New Synthetic Routes towards Soluble and Dissymmetric Triphenodioxazine Dyes Designed for Dye‐Sensitized Solar Cells

New π‐conjugated structures are constantly the subject of research in dyes and pigments industry and electronic organic field. In this context, the triphenodioxazine (TPDO) core has often been used as efficient photostable pigments and once integrated in air stable n‐type organic field‐effect transistor (OFET). However, little attention has been paid to the TPDO core as soluble materials for optoelectronic devices, possibly due to the harsh synthetic conditions and the insolubility of many compounds. To benefit from the photostability of TPDO in dye‐sensitized solar cells (DSCs), an original synthetic pathway has been established to provide soluble and dissymmetric molecules applied to a suitable design for the sensitizers of DSC. The study has been pursued by the theoretical modeling of opto‐electronic properties, the optical and electronic characterizations of dyes and elaboration of efficient devices. The discovery of new synthetic pathways opens the way to innovative designs of TPDO for materials used in organic electronics.     

Reduction of electroactive polymers via polyelectron transfer processes at solid electrodes

The reduction of an electroactive polymer at an electrode involves the transfer of a large number of electrons to a single molecule. A quantitative study of this process indicates whether the system behaves ideally. The electron transfer process in polyvinylbenzophenone and in polyvinylbenzophenone-co-styrene in N,N-dimethylformamide solution was investigated by voltammetry at a rotating disk electrode. It is concluded that benzophenone (BP) groups attached to the polymer backbone are noninteracting electroactive centers and that every BP group is reducible at the electrode. The relationship between limiting current and molecular weight was examined quantitatively for a series of polymers of low dispersity with molecular weights ranging up to 300,000, and with a controlled, varied content of electroactive groups. The diffusion coefficient was determined as a function of molecular weight from the electrochemical data, and was found to be in good agreement with the theoretical model based on transport properties. The dependence of the diffusion coefficient on concentration of polymer and on temperature were investigated and activation energies determined.     

Density functional theory and post-Hartree-Fock studies on molecular structure and harmonic vibrational spectrum of formaldehyde

Density functional theory (DFT) with the Becke's three-parameter exchange correlation functional and the functional of Lee, Yang and Parr, gradient-corrected functionals of Perdew, and Perdew and Wang [the DFT(B3LYP), DFT(B3P86) and DFT(B3PW91) methods, respectively], and several levels of conventional ab initio post-Hartree-Fock theory (second- and fourth-order perturbation theory M?ller-Plesset MP2 and MP4(SDTQ), coupled cluster with the single and double excitations (CCSD), and CCSD with perturbative triple excitation [CCSD(T)], configuration interaction with the single and double excitations [CISD], and quadratic configuration interaction method [QCISD(T)], using several basis sets [ranging from a simple 6-31G(d,p) basis set to a 6-311+ +G(3df, 2pd) one], were applied to study of the molecular structure (geometrical parameters, rotational constants, dipole moment) and harmonized infrared (IR) spectrum of formaldehyde (CH₂O). High-level ab initio methods CCSD(T) and QCISD(T) with the 6-311+ +G(3df, 2pd) predict correctly molecular parameters, vibrational harmonic wavenumbers and the shifts of the harmonic IR spectrum of ¹²CH₂ ¹⁶O upon isotopic substitution. Received: 30 January 1997 / Accepted: 7 May 1997     

Stable DOPG/Glycyrrhizin Vesicles with a Wide Range of Mixing Ratios: Structure and Stability as Seen by Scattering Experiments and Cryo-TEM

Phosphatidylglycerols represent a large share of the lipids in the plasmamembrane of procaryotes. Therefore, this study investigates the role of charged lipids in the plasma membrane with respect to the interaction of the antiviral saponin glycyrrhizin with such membranes. Glycyrrhizin is a natural triterpenic-based surfactant found in licorice. Vesicles made of 1,2-dioleoyl-sn-glycero-3-phospho-rac-(1’-glycerol) (DOPG)/glycyrrhizin are characterized by small-angle scattering with neutrons and X-rays (SANS and SAXS). Small-angle scattering data are first evaluated by the model-independent modified Kratky–Porod method and afterwards fitted by a model describing the shape of small unilamellar vesicles (SUV) with an internal head-tail contrast. Complete miscibility of DOPG and glycyrrhizin was revealed even at a ratio of lipid:saponin of 1:1. Additional information about the chain-chain correlation distance of the lipid/saponin mixtures in the SUV structures is obtained from wide-angle X-ray scattering (WAXS).     

Convex sweeping process in the framework of measure differential inclusions and evolution variational inequalities

In this paper, we analyze and discuss the well-posedness of two new variants of the so-called sweeping process, introduced by Moreau in the early 70s (Moreau in Sém Anal Convexe Montpellier, 1971) with motivation in plasticity theory. The first new variant is concerned with the perturbation of the normal cone to the moving convex subset \(C(t)\) , supposed to have a bounded variation, by a Lipschitz mapping. Under some assumptions on the data, we show that the perturbed differential measure inclusion has one and only one right continuous solution with bounded variation. The second variant, for which a large analysis is made, concerns a first order sweeping process with velocity in the moving set \(C(t)\) . This class of problems subsumes as a particular case, the evolution variational inequalities [widely used in applied mathematics and unilateral mechanics (Duvaut and Lions in Inequalities in mechanics and physics. Springer, Berlin, 1976]. Assuming that the moving subset \(C(t)\) has a continuous variation for every \(t\in [0,T]\) with \(C(0)\) bounded, we show that the problem has at least a Lipschitz continuous solution. The well-posedness of this class of sweeping process is obtained under the coercivity assumption of the involved operator. We also discuss some applications of the sweeping process to the study of vector hysteresis operators in the elastoplastic model (Krej?? in Eur J Appl Math 2:281–292, 1991), to the planning procedure in mathematical economy (Henry in J Math Anal Appl 41:179–186, 1973 and Cornet in J. Math. Anal. Appl. 96:130–147, 1983), and to nonregular electrical circuits containing nonsmooth electronic devices like diodes (Acary et al. Nonsmooth modeling and simulation for switched circuits. Lecture notes in electrical engineering. Springer, New York 2011). The theoretical results are supported by some numerical simulations to prove the efficiency of the algorithm used in the existence proof. Our methodology is based only on tools from convex analysis. Like other papers in this collection, we show in this presentation how elegant modern convex analysis was influenced by Moreau’s seminal work.     

