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Most of the information collected in different fields by Instituto de Investigación Biomédica de A Coruña (INIBIC) is classified as unstructured due to its high volume and heterogeneity. This situation, linked to the recent requirement of integrating it to the medical information, makes it necessary to implant specific architectures to collect and organize it before it can be analysed. The purpose of this article is to present the Hadoop framework as a solution to the problem of integrating research information in the Business Intelligence field. This framework can collect, explore, process and structure the aforementioned information, which allow us to develop an equivalent function to a data mart in an Intelligence Business system.

The geometry imposed by the coordination sphere around the metal, together with the choice of the "arms" can be advantageously used to build corannulene-based molecular tweezers, which show great affinities for C60 and C70, as revealed by NMR titration experiments, mass spectroscopy, DFT calculations and the single crystal X-ray structural analysis of the compound C60 ⊂1.

Pulmonary arterial hypertension and secondary pleural effusion have been reported in association with long-term therapy with the multi-tyrosine kinase inhibitor dasatinib, approved for the treatment of chronic myeloid leukemia. Here, we present the case of a 50-year-old man, diagnosed with chronic myeloid leukemia in August 2003, who developed pulmonary arterial hypertension after > 4 years of treatment with dasatinib. The complete remission of pulmonary arterial hypertension following dasatinib discontinuation suggests an etiological role of the drug in its development, although the administration of sildenafil may have played a therapeutic role.

Herein, we report several examples of stereoselective aldol additions of aldehydes or ketones to ReI tricarbonyl complexes to form monomeric derivatives in good yields. The metal-centered chirality defines the final stereochemistry of the carbon atom of the monomeric ReI complex after the addition. However, it cannot control the resulting stereochemistry of the enolate part, and thus, if the α-carbon atom of the reagent is prochiral, a mixture of diastereoisomers is obtained. On the other hand, all of the monomeric complexes can be reversibly dimerized in basic media to form cis dimers, for which an epimerization of the metal-centered chirality is required in order to avoid steric congestion. All of these results are supported by exhaustive crystallographic analysis., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The use of Schiff condensation followed by CuAAC affords complexes containing iminopyridine ligands functionalized either with a triazole ring or with a sulfonyl amido group via ring opening of the unstable sulfonyl triazole.

Transplant patients with long-term graft survival (LTS) may have developed mechanisms that prevent rejection and allow graft function under low or no immunosuppressive therapy. In murine models, T cell tolerance is associated with alterations in the expression/activation of proteins involved in T cell signaling. These alterations have not been reported in transplanted patients with different outcomes. This study aimed to evaluate calcium mobilization, the phosphorylation of different proteins involved in T cell signaling and the expression of molecules associated with anergy, in T cells from kidney transplant patients. No differences were observed in calcium mobilization, although transplanted patients had a tendency toward augmented calcium flux. Chronic rejection patients (ChrRx) displayed lower Lck basal phosphorylation levels compared with LTS patients, and the phosphorylation profile of proteins evaluated was different. Among the groups, phosphorylation of Zap-70 was higher in LTS patients compared with ChrRx, and LAT phosphorylation was lower in LTS and ChrRx patients compared with healthy controls. The expression of molecules related to the anergic phenotype was similar among the study groups. Results suggest that phosphorylation patterns, rather than phosphorylation levels, may correlate with transplant outcome and that anergy may not be the main mechanism mediating LTS., (© 2012 John Wiley & Sons A/S.)

A formal direct carboboration of carbonyl ligands to form manganese boroxycarbenes in a one-pot fashion is reported.

