Optical spectroscopy study of the interaction between curcumin and acrylic polymers.

This paper presents the results of a study conducted on the interaction between curcumin, a compound with several biomedical applications in traditional and modern medicine, and the acrylic polymers poly(methyl methacrylate), poly(ethyl methacrylate), and poly(n-butyl methacrylate), through photophysical experiments in curcumin/acrylic polymers casting films. Optical absorption intensity at ~340 nm increases relatively to its maximum at ~417 nm when the amount of curcumin in the polymeric film decreases, due to a significant change in the concentration of the isomers cis- or trans-form of curcumin, regardless of the acrylic polymer. Fluorescence (FL) spectra of the films depend on the curcumin concentration in the matrix with well-resolved line shape. They show two distinct bands, one at ~525 nm, for higher curcumin concentration (5.00 mmol.L-1), related to the aggregated curcumin species, and another at ~465 nm, for lower concentration of curcumin (0.10 mmol.L-1), related to the effects of the solvent on the conformational structure of the curcumin molecule and the presence of the trans-form of curcumin. The parameter Kagg, related to the contribution of the aggregated curcumin, shows the influence of the polymeric lateral chain length of the matrix in the de-aggregation of the curcumin. The Huang-Rhys factor indicates that curcumin aggregated species are conformationally more stable, and that the isolate species depends on the chemical environment and the matrix/curcumin interaction, decreasing its conformational degrees of freedom. Arrhenius plots, obtained via FL experiment in function of the sample temperature, show that, for higher curcumin concentration, the value for the relaxation energy process is not well defined, due the decrease in the interaction between the matrix and the curcumin molecules. With these results, it is possible to infer that the interaction matrix/curcumin must occur via lateral chemical alkyl groups.

Decoupling Temperature-Volume Effects on Poly[2-Methoxy-5-(2'-Ethylhexyloxy)-1,4-Phenylene-Vinylene] Films at the ß-Relaxation Temperature.

In this paper, we report a simple procedure to decouple effects from temperature and volume on the emission properties of thin films of poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene-vinylene] (MEH-PPV). This procedure consists of applying a positive pressure close to the ß-relaxation temperature, Tß (∼220 K), of MEH-PPV, which controls the molecular movement to retain a disordered state for the polymer chains even after the sample is cooled from room temperature. Such decoupling could be confirmed by calculating the photoluminescence (PL) spectra line shape using a semi-empirical model based on molecular exciton and Franck-Condon transitions, and with electron-vibrational modes coupling being parameterized with the Huang-Rhys factor. We also show that the decoupling between temperature and volume effects does not occur if the molecular movement is restricted either by thermal annealing or by depositing the MEH-PPV film on a rigid substrate. This latter finding may be exploited in designing thermally stable devices.

Temperature effect on the electron-vibrational mode coupling of a fully conjugated polyfluorene derivative.

Photoluminescence (PL) and electroluminescence (EL) spectra were used to probe the thermal relaxation processes of the poly(9,9'-n-dihexyl-2,7-fluorenediiylvinylene-alt-1,4-phenylenevinylene) (LaPPS16) electroluminescent polymer. A theoretical model of molecular excitons and Franck-Condon transitions were used to analyze the line shape of the radiative transitions. It was possible to correlate directly the electron-vibrational mode coupling, i.e., the Huang-Rhys parameter, and the polymer relaxation processes due to the effects of molecular dynamics on the electronic states. The results showed different dependences of the thermal relaxation process on PL and on EL due to the molecular dynamics restraints of LaPPS16. This could explain the efficiency variation in organic light emitting diodes where the external electric field would decrease the degrees of freedom of the polymer and activate specific non-radiative channels. Molecular relaxation temperatures of the LaPPS16 polymer are proposed.

Nanomolding the Surface of Polymer Films.

Slight changes in the experimental procedures of the micro contact printing (ACP) technique are introduced here, which allow for using polymers soluble in distinct solvents to fabricate submicrometric 2D periodic structures. Highly reproducible secondary and tertiary poly(dimethylsiloxane) (PDMS) molds could be produced, as demonstrated in atomic force microscopy images and light diffraction experiments. The replication of tertiary molds with no residues of PDMS demonstrates the feasibility of large-scale production with distinct polymers. The plane wave propagation along the tertiary poly(3,4-ethylenedioxythiophene) with poly(hydrogen 4-styrene sulfonate) molds was simulated with a finite-difference time-domain algorithm. A strong wave propagation was observed in the region containing the structures acting as a wave guide, in agreement with the results from the experimental absorption measurements. Furthermore, we show that the optical properties of the molds and their roughness can be tuned by choosing the polymers (including biopolymers) for printing pillars and tracks, thus bringing new possibilities for nanomolding of polymer surfaces for photonics, organic electronics and bioelectronics.