Longitudinal versus polar wrinkling of core-shell fibers with anisotropic size mismatches.

We consider a fiber made of a soft elastic material, encased in a stiff elastic shell (core-shell geometry). If the core and shell dimensions are mismatched, e.g., because the core shrinks while the shell does not, but the two remain attached, then an elastic instability is triggered whereby wrinkles may appear on the shell. The wrinkle orientation may be longitudinal (along the fiber axis), polar (along the fiber perimeter), or a mixture of both, depending on the fiber's geometrical and material parameters. Here we investigate under what conditions longitudinal or polar wrinkling will occur.

Luminescent elastomeric Janus particles.

We report on a low-cost and low-tech method for the preparation of luminescent micro- and millimeter elastomeric particles with asymmetric morphology. The method of fabrication consists in UV-irradiating soft urethane/urea fluorescent spheres, which are then extracted in toluene and dried. Wrinkles appear on the irradiated portions of the particles surfaces, and the spatial periodicity can be controlled with variation in UV irradiation time and the amount of the luminescent compound. The spheres are thus composed of an urethane/urea network in which the tris(8-hydroxyquinolinato)aluminum (Alq3) fluorescent compound was incorporated. The asymmetric morphology and the optical properties of the resultant particles have been confirmed by scanning electron microscopy, atomic force microscopy, optical microscopy, and UV-Vis spectrophotometry. The system shows negligible leaching, and the encapsulation of the Alq3 without recourse to covalent bonding to the polymeric matrix has the advantage of allowing the tuning of the spheres morphology and fluorescence.

Lack of association of GSTT1, GSTM1, GSTO1, GSTP1 and CYP1A1 polymorphisms for susceptibility and outcome in Brazilian prostate cancer patients.

The polymorphic inheritance of human drug-metabolizing enzymes, such as those encoded by the GST and CYP systems, has been implicated in both cancer risk and prognostic. In an effort to increase our understanding of the interaction between potential environmental exposure, lifestyle, and genetic factors in the predisposition and response to radiotherapy of prostate cancer patients, we examined GSTT1, GSTM1, GSTO1, GSTP1 and CYP1A1 genotypes in a Brazilian population. We studied 125 prostate cancer patients and 100 benign prostatic hyperplasia patients paired for ethnic and lifestyle characteristics. Lifetime occupational history, dietary patterns, cigarette-smoking, and other anamnestic data were obtained through interviews. Outcome was evaluated in 42 stage

Study of micro and nano surface structures from UV irradiated urethane/urea elastomers.

In this work we address new results obtained with a thin free standing flexible film (approximately 120 microm) of a urethane/urea copolymer related to the formation of micro and nano size structures [M.H. Godinho, A.C. Trindade, J.L. Figueirinhas, L.V. Melo, P. Brogueira, Synthetic Metals, 147(1-3), 209 (2004); M.H. Godinho, A.C. Trindade, J.L. Figueirinhas, L.V. Melo, P. Brogueira, Molecular Crystals and Liquid Crystals (2005)]. The copolymer was synthesized from a polypropylene oxide-based prepolymer with three isocyanate terminal groups (PU) and polybutadienediol (PBDO) with PBDO content of 40% wt. After casting and curing the film was cut into different samples and each exposed to UV radiation for different periods of time; 23, 25, 26, 31 and 49 h (lambda=254 nm) and later extracted with toluene and dried. The dried films were then studied by polarising optical microscopy (POM), small angle light scattering (SALS) and the surfaces exposed to UV radiation analyzed by means of atomic force microscopy (AFM). Before extraction with toluene a nanometer-flat surface, characterized by a mean roughness value Ra=0.59 nm, was obtained. Depending on exposure time to UV radiation and after extraction with toluene a corrugated surface, with features mum-sized in all axes, resulting in an increase of the overall mean roughness value to Ra=50.7 nm, starts to develop after 25 h of exposure time. This work gives evidence of the non-monotonous time behavior of the wrinkled surface growth that develops under the action of ultraviolet radiation. As the exposure time increases the free-standing films directly exposed surfaces show a decreasing density of the structures observed and an increasing characteristic peak-to-valley height. The peak-to-valley height measured for samples exposed for 23, 25, 26, 31 and 49 h, respectively 193, 383, 381, 1550 and 2039 nm and the corresponding mean roughness values are Ra=50.7 nm, 105.4, 116.8, 438.3 and 515.4 nm, respectively. Between 26 and 31 h exposure time a leap in both values, peak-to-valley and Ra, was observed. The sudden increase in these values is correlated to fabrication of wrinkles by uniaxially stretching PU/PBDO elastomer films.

Staphylococcus epidermidis adhesion on modified urea/urethane elastomers.

Block urea/urethane co-polymer films present elastomeric properties with the possible tuning of their surface properties within a wide range and are therefore considered relevant surfaces for possible medical applications. In particular, thin free standing films of urea/urethane elastomers with two soft segments, polypropylene oxide and more hydrophobic polybutadiene, develop multistable states with surface topography features with remarkable regularity. Moreover, complex surface structures may be obtained by UV radiation treatment followed by suitable mechanical action and also by extraction of the elastomer with a suitable solvent. In the present work, different modified elastomer samples were assayed for Staphylococcus epidermidis adhesion during 2 h and the extent of bacterial adhesion was evaluated by automatic cell enumeration. Bacterial adhesion assays demonstrate that the typical trend relating the increase in the number of adhered bacteria with the increase of the surface roughness does not hold for all materials. Results may be interpreted taking into account both the surface topography and the different types of micro-phase segregation of hydrophobic and hydrophilic parts of the elastomer.

Tuneable micro- and nano-periodic structures in a free-standing flexible urethane/urea elastomer film.

We have studied the control and manipulation of tuneable equilibrium structures in a free-standing urethane/urea elastomer film by means of atomic force microscopy, small-angle light scattering and polarising optical microscopy. The urethane/urea elastomer was prepared by reacting a poly(propyleneoxide)-based triisocyanate-terminated prepolymer (PU) with poly(butadienediol) (PBDO), with a weight ratio of 60% PU/40% PBDO. An elastomer film was shear-cast onto a glass plate and allowed to cure, first in an oven, then in air. Latent micro- and nano-periodic patterns are induced by ultra-violet (UV) irradiation of the film and can be "developed" by applying a plane uniaxial stress or by immersing the elastomer in an appropriate solvent and then drying it. For this elastomer we describe six pattern states, how they are related and how they can be manipulated. The morphological features of the UV-exposed film surface can be tuned, reproducibly and reversibly, by switching the direction of the applied mechanical field. Elastomers extracted in toluene exhibit different surface patterns depending upon the state in which they were developed. Stress-strain data collected for the films before and after UV irradiation reveal anisotropy induced by the shear-casting conditions and enhanced by the mechanical field. We have interpreted our results by assuming the film to consist of a thin, stiff surface layer ("skin") lying atop a thicker, softer substrate ("bulk"). The skin's higher stiffness is hypothesised to be due to the more extensive cross-linking of chains located near the surface by the UV radiation. Patterns would thus arise as a competition between the effects of bending the skin and stretching/compressing the bulk, as in the work of Cerda and Mahadevan (Phys. Rev. Lett. 90, 074302 (2003)). We present some preliminary results of a simulation of this model using the Finite Element package ABAQUS.