A macrocyclic ligand able to bind gallium(III) by preorganized pendant arms; coordination and kinetic studies

The equilibria and kinetics of the binding of gallium(III) to 4-(N),10-(N)-bis[2-(3-hydroxo-2-oxo-2-H-pyridine-1-y1)acetamido]-1,7-dimethyl-1,4,7,10-tetraazacyclododecane (L) were investigated in acidic medium at ionic strength 1 M (NaClO4). Spectrophotometric titrations in the UV region revealed that L is able to bind Ga3+ also at high H+ concentration. The kinetic (stopped-flow) experiments are interpreted on the basis of three parallel reaction paths (i) M3+ + H2L2+ = M(H2L)5+ where M(H2L)5+ is in a steady state, (ii) M(OH)2+ + H2L2+ = M(HL)4+ + H2O and (iii) M(OH)2+ + HL+ = ML3+ + H2O. The first-order rate constants for conversion of the outer-sphere into the inner-sphere complexes are similar to those of the Ga(III)/tropolone system which is known to react according to the dissociative Id mechanism and to the relevant rate constants for water exchange at the metal ion. The effects of pH on the UV-Vis absorption, fluorescence emission properties and NMR spectral features on the Ga(III)/L system were also investigated. Spectrophotometric titrations in the UV region reveal that, in acid medium the prevailing species is M(HL)4+ whereas the chelate ML3+ prevails for [H+] < 0.01 M. The results indicate metal coordination at the oxygen atoms of the 3-hydroxo-2-oxopyridine residues.     

Theoretical study of electromagnetic scattering by metal nanoparticles

Progress in near-field optical spectroscopy research on metal nanoparticles demands a better understanding of the role of particle-particle and tip-sample interactions. In this perspective, we investigate theoretically, at a very moderate level of sophistication, the optical behavior of simple silver nanoparticle aggregates, in terms of a formalism involving a multipolar expansion of the fields involved, along with a simplified model for the optical behavior of nanostructures previously developed. In particular, the tip-sample interaction is taken into account roughly, treating the tip as an additional, single particle, characterized by proper dielectric behavior.     

One-dimensional random lasing in a single organic nanofiber

One-dimensional light amplification in individual p-sexiphenyl nanofibers is investigated. The influence of fiber morphology on light propagation properties is studied via optical and atomic force microscopy. Isolated nanofibers are shown to yield low-threshold random laser emission in the deep blue. Model calculations of coherent light propagation in one-dimensional random media qualitatively reproduce the experimental results. Implications for photonic nanosensors are briefly discussed.     

A multivariate FGD technique to improve VaR computation in equity markets

It is difficult to compute Value-at-Risk (VaR) using multivariate models able to take into account the dependence structure between large numbers of assets and being still computationally feasible. A possible procedure is based on functional gradient descent (FGD) estimation for the volatility matrix in connection with asset historical simulation. Backtest analysis on simulated and real data provides strong empirical evidence of the better predictive ability of the proposed procedure over classical filtered historical simulation, with a resulting significant improvement in the measurement of risk.Francesco Audrino and Giovanni Barone-Adesi: The authors would like to thank Peter Bühlmann and two anonymous referees for some helpful comments. Financial support by the National Centre of Competence in Research Financial Valuation and Risk Management (NCCR FINRISK) is gratefully acknowledged.     

Three-dimensional image fusion by use of multiwavelength digital holography

We present three-dimensional (3D) image fusion by use of digital holography. We demonstrate experimentally that, through the image fusion technique with multiresolution wavelet decomposition, it is possible to increase the details and contrast of 3D reconstructed images obtained by multiwavelength digital holography. Although there is substantial activity in the fields of image fusion and holography, to the best of our knowledge, this is the first report of 3D image fusion by use of digital holography.     

de Sitter vacua via consistent terms

We introduce a new mechanism for producing locally stable de Sitter or Minkowski vacua, with spontaneously broken N = 1 supersymmetry and no massless scalars, applicable to superstring and M-theory compactifications with fluxes. We illustrate the mechanism with a simple N = 1 supergravity model that provides parametric control on the sign and the size of the vacuum energy. The crucial ingredient is a gauged U(1) that involves both an axionic shift and an R symmetry, and severely constrains the F- and D-term contributions to the potential.     

Scaling exponents and probability distributions of DNA end-to-end distance

The scaling of the average gyration radius of polymers as a function of their length can be experimentally determined from ensemble measurements, such as light scattering, and agrees with analytical estimates. Ensemble techniques, yet, do not give access to the full probability distributions. Single molecule techniques, instead, can deliver information on both average quantities and distribution functions. Here we exploit the high resolution of atomic force microscopy over long DNA molecules adsorbed on a surface to measure the average end-to-end distance as a function of the DNA length, and its full distribution function. We find that all the scaling exponents are close to the predicted 3D values (upsilon=0.589+/-0.006 and delta=2.58+/-0.77). These results suggest that the adsorption process is akin to a geometric projection from 3D to 2D, known to preserve the scaling properties of fractal objects of dimension df<2.     

Nonlinear evolution of the lower-hybrid drift instability in a current sheet

The lower-hybrid drift instability is simulated in an ion-scale current sheet using a fully kinetic approach with values of the ion to electron mass ratio up to m(i)/m(e)=1836. Although the instability is localized on the edge of the layer, the nonlinear development increases the electron flow velocity in the central region resulting in a strong bifurcation of the current density and significant anisotropic heating of the electrons. This dramatically enhances the collisionless tearing mode and may lead to the rapid onset of magnetic reconnection for current sheets near the critical scale.     

Identification and quantification of major species of arsenic in rice

A study was undertaken to develop a method for the chemical speciation of As in rice on the basis of current knowledge in this field for use in preparing a certified reference material (CRM). Samples of the Arborio rice variety were ground to a fine powder, which was extracted under sonication with a water-methanol mixture (1 + 1, v/v). The resulting solutions were injected into a high-performance liquid chromatograph combined on-line with a quadrupole inductively coupled plasma-mass spectrometer. This hyphenated system allowed for the quantification of As species in one analytical step. Four forms of As were detected: inorganic As (III), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), and inorganic As (V) at concentrations of 88.2 +/- 7.1, 50.8 +/- 5.0, 15.2 +/- 1.7, and 51.2 +/- 3.5 ng/g, respectively. The concentration of total As was 211 +/- 7 ng/g. The limits of detection (3sigma criterion) and the quantitation (10sigma criterion) were, respectively, as follows (in ng/g): As (III), 0.095 and 0.320; As (V), 0.082 and 0.273; MMA, 0.110 and 0.367; and DMA, 0.145 and 0.480. Ten hours were needed for the extraction procedure, 6 h for the evaporation, and 30 min for quantification of the analytes. This investigation was performed in the frame of a European Commission Project on the feasibility of CRMs for As and Se species.     

Accelerated Koenigs-Knorr glucuronidation of a deactivated nitrophenol: unveiling the role of polyamine additive 1,1,4,7,10,10-hexamethyltriethylenetetramine through design of experiments

1,1,4,7,10,10-Hexamethyltriethylenetetramine (HMTTA) emerged from a limited parallel screening of selected polyamines as the most appropriate additive for an especially problematic Koenigs-Knorr glucuronidation. This initial finding rapidly evolved into a reliable and high-yielding procedure through the use of two sets of experimental designs. The detailed effect of the stoichiometry of reagents and the amount of amine additive on reaction yield was elucidated. The complexity of the response surface for product yield, described by a third-order polynomial equation, together with ancillary kinetic experiments evidenced the multiple role of HMTTA in the present glucuronidation process.