The hydration of Cu2+: Can the Jahn-Teller effect be detected in liquid solution?

The long elusive structure of Cu(II) hydrate in aqueous solutions, classically described as a Jahn-Teller distorted octahedron and recently proposed to be a fivefold coordination structure [Pasquarello et al., Science 291, 856 (2001)], has been probed with x-ray-absorption spectroscopy by performing a combined theoretical and experimental analysis. Two absorption channels were needed to obtain a proper reproduction of the x-ray-absorption near-edge structure (XANES) region spectrum, as already observed in other Cu(II) complexes [Chaboy et al., Phys. Rev. B 71, 134208 (2005)]. The extended x-ray-absorption fine-structure (EXAFS) spectrum was analyzed as well within this approach. Quite good reproductions of both XANES and EXAFS spectra were attained for several distorted and undistorted structures previously proposed. Nevertheless, there is not a clearly preferred structure among those including four-, five-, and sixfold coordinated Cu(II) ions. Taking into account our results, as well as many more from several other authors using different techniques, the picture of a distorted octahedron for the Cu(II) hexahydrate in aqueous solution, paradigm of the Jahn-Teller effect, is no longer supported. In solution a dynamical view where the different structures exchange among themselves is the picture that better suits the results presented here.     

Some Geometric Characterizations of the Hopf Fibrations of the Three-Sphere

The Fréchet manifold of all embeddings (up to orientation preserving reparametrizations) of the circle in S ³ has a canonical weak Riemannian metric. We use the characterization obtained by H. Gluck and F. Warner of the oriented great circle fibrations of S ³ to prove that among all such fibrations π:S ³→B, the manifold B consisting of the oriented fibers is totally geodesic in , or has minimum volume or diameter with the induced metric, exactly when π is a Hopf fibration. Partially supported by foncyt, Antorchas, ciem (conicet) and secyt (unc).     

Do the neighboring residues in a polypeptide affect the electron distribution of an amino acid significantly? A quantitative study using the quantum theory of atoms in molecules (QTAIM)

Geometries, as well as bond and atomic properties obtained with the atoms-in-molecules theory applied on B3LYP/6-31++G//B3LYP/6-31G charge densities, of the N-formyl amides of the nine tripeptides obtained by combining glycine, alanine, and serine around a central glycine residue were analyzed to check how the properties of the central residue are modified by other amino acids bonded to it. All of the molecules were optimized from an alpha-helix conformation that was also displayed by the optimized structure. Significant variations of the geometry (especially remarkable for dihedral angles) and atomic properties of the central glycine residue are observed when it is attached to a serine residue whose side chain is involved in a hydrogen bond.     

Multipartite entanglement signature of quantum phase transitions

We derive a general relation between the nonanalyticities of the ground state energy and those of a subclass of the multipartite generalized global entanglement (GGE) measure defined by de Oliveira et al. [Phys. Rev. A 73, 010305(R) (2006)] for many-particle systems. We show that GGE signals both a critical point location and the order of a quantum phase transition (QPT). We also show that GGE allows us to study the relation between multipartite entanglement and QPTs, suggesting that multipartite but not bipartite entanglement is favored at the critical point. Finally, using GGE we were able, at a second-order QPT, to define a diverging entanglement length (EL) in terms of the usual correlation length. We exemplify this with the XY spin-1/2 chain and show that the EL is half the correlation length.     

NMR relaxometry and imaging of water absorbed in biodegradable polymer scaffolds

Porous substrates made of poly(3-hydroxybutyrate-3-hydroxyvalerate) (PHBHV) were prepared by a particulate leaching method. After removing the salt by extraction in water, proton nuclear magnetic resonance (NMR) relaxometry and imaging were performed on sets of PHBHV substrates immersed in phosphate-buffered solution during 3 months at different time points. Polarized optical microscopy studies were performed on thin sections, 25 and 5 mum, of the PHBHV samples. The results of NMR relaxometry showed two (1)H nuclei populations, well distinguishable on the free induction decay (FID), due to the different decay time constants, a factor of 10(2) apart. Thus, it was possible to separate the two populations, giving separate distributions of T(1) relaxation times. One population could be associated with water protons in the pores and the other to macromolecular protons. The distributions of T(1) and T(2) of the water proton shifted to lower values with increasing immersion time to a constant value after 30 days. The results obtained by NMR imaging showed an initial increase in the apparent porosity, reaching a plateau after 25 days of immersion. This increase is attributed mainly to the absorption of water in the microporosity as supported by the results of the relaxometry measurements and shown by scanning electron microscopy. The average porosity measured by NMR imaging at the plateau, 78+/-3%, is slightly higher than that determined by optical microscopy, 73+/-9%, which may be due to the fact that the latter method did not resolve the microporosity. Overall, the results suggest that at early stages after immersing the scaffolds in the aqueous medium, first 30 days approximately, NMR imaging could underestimate the porosity of the substrate.     

