Fast O2 binding at dicopper complexes containing Schiff-base dinucleating ligands

A new family of dicopper(I) complexes [CuI2RL](X)2 (R=H, 1X, R=tBu, 2X and R=NO2, 3X, X=CF3SO3, ClO4, SbF6, or BArF, BArF=[B{3,5-(CF3)2C6H3}4]-), where RL is a Schiff-base ligand containing two tridentate binding sites linked by a xylyl spacer, has been prepared and characterized, and its reaction with O2 has been studied. The complexes were designed with the aim of reproducing structural aspects of the active site of type 3 dicopper proteins; they contain two three-coordinate copper sites and a rather flexible podand ligand backbone. The solid-state structures of 1ClO4, 2CF3SO3, 2ClO4, and 3BArF.CH3CN have been established by single-crystal X-ray diffraction analysis. 1ClO4 adopts a polymeric structure in the solid state while 2CF3SO3, 2ClO4, and 3BArF.CH3CN are monomeric. The complexes have been studied in solution by means of 1H and 19F NMR spectroscopy, which put forward the presence of dynamic processes. 1-3BArF and 1-3CF3SO3 in acetone react rapidly with O2 to generate metaestable [CuIII2(mu-O)2(RL)]2+ 1-3(O2) and [CuIII2(mu-O)2(CF3SO3)(RL)]+ 1-3(O2)(CF3SO3) species, respectively, that have been characterized by UV-vis spectroscopy and resonance Raman analysis. Instead, reaction of 1-3BArF with O2 in CH2Cl2 results in intermolecular O2 binding. DFT methods have been used to study the chemical identities and structural parameters of the O2 adducts, and the relative stability of the CuIII2(mu-O)2 form with respect to the CuII2(mu-eta2:eta2-O2) isomer. The reaction of 1X, X = CF3SO3 and BArF, with O2 in acetone has been studied by stopped-flow UV-vis exhibiting an unexpected very fast reaction rate (k=3.82(4)x10(3) M-1 s-1, DeltaH=4.9+/-0.5 kJ.mol-1, DeltaS=-148+/-5 J.K-1.mol-1), nearly 3 orders of magnitude faster than in the parent [CuI2(m-XYLMeAN)]2+. Thermal decomposition of 1-3(O2) does not result in aromatic hydroxylation. The mechanism and kinetics of O2 binding to 1X (X=CF3SO3 and BArF) are discussed and compared with those associated with selected examples of reported models of O2-processing copper proteins. A synergistic role of the copper ions in O2 binding and activation is clearly established from this analysis.     

X-ray absorption spectroscopic studies of high-spin nonheme (alkylperoxo)iron(III) intermediates

The reactions of iron(II) complexes [Fe(T(pt-Bu,i-Pr))(OH)] (1a, Tp(t-Bu,i-Pr) = hydrotris(3-tert-butyl-5-isopropyl-1-pyrazolyl)borate), [Fe(6-Me2BPMCN)(OTf)2] (1b, 6-Me2BPMCN = N,N'-bis((2-methylpyridin-6-yl)methyl)-N,N'-dimethyl-trans-1,2-diaminocyclohexane), and [Fe(L8Py2)(OTf)](OTf) (1c, L8Py2 = 1,5-bis(pyridin-2-ylmethyl)-1,5-diazacyclooctane) with tert-BuOOH give rise to high-spin FeIII-OOR complexes. X-ray absorption spectra (XAS) of these high-spin species show characteristic features, distinct from those of low-spin Fe-OOR complexes (Rohde, J.-U.; et al. J. Am. Chem. Soc. 2004, 126, 16750-16761). These include (1) an intense 1s --> 3d preedge feature, with an area around 20 units, (2) an edge energy, ranging from 7122 to 7126 eV, that is affected by the coordination environment, and (3) a 1.86-1.96 A Fe-OOR bond, compared to the 1.78 A Fe-OOR bond in low-spin complexes. These unique features likely arise from a flexible first coordination sphere in those complexes. The difference in Fe-OOR bond length may rationalize differences in reactivity between low-spin and high-spin FeIII-OOR species.     