A Turning-Band Method for the Simulation of Anisotropic Fractional Brownian Fields

In this article, we propose a method for simulating realizations of two-dimensional anisotropic fractional Brownian fields (AFBF) introduced by Bonami and Estrade. The method is adapted from a generic simulation method called the turning-band method (TBM) due to Matheron. The TBM reduces the problem of simulating a field in two dimensions by combining independent processes simulated on oriented bands. In the AFBF context, the simulation fields are constructed by discretizing an integral equation arising from the application of the TBM to nonstationary anisotropic fields. This guarantees the convergence of simulations as the step of discretization is decreased. The construction is followed by a theoretical study of the convergence rate (the detailed proofs are available in the online supplementary materials). Another key feature of this work is the simulation of band processes. Using self-similarity properties, processes are simulated exactly on bands with a circulant embedding method, so that simulation errors are exclusively due to the field approximation. Moreover, we design a dynamic programming algorithm that selects band orientations achieving the optimal trade-off between computational cost and precision. Finally, we conduct a numerical study showing that the approximation error does not significantly depend on the regularity of the fields to be simulated, nor on their degree of anisotropy. Experiments also suggest that simulations preserve the statistical properties of the original field.     

Speeding-up structured probabilistic inference using pattern mining

In many domains where experts are the main source of knowledge, e.g., in reliability and risk management, a framework well suited for modeling, maintenance and exploitation of complex probabilistic systems is essential. In these domains, models usually define closed-world systems and result from the aggregation of multiple patterns repeated many times. Object Oriented-based Frameworks such as Probabilistic Relational Models (PRM) thus offer an effective way to represent such systems. They define patterns as classes and substitute large Bayesian networks (BN) by graphs of instances of these classes. In this framework, Structured Inference avoids many computation redundancies by exploiting class knowledge, hence reducing BN inference times by orders of magnitude. However, to keep modeling and maintenance costs low, object oriented-based framework’s classes often encode only generic situations. More complex situations, even those repeated many times, are only represented by combinations of instances. In this paper, we propose to determine online such combination patterns and exploit them as classes to speed-up Structured Inference. We prove that determining an optimal set of patterns is NP-hard. We also provide an efficient algorithm to approximate this set and show numerical experiments that highlight its practical efficiency.     

Pyrromethene–BF2 complexes as laser dyes:1.

Condensations between 3-X-2,4-dimethylpyrroles (X = H, CH₃, C₂H₅, and CO₂C₂H₅) and acyl chlorides gave derivatives of 3,5,3′,5′-tetramethylpyrromethene (isolated as their hydrochloride salts): 6-methyl, 6-ethyl, 4,4′,6-trimethyl, 4,4′-diethyl-6-methyl, and 4,4′-dicarboethoxy-6-ethyl derivatives for conversion on treatment with boron trifluoride to 1,3,5,7-tetramethylpyrromethene–BF₂ complex (TMP–BF₂) and its 8-methyl (PMP–BF₂), 8-ethyl, 2,6,8-trimethyl (HMP–BF₂),2,6,-diethyl-8-methyl (PMDEP–BF₂), and 2,6-dicarboethoxy-8-ethyl derivatives. Chlorosulfonation converted, 1,3,5,7,8-pentamethylpyrromethene–BF₂ complex to its 2,6-disulfonic acid isolated as the lithium, sodium (PMPDS–BF₂), potassium, rubidium, cesium, ammonium, and tetramethylammonium disulfonate salts and the methyl disulfonate ester. Sodium 1,3,5,7-tetramethyl-8-ethylpyrromethene-2,6-disulfonate–BF₂ complex was obtained from the 8-ethyl derivative of TMP–BF₂. Nitration and bromination converted PMP–BF₂ to its 2,6-dinitro-(PMDNP–BF₂) and 2,6-dibromo- derivatives. The time required for loss of fluorescence by irradiation from a sunlamp showed the following order for P–BF₂ compounds (10⁻³ to 10⁻⁴ M) in ethanol: PMPDS–BF₂, 7 weeks; PMP–BF₂, 5 days; PMDNP–BF₂, 72 h; HMP–BF₂, 70 h; and PMDEP–BF₂, 65 h. Under similar irradiation PMPDS–BF₂ in water lost fluorescence after 55 h. The dibromo derivative was inactive, but each of the other pyrromethene–BF₂ complexes under flashlamp excitation showed broadband laser activity in the region λ 530–580 nm. In methanol PMPDS–BF₂ was six times more resistant to degradation by flashlamp pulses than was observed for Rhodamine-6G (R-6G). An improvement (up to 66%) in the laser power efficiency of PMPDS–BF₂ (10⁻⁴ M in methanol) in the presence of caffeine (a filter for light <300 nm) was dependent on flashlamp pulse width (2.0 to 7.0 μsec).