Universality and asymptotics of graph counting problems in non-orientable surfaces

Bender-Canfield showed that a plethora of graph counting problems in orientable/non-orientable surfaces involve two constants tg and pg for the orientable and the non-orientable case, respectively. T.T.Q. Le and the authors recently discovered a hidden relation between the sequence tg and a formal power series solution u(z) of the Painlevé I equation which, among other things, allows to give exact asymptotic expansion of tg to all orders in 1/g for large g. The paper introduces a formal power series solution v(z) of a Riccati equation, gives a non-linear recursion for its coefficients and an exact asymptotic expansion to all orders in g for large g, using the theory of Borel transforms. In addition, we conjecture a precise relation between the sequence pg and v(z). Our conjecture is motivated by the enumerative aspects of a quartic matrix model for real symmetric matrices, and the analytic properties of its double scaling limit. In particular, the matrix model provides a computation of the number of rooted quadrangulations in the 2-dimensional projective plane. Our conjecture implies analyticity of the O(N)- and Sp(N)-types of free energy of an arbitrary closed 3-manifold in a neighborhood of zero. Finally, we give a matrix model calculation of the Stokes constants, pose several problems that can be answered by the Riemann-Hilbert approach, and provide ample numerical evidence for our results.     

On classes of structures axiomatizable by universal d-Horn sentences and universal positive disjunctions

We provide universal algebraic characterizations (in the sense of not involving any “logical notion”) of some elementary classes of structures whose definitions involve universal d-Horn sentences and universally closed disjunctions of atomic formulas. These include, in particular, the classes of fields, of non-trivial rings, and of directed graphs without loops where every two elements are adjacent. The classical example of this kind of characterization result is the HSP theorem, but there are myriad other examples (e.g., the characterization of elementary classes using isomorphic images, ultraproducts and ultrapowers due to Keisler and Shelah).     

Cocompactness and minimizers for inequalities of Hardy–Sobolev type involving N-Laplacian

The paper studies quasilinear elliptic problems in the Sobolev spaces W ^1,p (Ω), ${\Omega\subset{\mathbb R}^N}The paper studies quasilinear elliptic problems in the Sobolev spaces W ^1,p (Ω), W ì \mathbb R^N{\Omega\subset{\mathbb R}^N} , with p = N, that is, the case of Pohozhaev–Trudinger–Moser inequality. Similarly to the case p < N where the loss of compactness in W^1,p(\mathbb R^N){W^{1,p}({\mathbb R}^N)} occurs due to dilation operators u ?t^(N-p)/pu(tx){u {\mapsto}t^{(N-p)/p}u(tx)} , t > 0, and can be accounted for in decompositions of the type of Struwe’s “global compactness” and its later refinements, this paper presents a previously unknown group of isometric operators that leads to loss of compactness in W₀^1,N{W_0^{1,N}} over a ball in \mathbb R^N{{\mathbb R}^N} . We give a one-parameter scale of Hardy–Sobolev functionals, a “p = N”-counterpart of the H?lder interpolation scale, for p > N, between the Hardy functional ò\frac|u|^p|x|^p dx{\int \frac{|u|^p}{|x|^p}\,{\rm d}x} and the Sobolev functional ò|u|^pN/(N-mp)  dx{\int |u|^{pN/(N-mp)} \,{\rm d}x} . Like in the case p < N, these functionals are invariant with respect to the dilation operators above, and the respective concentration-compactness argument yields existence of minimizers for W ^1,N -norms under Hardy–Sobolev constraints.     

The multicriteria analysis for construction of benchmarkers to support the Clinical Engineering in the Healthcare Technology Management

In developing countries, approximately half of the healthcare equipments are not in full use and the main cause of this is the inadequate management of them. The Clinical Engineering might face this problem in the healthcare environment analyzing the equipment with a health technological process perspective to identify opportunities of improvements. Generally, the inadequate management is a result of lack of systemized and contextualized information about the health technological process. The effort to make an adequate management generates an increasing interest in the use of benchmarker. Currently, the benchmarkers used by the Clinical Engineering are not representative of a health technological process as a whole. Health technological process concept is stated in this article. The multicriteria analysis methodology MCDA (Multicriteria Decision Aid) is used to obtain benchmarkers and to identify opportunities of improvements, thus generating conditions for that the Clinical Engineering consolidates its relevant contribution for the healthcare.