The use of bone grafts permits the filling of a bone defect without risk of virus transmission. In this work, pure bioactive glass (46S6) and zinc-doped bioactive glass (46S6Zn10) with 0.1 wt% zinc are used to elaborate highly bioactive materials by melting and rapid quenching. Cylinders of both types of glasses were soaked in a simulated body fluid (SBF) solution with the aim of determining the effect of zinc addition as a trace element on the chemical reactivity and bioactivity of glass. Several physico-chemical characterization methods such as x-ray diffraction, Fourier transform infrared spectroscopy and nuclear magnetic resonance methods, with particular focus on the latter, were chosen to investigate the fine structural behaviour of pure and Zn-doped bioactive glasses as a function of the soaking time of immersion in SBF. Inductively coupled plasma-optical emission spectroscopy (ICP-OES) was used to measure the concentrations of Ca and P ions in the SBF solution after different durations of immersion. The effect of the investigated samples on the proliferation rate of human osteoblast cells was assessed by the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay, and tested on two different sizes of pure and zinc-doped glasses in powder form, with particle sizes that ranged between 40 to 63 µm and 500 to 600 µm. The obtained results showed the delay release of ions by Zn-doped glass (46S6Zn10) and the slower CaP deposition. Cytotoxicity and cell viability were affected by the particle size of the glass. The release rate of ions was found to influence the cell viability.

International audienceA series of thin-film n-channel organic field-effect transistors based on various birhodanines, 3,3'-dialkyl-5,5'-bithiazolidinylidene-2,2'-dione-4,4'-dithiones (OS-R) and their sulfur analogues, 3,3'-dialkyl-5,5'-bithiazolidinylidene-2,4,2',4'-tetrathiones (SS-R) are studied. The SS-R compounds have tilted stacking crystal structures, whereas the OS-R compounds show basically herringbone structures. The alkyl chain R length and the intermolecular S-S interactions influence the molecular packing to realize excellent long-term air stability in the thin-film transistors

The embedding of functional inorganic entities into polymer matrices has become an intense field of investigation in which the main challenges are to keep the added value of the inorganic entities while preventing their self-aggregation within the organic matrix. We present a simple way to obtain a homogeneous highly red-NIR luminescent hybrid copolymer that contains covalently bonded nanometric-sized {Re(6)} octahedral clusters. The [Re(6)Se(i)(8)(OH)(a)(6)](4-) cluster complexes are primarily functionalized in two steps with tert-butylpyridine (TBP) and methacrylic acid (MAC) to give neutral [Re(6)Se(8)(TBP)(4)(MAC)(2)] building blocks that are copolymerized with methyl methacrylate (MMA) either in solution or in bulk in the presence of azobisisobutyronitrile as an initiator. Several samples containing 0, 0.025, 0.05, and 0.1 wt % of functionalized {Re(6)} clusters were prepared. As the {Re(6)} cluster/MMA ratio is very low, the obtained copolymers keep the entire processability of pure poly(methyl methacrylate) (PMMA), as demonstrated by differential scanning calorimetry and thermogravimetric analysis. Voltammetric and luminescence studies also indicate that the intrinsic properties of the clusters are preserved within the polymer matrix. All the samples show a bright (emission quantum yield=0.07), broad, and structureless emission band, which extends from lambda=600 nm to more than lambda=950 nm, with the maximum wavelength centered around lambda(em)=710 nm either in solution or in the solid state. Moreover, the high stability of the incorporated inorganic phosphors prevents the material from photobleaching, and thus the luminescence properties are kept entirely even after nine months of ageing.

A new trimethyltetrathiafulvalene (Me3TTF) derivative Me3TTF-CH=CH-py bearing a pyridyl was synthesized and coordinated to a cobalt(II) benzoate dimer, having paddlewheel core structure, leading to a complex formulated as Co2(PhCOO)4(Me3TTF-CH=CH-py)2. Single-crystal X-ray diffraction studies of the complex performed at 293 and 100 K evidenced the existence of a weak metal-metal interaction. Magnetic studies revealed an antiferromagnetic behavior, which is explained as the result of the direct exchange between metal centers.