The first η(6)-complexes of iridium and ruthenium coordinated to helicenes have been obtained. Hexahelicene (1), 2,15-dimethylhexahelicene (2), and 2,15-dibromohexahelicene (3) react with [Cp*IrCl(2)](2) and AgBF(4) in CD(3)NO(2) to afford quantitatively the complexes [Cp*Ir(η(6)-1)][BF(4)](2) (4A), [Cp*Ir(η(6)-2)][BF(4)](2) (5A), and [Cp*Ir(η(6)-3)][BF(4)](2) (6A), respectively. In all cases, the final thermodynamic products are similar, and they exhibit coordination between the 12 e(-) metal fragment [IrCp*](2+) and the terminal ring of the helicene. Monitoring the reaction by NMR shows formation of intermediates, some of which have been fully characterized in solution. These intermediates exhibit the metal fragment coordinated to the internal rings. We have also synthesized the bimetallic complex [(Cp*Ir)(2)(μ(2)-η(6):η(6)-2)][BF(4)](4) (7), achieving coordination between two units [IrCp*](2+) and the helicene 2. Following an analogous methodology, we have prepared the complex [(η(6)-cymene)Ru(η(6)-2)][BF(4)](2) (8), which has been studied by X-ray diffraction, confirming the preferential binding to the terminal aromatic ring.

The exceptional versatility of the 1,2,3-triazole ring in tridentate carbonyl rhenium complexes has been explored starting from a "click chemistry" unexpected product obtained from the spontaneous copper to rhenium transmetalation, which opens the way to successive transformation to C-triazolyl and triazolylidene mesoionic carbene.

Condensation of two molecules of pyridine-2-carboxaldehyde (pyca), in the presence of MnCl(2) and ammonium diethyldithiophosphate, produced, in a one-pot reaction, Mn(II) complexes containing 3-(pyridin-2-yl)imidazo[1,5-a]pyridines as κ(2)(N,N) chelate ligands which could be easily separated from the metal, this being a convenient way to pyridyl-aza-indolizine heterocycles.

The existence of a strong hydrogen bond between two molecules of an (alkoxoimino)pyridinemanganese(I) complex induces their dimerization and the formation of a metallamacrocycle. The expected intramolecular attack of the alkoxo moiety is disfavored.

Complexes containing pyridine-2-carboxaldehyde (pyca) ligand acting as κ(2)-(N,O) chelates in [MX(CO)(3)(pyca)] (M = Mn, Re; X = Cl, Br), or [MoX(methallyl)(CO)(2)(pyca)] (X = Cl, Br), are good precursors for iminopyridine complexes derived from amino esters and peptides of formula [MX(CO)(3)(py-2-C(H)═NCHX-COOY)] or [MoX(methallyl)(CO)(2)(py-2-C(H)═NCHX-COOY)], via Schiff condensation of the aldehyde function of pyca with the terminal NH(2) group of the amino ester or peptide. X-ray determinations confirm the structures and show that in solid phase the peptide chains assemble through H-bonds adopting different patterns which depend on the geometry of the metal-ligand fragments. The H-bonding patterns have been analyzed in detail and described by using graph set methods. In most cases, Mo complexes show intramolecular arrangement involving the halogen (Cl or Br) and an NH group of the side chain. For the Mn and Re complexes, the peptide side arms form infinite chains, helices, and rings. In many cases, the terminal carboxylic O-H function is engaged in a "terminal" H-bond with a polar molecule of solvent (THF or acetone), instead of forming the usual head-to-head arrangement found in simple carboxylic acids. For the longer tripeptide Gly-Gly-Gly, a discrete, dimeric association is observed, in which the peptide chains show antiparallel arrangement with a complementary disposition of the internal N-H and C═O functions. DOSY experiments in solution show significant changes in the diffusion rates upon addition of OPBu(3), which indicate H-bonding interaction of OPBu(3) with the peptide hydrogens.

