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The present Deliverable, D4.2, illustrates the activity carried out, within Task 4.2 and Task 4.3, in the first 22 months of the project. It provides an overview of the algorithms used or developed to retrieve environmental variables (EVs) for the ECOPOTENTIAL PAs distributed across Europe, in Israel and South Africa and selected for study. For classification, the Earth Observation Data for Ecosystem Monitoring (EODESM) system stands out as it makes full use of and integrates all of the EVs retrieved for the different PAs in the classification of land This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 641762 cover (LC). Its development also considered the storylines described through ECOPOTENTIAL and outlined in Deliverable 2.2.

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We present a selection of metal-organic frameworks based on d–f and f–f linkages, discussing their structural features and properties from experimental and theoretical viewpoints. We give an overview of our own synthetic and modeling methodologies, highlighting the complexity of the interdisciplinary approach developed. Significant experimental and computational strategies of other researchers are also reviewed. The bonding regime of lanthanide units in MOFs is similar to those encountered in mono- or polynuclear f-type coordination compounds. However, the steric demands of constructing a three-dimensional network determine specific ligand composition and topologies at the local f nodes. Due to weak interaction propensity of the inner shell f orbitals, the electronic structure treatments of lanthanide units require certain conceptual and technical subtleties. With proper handling, multiconfiguration wave function approaches as well as density functional theory (DFT) treatments can be analyzed in terms of meaningful ligand field (LF) modeling. The interplay of LF and spin–orbit (SO) effects in determining the magnetic anisotropy is illustrated, after reviewing the experimental magnetic behavior of several d–f cyanide-bridged systems.

Correctly folded recombinant wild-type human serum albumin and the single-residue mutants K199A, W214A, R218H and H242Q were produced with the use of a yeast expression system. The changes in R218H resulted in a pronounced decrease in intrinsic fluorescence. Thermodynamic parameters for thermal denaturation of the present mutants and of five additional mutants have been determined, showing small increases in stability for two mutants (R218H and H242Q) and a larger decrease in stability for one (W214A). In the last of these, denaturation was a heterogeneous process starting at physiological temperature. The high-affinity binding constant for warfarin at pH7.4 was determined by fluorescence spectroscopy: there was a significant increase in affinity for binding of warfarin to H242Q and K199A and a smaller decrease in affinity for W214A and R218H. The findings show that Trp-214 is not as essential for the high-affinity binding of warfarin as has previously been thought.

We present evidence of 1D S=1/2 anisotropic XY ferromagnetism in the paramagnetic phase of the cyanido-bridged chain complex [Tb(pzam)3(H2O)M(CN)8]H2O, with M=W(V), based upon the measurement of the specific heat, the uniform susceptibility and the magnetization curve on a powder sample. Both the specific heat and the susceptibility exhibit a transition peak to long-range ferromagnetism, mediated by the residual interchain couplings, at a critical temperature Tc=1.15 K. Yet in the temperature range T > Tc the specific heat exhibits a broad Schottky anomaly which can be very well fitted by the exact result for the 1D S=1/2 XY model with strong anisotropy in the XY plane (Jx = 1.89 K, Jy=2Jx). For the analysis of the susceptibility and magnetization, not directly accessible theoretically via the exact solution of the XY model, we resort to numerically exact quantum Monte Carlo simulations. Very good agreement is found between the powder-sample data and the Monte Carlo data using an effective average g-factor., 6 pages, 6 figures, journal paper

