Acylsilane Directed Rh-Catalyzed Arene C-H Alkylation with Maleimides and Visible-Light-Induced Siloxycarbene-Amide Cyclization: [3 + 2] Carbo-Annulation in Ru Catalysis.

We herein demonstrate the acylsilane-directed Rh-catalyzed arene C-H bond alkylation with maleimides. The resulting derivatives were utilized in visible-light-induced intramolecular siloxycarbene-amide cyclization for the synthesis of new tricyclic γ-lactams. In parallel, we also harnessed the same acylsilane and maleimide units through [3 + 2] carbo-annulation by using Ru-catalysis.

A Blue Diketopyrrolopyrrole Sensitizer with High Efficiency in Nickel-Oxide-based Dye-Sensitized Solar Cells.

We prepared a series of four new diketopyrrolopyrroles (DPPs)-based sensitizers that exhibit high-molar extinction coefficients, extended absorption into the long wavelengths, and well-suited photoredox properties to act as sensitizers in p-type dye-sensitized solar cells (p-DSSCs). These new DPP dyes, composed of a thienyl DPP core, are substituted on one end either by a thiophene carboxylic (Th) or a 4,4'-[(phenyl)aza]dibenzoic acid as anchoring group and, on the other extremity, either by a proton or a naphthalene diimide (NDI) moiety. These new dyes were completely characterized by absorption and emission spectroscopy along with electrochemistry and they were modeled by time-dependent DFT (TD-DFT) quantum chemical calculations.

Is energy transfer limiting multiphotochromism? answers from ab initio quantifications.

Dithienylethenes (DTEs) can be assembled to form supramolecular multiphotochromic systems that are highly functional molecular architectures of potential interest for building complex optoelectronic devices. Yet even simple DTE dimers relying on an organic linker may suffer from a partial photoactivity, i.e.

Singlet oxygen generation properties of isometrically dibromated thienyl-containing aza-BODIPYs.

Isometrically dibromated thienyl-containing aza-BODIPYs CDB-1 and BDB-2 with potential use as photosensitizers (PSs) were successfully prepared and their photophysical properties were fully characterized. Singlet oxygen generation experiments were also performed. In this regard, PS CDB-1 was found to be more effective and had about two-fold rate enhancement compared to PS BDB-2.

All-solid all-chalcogenide microstructured optical fiber.

The realization of an all-solid microstructured optical fiber based on chalcogenide glasses was achieved. The fiber presents As(2)S(3) inclusions selected as low refractive index material (n = 2.4) embedded in a As(38)Se(62) glass matrix (n = 2.

Ruthenium-catalysed synthesis of functional conjugated dienes from propargylic carbonates and silyl diazo compounds.

Ru being served? The reactions of propargylic carbonates with silyl diazo compounds in the presence of [Cp*RuCl(cod)] as a catalyst precursor led to the formation of dienyl carbonates in excellent yields under mild conditions (see scheme; Y = SiMe(3)).

Optical amplification of Pr3+ -doped ZBLA channel waveguides for visible Laser emission.

We report on the first observation of optical signal amplification in the visible range into praseodymium doped ZBLA glass channel waveguides obtained by ion exchange. Up to 30% signal amplification was obtained at 639 nm. This result shows the potential of rare earth doped fluoride glasses in the form of channel waveguides for integrated solid state visible laser sources.

Structure-activity relationship of selected polyphenol derivatives as inhibitors of Bax/Bcl-xL interaction.

This paper describes the synthesis of nine selected diaryl/heteroaryl-containing phenol and polyphenol derivatives which have been evaluated against Bax/Bcl-xL interaction in comparison with ABT-737. Using a BRET assay, six of these derivatives exhibit activity comparable to ABT-737 to disrupt Bax/Bcl-xL interaction. These preliminary results demonstrate that such polyphenol-derived molecules are attractive compounds regarding anticancer activity and that the phenol at position 3 is important regarding disruption of Bax/Bcl-xL interaction.

Allosterically driven self-assemblies of interlocked calix[6]arene receptors.

The construction of self-assembled receptors based on flexible concave subunits is a challenging task and constitutes an interesting approach to mimic binding processes occurring in biological systems. The receptors studied herein are based on flexible calix[6]arene skeletons bearing three (or more) acid-base functionalities at their narrow rim. When complementary, they self-assemble in a tail-to-tail manner to give a diabolo-like complex, provided that each calixarene subunit hosts a guest.

Structural characterization of zinc and iron (II/III) complexes of a porphyrin bearing two built-in nitrogen bases. An example of high-spin diaqua-iron(III) bromo complex.

