Photophysics of Calix[4]biscrown-Based Ditopic Receptors of Caesium Containing One or Two Dioxocoumarin Fluorophores

The ditopic receptors Calix-COU1 and Calix-COU2 consist of a calix[4]biscrown containing one or two dioxycoumarin fluorophores, respectively, inserted into the crown. They can form 1:1 and 2:1 (metal:ligand) complexes with caesium ions. The photophysical properties of the 1:1 complexes can be explained by (i) cation tunneling through the tube-shaped cavity (composed of the four phenyl rings) of the calix[4]biscrown, (ii) photodisruption of the interaction between the bound cation and the oxygen atoms belonging to both the coumarin moiety and the crown, (iii) photoinduced motions of the cation.     

Self-energy of one electron in non-relativistic QED

We investigate the self-energy of one electron coupled to a quantized radiation field by extending the ideas developed in Hainzl (Ann. H. Poincaré, in press). We fix an arbitrary cut-off parameter Λ and recover the α²-term of the self-energy, where α is the coupling parameter representing the fine structure constant. Thereby we develop a method which allows to expand the self-energy up to any power of α. This implies that perturbation theory in α is correct if Λ is fix. As an immediate consequence we obtain enhanced binding for electrons.     

Courbes nodales et ramification sauvage virtuelle

Let S be the spectrum of a discrete valuation ring of residue characteristic p>0. Let Z be a scheme separated and of finite type over S, and denote by K_c(Z,) (l≠p) the Grothendieck group of -constructible sheaves on the etale site of Z. In this article, we introduce the subgroup of virtual sheaves with virtual wild ramification zero, and we prove that this subgroup is preserved by the formalism of six operations “à la Grothendieck”.     

Local Dispersive and Strichartz Estimates for the Schrödinger Operator on the Heisenberg Group

It was proved by Bahouri et al. [9] that the Schrödinger equation on the Heisenberg group $\mathbb{H}^d,$ involving the sublaplacian, is an example of a totally non-dispersive evolution equation: for this reason global dispersive estimates cannot hold. This paper aims at establishing local dispersive estimates on $\mathbb{H}^d$ for the linear Schrödinger equation, by a refined study of the Schrödinger kernel $S_t$ on $\mathbb{H}^d.$ The sharpness of these estimates is discussed through several examples. Our approach, based on the explicit formula of the heat kernel on $\mathbb{H}^d$ derived by Gaveau [19], is achieved by combining complex analysis and Fourier-Heisenberg tools. As a by-product of our results we establish local Strichartz estimates and prove that the kernel $S_t$ concentrates on quantized horizontal hyperplanes of $\mathbb{H}^d.$     

Nash constructible functions

Nash constructible functions on a real algebraic set V are defined as linear combinations, with integer coefficients, of Euler characteristic of fibres of proper regular morphisms restricted to connected components of algebraic sets. We prove that if V is compact, these functions are sums of signs of semialgebraic arc-analytic functions (i.e. functions which become analytic when composed with any analytic arc). We also give a sharp upper bound to the number of semialgebraic arc-analytic functions which are necessary to define any given Nash constructible functions.     

Infrared and visible emission of Er in combustion-synthesized CaAl2O4 phosphors

New near-infrared luminescent, monoclinic CaAl₂O₄:Er³⁺ phosphor was prepared by using the combustion route at furnace temperatures as low as 500 °C in a few minutes. Combustion synthesized phosphor has been well characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive analysis of X-ray (EDAX) mapping studies. The luminescence spectra of Er³⁺-doped calcium aluminate were studied at UV (380 nm), vis (488 nm) and IR (980 nm) excitation. Upon UV and vis excitation, the CaAl₂O₄:Er³⁺ phosphor exhibits emission bands at ~523 nm and at ~547 nm, corresponding to transitions from the ²H_11/2 and ⁴S_3/2 erbium levels to the ⁴I_15/2 ground state. A strong luminescence at 1.55 μm in the infrared (IR) region due to ⁴I_13/2→⁴I_15/2 transition has been observed in CaAl₂O₄:Er³⁺ phosphor upon 980 nm CW pumping. In the spectrum of IR-excited up-conversion luminescence, green (~523 and ~547 nm) and red (662 nm) luminescence bands were present, the latter associated with the ⁴F_9/2→⁴I_15/2 transitions of Er³⁺ ions. Both excited state absorption and energy transfer may be proposed as processes responsible for the population of the ⁴S_3/2 and ⁴F_9/2 erbium levels upon IR excitation. The mechanisms responsible for the up-conversion luminescence are discussed.     

