an out-of-plane transition for the LC director as the period was reduced. These results agree with data in the literature for patterned substrates with completely distinct architectures. This indicates that for a particular LC sample the overall behavior depends basically on the texture period instead of the texture architecture. The textures were characterized with a scanning near-field optical microscope (SNOM), which allowed simultaneous morphological and optical images in the submicrometer range.

Phenomenological analysis of the light intensity dependence of the photoalignment process in azo-containing polymeric films.

A phenomenological model is proposed to analyze the influence of the incident light intensity on the photoinduced anisotropy of an azobenzene-containing polymer film. The optical anisotropy was generated in the films by the incidence of linearly polarized light and monitored by transmittance measurements.

In situ UV-vis absorbance measurements for Langmuir films of poly[4'-[[2-(methacryloyloxy)-ethyl]ethylamino]-2-chloro-4-nitroazobenzene] (HPDR13) azopolymer.

In situ UV-vis absorbance measurements are used to investigate aggregation in Langmuir films from the azopolymer poly[4'-[[2-(methacryloyloxy)-ethyl]ethylamino]-2-chloro-4-nitroazobenzene] (HPDR13), a methacrylate derivative of DR13. The level of aggregation in a Langmuir film is intermediate between that of HPDR13 in chloroform solution and in a deposited LB film, as expected. Absorption is negligible at large areas per monomer, and starts to increase at a critical area that is the same as the one obtained in surface potential isotherms, being close to twice the area per monomer for a condensed film. This indicates that the onset for light absorption coincides with a critical packing density where monolayer structuring occurs and there is a sharp change in the effective dielectric constant of the film/water interface. Consistent with a featureless pressure-area isotherm for HPDR13, denoting no significant molecular rearrangement upon film compression, the UV-vis spectra did not vary with the surface pressure. The intensity of absorbed light increased, though, as the film was compressed owing to a higher density of chromophores. At higher subphase temperatures, larger flexibility of HPDR13 chains led to a more compact arrangement, causing the area per monomer to decrease and the absorbed light to increase-with approximately opposite trends.

Manipulation of anchoring strength in an azo-dye side chain polymer by photoisomerization.

The generation of surface anisotropy by photochemical means has been proposed as an attractive method to align liquid crystals. In this paper, we present an experimental study of the alignment induced on a liquid crystal by a polymer film containing azo-dye groups in the side chain. Optical measurements were performed in nematic liquid crystal cells to determine the azimuthal and zenithal anchoring strengths as a function of the irradiation energy and chromophores concentration. It was observed that the director tends to align perpendicular to the polarization direction of the incident light and the orientation process consists essentially of a rotation of the director in the plane parallel to the boundary surfaces. However, the concentration of azo-dye groups in the polymer film must exceed a minimum value to get a macroscopical effect on the liquid crystal alignment. It is shown that the azimuthal anchoring strength can be varied two orders of magnitude by controlling the irradiation energy and azo-dye concentration.

Surface enhanced fluorescence and Raman imaging of Langmuir-Blodgett azopolymer films.

The spectroscopic properties and surface-enhanced spectra of Langmuir-Blodgett (LB) films of methacrylic homopolymer (HPDR13) are presented. It is shown that LB film displays strong fluorescence attributed to the spatial restrictions imposed by its structure. The emission is observed in conjunction with photoisomerization, a process clearly demonstrated by the formation of surface-relief gratings in the LB film [C.R. Mendonça et al., Macromolecules 32 (1999) 1493]. Surface-enhanced Raman scattering (SERS), Surface-enhanced resonance Raman scattering (SERRS) and surface-enhanced fluorescence (SEF) were observed for LB films of HPDR13 deposited onto silver island films. SERS measurements were also carried out on a sample fabricated with one monolayer LB film deposited onto silver islands followed by one overlayer of silver (LB sandwiched between two layers of silver islands). The polymer interacts very weakly with the metal surface (physisorption), and the enhancement effect is determined by the local electric field enhancement. The strong SERS and SERRS signals were suitable for micro-Raman imaging. Line, area mapping and global images of the LB monolayer on silver island are reported. The transfer ratio in the fabrication of the LB suggests a homogeneous coating of the silver islands, thereby the chemical images show the variation of the SERS intensity due to surface enhancement.