Redox control of light-induced charge separation in a transition metal cluster: photochemistry of a methyl viologen-substituted [Os-3(CO)10(a-diimine)] cluster

Sub)picosecond transient absorption (TA) and time-resolved infrared (TRIR) spectra of the cluster [OS3(CO)(10-) (AcPy-MV)](2+) (the clication AcPy-MV = Acpy-MV2+ = [2-pyridylacetimine-N-(2-(1'-methyl-4,4'-bipyridine-1,1'-diium-1-yl) ethyl)] (PF6)(2)) (1(2+)) reveal that photoinduced electron transfer to the electron-accepting 4,4'-bipyridine-1,1'diium (MV2+) moiety competes with the fast relaxation of the initially populated sigmapi* excited state of the cluster to the ground state and/or cleavage of an Os-Os bond. The TA spectra of cluster 12 in acetone, obtained by irradiation into its lowest-energy absorption band, show the characteristic absorptions of the one-electron-reduced MV*(+) unit at 400 and 615 nm, in accordance with population of a charge-separated (CS) state in which a cluster-core electron has been transferred to the lowest pi* orbital of the remote MV2+ unit. This assignment is confirmed by picosecond TRIR spectra that show a large shift of the pilot highest-frequency nu(CO) band of 1(2+) by ca. +40 cm(-1), reflecting the photooxidation of the cluster core. The CS state is populated via fast (4.2 x 10(11) s(-1)) and efficient (88%) oxidative quenching of the optically populated sigmapi* excited state and decays biexponentially with lifetimes of 38 and 166 ps (1:2:1 ratio) with a complete regeneration of the parent cluster. About 12% of the cluster molecules in the sigmapi* excited state form long-lived open-core biradicals. In strongly coordinating acetonitrile, however, the cluster core-to-MV2+ electron transfer in cluster 12+ results in the irreversible formation of secondary photoproducts with a photooxidized cluster core. The photochemical behavior of the [Os-3(CO)(10)(alpha-diimine-MV)](2+) (donor-acceptor) dyad can be controlled by an externally applied electronic bias. Electrochemical one-electron reduction of the MV2+ moiety prior to the irradiation reduces its electron-accepting character to such an extent that the photoinduced electron transfer to MV*+ is no longer feasible. Instead, the irradiation of reduced cluster 1(.)+ results in the reversible formation of an open-core zwitterion, the ultimate photoproduct also observed upon irradiation of related nonsubstituted clusters [Os-3(CO)(10)(alpha-diimine)] in strongly coordinating solvents such as acetonitrile.

Comunicação, informação e controle social no SUSUm estudo em dois municípios da região metropolitana de Belo Horizonte/MG

Esse trabalho se propôs a estudar a comunicação e informação para o controle social no Sistema Único de Saúde (SUS). Os objetos empíricos desse estudo foram os Conselhos de saúde de dois municípios de pequeno porte, situados na Região Metropolitana de Belo Horizonte/MG: Brumadinho e Sarzedo. Partindo do pressuposto de que qualquer forma de controle social se faz com práticas comunicacionais e informacionais, objetivou-se analisar até que ponto há um uso efetivo da comunicação e informação para o controle social: seja no interior dos conselhos na sua prática cotidiana ou, externamente, na comunicação com a sociedade. A metodologia utilizada foi a pesquisa qualitativa, utilizando-se o método de análise documental, entrevista com conselheiros de saúde e observação participante. Na análise documental, foram analisados relatórios de conferências de saúde, atas e pautas das reuniões dos conselhos de saúde, com temas que se relacionavam com comunicação e informação para o controle social A entrevista com conselheiros foi realizada a partir de questionario semiestruturado a fim de obter informacoes sobre a percepcao dos conselheiros sobre o tema \comunicacao e informacao para exercicio do controle social no SUS.. A observacao participante permitiu verificar como ocorrem as relacoes comunicacionais nos espacos das reunioes dos conselhos. Os resultados da pesquisa confirmaram a nossa hipotese, de que ha poucos investimentos informacionais e comunicacionais nos conselhos de saude e isso dificulta e compromete a participacao dos conselheiros. A falta de dialogo do conselho com a sociedade acarreta o desconhecimento sobre as suas acoes e isso atribui um grau de pouca importancia do orgao pela populacao

Iron homeostasis and management of oxidative stress response in bacteria

Iron is both an essential nutrient for the growth of microorganisms, as well as a dangerous metal due to its capacity to generate reactive oxygen species (ROS) via the Fenton reaction. For these reasons, bacteria must tightly control the uptake and storage of iron in a manner that restricts the build-up of ROS. Therefore, it is not surprising to find that the control of iron homeostasis and responses to oxidative stress are coordinated. The mechanisms concerned with these processes, and the interactions involved, are the subject of this review.

An investigation on sliding wear behavior of PVD coatings

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Correlation of microcrack fracture size with fatigue cycling on non-crimp fabric/RTM6 composite in the uniaxial fatigue test

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

Fatigue strength of HVOF sprayed Cr(3)C(2)-25NiCr and WC-10Ni on AISI 4340 steel

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

Composite materials obtained from textile fiber residue

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Evaluation on fatigue strength of AISI 4340 steel aluminum coated by electroplating and IVD processes

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

Image analysis of modified cellulose fibers from sugarcane bagasse by zirconium oxychloride

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Evaluation of fatigue behavior on repaired carbon fiber/epoxy composites

The continuous use of structural polymer composites in aeronautical industry has required the development of repairing techniques of damages found in different types of laminates. The most usually adopted procedure to investigate the repair of composite laminates has been by repairing damages simulated in laminated composite specimens. This work shows the influence of structural repair technique on mechanical properties of a typical carbon fiber/epoxy laminate used in aerospace industry. When analyzed by tensile test, the laminates with and without repair present tensile strength values of 670 and 892 MPa, respectively, and tensile modulus of 53.0 and 67.2 GPa, respectively. By this result, it is possible to observe a decrease of the measured mechanical properties of the repaired composites. When submitted to fatigue test, it is observed that in loads higher than 250 MPa, this laminate presents a low life cycle (lower than 400,000 cycles). The fatigue performance of both laminates is comparable, but the non-repaired laminate presented higher tensile and fatigue resistance when compared with the repaired laminate.

Improvement in the fatigue strength of chromium electroplated AISI 4340 steel by shot peening

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

PREPARATION and CHARACTERIZATION of CELLULOSE/HYDROUS NIOBIUM PHOSPHATE HYBRID

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

SUGARCANE BAGASSE PULPING and BLEACHING: THERMAL and CHEMICAL CHARACTERIZATION

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

CHEMICAL MODIFICATION EFFECT on THE MECHANICAL PROPERTIES of HIPS/COCONUT FIBER COMPOSITES

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The surface treatment influence on the fatigue crack propagation of Al 7050-T7451 alloy

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