A linear trinuclear copper(II) complex containing phenoxido- and alkoxido-bridges between the metal centers has been isolated and structurally characterized. The complex cation consists of a linear array of three copper ions, assembled by means of two doubly deprotonated ligands. The octahedral coordination sphere of the two peripheral copper(II) ions is completed by weakly bound methanol molecules, and the square-planar central metal ion is located on an exact, crystallographic inversion center. Temperature-dependent magnetic susceptibility studies reveal the presence of antiferromagnetic exchange coupling between the copper(II) ions in the trinuclear unit along with small intermolecular antiferromagnetic interactions in the low temperature range. The results were fitted in two different ways, (i) taking into account solely the exchange interaction between the adjacent metal centers or, (ii) regarding exchange interactions between both adjacent and non-adjacent copper(II) ions. Solid-state temperature-dependent X-band EPR studies in the range 4.2–250 K indicate a doublet ground spin state |½, 1>. In solution, the ground spin state of the complex is found to be a quartet (S =3/2 ), suggesting a modification of the exchange coupling interactions between the copper(II) ions. The simulation of the 4.2 K solution spectrum gives rise to the best parameters D > 0.8 cm–1, g = 2.04 and g = 2.21

Iron complexes of two ligands, HphoxCOOH and HphoxiPr, have been synthesized and characterized by crystal structure analyses. The complexes (HNEt3)2[Fe(phoxCOO)2](ClO4) and [Fe(phoxiPr)3] are reported. Reactions of the ligands rac-HphoxCOOH and rac- HphoxiPr with iron(II) or iron(III) perchlorate result in the formation of iron(III) complexes with pseudo-octahedral geometry around the metal center. The iron complex obtained from rac-HphoxCOOH crystallized in the centrosymmetric space group Cmca. The two ligands are bound in a tridentate manner generating a meridional coordination with both dianionic ligands on a metal center having the same chirality; due to the center of symmetry the complex with opposite chirality is also present. The complex (HNEt3)2[Fe(phox- COO)2](ClO4) is the first accurate structural model of the iron complex of a siderophore analog commonly observed in mycobactins. The three didentate ligands in the complex [Fe(phoxiPr)3] are bound with like atoms in a meridional manner to the metal center. The metal ion is surrounded by two ligands of the same chirality and one ligand of opposite chirality (ie. RRS or SSR); due to the presence of a center of symmetry both isomers are present in the crystal structure. The complex (HNEt3)2[Fe(phoxCOO)2](ClO4) shows promising activity in the oxidation of alkanes, such as toluene, ethylbenzene and cumene, while the complex [Fe(phoxiPr)3] does not show any catalytic activity in alkane oxidations under the conditions tested. The complex (HNEt3)2[Fe(phoxCOO)2](ClO4) is reasonably efficient in the conversion of H2O2 to oxidation products.

Item does not contain fulltext New complexes with 5(3)-(2-hydroxyphenyl)-3(5)-methylpyrazole (H(2)phpz), [Co-2(H(2)phpz)(Hphpz)(2)(phpz)(2)](.)3CH(3)CN (1), [Ni(Hphpz)(2)] (2) and [Cu(HphpZ)(2)] (3), were synthesized and structurally characterized. The ligand coordinates in the form of 3-(2-hydroxyphenyl)-5-methylpyrazole in all cases, except for one ligand in the Co-III complex, where it coordinates in the 5-(2-hydroxyphenyl)-3-methylpyrazole mode. Crystallographic analysis revealed that 1 contains two chemically and crystallographically distinct cobalt(III) ions triply bridged by one phenoxide and two pyrazolate groups, giving rise to a [Co-2(N-N)(2)O] core with a (CoCo)-Co-... distance of 3.154 angstrom. Additionally, the H(2)phpz ligand shows four different coordination modes with the metal ions, demonstrating its versatility. The dinuclear unit of 1 is stabilized by strong intramolecular N-(HO)-O-... hydrogen-bonding interactions involving the phenol oxygen atom of the H(2)phpz ligand and the N-H functionality of the pyrazole ring. The crystal structure of the isomorphous complexes 2 and 3 reveals the presence of centrosymmetric mononuclear units with the MN2O2 [M = Ni-II (2), Cu-II (3)] chromophore displaying a slightly distorted square-planar geometry. The mononuclear structures of 2 and 3 are further stabilized by intramolecular hydrogen bonds established between the acid N-H group as donor and the phenoxide group of the H(2)phpz ligand as acceptor. Spectroscopic studies, ESI-MS and cyclic voltammetry were performed, supporting the crystallographic analysis. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007).