Stereochemistry at the metal centre in a Re(I) complex can be modified by manipulating the pH: while acidic conditions favour a monomeric system, basic conditions induce a dimerization which concomitantly epimerizes the metal centre., (This journal is © The Royal Society of Chemistry 2011)

We report on femto- to nanosecond studies of the excited state intermolecular proton transfer (ESPT) reaction of trisodium 8-hydroxypyrene-1,3,6-trisulfonate (pyranine, HPTS) with the human serum albumin (HSA) protein. The formed robust 1:1 complexes (K(eq) = (2.6 ± 0.1) × 10(6) M(-1)) show both photoacid (∼430 nm) and conjugated photobase (∼500 nm) emissions of the caged HPTS in its protonated structure. The proton-transfer reactions in these complexes proceed in a large time window, spanning from 150 fs to ∼1.2 ns. The ultrafast component reflects a direct H-bond breaking and making in the robust complexes, involving the carboxylate groups of the amino acids, while the slowest one is arising from the slow dynamics of the so-called biological water. Additional time constants of the caged photoacid to give the conjugated photobase are observed, assigned to the ESPT reaction within "loose" complexes (3 to tens of picoseconds), and 130 ps and 1.2 ns due to the slow dynamics of the water molecules around the protein residues and involved in the proton transfer. The fs-ns anisotropy measurements confirm the robustness of the HPTS:HSA complexes. Our results indicate that, even though robust 1:1 complexes between HPTS and the HSA are formed, the system is heterogeneous, due to different possible interactions of the dye with the inside/outside parts of the protein. Furthermore, we find lower values of the initial anisotropy (r(0)) in the protein (0.33) and in γ-CD (0.28) in comparison with buffered aqueous solution (0.385). We propose that caging HPTS by the HSA protein and by the cyclodextrin affects the electronic redistribution in a different degree of mixing between the (1)L(a) and (1)L(b) states in the formed deprotonated form, for which the interactions of the sulfonate groups with the surroundings should play a key role., (© 2011 American Chemical Society)

Single molecule studies of the free DY-630-MI and interacting with MCM-41 and (Al)MCM-41, show the conformational diversity of the molecule. The free dye is characterized by a single broad (fwhm = 0.7 ns) lifetime distribution histogram centered on 1.47 ns, which is also reflected in the broadness of the polarization value distribution histogram, covering almost the full range of values from -1 to 1. The fluorescence intensity traces of the free DY-630-MI show strong blinking behavior and weak photostability. Upon interaction with the mesoporous silica nanomaterials, MCM-41 and (Al)MCM-41, the dye molecule becomes more stable, with less blinking present in the fluorescence traces. The lifetime distribution histogram in the case of DY-630-MI/MCM-41 complexes is fitted by 3 Gaussians, indicating 3 distinct interaction sites. The Gaussian with the largest amplitude is centered on 2.19 ns, consistent with the confinement effect of MCM-41 and in agreement with the ensemble average studies. The polarization value distribution histogram becomes narrower in comparison with the free molecule and is more biased towards the positive limit. Replacing few Si(4+) ions with Al(3+) ones in the regular MCM-41 changes the local electrostatic field within the nanotube. This atomic substitution in the nanohosts results in a more selective orientation of the dye molecules, giving two populations with time constants 1.56 and 2.10 ns.

The title compound, [Cu(2)(C(18)H(19)N(3)O(2))(2)]·2C(2)H(6)OS or [Cu(2)(SalenN(3)H)(2)]·2DMSO, where SalenN(3)H is the multidentate Schiff base 2,2'-[(3-aza-pentane-1,5-di-yl)bis-(nitrilo-methyl-idyne)]diphenolate dianion and DMSO is dimethyl sulfoxide, is a solvated dinuclear Cu(II) complex. The neutral complex is built from two Cu(SalenN(3)H) units related by an inversion center. All heteroatoms in the Schiff bases coordinate the Cu(II) ions, which display highly distorted trigonal bipyramidal geometries. The solvent mol-ecules are located in the structural voids of the complex and are disordered over two positions with occupancies of 0.642 (15) and 0.358 (15). The previously characterized acetone disolvate of the same complex presents identical mol-ecular and crystal structures, and crystallizes with cell parameters very close to those of the DMSO disolvate reported here.