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Photochemical studies of cis-[Ru(bpy)2(4-bzpy)(CO)](PF6)2 and cis-[Ru(bpy)2(4-bzpy)(Cl)](PF6): Blue light-induced nucleobase binding.
The ruthenium(II) compounds cis-[Ru(bpy)2(4-bzpy)(CO)](PF6)2 (I) and cis-[Ru(bpy)2(4-bzpy)(Cl)](PF6) (II) (4-bzpy=4-benzoylpyridine, bpy=2,2'-bipyridine) were synthesized and characterized by spectroscopic and electrochemical techniques. The crystal structure of II was determined by X-ray diffraction. The photochemical behavior of I in aqueous solution shows that irradiation with ultraviolet light (365nm) releases both CO and 4-bzpy leading to the formation of the cis-[Ru(bpy)2(H2O)2]2+ ion as identified by NMR and electronic spectroscopy. Carbon monoxide release was confirmed with the myoglobin method and by gas chromatographic analysis of the headspace. CO release was not observed when aqueous I was irradiated with blue light (453nm). Changes in the electronic and 1H NMR spectra indicate that I undergoes photoaquation of 4-bzpy to form cis-[Ru(bpy)2(CO)(H2O)]2+. Blue light irradiation of aqueous II released the coordinated 4-bzpy to give the cis-[Ru(bpy)2(H2O)(Cl)]2+ ion. When the latter reaction was carried out in the presence of the nucleobase guanine, Ru-guanine adducts were formed, indicating that the metal containing photoproduct may also participate in biologically relevant reactions. The photochemical behavior of I indicates that it can release either CO or 4-bzpy depending on the wavelength chosen, a feature that may have therapeutic application
Exponential Distributions in a Mechanical Model for Earthquakes
We study statistical distributions in a mechanical model for an earthquake
fault introduced by Burridge and Knopoff [R. Burridge and L. Knopoff, {\sl
Bull. Seismol. Soc. Am.} {\bf 57}, 341 (1967)]. Our investigations on the size
(moment), time duration and number of blocks involved in an event show that
exponential distributions are found in a given range of the paramenter space.
This occurs when the two kinds of springs present in the model have the same,
or approximately the same, value for the elastic constants. Exponential
distributions have also been seen recently in an experimental system to model
earthquake-like dynamics [M. A. Rubio and J. Galeano, {\sl Phys. Rev. E} {\bf
50}, 1000 (1994)].Comment: 11 pages, uuencoded (submitted to Phys. Rev. E
Sinusoidal electromagnon in RMnO3: Indication of anomalous magnetoelectric coupling
The optical spectra in the family of multiferroic manganites RMnO3 is a great
puzzle. Current models can not explain the fact that two strong electromagnons
are present in the non-collinear spin cycloidal phase, with only one
electromagnon surviving the transition into the collinear spin sinusoidal
phase. We show that this is a signature of the presence of anomalous
magnetoelectric coupling that breaks rotational invariance in spin space and
generates oscillatory polarization in the ground state.Comment: 5 pages, 2 figure
Site-dependent hydrogenation on graphdiyne
Graphene is one of the most important materials in science today due to its
unique and remarkable electronic, thermal and mechanical properties. However in
its pristine state, graphene is a gapless semiconductor, what limits its use in
transistor electronics. In part due to the revolution created by graphene in
materials science, there is a renewed interest in other possible graphene-like
two-dimensional structures. Examples of these structures are graphynes and
graphdiynes, which are two-dimensional structures, composed of carbon atoms in
sp2 and sp-hybridized states. Graphdiynes (benzenoid rings connecting two
acetylenic groups) were recently synthesized and some of them are intrinsically
nonzero gap systems. These systems can be easily hydrogenated and the relative
level of hydrogenation can be used to tune the band gap values. We have
investigated, using fully reactive molecular dynamics (ReaxFF), the structural
and dynamics aspects of the hydrogenation mechanisms of graphdiyne membranes.
Our results showed that the hydrogen bindings have different atom incorporation
rates and that the hydrogenation patterns change in time in a very complex way.
The formation of correlated domains reported to hydrogenated graphene is no
longer observed in graphdiyne cases.Comment: Submitted to Carbo
25 anos de melhoramento genético de trigo em Mato Grosso do Sul.
Historico; Producao de trigo em Mato Grosso do Sul; Melhoramento de trigo em Mato Grosso do Sul.bitstream/item/40075/1/DOC9-99-MGT.pd
A simple deterministic self-organized critical system
We introduce a new continuous cellular automaton that presents self-organized
criticality. It is one-dimensional, totally deterministic, without any kind of
embedded randomness, not even in the initial conditions. This system is in the
same universality class as the Oslo rice pile system, boundary driven interface
depinning and the train model for earthquakes. Although the system is chaotic,
in the thermodynamic limit chaos occurs only in a microscopic level.Comment: System slightly modified. New results on Liapunov exponents.
Submitted for publication (8 pages
Some properties of two Nambu--Jona-Lasinio -type models with inputs from lattice QCD
We investigate the phase diagram of the so-called
Polyakov--Nambu--Jona-Lasinio (PNJL) model at finite temperature and nonzero
chemical potential. The calculations are performed in the light and strange
quark sectors (, , ), which includes the 't Hooft instanton induced
interaction term that breaks the axial symmetry, and the quarks are coupled to
the (spatially constant) temporal background gauge field. On one hand, a
special attention is payed to the critical end point (CEP). The strength of the
flavor-mixing interaction alters the CEP location, since when it becomes weaker
the CEP moves to low temperatures and can even disappear. On the other hand, we
also explore the connection between QCD, a nonlocal Nambu--Jona-Lasinio type
model and the Landau gauge gluon propagator. Possible links between the
quenched gluon propagator and low energy hadronic phenomenology are
investigated.Comment: Contribution to the International Meeting "Excited QCD", Peniche,
Portugal, 06 - 12 May 201
African Peace and Security Architecture (APSA) subsidiarity and the Horn of Africa: the Intergovernmental Authority on Development (IGAD)
The new African Peace and Security Architecture is based on the principle of subsidiarity governing the relationship between the United Nations, African Union and regional mechanisms. Nevertheless it is still unclear how subsidiarity will be implemented in the decision-making mechanism, division of labour and burden sharing. This paper analyses the challenges of subsidiarity in two IGAD processes: the renewal of the security mandate started at IGAD in 2005 and Ethiopian intervention in Somalia in 2006. It finds that regional rivalries and historical legacies prevent the development of IGAD’s security mandate and an intervention policy while international interests determine the projection of the Somalia case. It concludes that sub-regional inter-state institutional coordination and capacity-building are essential requirements for the implementation of subsidiarity.FCT - Fundação para a Ciência e a Tecnologi
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