Pion radiative weak decays in nonlocal chiral quark models

We analyze the radiative pion decay π⁺→e⁺νeγ${\pi }^{+}\to e^{+}{\nu }_e\gamma$ within nonlocal chiral quark models that include wave function renormalization. In this framework we calculate the vector and axial-vector form factors FV$F_V$ and FA$F_A$ at q²=0$q^2=0$ — where q²$q^2$ is the e⁺νe$e^{+}{\nu }_e$ squared invariant mass — and the slope a   of FV(q²)$F_V(q^2)$ at q²→0$q^2\to 0$. The calculations are carried out considering different nonlocal form factors, in particular those taken from lattice QCD evaluations, showing a reasonable agreement with the corresponding experimental data. The comparison of our results with those obtained in the (local) NJL model and the relation of FV$F_V$ and a   with the form factor in π⁰→γ^?γ${\pi }^0\to {\gamma }^{?}\gamma$ decays are discussed.     

The maximum and the addition of assignment games

In the framework of two-sided assignment markets, we first consider that, with several markets available, the players may choose where to trade. It is shown that the corresponding game, represented by the maximum of a finite set of assignment games, may not be balanced. Some conditions for balancedness are provided and, in that case, properties of the core are analyzed. Secondly, we consider that players may trade simultaneously in more than one market and then add up the profits. The corresponding game, represented by the sum of a finite set of assignment games, is balanced. Moreover, under some conditions, the sum of the cores of two assignment games coincides with the core of the sum game.     

Zero-finder methods derived using Runge-Kutta techniques

In this paper some families of zero-finding iterative methods for nonlinear equations are presented. The key idea to derive them is to solve an initial value problem applying Runge-Kutta techniques. More explicitly, these methods are used to solve the problem that consists in a differential equation in what appears the inverse function of the one which zero will be computed and the condition given by the value attained by it at the initial approximation. Carrying out this procedure several families of different orders of local convergence are obtained. Furthermore, the efficiency of these families are computed and two new families using like-Newton’s methods that improve the most efficient one are also given.     

Optimizing microwind rural electrification projects. A case study in Peru

Electrification systems based on the use of renewable energy sources are suitable for providing electricity to isolated communities autonomously. Specifically, electrification by wind power is one of the technological options that have been used recently in projects implemented in the Andean highlands of Peru. To date, these projects have tended to install individual microwind turbines at each demand point. Alternatively, we propose a solution that considers both individual generators and microgrids. We develop a mathematical model that gives the location and size or type of the wind turbines and the design of the microgrids, taking into account the demand of the consumption points and the wind potential. The criterion is the minimization of the initial investment cost required to meet the demand. The model is validated by application to a real case in the northern highlands of Peru. Results show that microgrids are used despite the village dispersion, and the solutions significantly reduce the initial investment costs.     

Aryl-O reductive elimination from reaction of well-defined aryl-Cu(III) species with phenolates: the importance of ligand reactivity

Well-defined aryl-Cu(III) species undergo rapid reductive elimination upon reaction with phenolates (PhO(-)), to form aryl-OPh cross-coupling products. Kinetic studies show that the reaction follows a different mechanistic pathway compared to the reaction with phenols. The pH active cyclized pincer-like ligand undergoes an initial amine deprotonation that triggers a faster reactivity at room temperature. A mechanistic proposal for the enhanced reactivity and the role of EPR-detected Cu(II) species will be discussed in detail.     

Carbon nanoparticles in lateral flow methods to detect genes encoding virulence factors of Shiga toxin-producing <Emphasis Type="Italic">Escherichia coli</Emphasis>

The use of carbon nanoparticles is shown for the detection and identification of different Shiga toxin-producing Escherichia coli virulence factors (vt1, vt2, eae and ehxA) and a 16S control (specific for E. coli) based on the use of lateral flow strips (nucleic acid lateral flow immunoassay, NALFIA). Prior to the detection with NALFIA, a rapid amplification method with tagged primers was applied. In the evaluation of the optimised NALFIA strips, no cross-reactivity was found for any of the antibodies used. The limit of detection was higher than for quantitative PCR (q-PCR), in most cases between 10⁴ and 10⁵ colony forming units/mL or 0.1–0.9 ng/μL DNA. NALFIA strips were applied to 48 isolates from cattle faeces, and results were compared to those achieved by q-PCR. E. coli virulence factors identified by NALFIA were in very good agreement with those observed in q-PCR, showing in most cases sensitivity and specificity values of 1.0 and an almost perfect agreement between both methods (kappa coefficient larger than 0.9). The results demonstrate that the screening method developed is reliable, cost-effective and user-friendly, and that the procedure is fast as the total time required is <1 h, which includes amplification.