4D-π-1A type ß-substituted ZnII-porphyrins: ideal green sensitizers for building-integrated photovoltaics.

Two novel green ß-substituted ZnII-porphyrins, G1 and G2, based on a 4D-π-1A type substitution pattern have been synthesized. Their enhanced push-pull character, by reduction of H-L energy gaps, promotes broadening and red-shifting of absorption bands. The effective synthetic pathway and the remarkable spectroscopic properties make G2 ideal for BIPV application.

A nonlinear optical active polymer film based on Pd(ii) dithione/dithiolate second-order NLO chromophores.

A film of [Pd(R2pipdt)(dmit)] (1), where R2pipdt = 1,4-didodecyl-piperazine-2,3-dithione (acceptor) and dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate (donor) incorporated into a polymethylmethacrylate (PMMA) matrix, showing a good second-harmonic generation, has been prepared for the first time in the class of dithione-dithiolate 2nd order NLO-chromophores. Moreover full characterization of 1, including molecular second-order NLO properties in solution, is reported.

Influence of alkoxy chain envelopes on the interfacial photoinduced processes in tetraarylporphyrin-sensitized solar cells.

The introduction of alkoxy chains in the molecular architecture of meso push-pull porphyrins is of paramount importance aiming at high performing dye-sensitized solar cells (DSSCs) based on these specific sensitizers. Recently, we have demonstrated that the same approach is fruitful even if it is applied to tetraarylporphyrins with an acceptor/anchoring substituent in the ß-pyrrolic position. In particular, among the ortho-ortho, the ortho-para and the ortho-functionalization of the aryl rings with an octyloxy chain, we identified the latter as the most performing in the series, showing a good balance between the dye loading and the reduction of π-π aggregation. Herein, focusing our attention on the mono-ortho-functionalized molecular structure, we have investigated the effect of the alkoxy chain length and nature on the reduction of dye-to-dye aggregation as well as on the enhancement of light harvesting capabilities, finding an almost linear relationship between the device photon conversion efficiency (PCE) and the alkoxy chain length both in the presence and in the absence of a co-disaggregating agent.

Solid state and solution fine tuning of the linear and nonlinear optical properties of (2-pyrene-1-yl-vinyl)pyridine by protonation-deprotonation reactions.

The unexpected and acido-triggered reversible luminescence and nonlinear optical properties of (2-pyrene-1-yl-vinyl)pyridine, a simple and highly transparent chromophore, are studied both in solution and in the solid state. Remarkably, for the first time the acidomodulation of the NLO response of a poled thin film is reported.

Effectiveness of thalidomide and tamoxifen in preventing neointimal hyperplasia in experimental vascular injury in rats.

INTRODUCTION: Chronic allograft vasculopathy is an important cause of graft loss. Considering the inflammatory response in the development of chronic vascular lesions, therapeutic approaches to target the inflammatory process may be useful. We sought to investigate the possible protective effects on balloon catheter-induced vascular injury of thalidomide and tamoxifen, 2 drugs with powerful anti-inflammatory, immunomodulatory, and antifibrotic effects, using an animal model that mimics the morphologic features of chronic allograft vasculopathy. METHODS: Male Wistar rats subjected to balloon catheter carotid injury (INJ) were treated with thalidomide (100 mg/kg), or tamoxifen (10 mg/kg), or vehicle. Contralateral right carotid arteries were used as uninjured controls. Morphometric and immunohistochemical analyses were performed at 14 days postinjury. RESULTS: Injured carotid arteries showed marked neointimal hyperplasia, which was significantly inhibited among animals treated with thalidomide or tamoxifen: neointimal/media ratios of 1.4 +/- 0.4 versus 0.2 +/- 0.1 versus 0.4 +/- 0.2, for INJ, INJ + Thalid, and INJ + Tamox; respectively (P < .001). The endothelial cell loss was significantly less pronounced among animals subjected to carotid balloon injury that were treated with thalidomide (24 +/- 14 vs 1 +/- 1 cells per section in INJ, respectively (P < .05). Therapy with either thalidomide or tamoxifen effectively maintained alpha-smooth muscle actin expression in the media, similar to uninjured arteries. In this setting, tamoxifen was additionally effective to prevent the migration of myofibroblasts in to the intima. CONCLUSION: Thalidomide and tamoxifen were effective to reduce neointimal hyperplasia secondary to vascular damage. The vasculoprotective effects of thalidomide were more pronounced to preserve endothelial cells, whereas tamoxifen inhibited smooth muscle cell migration and proliferation. A possible beneficial effect of combined therapy with thalidomide plus tamoxifen should be addressed in future studies.

Ultrafast intrachain photoexcitation of polymeric semiconductors.

We report on excited state dynamics in isolated poly(9,9-dioctylfluorene) chains obtained by embedding the polymer in an inert plastic matrix. Early events (<300 fs) of intrachain photophysics are detected by pump-probe spectroscopy using tunable UV 25-fs pump pulses and sub-10-fs visible probe pulses. We show that higher-lying optical states, reached by multiphoton transitions, give rise to on-chain charge separation on the ultrafast time scale. The intrachain charge pair decays geminately within 500 fs to the lowest singlet state. Characteristic time scales for internal conversion and intramolecular vibrational redistribution are also determined.