The photophysical and hydrodynamic properties of dendrimers (GnPZn and GnTPPH2) with zinc porphyrin (PZn) and tetraphenylporphyrin (TPP) cores are studied in tetrahydrofuran (THF) and dimethylformamide (DMF). UV−vis absorption spectra of GnPZn exhibit a small red shift of the Soret band upon increasing the generation as a result of interactions between the dendrons and the core. All fluorescence decays obtained from global analysis show a monoexponential profile. The intrinsic viscosity obtained for GnPZn from the hydrodynamic volume (V h) passes through a maximum as a function of generation (G) in agreement with earlier experimental findings and calculations suggesting that the internal density profile of dendrimers decrease monotonically outward from the center of the molecule. Within the investigated range (G = 1−3), GnTPPH2 exhibits an approximately constant intrinsic viscosity due to the linear dependence between the hydrodynamic volume and the molecular weight. The differences observed between GnPZn and GnTPPH2 are correlated to structural differences in their cores. The additional phenyl group of the TPP in GnTPPH2 increases the distance between the branches and the porphyrin moiety compared to GnPZn, resulting in a more flexible structure. The enhanced flexibility allows the terminal groups to sample more conformational space and therefore decreases the volume of the dendrimer as compared to the theoretical fully extended structure where V h ∝ G 3. A comparison of the results obtained from analysis of fluorescence anisotropy decays with previously reported viscometry measurements shows a dependence of the structural collapse on the core size.

Analisa o impacto do Programa de Inclusão Social da Universidade de São Paulo (Inclusp) no acesso de estudantes de escola pública ao ensino superior público gratuito. Os dados foram coletados priorizando-se informações sobre renda, cor e outros aspectos de interesse relacionados aos candidatos oriundos de escola pública, em diferentes etapas do vestibular. Como resultado, foi observada a contribuição significativa do sistema de pontuação acrescida para o ingresso de estudantes de escola pública nos cursos de graduação da USP. Todavia, a contínua e intensa diminuição do percentual desses estudantes no vestibular tem contribuído para a diminuição do impacto das políticas de inclusão social implementadas, indicando a necessidade de maior aproximação entre a Universidade e as escolas públicas, bem como a ampliação das ações de inclusão social em desenvolvimento, visando reverter essa tendência.

The fluorescence quenching kinetics of two porphyrin dendrimer series (GnTPPH(2) and GnPZn) by different type of quenchers is reported. The microenvironment surrounding the core in GnPZn was probing by core-quencher interactions using benzimidazole. The dependence of quencher binding constant (K ( a )) on generation indicates the presence of a weak interaction between branches and the core of the porphyrin dendrimer. The similar free volume in dendrimers of third and fourth generation suggests that structural collapse in high generations occurs by packing of the dendrimer peripheral layer. Dynamic fluorescence quenching of the porphyrin core by 1,3-dicyanomethylene-2-methyl-2-pentyl-indan (PDCMI) in GnTPPH(2) is a distance dependent electron transfer process with an exponential attenuation factor beta = 0.33 A(-1). The quenching by 1,2-dibromobenzene occurs by diffusion process of the quencher toward to the porphyrin core, and its rate constant is practically independent of dendrimer generation.

No abstract