A bis-strapped porphyrin with two intramolecular nitrogen bases was synthesized, and its zinc(II), iron(II), and iron(III) complexes have been structurally characterized. Whereas the zinc(II) complex is square pyramidal five-coordinate and the iron(II) complex is six-coordinate despite a significant distortion of the macrocycle induced by the rigidity of the straps, the iron(III) complex exhibits a peculiar bis-aqua structure in which no intramolecular axial base is bound to the iron atom in the porphyrin. Furthermore, on one side, the bromide counteranion of the iron is bound inside the cycle formed by a strap and establishes a hydrogen bond with an axially bound water molecule.

Characterization of a six-coordinate ferrous high-spin heme with both intramolecular axial carboxylic acid and pyridine.

Synthesis of a bis-strapped porphyrin with a pyridyl residue on one side and a malonic acid on the other side gives after iron(II) insertion a six-coordinate complex in which both apical groups are the two axial ligands of the iron atom. Unexpectedly, this six-coordinate iron(II) complex proves to be high-spin, likely due to some stabilization of the axial metal-ligand antibonding orbitals.

Steric decompression of picket-strapped porphyrins for the synthesis of side-differentiated chelates.

A general method to synthesize various alphabeta alphabeta bis-strapped porphyrins, with a different functionalization on each side of the macrocycle, is described. The resulting new chelates may find applications as analogues of heme protein active sites, bifunctional chelates, or specific bis-chelating molecules with potential medical utility.

Coordination of bismuth and lead in porphyrins: towards an in-situ generator for alpha-radiotherapy?

In order to investigate the possible coordination of both bismuth(III) and lead(II) by porphyrins for an application in alpha-radioimmunotherapy, several series of functionalized bismuth porphyrins have been synthesized and their stabilities in acidic medium were compared. Where unfunctionalized porphyrins are not suitable for such a purpose, strapped hanging carboxylate porphyrins are stable and allow a rapid coordination of both bismuth and lead. This property could lead to the preparation of an in-situ generator of alpha particles by a pre-complexation of (212)lead, the radioactive parent of (212)bismuth, in the ligand.

Lattice dynamics to trigger low temperature oxygen mobility in solid oxide ion conductors.

SrFeO(2.5) and SrCoO(2.5) are able to intercalate oxygen in a reversible topotactic redox reaction already at room temperature to form the cubic perovskites Sr(Fe,Co)O(3), while CaFeO(2.

Efficient and versatile synthesis of new porphyrins bearing an N3O moiety: ligands for mimicking cytochrome c oxidase.

Two new generations of ligands for cytochrome c oxidase mimicking have been designed and synthesized via an efficient, convergent, and versatile synthesis. These porphyrins are functionalized with both an internal nitrogen base on one side and a triaza (N3) or a triaza-phenol (N3O) moiety on the other side, attached to the macrocycle by various spacers. Unlike tailed porphyrins, the triaza motif as well as the nitrogen base are linked by two points.

Comparison of the bony remodelling of two synthetic biomaterials: aragonite 55% and aragonite 55% with active substance.

In this work, the in vivo behaviour of pure aragonite and vectabone, which is an association of aragonite and an active substance such as gentamicin, was studied to highlight the kinetic resorption of these two biomaterials with 55% of porosity destined for the filling or replacement of bony defects. The synthesis conditions and parameters we used permit us to obtain a biomaterial without a sintering stage. These conditions allow introducing of active substances at the first stage of the elaboration.

Aluminosilicates and biphasic HA-TCP composites: studies of properties for bony filling.

Aluminosilicate materials synthesized at room temperature present good mechanical properties. Hydroxyapatite, tricalcium phosphate or both offer a high biocompatibility in the biomedical field. In this work, we focused on the composites resulting from associations of these materials.

Nonlinear optical and two-photon absorption properties of octupolar tris(bipyridyl)metal complexes.

The linear (absorption and emission) and nonlinear optical (NLO) properties of a series of D(3) [(Fe(II), Ru(II), Ni(II), Cu(II), Zn(II)] octupolar metal complexes featuring the 4,4'-bis[(dibutylamino)styryl]-2,2'-bipyridine ligand are reported. Zinc(II), nickel(II), and copper(II) complexes exhibit similar absorption spectra in the visible region (lambda(ILCT) = 474-476 nm) which are assigned to intraligand charge-transfer (ILCT) bands. The quadratic and cubic NLO properties are strongly influenced by the nature of the metallic center.

Dioxygen binding of water-soluble iron(II) porphyrins in phosphate buffer at room temperature.

Two water-soluble tris(2-aminoethylamine) (tren) capped iron porphyrins were synthesized. The stability of their dioxygen adducts was studied in phosphate buffer, leading to half-life times around 7 min for the oxygenated species.