Intrachain Energy Migration to Weak Charge-Transfer State in Polyfluorene End-Capped with Naphthalimide Derivative

Polyfluorene end-capped with N-(2-benzothiazole)-1 8-naphthalimide (PF-BNI) is a highly fluorescent material with fluorescence emission modulated by solvent polarity Its low energy excited state is assigned as a mixed configuration state between the singlet S(1) of the fluorene backbone (F) with the charge transfer (CI) of the end group BNI The triexponential fluorescence decays of PF-BNI were associated with fast energy migration to form an intrachain charge-transfer (ICCT) state polyfluorene backbone decay and ICCT deactivation Time-resolved fluorescence anisotropy exhibited biexponential relaxation with a fast component of 12-16 ps in addition to a slow one in the range 0 8-1 4 ns depending on the solvent showing that depolarization occurs from two different processes energy migration to form the ICCT state and slow rotational diffusion motion of end segments at a longer time Results from femtosecond transient absorption measurements agreed with anisotropy decay and showed a decay component of about 16 ps at 605 nm in PF BNI ascribed to the conversion of S(1) to the ICCT excited state From the ratio of asymptotic and initial amplitudes of the transient absorption measurement the efficiency of intrachain ICCT formation is estimated in 0 5 which means that on average, half of the excited state formed in a BNI-(F)(n)-BNI chain with n = 32 is converted to its low energy intrachain charge-transfer (ICCT) state

Axial ligand influence on geometries, charge distributions and electronic structures of iron tetraazamacrocycle [Fe((II))TIM(X)(Y)](2+) complexes assessed by Density Functional Theory

We employed the Density Functional Theory along with small basis sets, B3LYP/LANL2DZ, for the study of FeTIM complexes with different pairs of axial ligands (CO, H(2)O, NH(3), imidazole and CH(3)CN). These calculations did not result in relevant changes of molecular quantities as bond lengths, vibrational frequencies and electronic populations supporting any significant back-donation to the carbonyl or acetonitrile axial ligands. Moreover, a back-donation mechanism to the macrocycle cannot be used to explain the observed changes in molecular properties along these complexes with CO or CH(3)CN. This work also indicates that complexes with CO show smaller binding energies and are less stable than complexes with CH(3)CN. Further, the electronic band with the largest intensity in the visible region (or close to this region) is associated to the transition from an occupied 3d orbital on iron to an empty pi* orbital located at the macrocycle. The energy of this Metal-to-Ligand Charge Transfer (MLCT) transition shows a linear relation to the total charge of the macrocycle in these complexes as given by Mulliken or Natural Population Analysis (NPA) formalisms. Finally, the macrocycle total charge seems to be influenced by the field induced by the axial ligands. (C) 2011 Elsevier Ltd. All rights reserved.

Analytical Assessment of a Home Made Capillary Electrophoresis Equipment with Linear Charge Coupled Device for Visible Light Absorption Detection in the Determination of Food Dyes

The performance of modular home made capillary electrophoresis equipment with spectrophotometric detection, at a visible region by means of a miniaturized linear charge coupled device, was evaluated for the determination of four food dyes. This system presents a simple but efficient home made cell detection scheme. A computer program that converts the spectral data after each run into the electropherograms was developed to evaluate the analytical parameters. The dyes selected for analytical evaluation of the system were Brilliant Blue FCF, Fast Green FCF, Sunset Yellow FCF, and Amaranth. Separation was carried out in a 29cm length and 75 mu m I.D fused silica capillary, using 10mmolL-1 borate buffer at pH 9, with separation voltage of 7.5kV. The detection limits for the dyes were between 0.3 and 1.5mgL-1 and the method presented adequate linearity over the ranges studied, with correlation coefficients greater than 0.99. The method was applied for determination and quantification of these dyes in fruit juices and candies.