Infrared emission and defect centres in Er and Yb codoped Y3Al5O12 phosphors

YAG phosphor powders doped/codoped with Er³⁺/(Er³⁺ + Yb³⁺) have been synthesised by using the solution combustion method. The effect of direct pumping into the ⁴I_11/2 level under 980 nm excitation of doped/codoped Er³⁺/Yb³⁺−Er³⁺ in Y₃Al₅O₁₂ (YAG) phosphor responsible for an infrared (IR) emission peaking at ∼1.53 μm corresponding to the ⁴I_13/2→⁴I_15/2 transition has been studied. YAG exhibits three thermally-stimulated luminescence (TSL) peaks at around 140°C, 210°C and 445°C. Electron spin resonance (ESR) studies were carried out to identify the centres responsible for the TSL peaks. The room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0176 is identified as O⁻ ion, while centre II with an isotropic g-factor 2.0020 is assigned to an F⁺ centre (singly ionised oxygen vacancy). An additional defect centre is observed during thermal-annealing experiments and this centre (assigned to F⁺ centre) seems to originate from an F-centre (oxygen vacancy with two electrons) and these two centres appear to correlate with the observed high-temperature TSL peak in YAG phosphor.     

Photoinduced magnetization in copper octacyanomolybdate

This article describes the studies of a photomagnetic cyanide-bridged Cu-Mo bimetallic assembly, Cu(II)(2)[Mo(IV)(CN)(8)].8H(2)O (Cu(II), S = (1)/(2); Mo(IV), S = 0) (1), which has an intervalence transfer (IT) band from Mo(IV)-CN-Cu(II) to Mo(V)-CN-Cu(I) around 480 nm. Wide-angle X-ray scattering and X-ray spectroscopic studies provide precise information about the 3D connectivity and the local environment of the transition metal ions. Irradiating with blue light causes solid 1 to exhibit a spontaneous magnetization (Curie temperature = 25 K). The thermal reversibility is carefully studied and shows the long-time stability of the photoinduced state up to 100 K. Photoreversibility is also observed; i.e., the magnetization is induced by irradiation with light below 520 nm, while the magnetization is reduced by irradiation with light above 520 nm. The UV-vis absorption spectrum after irradiation shows a decrease of the IT band and the appearance of the reverse-IT band in the region of 600-900 nm (lambda(max) = 710 nm). This UV-vis absorption spectrum is recovered to the original spectrum by irradiation with 658-, 785-, and 840-nm light. In this photomagnetic effect, the excitation of the IT band causes an electron transfer from Mo(IV) to Cu(II), producing a ferromagnetic mixed-valence isomer of Cu(I)Cu(II)[Mo(V)(CN)(8)].8H(2)O (Cu(I), S = 0; Cu(II), S = (1)/(2); Mo(V), S = (1)/(2)) (1'). 1' returns to 1 by irradiation of the reverse-IT band, which obeys the scheme for the potential energy surface in mixed-valence class II compounds.     

New strategies to study the chemical nature of wine oligomeric procyanidins

Tannins represent a key element in red wine flavors, so researchers have made a lot of effort to try to understand the role of their structure in wine taste in recent decades. We report some new routes to achieve a true structure–taste relationship for the major tannins found in wine, which are procyanidins in their monomeric or oligomeric state. All these routes use synthetic standards. New advances in their synthesis and their analyses using chromatographic methods, NMR spectroscopy, and mass spectrometry to obtain more precise information about their chemical structure, including their stereochemistry and their precise degree of polymerization and galloylation, are described.