Generic singularities of the 3D-contact sub-Riemannian conjugate locus

In this paper, we extend and complete the classification of the generic singularities of the 3D-contact sub-Riemmanian conjugate locus in a neighborhood of the origin.     

Tuning the electronic structure of octahedral iron complexes [FeL(X)] (L = 1-alkyl-4,7-bis(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane,X = Cl,CH(3)O,CN, NO). The S = 1/2 <==>3/2 Spin equilibrium of [FeL(Pr)(NO)

Two new pentadentate, pendent arm macrocyclic ligands of the type 1-alkyl-4,7-bis(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane where alkyl represents an isopropyl, (L(Pr))(2-), or an ethyl group, (L(Et))(2-), have been synthesized. It is shown that they bind strongly to ferric ions generating six-coordinate species of the type [Fe(L(alk))X]. The ground state of these complexes is governed by the nature of the sixth ligand, X: [Fe(III)(L(Et))Cl] (2) possesses an S = 5/2 ground state as do [Fe(III)(L(Et))(OCH(3))] (3) and [Fe(III)(L(Pr))(OCH(3))] (4). In contrast, the cyano complexes [Fe(III)(L(Et))(CN)] (5) and [Fe(III)(L(Pr))(CN)] (6) are low spin ferric species (S = 1/2). The octahedral [FeNO](7) nitrosyl complex [Fe(L(Pr))(NO)] (7) displays spin equilibrium behavior S = 1/2<==>S = (3)/(2) in the solid state. Complexes [Zn(L(Pr))] (1), 4.CH(3)OH, 5.0.5toluene.CH(2)Cl(2), and 7.2.5CH(2)Cl(2) have been structurally characterized by low-temperature (100 K) X-ray crystallography. All iron complexes have been carefully studied by zero- and applied-field M?ssbauer spectroscopy. In addition, Sellmann's complexes [Fe(pyS(4))(NO)](0/1+) and [Fe(pyS(4))X] (X = PR(3), CO, SR(2)) have been studied by EPR and M?ssbauer spectroscopies and DFT calculations (pyS(4) = 2,6-bis(2-mercaptophenylthiomethyl)pyridine(2-)). It is concluded that the electronic structure of 7 with an S = 1/2 ground state is low spin ferrous (S(Fe) = 0) with a coordinated neutral NO radical (Fe(II)-NO) whereas the S = 3/2 state corresponds to a high spin ferric (S(Fe) = 5/2) antiferromagnetically coupled to an NO(-) anion (S = 1). The S = 1/2<==>S = 3/2 equilibrium is then that of valence tautomers rather than that of a simple high spin<==>low spin crossover.     

Topological sensitivity of energy cost functional for wave-based defect identification

This article is concerned with establishing the topological sensitivity (TS) against the nucleation of small trial inclusions of an energy-like cost function. The latter measures the discrepancy between two time-harmonic elastodynamic states (respectively defined, for cases where overdetermined boundary data is available for identification purposes, in terms of Dirichlet or Neumann boundary data for the same reference solid) as the strain energy of their difference. Such cost function constitutes a particular form of error in constitutive relation and may be used for e.g. defect identification. The TS is expressed in terms of four elastodynamic fields, namely the free and adjoint solutions for Dirichlet or Neumann data. A similar result is also given for the linear acoustic scalar case. A synthetic numerical example where the TS result is used for the qualitative identification of an inclusion is presented for a simple 2D acoustic configuration.     

Experimental characterization of an Yb-doped fiber ring laser with frequency-shifted feedback

We present experimental characteristics of an Yb³⁺-doped fiber ring laser operating with frequency-shifted feedback (FSF) through an acousto-optic modulator (AOM) and seeded by both a stationary continuous-wave (CW) laser and spontaneous emission. We show the spectrum and output characteristics for operations with several effective gain bandwidths, as established by Fabry-Perot etalons inside the cavity. Observation using a high finesse Fabry-Perot interferometer shows that, as expected from earlier work, although the spectrum of the FSF laser without seeding is continuous, when seeded by a CW-laser the spectrum consists of a comb of discrete modes, each offset from the seed by an integer number of AOM frequency shifts. The experimental results are in excellent quantitative agreement with the theory developed earlier [L. Yatsenko, B.W. Shore, K. Bergmann, Opt. Commun. 236 (2004) 183].     

Electronic properties and band structure of IrSe2

Transport coefficient measurements (DC conductivity and thermoelectric power) were performed on compacted bars of polycrystalline IrSe₂ in the 100–570 K temperature range. The experimental results are interpeted on the basis of an n-type compensated semiconductor model. At low temperatures, a narrow band which originates from non-stoichiometry mainly participates in the conduction by thermally activated hopping of small polarons. The charge balance adopted by anionic groups is discussed. The schematic band model which is retained takes into account all the transport properties and the ion charge balance Ir³⁺Se^2-(Se₂)^2-_{1/ 2}. Moreover, IrSe₂ has recently been shown to function as a cathode material in lithium batteries.     

Ruthenium-Decorated Lipid Vesicles: Light-Induced Release of [Ru(terpy)(bpy)(OH(2))](2+) and Thermal Back Coordination

Electrostatic forces play an important role in the interaction between large transition metal complexes and lipid bilayers. In this work, a thioether-cholestanol hybrid ligand (4) was synthesized, which coordinates to ruthenium(II) via its sulfur atom and intercalates into lipid bilayers via its apolar tail. By mixing its ruthenium complex [Ru(terpy)(bpy)(4)](2+) (terpy = 2,2';6',2'-terpyridine; bpy = 2,2'-bipyridine) with either the negatively charged lipid dimyristoylphosphatidylglycerol (DMPG) or with the zwitterionic lipid dimyristoylphosphatidylcholine (DMPC), large unilamellar vesicles decorated with ruthenium polypyridyl complexes are formed. Upon visible light irradiation the ruthenium-sulfur coordination bond is selectively broken, releasing the ruthenium fragment as the free aqua complex [Ru(terpy)(bpy)(OH(2))](2+). The photochemical quantum yield under blue light irradiation (452 nm) is 0.0074(8) for DMPG vesicles and 0.0073(8) for DMPC vesicles (at 25 °C), which is not significantly different from similar homogeneous systems. Dynamic light scattering and cryo-TEM pictures show that the size and shape of the vesicles are not perturbed by light irradiation. Depending on the charge of the lipids, the cationic aqua complex either strongly interacts with the membrane (DMPG) or diffuses away from it (DMPC). Back coordination of [Ru(terpy)(bpy)(OH(2))](2+) to the thioether-decorated vesicles takes place only at DMPG bilayers with high ligand concentrations (25 mol %) and elevated temperatures (70 °C). During this process, partial vesicle fusion was also observed. We discuss the potential of such ruthenium-decorated vesicles in the context of light-controlled molecular motion and light-triggered drug delivery.