The tetrathiafulvalene-amido-2-pyridine-N-oxide (L) ligand has been employed to coordinate 4f elements. The architecture of the complexes mainly depends on the ionic radii of the lanthanides. Thus, the reaction of L in the same experimental protocol leads to three different molecular structure series. Binuclear [Ln(2)(hfac)(5)(O(2)CPhCl)(L)(3)]·2 H(2)O (hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate anion, O(2)CPhCl(-)=3-chlorobenzoate anion) and mononuclear [Ln(hfac)(3)(L)(2)] complexes were obtained by using rare-earth ions with either large (Ln(III)=Pr, Gd) or small (Ln(III)=Y, Yb) ionic radius, respectively, whereas the use of Tb(III) that possesses an intermediate ionic radius led to the formation of a binuclear complex of formula [Tb(2)(hfac)(4)(O(2)CPhCl)(2)(L)(2)]. Antiferromagnetic interactions have been observed in the three dinuclear compounds by using an extended empirical method. Photophysical properties of the coordination complexes have been studied by solid-state absorption spectroscopy, whereas time-dependent density functional theory (TD-DFT) calculations have been carried out on the diamagnetic Y(III) derivative to build a molecular orbital diagram and to reproduce the absorption spectrum. For the [Yb(hfac)(3)(L)(2)] complex, the excitation at 19,600 cm(-1) of the HOMO→LUMO+1/LUMO+2 charge-transfer transition induces both line-shape emissions in the near-IR spectral range assigned to the (2)F(5/2)→(2)F(7/2) (9860 cm(-1)) ytterbium-centered transition and a residual charge-transfer emission around 13,150 cm(-1). An efficient antenna effect that proceeds through energy transfer from the singlet excited state of the tetrathiafulvalene-amido-2-pyridine-N-oxide chromophore is evidence of the Yb(III) sensitization.

A Dy(III)-based dinuclear complex was synthesised and characterised by X-ray diffraction on single crystal and magnetic investigations. Dynamic magnetic measurements reveal a single molecule magnet behaviour for 1 which can be described as two single-ion magnets in a D(3h) local symmetry bridged by an acceptor-donor-acceptor ligand.

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The reactions between the [Ln(tta)(3)]·2H(2)O precursors (tta(-)=2-thenoyltrifluoroacetonate anion) and the tetrathiafulvalene-3-pyridine-N-oxide ligands (L(1)) lead to dinuclear complexes of formula [{Ln(tta)(3)(L(1))}(2)]·xCH(2)Cl(2) (x=0.5 for Ln=Dy(III) (1) and x=0 for Ln=Gd(III) (2)). The crystal structure reveals that two {Ln(tta)(3)} moieties are bridged by two donors through the nitroxide groups. The Dy(III) centre adopts a distorted square antiprismatic oxygenated polyhedron structure. The antiferromagnetic nature of the exchange interaction between the two Dy(III) ions has been determined by two methods: 1) an empirical method using the [Dy(hfac)(3)(L(2))(2)] mononuclear complex as a model (3) (hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate anion, L(2)=tetrathiafulvaleneamido-2-pyridine-N-oxide ligand), and 2) assuming an Ising model for the Dy(III) ion giving an exchange energy of -2.30 cm(-1), g=19.2 in the temperature range of 2-10 K. The antiferromagnetic interactions have been confirmed by a quantitative determination of J for the isotropic Gd(III) derivative (J=-0.031 cm(-1), g=2.003). Compound 1 displays a slow magnetisation relaxation without applied external magnetic fields. Alternating current susceptibility shows a thermally activated behaviour with pre-exponential factors of 5.48(4)×10(-7) s and an energy barrier of 87(1) K. The application of an external field of 1.6 kOe compensates the antiferromagnetic interactions and opens a new quantum tunnelling path.