Synthesis, magnetostructural correlation, and catalytic promiscuity of unsymmetric dinuclear copper(II) complexes: models for catechol oxidases and hydrolases

Herein, we report the synthesis and characterization, through elemental analysis, electronic spectroscopy, electrochemistry, potentiometric titration, electron paramagnetic resonance, and magnetochemistry, of two dinuclear copper(II) complexes, using the unsymmetrical ligands N',N',N-tris(2-pyridylmethyl)-N-(2-hydroxy-3,5-di-tert-butylbenzyl)-1,3-propanediamin-2-ol (L1) and N',N'-bis(2-pyridylmethyl)-N,N-(2-hydroxybenzyl)(2-hydroxy-3,5-di-tert-butylbenzyl)-1,3-propanediamin-2-ol (L2). The structures of the complexes [Cu(2)(L1)(μ-OAc)](ClO(4))(2)·(CH(3))(2)CHOH (1) and [Cu(2)(L2)(μ-OAc)](ClO(4))·H(2)O·(CH(3))(2)CHOH (2) were determined by X-ray crystallography. The complex [Cu(2)(L3)(μ-OAc)](2+) [3; L3 = N-(2-hydroxybenzyl)-N',N',N-tris(2-pyridylmethyl)-1,3-propanediamin-2-ol] was included in this study for comparison purposes only (Neves et al. Inorg. Chim. Acta2005, 358, 1807-1822). Magnetic data show that the Cu(II) centers in 1 and 2 are antiferromagnetically coupled and that the difference in the exchange coupling J found for these complexes (J = -4.3 cm(-1) for 1 and J = -40.0 cm(-1) for 2) is a function of the Cu-O-Cu bridging angle. In addition, 1 and 2 were tested as catalysts in the oxidation of the model substrate 3,5-di-tert-butylcatechol and can be considered as functional models for catechol oxidase. Because these complexes possess labile sites in their structures and in solution they have a potential nucleophile constituted by a terminal Cu(II)-bound hydroxo group, their activity toward hydrolysis of the model substrate 2,4-bis(dinitrophenyl)phosphate and DNA was also investigated. Double electrophilic activation of the phosphodiester by monodentate coordination to the Cu(II) center that contains the phenol group with tert-butyl substituents and hydrogen bonding of the protonated phenol with the phosphate O atom are proposed to increase the hydrolase activity (K(ass.) and k(cat.)) of 1 and 2 in comparison with that found for complex 3. In fact, complexes 1 and 2 show both oxidoreductase and hydrolase/nuclease activities and can thus be regarded as man-made models for studying catalytic promiscuity.     

Adaptive policies for time-varying stochastic systems under discounted criterion

We consider a class of time-varying stochastic control systems, with Borel state and action spaces, and possibly unbounded costs. The processes evolve according to a discrete-time equation x _{n + 1}=G _n (x _n , a _n , ξ_n), n=0, 1, … , where the ξ_n are i.i.d. ℜ^k-valued random vectors whose common density is unknown, and the G _n are given functions converging, in a restricted way, to some function G _∞ as n→∞. Assuming observability of ξ_n, we construct an adaptive policy which is asymptotically discounted cost optimal for the limiting control system x _n+1=G _∞ (x _n , a _n , ξ_n).     

Probing Proteins in Solution by Xe NMR Spectroscopy

The interaction of xenon with different proteins in aqueous solution is investigated by ¹²⁹Xe NMR spectroscopy. Chemical shifts are measured in horse metmyoglobin, hen egg white lysozyme, and horse cytochrome c solutions as a function of xenon concentration. In these systems, xenon is in fast exchange between all possible environments. The results suggest that nonspecific interactions exist between xenon and the protein exteriors and the data are analyzed in term of parameters which characterize the protein surfaces. The experimental data for horse metmyoglobin are interpreted using a model in which xenon forms a 1:1 complex with the protein and the chemical shift of the complexed xenon is reported (Locci et al., Keystone Symposia “Frontiers of NMR in Molecular Biology VI”, Jan. 9–15, 1999, Breckenridge, CO, Abstract E216, p. 53; Locci et al., XeMAT 2000 “Optical Polarization and Xenon NMR of Materials”, June 28–30, 2000, Sestri Levante, Italy, p. 46).     

