Novel Tetrazine Organometallic Complexes for Nonlinear Optical Switching: a Combined Density Functional Theory and Experimental Study

Over the past decade, mono- and bi- and oligonuclear organometallic complexes have been deal of great interest by material chemists and engineers due to their remarkable nonlinear optical (NLO), magnetic and electric properties. [1] They were furthermore envisaged as powerful candidates for quantum computing, molecular devices and more interestingly as molecular switches. The definition of molecular switch implies that a compound should have two interconvertable stable forms that have a significant difference in the magnitude of, at least, one of their physico-chemical properties. [2] In the case of organometallic complexes the most expedite way to achieve such interconversion is by redox means, where one takes advantage of the different oxidations states allowed by a single or multiple metal centers that interact with each other, and with the ligands therein. It is known that the choice of an appropriate π-bridging system between the metal centers is crucial to obtain the adequate electronic environment for efficient metal-to-metal and metal-to-ligand interactions, and hence fine tune the optical, electric and magnetic macroscopic properties. Mixed-valance metal complexes from group VIII, particular Fe(II)/Fe(III) and Ru(II)/Ru(III) systems [3,4], have been successfully synthesized as stable species that possess strong metal-to-ligand charge transfer (MLCT) and inter-valence charge transfer (IVCT) absorption bands in visible and NIR regions, respectively.[5, 6] This is the case of the well known Creutz-Taube ion [(H3N)5Ru(m-pz)Ru(NH3)5]5+ (pz=pyrazine) and related compounds. Substituted 1,2,4,5-tetrazine (tz) strongly enhance both the stability and the MLCT and IVCT phenomenon’s since they act as a strong π-acceptor and can stimulate the metal-to-metal interaction. [6] In this work, we present our ongoing studies in the use of substituted 1,2,4,5-tetrazine (tz) ligands as the π-bridge between two transition metal centers, both experimentally and by means of Density Functional Theory (DFT). Synthesis and characterization by NMR, voltammetric and UV-Vis. spectra are presented. The DFT calculations were used to evaluate the nature of the electronic transitions as well as the switching of the NLO properties. The compounds showed to be great candidates for NLO switching since the magnitude of such property can change upon redox stimulus at the metal centers

A proposal of sensitive indicators of the rehabilitation nursing care of people in the surgical process, to be included in the ontology of aging

Given the complex surgical scenario observed today, it is necessary to change the urgent definition of a specific ontology, especially in terms of aging. The interventions of the Specialist Nurse in Rehabilitation Nursing to the person in the surgical process are primordial for the maintenance of the functional capacities, prevention of complications and impediment of incapacities. However, it is necessary to provide individualized and fostered care in a practice of excellence, and the consequent organized reading of records of an aging ontology for decision making on rehabilitation indicators. Method: a systematic review of the literature was carried out using the EBSCO host (MEDLINE with Full Text, CINAHL Plus with Full Text and MedicLatina), using the PI [C] O method, and 11 articles were selected. Results: 41 indicators were identified to be included in the ontology classes of aging: pain control, patient and family education, support and communication, reduction of postoperative complications, gain of functionality, restoration of physical function, mobility, multidisciplinary intervention and the frequency of interventions. Conclusion: it is considered that it was imperative to identify sensitive indicators for rehabilitation nursing care, based on scientific evidence and thus provide an opportunity for nurses to reflect on their daily practices and conduct their actions towards excellence in care, to propose a set of 41 classes internationally on the ontology of aging

Evolution of a sandpile in a thick flow regime

We solve a one-dimensional sandpile problem analytically in a thick flow regime when the pile evolution may be described by a set of linear equations. We demonstrate that, if an income flow is constant, a space periodicity takes place while the sandpile evolves even for a pile of only one type of particles. Hence, grains are piling layer by layer. The thickness of the layers is proportional to the input flow of particles $r_0$ and coincides with the thickness of stratified layers in a two-component sandpile problem which were observed recently. We find that the surface angle $\theta$ of the pile reaches its final critical value ($\theta_f$) only at long times after a complicated relaxation process. The deviation ($\theta_f - \theta$) behaves asymptotically as $(t/r_{0})^{-1/2}$. It appears that the pile evolution depends on initial conditions. We consider two cases: (i) grains are absent at the initial moment, and (ii) there is already a pile with a critical slope initially. Although at long times the behavior appears to be similar in both cases, some differences are observed for the different initial conditions are observed. We show that the periodicity disappears if the input flow increases with time.Comment: 14 pages, 7 figure