'In Charge of the Truffula Seeds' : On Children's Literature, Rationality and Children's Voices in Philosophy

In this paper I investigate how philosophy can speak for children and how children can have a voice in philosophy and speak for philosophy. I argue that we should understand children as responsible rational individuals who are involved in their own philosophical inquiries and who can be involved in our own philosophical investigations-not because of their rational abilities, but because we acknowledge them as conversational partners, acknowledge their reasons as reasons, and speak for them as well as let them speak for us and our rational community. In order to argue this I turn, first, to Gareth Matthews' philosophy of childhood and suggest a reconstruction of some of his concepts in line with the philosophy of Stanley Cavell. Second, in order to examine more closely our conceptions of rationality and our pictures of children, I consider the children's books, The Lorax and Where is My Sister? and Henrik Ibsen's play, The Wild Duck.

Acionamento de frames e esquemas no processo de construção de sentidos no padrão discursivo charge por alunos do ensino médio

Our research has as goal to describe and analyze the main processes related to the activation of conceptual domains underlying the comprehension in the discourse pattern cartoons by the students of third grades of high school, at Professor Antonio Basílio Filho School. Theoretically, we are grounded on assumptions of Conceptual Linguistics, whose interest analyzes our cognitive apparatus in correlation with our socio-cultural and bodies experiences. We intend to check how is the process of meaning construction and integration of various cognitive domains that are activated during the reading activity. That s why, we take the concept of cognitive domains as equivalent to the structures that are stored in our memory from our sociocultural and corporeal experiences and they are stabilized, respectively, through the frames and schemas. The activation of these conceptual domains, as evidenced by our data, supports the assumption that previous knowledge from our inclusion in specific sociocultural contexts, concurrently with the functioning of our sensory-motor system are essential during the construction activity direction. With this research, we still intend to present a proposal confront the expectations of responses produced by students from the activation of frames and schemas with our predictions

Uma visão axiológica do riso na charge

O objetivo deste trabalho é investigar a construção axiológica do riso na charge. Nesse gênero discursivo abordaremos a construção do riso, partindo da hipótese de que o riso constitutivo das relações dialógicas na charge é construído axiologicamente, ou seja, é um riso que presentifica enunciativamente e é por meio dele que chegamos ao axiológico, aos posicionamentos, ao ideológico. Para tanto, nos deteremos na investigação dos elementos verbo-visuais presentes na forma composicional como também do projeto de dizer constituidor/constituinte da forma arquitetônica. Tomamos como fundamento teórico-metodológico as formulações sobre linguagem advindas do Círculo de Bakhtin (2010, 2011, 1998) e outros tais como Faraco (2009), Brait (2009, 2006), Ponzio (2009) que comungam dessa concepção de linguagem. Especificamente sobre o gênero discursivo charge, nos reportamos a Ramos (2009, 2010, 2011) e Vergueiro (2009, 2010). Quanto ao riso, apoiamo-nos em autores como Possenti (2010), Minois (2003), Propp (1992), Bergson (2001), Skinner (2002), no entanto, tendo por principal referência a obra de Bakhtin sobre cosmovisão carnavalesca e riso (1997, 2010). Este trabalho se insere na área da Linguística Aplicada de perspectiva sócio-histórica e tem como tema linguagem, axiologia e riso

Photoinduced hole-transfer in semiconducting polymer/low-bandgap cyanine dye blends: evidence for unit charge separation quantum yield

Power-conversion efficiencies of organic heterojunction solar cells can be increased by using semiconducting donor-acceptor materials with complementary absorption spectra extending to the near-infrared region. Here, we used continuous wave fluorescence and absorption, as well as nanosecond transient absorption spectroscopy to study the initial charge transfer step for blends of a donor poly(p-phenylenevinylene) derivative and low-band gap cyanine dyes serving as electron acceptors. Electron transfer is the dominant relaxation process after photoexcitation of the donor. Hole transfer after cyanine photoexcitation occurs with an efficiency close to unity up to dye concentrations of similar to 30 wt%. Cyanines present an efficient self-quenching mechanism of their fluorescence, and for higher dye loadings in the blend, or pure cyanine films, this process effectively reduces the hole transfer. Comparison between dye emission in an inert polystyrene matrix and the donor matrix allowed us to separate the influence of self-quenching and charge transfer mechanisms. Favorable photovoltaic bilayer performance, including high open-circuit voltages of similar to 1 V confirmed the results from optical experiments. The characteristics of solar cells using different dyes also highlighted the need for balanced adjustment of the energy levels and their offsets at the heterojunction when using low-bandgap materials, and accentuated important effects of interface interactions and solid-state packing on charge generation and transport.

