Exciton Interactions,Excimer Formation,and [2π+2π] Photodimerization in Nonconjugated Curcuminoid-BF2 Dimers

We describe the synthesis of a series of covalently linked dimers of quadrupolar curcuminoid-BF₂ dyes and the detailed investigation of their solvent-dependent spectroscopic and photophysical properties. In solvents of low polarity, intramolecular folding induces the formation of aggregated chromophores, the UV/Vis absorption spectra of which display the optical signature characteristic of weakly-coupled H-aggregates. The extent of folding and, in turn, of ground-state aggregation is strongly dependent on the nature of the flexible linker. Steady-state and time-resolved fluorescence emission spectroscopies show that the Frenkel exciton relaxes into a fluorescent symmetrical excimer state with a long lifetime. Furthermore, our in-depth studies show that a weakly emitting excimer lies on the pathway toward a photocyclomer. Two-dimensional ¹H NMR spectroscopy and density functional theory (DFT) allowed the structure of the photoproduct to be established. To our knowledge, this represents the first example of a [2π+2π] photodimerization of the curcuminoid chromophore.     

Formation of helical beams by use of Pancharatnam-Berry phase optical elements

Spiral phase elements with topological charges based on space-variant Pancharatnam-Berry phase optical elements are presented. Such elements can be achieved by use of continuous computer-generated space-variant subwavelength dielectric gratings. We present a theoretical analysis and experimentally demonstrate spiral geometrical phases for infrared radiation at a wavelength of 10.6microm .     

Path Relinking, Cycle-Based Neighbourhoods and Capacitated Multicommodity Network Design

In this paper, we propose a path relinking procedure for the fixed-charge capacitated multicommodity network design problem. Cycle-based neighbourhoods are used both to move along paths between elite solutions and to generate the elite candidate set by a tabu-like local search procedure. Several variants of the method are implemented and compared. Extensive computational experiments indicate that the path relinking procedure offers excellent results. It systematically outperforms the cycle-based tabu search method in both solution quality and computational effort and offers the best current meta-heuristic for this difficult class of problems.     

On Anosov energy levels of hamiltonians on twisted cotangent bundles

LetT ^* M denote the cotangent bundle of a manifoldM endowed with a twisted symplectic structure [1]. We consider the Hamiltonian flow generated (with respect to that symplectic structure) by a convex HamiltonianH: T ^* M, and we consider a compact regular energy level ofH, on which this flow admits a continuous invariant Lagrangian subbundleE. When dimM3, it is known [9] that such energy level projects onto the whole manifoldM, and thatE is transversal to the vertical subbundle. Here we study the case dimM=2, proving that the projection property still holds, while the transversality property may fail. However, we prove that in the case whenE is the stable or unstable subbundle of an Anosov flow, both properties hold.     

Convergence de mesures spectrales aléatoires et applications à des principes d'invariance

Nous présentons un cadre unificateur pour un certain nombre de résultats connus de convergence en loi pour des processus admettant une représentation linéaire par rapport à un bruit blanc faible pour lequel il existe un principe dinvariance faible. Nous montrons que ce principe dinvariance est équivalent à la convergence dune suite de mesures aléatoires spectrales. Ceci permet daffaiblir les hypothèses usuelles et donc dobtenir des résultats nouveaux de convergence en loi, notamment pour des processus à longue portée.     

Optimal Paths for Symmetric Actions in the Unitary Group

Given a positive and unitarily invariant Lagrangian ${\mathcal{L}}$ defined in the algebra of matrices, and a fixed time interval ${[0,t_0]\subset\mathbb R}$ , we study the action defined in the Lie group of ${n\times n}$ unitary matrices ${\mathcal{U}(n)}$ by $$\mathcal{S}(\alpha)=\int_0^{t_0} \mathcal{L}(\dot\alpha(t))\,dt, $$ where ${\alpha:[0,t_0]\to\mathcal{U}(n)}$ is a rectifiable curve. We prove that the one-parameter subgroups of ${\mathcal{U}(n)}$ are the optimal paths, provided the spectrum of the exponent is bounded by π. Moreover, if ${\mathcal{L}}$ is strictly convex, we prove that one-parameter subgroups are the unique optimal curves joining given endpoints. Finally, we also study the connection of these results with unitarily invariant metrics in ${\mathcal{U}(n)}$ as well as angular metrics in the Grassmann manifold.     

Unstable Particles, Gauge Invariance and the Δ++ Resonance Parameters

The elastic and radiative ⁺ p scattering are studied in the framework of an effective Lagrangian model for the ⁺⁺ resonance and its interactions. The finite width effects of this spin-3/2 resonance are introduced in the scattering amplitudes through a complex mass scheme to respect electromagnetic gauge invariance. The resonant pole ( ⁺⁺) and background contributions ( ⁰, , , and neutron states) are separated according to the principles of the analytic S-matrix theory. The mass and width parameters of the ⁺⁺ obtained from a fit to experimental data on the total cross section are in agreement with the results of a model-independent analysis based on the analytic S-matrix approach. The magnetic dipole moment determined from the radiative ⁺ p scattering is nuclear magnetons.     

Use of hydrogen peroxide to achieve interference-free stripping voltammetric determination of copper at the bismuth-film electrode

In this work, a new approach is presented to allow interference-free determination of Cu (II) by stripping voltammetry using the bismuth-film electrode. The addition of hydrogen peroxide to the electroanalytical cell has promoted complete resolution between re-dissolution peaks of Bi (III) and Cu (II). The absence of interference could be evaluated by the correlation coefficient (r > 0.99) between Cu (II) concentration and its shifted current peak (at +212 mV) while achieving a slightly fluctuation of the bismuth current peak at −180 mV. Studies were performed aiming towards the optimum conditions for trace determination of Cu (II) using hydrogen peroxide. The methodology was applied to a real sample (sugarcane spirits) and the results were compared to those from graphite furnace atomic absorption spectrometry. The analytical parameters of merit and the results of the analysis indicated that the analytical methodology could be readily used for trace determination of Cu (II).     

How important are temperature effects for cluster polarizabilities?

State-of-the-art first-principle all-electron density functional theory calculations on small sodium clusters are performed to study the temperature dependency of their polarizabilities. For this purpose Born-Oppenheimer molecular dynamics simulations with more than 100,000 time steps (>200 ps) are recorded employing gradient corrected functionals in combination with a double-zeta valence polarization basis set. For each cluster 18 trajectories between 50 and 900 K are collected. The cluster polarizabilities are then calculated along these trajectories employing a triple-zeta valence polarization basis set augmented with field-induced polarization functions. The analysis of these calculations shows that the temperature dependency of the sodium cluster polarizabilities varies strongly with cluster size. For several clusters characteristic changes in the polarizability per atom as a function of temperature are observed. It is shown that the inclusion of finite temperature effects resolves the long-standing mismatch between calculated and measured sodium cluster polarizabilities.     

Ultra-fast chromatographic micro-assay for quantification of diphenidol in plasma: application in an oral multi-dose switchability trial

Pharmacokinetics of diphenidol (DPN) is limited due to the lack of analytical methodology. Here, a micro-assay for DPN quantification was developed, by coupling ultra-performance liquid chromatography with tandem mass spectrometry. The procedure involved plasma precipitation and injection of supernatant into UPLC with an Acquitytrade mark C18 column. Detection was in positive electrospray, following transitions of m/z 310.3 --> 292.3 and m/z 275.3 --> 230.2 for DPN and chlorphenamine (internal standard), respectively. The method was linear with a range of 4-400 ng/mL, and a 2 min run time. This method was applied in a switchability trial, where both formulations of DPN were bioequivalent.