Tuning of the Self-Threading of Ring-in-Ring Structures in Aqueous Media

A series of aryl-extended N-monoalkyl-4,4′-bipyridinium salts L (aryl=1,4-phenyl, 4,4′-biphenyl, 2,6-naphthyl and 9,10-anthracenyl) have been implemented by Pd^II/Pt^II-directed self-assembly into constitutionally dynamic systems (CDSs). As a result, the intended processes produced not only (en) M ₂ L ₂ (en=ethylenediamine) metallacyclic species but also (en) M ₄ L ₄ ring-in-ring aggregates, in equilibrium with the former, as a consequence of the hydrophobic nature of the aryl rings within the 4,4′-bipyridinium scaffold. The key feature of the obtained dynamic systems is the possibility of modulating their response against external stimuli by modifying the hydrophobic character of the ligand. While the different dynamic libraries follow the same trends upon changes in concentration, temperature, polarity of the medium, or addition of an aromatic chemical effector, subtle changes in the ligand hydrophobic core results in a fine-tuning of the speciation when applying a certain degree of the different stimulus. The exception is the anthracene-containing derivative, which does not form inclusion complexes or self-threaded structures.     

Relaxation of quasi-stationary states in long range interacting systems and a classification of the range of pair interactions

Systems of particles interacting with long range interactions present generically ”quasi-stationary states” (QSS), which are approximately time-independent out of equilibrium states. In this proceedings, we explore the generalization of the formation of such QSS and their relaxation from the much studied case of gravity to a generic pair interaction with the asymptotic form of the potential v(r) ∼ 1/r ^γ with γ > 0 in d dimensions. We compute analytic estimations of the relaxation time calculating the rate of two body collisionality in a virialized system approximated as homogeneous. We show that for γ < (d − 1/2), the collision integral is dominated by the size of the system, while for γ > (d − 1/2), it is dominated by small impact parameters. In addition, the lifetime of QSS increases with the number of particles if γ < d − 1 (i.e. the force is not integrable) and decreases if γ > d − 1. Using numerical simulations we confirm our analytic results. A corollary of our work gives a ”dynamical” classification of interactions: the dynamical properties of the system depend on whether the pair force is integrable or not.     

Electronic and vibrational hyperpolarizabilities of alkali- and alkaline-earth-doped boron nitride nanotubes

This work reports the results of the vibrational corrections and frequency dependence to the first hyperpolarizabilities of the alkali- and alkaline-earth-doped boron nitride nanotubes. The electronic contributions were computed by means of the density functional theory with the M06-2X functional, and the vibrational corrections were calculated using the perturbation theoretical method and the field-induced coordinates methodology. The results for the electronic contribution show that such materials exhibit large first hyperpolarizabilities and electride characteristic. We also show that the distribution of the excess electron, which originates from the doping atoms, plays an important role in the large electronic hyperpolarizabilities (β^el). Moreover, our findings strongly indicate that the effect of vibrations on the hyperpolarizabilities can be quite important and can even be much larger than the electronic counterpart.     

Reliability-Based Optimization of Structural Systems involving Discrete Design Variables

This contribution proposes an approach for solving Reliability–based optimization (RBO) problems involving discrete design variables. The proposed approach is based on a decoupling approach and sequential approximations. An application example involving a linear structure under dynamic loading is presented, showing the efficiency of the proposed method. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Europium(III) Concentration Effect on the Spectroscopic and Photoluminescent Properties of BaMoO4:Eu

BaMoO₄:Eu (BEMO) powders were synthesized by the polymeric precursor method (PPM), heat treated at 800 °C for 2 h in a heating rate of 5 °C/min and characterized by powder X-ray diffraction patterns (XRD), Fourier Transform Infra-Red (FTIR) and Raman spectroscopy, besides room temperature Photoluminescence (PL) measurements. The emission spectra of BEMO samples under excitation of 394 nm present the characteristic Eu³⁺ transitions. The relative intensities of the Eu³⁺ emissions increase as the concentration of this ion increases from 0.01 to 0.075 mol, but the luminescence is drastically quenched for the Ba_0.855Eu_0.145MoO₄ sample. The one exponential decay curves of the Eu^{3+ 5}D₀→⁷F₂ transition, λ _exc = 394 nm and λ _em = 614 nm, provided the decay times of around 0.54 ms for all samples. It was observed a broadening of the Bragg reflections and Raman bands when the Eu⁺³ concentration increases as a consequence of a more disordered material. The presence of MoO₃ and Eu₂Mo₂O₇ as additional phases in the BEMO samples where observed when the Eu³⁺ concentration was 14.5 mol%.     

Simultaneous Determination of Glucose and Choline Based on the Intrinsic Fluorescence of the Enzymes

It has been possible to perform the simultaneous determination of choline and glucose using the intrinsic fluorescence of the corresponding enzyme as an analytical signal. This can be done in two ways. First, for low glucose and choline concentrations (about 0.55 mM and 0.75 μM respectively) two differentiated signals, without mutual interference, are obtained for both analytes in the same measurement. Second, when glucose and choline concentrations are higher, a new model has been designed which permits the concentrations to be accurately determined in samples containing from 0.55 mM to 3.75 mM glucose and from 0.75 μM to 11.0 μM choline; the method has been applied to simultaneous glucose and choline determinations in serum samples with good results. This method gives a better performance than multivariate calibration based on Partial Least Squares Regression. The methodology here shown could be also used for the simultaneous determination of other pairs of analytes. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A chemical strategy to control the shape of oxide nanoparticles

A new strategy, epoxide-assisted precipitation route presented in this work, allows the shape control synthesis of Co₃O₄ nanoparticles. The shape of the nanoparticles is determined by the nature of the precursor cobalt salts (Co(NO₃)₂ · 6H₂O, CoCl₂ · 6H₂O) used for the preparation of the particles. The different reaction dynamics of the two salts in ethanolic and aqueous solutions with propylene oxide result in precursor particles with different structures, which lead to the formation of oxide nanoparticles with different shapes during the heat treatment. Spherical particles of about 20 nm are obtained from the ethanolic solution of Co(NO₃)₂ · 6H₂O; cubic-shaped particles of about 30 nm can be prepared from the ethanolic solution of CoCl₂ · 6H₂O; whereas platelet-like particles of more than 100 nm are synthesized from the aqueous solution of the mixture of Co(NO₃)₂ · 6H₂O and CoCl₂ · 6H₂O.     

Ontogeny of ATP hydrolysis and isoform expression of the Plasma Membrane Ca2+-ATPase in mouse brain

Background  

Plasma membrane Ca²⁺-ATPases (PMCAs) are high affinity Ca²⁺ transporters actively involved in intracellular Ca²⁺ homeostasis. Considering the critical role of Ca²⁺ signalling in neuronal development and plasticity, we have analyzed PMCA-mediated Ca²⁺-ATPase activity and PMCA-isoform content in membranes from mouse cortex, hippocampus and cerebellum during postnatal development.