Contains fulltext : 35014.pdf (Publisher’s version ) (Closed access) The synthesis and characterization of two new iron(II) complexes, [Fe(pca)(2)(py)(2)]center dot py (1) and {[Fe(pca)(2)(H2O))] center dot H2O}(n) (2) and one new iron(m) complex, Na-2{[Fe(pca)(3))](2)O}center dot 2H(2)O center dot 2CH(3)CN (3) (pca(-) stands for 2-pyrazinecarboxylate), are reported. Complex 1 is obtained from the reaction of iron powder with 2-pyrazinecarboxylic acid. The reaction of Fe(ClO4)(3)center dot 10H(2)O with Hpca in the presence of 3 equiv. of Bu4NOH yields 2, whereas the presence of NaOH yields 3. The molecular structure of 1 contains ail iron(II) ion with a pseudo-octahedral environment resulting from the coordination of two pca- ligands in a bidentate chelating fashion and two pyridine molecules; pi-pi stacking interactions between pyridine and pyrazine rings lead to a one-dimensional chain. Complex 2 is ail iron(II) coordination polymer with an infinite zig-zag motif and an Fe center dot center dot center dot Fe separation of 7. 1 angstrom. In 2, the pi-pi stacking interactions involving the pyrazine rings and the strong hydrogen bonds between the coordinated water molecule and the carboxylate oxygens of two pca(-) ligands result in a three-dimensional network structure. Complex 3 consists of an anionic mu-oxo-bridged diiron(III) core with two crystallographically distinct iron(III) ions; the negative charge is compensated by two sodium cations. Complex 3 is assembled in a three dimensional network structure through coordination of Na(I) and hydrogen bond interactions. Temperature dependent magnetic susceptibility and Mossbauer spectroscopic studies indicate that 1 and 2 have similar magnetic properties. Both complexes are paramagnetic above 12 K, whereas antiferromagnetic ordering is observed below 12 K. The magnetic properties of 3 reveal strong intramolecular antiferromagnetic interactions between the two iron(III) ions with a J value of -221 cm(-1); no long range intermolecular magnetic coupling is observed between 295 and 4.2 K.

The effect of two arginine-specific cysteine proteinases (gingipains R) from Porphyromonas gingivalis, an aetiological factor of adult periodontitis, on the activation of human factor IX was investigated in the presence of ethylene glycol, an activity enhancer of activated factor IX (factor IXa), with the use of a fluorogenic oligopeptide substrate. Each gingipain R rapidly activated factor IX but the 95 kDa proteinase complex (HRgpA) that contains both haemagglutinin/adhesion and catalytic domains was 2.4-fold more efficient than the single-chain 50 kDa gingipain R (RgpB), which has only a catalytic domain. SDS/PAGE and N-terminal sequence analysis of factor IX digestion fragments indicated that, like all endogenous activators, gingipains R also produce factor IXabeta via an IXa intermediate. Significantly, phospholipids augmented the activation of factor IX by HRgpA but not by RgpB in a Ca(2+)-dependent manner. In the presence of both cofactors the kinetic efficiency of HRgpA to activate factor IX (k(cat)/K(m)=1.9x10(6) M(-1).s(-1)) was 8.5-fold higher than that of RgpB (k(cat)/K(m)=2.3x10(5) M(-1).s(-1)) and double that of the factor VIIa-tissue factor complex, but 8-fold lower than that for factor XIa. A comparison of the relative activation rates of factor IX, factor X and prothrombin directly in plasma by HRgpA suggests a significant contribution for factor IX conversion in blood coagulation induced by gingipains R. Taken together, gingipains R are the first-reported activators of factor IX of bacterial origin. By this effect they could be involved in the production of thrombin as well as the subsequent generation of prostaglandins and interleukin 1, all of which have been found to be associated with the development and progression of periodontitis.