Relating pseudospin and spin symmetries through charge conjugation and chiral transformations: the case of the relativistic harmonic oscillator

We solve the generalized relativistic harmonic oscillator in 1+1 dimensions, i.e., including a linear pseudoscalar potential and quadratic scalar and vector potentials which have equal or opposite signs. We consider positive and negative quadratic potentials and discuss in detail their bound-state solutions for fermions and antifermions. The main features of these bound states are the same as the ones of the generalized three-dimensional relativistic harmonic oscillator bound states. The solutions found for zero pseudoscalar potential are related to the spin and pseudospin symmetry of the Dirac equation in 3+1 dimensions. We show how the charge conjugation and gamma(5) chiral transformations relate the several spectra obtained and find that for massless particles the spin and pseudospin symmetry-related problems have the same spectrum but different spinor solutions. Finally, we establish a relation of the solutions found with single-particle states of nuclei described by relativistic mean-field theories with scalar, vector, and isoscalar tensor interactions and discuss the conditions in which one may have both nucleon and antinucleon bound states.

Study of charge transport in blends of natural rubber and poly(o-methoxyaniline) based on a resistor network statistical model

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Mechanism of charge transport in castor oil-based polyurethane/carbon black composite (PU/CB)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Interfacial surface charge and free accessibility to the PLA(2)-active site-like region are essential requirements for the activity of Lys49 PLA(2) homologues

Lys49 phospholipase A(2) homologues are highly myotoxic and cause extensive tissue damage but do not display hydrolytic activity towards natural phospholipids. The binding of heparin, heparin derivatives and polyanionic compounds such as suramin result in partial inhibition (up to 60%) of the myotoxic effects due to a change in the overall charge of the interfacial surface. In vivo experiments demonstrate that polyethylene glycol inhibits more than 90% of the myotoxic effects without exhibiting secondary toxic effects. The crystal structure of bothropstoxin-I complexed with polyethylene glycol reveals that this inhibition is due to steric hindrance of the access to the PLA(2)-active site-like region. These two inhibitory pathways indicate the roles of the overall surface charge and free accessibility to the PLA2-active site-like region in the functioning of Lys49 phospholipases A(2) homologues. Molecular dynamics simulations, small angle X-ray scattering and structural analysis indicate that the oligomeric states both in solution and in the crystalline states of Lys49 phospholipases A2 are principally mediated by hydrophobic contacts formed between the interfacial surfaces. These results provide the framework for the potential application of both clinically approved drugs for the treatment of Viperidae snakebites. (c) 2006 Elsevier Ltd. All rights reserved.

Efficiency of extrinsic and intrinsic charge-carrier photogeneration processes obtained from the steady-state photocurrent action spectra of poly(p-phenylene vinylene) derivatives

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Nonlocal description of the nuclear interaction

Extensive systematizations of theoretical and experimental nuclear densities and of optical potential strengths extracted from heavy-ion elastic scattering data analyses at low and intermediate energies are presented. The energy-dependence of the nuclear potential is accounted for within a model based on the nonlocal nature of the interaction. The systematics indicates that the heavy-ion nuclear potential can be described in a simple global way through a double-folding shape, which basically depends only on the density of nucleons of the partners in the collision. The possibility of extracting information about the nucleon-nucleon interaction from the heavy-ion potential is investigated.

A mass-transportation approach to a one dimensional fluid mechanics model with nonlocal velocity

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

SU(2,R)(q) symmetries of Non-Abelian Toda theories

The classical and quantum algebras of a class of conformal NA-Toda models are studied. It is shown that the SL(2,R)(q) Poisson brackets algebra generated by certain chiral and antichiral charges of the nonlocal currents and the global U(1) charge appears as an algebra of the symmetries of these models. (C) 1998 Elsevier B.V. B.V. All rights reserved.