Photochromic Polyurethanes Showing a Strong Change of Transparency and Refractive Index.

Photochromic polymers have been studied as rewritable systems for optical elements with tunable transparency in the visible and refractive index in the NIR. Six diarylethene monomers have been synthesized to give thin films of photochromic polyurethanes. The absorption properties of the monomers in solution and of the corresponding polymeric films have been evaluated showing that a transparency contrast in the visible spectrum of the order of 10 3 can be obtained by a suitable choice of the chemical structure and illumination wavelength. The change in the refractive index in the NIR have been determined by ellipsometry showing changes larger than 10 - 2 . A trend of this variation with the absorption properties has been also highlighted. Fresnel lenses working on the basis of both a change of the transparency and the refractive index (amplitude and phase) have been demonstrated.

Fabrication of Gold-Coated Ultra-Thin Anodic Porous Alumina Substrates for Augmented SERS.

Anodic porous alumina (APA) is a nanostructured material used as a template in several nanotechnological applications. We propose the use of APA in ultra-thin form (<100 nm) for augmented surface-enhanced Raman scattering (SERS). Here, the effect of in-depth thinning of the APA nanostructures for possible maximization of SERS was addressed. Anodization was carried out on ultra-thin films of aluminum on glass and/or silicon, followed by pore-opening. Gold (Au) was overcoated and micro­Raman/SERS measurements were carried out on test target analytes. Finite integration technique simulations of the APA-Au substrate were used both for the experimental design and simulations. It was observed that, under optimized conditions of APA and Au thickness, the SERS enhancement is higher than on standard APA-Au substrates based on thin (~100 nm) APA by up to a factor of ~20 for test molecules of mercaptobenzoic acid. The agreement between model and experimental results confirms the current understanding of SERS as being mainly due to the physical origin of plasmon resonances. The reported results represent one step towards micro-technological, integrated, disposable, high-sensitivity SERS chemical sensors and biosensors based on similar substrates.

Multifunctional substrates of thin porous alumina for cell biosensors.

We have fabricated anodic porous alumina from thin films (100/500 nm) of aluminium deposited on technological substrates of silicon/glass, and investigated the feasibility of this material as a surface for the development of analytical biosensors aiming to assess the status of living cells. To this goal, porous alumina surfaces with fixed pitch and variable pore size were analyzed for various functionalities. Gold coated (about 25 nm) alumina revealed surface enhanced Raman scattering increasing with the decrease in wall thickness, with factor up to values of approximately 10(4) with respect to the flat gold surface. Bare porous alumina was employed for micro-patterning and observation via fluorescence images of dye molecules, which demonstrated the surface capability for a drug-loading device. NIH-3T3 fibroblast cells were cultured in vitro and examined after 2 days since seeding, and no significant (P > 0.05) differences in their proliferation were observed on porous and non-porous materials. The effect on cell cultures of pore size in the range of 50-130 nm--with pore pitch of about 250 nm--showed no significant differences in cell viability and similar levels in all cases as on a control substrate. Future work will address combination of all above capabilities into a single device.

Spectroscopic ellipsometry of self assembled monolayers: interface effects. The case of phenyl selenide SAMs on gold.

This work focuses on the quantitative application of spectroscopic ellipsometry to the study of optical properties and thickness of self assembled monolayers (SAMs) of phenyl selenide deposited from the liquid phase on gold. STM, XPS and cyclic voltammetry measurements provide additional chemical and morphological characterization of the SAMs. While routine ellipsometry analysis of SAMs often relies on the film-induced Î´Δ change in the Δ ellipsometric angle and discards SAM-substrate interface effects, the present data show a distinctive behaviour of the Î´Ψ data that we assign to interface effects, stronger than those previously found for densely packed alkanethiol SAMs. An inaccurate modelling of the variations in Ψ related to the nano-structured SAM-substrate interface leads to a large overestimation of the film thickness. A simple model, which takes into account an effective approximation for the interface layer between the film and the substrate, and the molecular optical absorptions, provides a good agreement between the data and a reliable thickness estimate of the SAM.

Optical properties of Yeast Cytochrome c monolayer on gold: an in situ spectroscopic ellipsometry investigation.

The adsorption of Yeast Cytochrome c (YCC) on well defined, flat gold substrates has been studied by Spectroscopic Ellipsometry (SE) in the 245-1000 nm wavelength range. The investigation has been performed in aqueous ambient at room temperature, focusing on monolayer-thick films. In situ Î´Ψ and Î´Δ difference spectra have shown reproducibly well-defined features related to molecular optical absorptions typical of the so-called heme group. The data have been reproduced quantitatively by a simple isotropic optical model, accounting for the molecular absorption spectrum and film-substrate interface effects. The simulations allowed a reliable estimate of the film thickness and the determination of the position and the shape of the so-called Soret absorption peak that, within the experimental uncertainty, is the same found for molecules in liquid. These findings suggest that YCC preserves its native structure upon adsorption. The same optical model was able to reproduce also ex situ results on rinsed and dried samples, dominated by the spectral features associated to the polypeptide chain that tend to overwhelm the heme absorption features.