Reactions of 6‐aminopyrimidines with 2‐dimethylaminomethylenetetralone. Regiospecific Synthesis Of 5,6‐Dihydrobenzo [h]pyrimido [4,5‐b] quinolines

Benzo[h]pyrimido[4,5‐b]quinolines ( 3 ) have been synthesized via a regiospecific cyclocondensation reaction between 6‐aminopyrimidines ( 1 ) and 2‐dimethylaminomethylentetralone hydrochloride ( 2 ). The linear structure of the final compounds were determined by nmr measurements, especially by ¹H,¹H, ¹H,¹³C COSY and DEPT experiments.     

Methyl 2‐methyl‐6‐methyl­thio‐1,3‐dioxo‐4‐[(2,3,4,6‐tetra‐O‐acetyl‐β‐d‐gluco­pyran­osyl)­amino]‐2,3‐di­hydro‐1H‐pyrrolo­[3,4‐c]­pyridine‐7‐carboxyl­ate

The title compound, C₂₅H₂₉N₃O₁₃S, has peripheral acetyl and carbo­methoxy groups which show disorder. The absolute structure, although known from the starting materials, was confirmed by the analysis. There are no intermolecular hydrogen bonds. This structure is of importance because it elucidates the pathway for hetero‐Diels–Alder reactions between di­methyl acetyl­enedi­carboxyl­ate and 6‐amino­pyridin‐4(3H)‐one derivatives catalyzed by tri­fluoro­acetic acid.     

Ethyl 6‐amino‐2‐methoxypyridine‐3‐carboxyl­ate,interplay of molecular and supramolecular structure

The title compound, C₉H₁₂N₂O₃, crystallizes with two mol­ecules in the asymmetric unit. There is extensive hydrogen bonding which results in the formation of a two‐dimensional corrugated sheet. This supramolecular structure is determined by the formation of hydrogen‐bonded chains resulting from the presence of a 6‐amino group and an ethoxy­carbonyl group as substituents on a pyridine ring in relative para positions which constitute a π‐electron `push–pull' system.     

PtFe catalysts supported on hierarchical porous carbon toward oxygen reduction reaction in microbial fuel cells

Journal of Solid State Electrochemistry - A new family of PtFe catalysts supported on hierarchical porous carbon (HPC), with different porous sizes, was developed and tested as cathodes in oxygen...     

Overview of DWDM/ODC Project

This article introduces the main achievements resulting from the DWDM/ODC project. The five areas of research activity within the DWDM/ODC project cover some of the main issues of design and development of dense wavelength division multiplexing systems for transparent optical networks. These issues are: performance assessment with arbitrary optical filtering; performance of signaling formats; dispersion compensation strategies for directly and externally modulated systems in presence of nonlinear transmission-induced degradation; and the impact of noise and crosstalk in the extent of transparent optical networks. All five areas of research activity have contributed significantly to a better understanding of the limitations present in dense wavelength division multiplexing systems.     

Molecular associations of 5-membered benzofused heterocyclic donors with organic acceptors

Benzofused heterocycles like 10H-[1]benzo thieno[3,2-b] indole and thieno[3,2-b]benzo[b]thiophene form molecular associations with ^* organic acceptors. The weak interactions involved are viewed in terms of UV-Vis and IR techniques. The results, mainly in the case of complexes of 10H-[1]benzo thieno[3,2-b] indole, are in some disagreement with the literature. The structure of the complex 10H-[1]benzo thieno[3,2-b] indole/tetracyanoethylene is also reported. The four condensed rings constitute a conjugate system with significant lengthenings of the aromatic ring bonds and a shortening of those of the five-membered rings. The fragment as a whole is almost planar, and forms a dihedral angle of 39.9(1)° with the planar tetracyanoethylene molecule.     

A one-step solvothermal route for the synthesis of nanocrystalline anatase TiO2 doped with lanthanide ions

A one-step solvothermal synthesis is proposed for the preparation of nanocrystalline single-phase TiO₂ in the anatase form doped with lanthanide ions Eu³⁺, Er³⁺ and Sm³⁺. The structural properties of these products have been investigated by using X-ray powder diffraction, electron microscopy and Raman spectroscopy. Furthermore, the laser-excited luminescence spectra of the samples have been measured and analyzed. Following this route, the doping process turns out to be highly favorite and the resulting materials show an efficient luminescence in the visible region.