Degree-dependent intervertex separation in complex networks

We study the mean length $\ell(k)$ of the shortest paths between a vertex of degree $k$ and other vertices in growing networks, where correlations are essential. In a number of deterministic scale-free networks we observe a power-law correction to a logarithmic dependence, $\ell(k) = A\ln [N/k^{(\gamma-1)/2}] - C k^{\gamma-1}/N + ...$ in a wide range of network sizes. Here $N$ is the number of vertices in the network, $\gamma$ is the degree distribution exponent, and the coefficients $A$ and $C$ depend on a network. We compare this law with a corresponding $\ell(k)$ dependence obtained for random scale-free networks growing through the preferential attachment mechanism. In stochastic and deterministic growing trees with an exponential degree distribution, we observe a linear dependence on degree, $\ell(k) \cong A\ln N - C k$. We compare our findings for growing networks with those for uncorrelated graphs.Comment: 8 pages, 3 figure

New geochemical and isotopic constraints on the genesis of the Oliveira Azeméis granitoid melts (Porto-Tomar Shear Zone, Iberian Variscan Chain, Central-Western Portugal).

The Porto-Tomar Shear Zone (PTSZ) is a very important tectonic structure that separates, in central-western Portugal, two of the major tectonic units of the Iberian Variscan Chain: the Ossa-Morena Zone, to the west, and the Central Iberian Zone, to the east. The Oliveira de Azeméis area lies in the northern sector of the PTZC and it is characterized by the occurrence of strongly deformed granitoids. Country rocks are dominantly pelitic metasediments which, according to recent geological mapping (Pereira et al., 2007), belong to the Precambrian Lourosa Formation and the Ordovician São João de Ver Formation. Using Rb-Sr whole-rock isotopic data, Pinto (1979) proposed an age of 379 12 Ma for the Oliveira de Azeméis granitoids. In this work, new results were obtained on these granitoids in the area between the villages of Travanca and Curval, especially in the Sacramento quarry. In this critical outcrop, strongly deformed two-mica granite (displaying S-C structures, with dextral NNW-SSE shear planes) pass into diatexites and metatexites with garnet, cordierite and sillimanite-bearing melanosomes. Leucosomes seem to have mainly granitic s.s. compositions, but cm-thick bands of leucotonalite were also found. Major element geochemistry of granite samples shows the following ranges: 71.4% SiO2 74.2%; 0.74% Fe2O3t 2.48%; 0.35% MgO 0.60%; 0.49% CaO 1.32%; 2.90% Na2O 3.11%; 4.70% K2O 5.47%; 1.17 ASI 1.36. Trace element data reveal a strong fractionation between highly incompatible LILE and less incompatible HFSE (248 PM normalized Rb/Y 671) and between LREE and HREE (18.6 PM normalized La/Lu 54.7). These features, in particular the peraluminous composition, the high K contents and the distinct rare-earth fractionation suggest that the Oliveira de Azeméis granites are mostly the result of partial melting of metasediments with a large pelitic component and that garnet is a likely residual phase. Isotope geochemistry data show that the previously reported isochron should not correspond to a true age since the 87Sr/86Sr(380Ma) obtained in the granite samples analysed in the present work are very low, varying from 0.6978 to 0.7063, with an average value of 0.7023, which are unrealistic in S-type granitic melts. Probably, the 380 Ma date is the consequence of mixing of different melt source components in the samples used in its calculation. Using the granite whole-rock samples collected in this work, a 328 28 Ma errorchron (MSWD=4.0; initial 87Sr/86Sr=0,7106 0.0045) is now obtained. Assuming a typical syn-tectonic Variscan age of 320 Ma for the studied granites, 87Sr/86Sr and "Nd range from 0.7100 to 0.7133 and from -6.5 to -7.9, respectively. A micaschist sample collected in this area displays 87Sr/86Sr(320Ma) = 0.7146 and "Nd(320Ma) = -9.2. Therefore, the Sr and Nd isotope composition agrees with the clearly dominance of a melt component derived by anatexis of a metapelitic source. Two samples of a garnet-bearing (and comparatively zircon-rich) diatexite show 87Sr/86Sr(320Ma) values (0.7120 and 0.7102) similar to those found in granites, but have higher "Nd(320Ma): -2.0 and -1.6. This may be explained by either (a) the involvement of a different source in the genesis of this diatexite or (b) the occurrence of Nd isotope disequilibrium during the melting process, with the preservation of high 143Nd/144Nd ratios in refractory phases such as garnet and/or zircon. A Rb-Sr wr-feldspar-biotite-muscovite isochron of 301.2 5.6 Ma (MSWD=0.42; initial 87Sr/86Sr=0,71516 0.00074) in a granite sample is interpreted as recording the final stage of the operation of the shear zone, which was accompanied by mica recrystallization. Funding: projects Petrochron (PTDC/CTE-GIX/112561/2009) and Geobiotec (PEst-C/CTE/UI4035/2011). References Pereira E. et allia (2007) – Carta Geológica 1/50000 de Oliveira de Azeméis. INETI, Lisboa. Pinto M.S. (1979) – PhD Thesis. Univ. Leed