Nickel and cobalt hexamethylentetramine complexes (NO3)2Me(H2O)6(HMTA)2.4H2O (Me = Co2+, Ni2+): new molecular precursors for the preparation of metal dispersions

Nickel and cobalt hexamethylenetetramine (HMTA) complexes (NO3)2Me(H2O)6(HMTA)2.4H2O were prepared and characterized structurally by single-crystal X-ray diffraction. Both compounds crystallize in the triclinic P1 space group with the same structure. The structures are three-dimensional hydrogen-bonded supramolecular frameworks containing two-dimensional cationic assemblies connected with proton acceptors, which are noncoordinated anionic species (nitrate) and neutral HMTA molecules. Thermal decomposition of these compounds under an inert atmosphere leads to the high-surface-area metal-carbon foams containing nickel and cobalt nanoparticles embedded within onionlike carbon shells. The decomposition process as studied by thermal analysis and in situ X-ray absorption spectroscopy (XAS) measurements occurs as a rapid loss of oxygen in the form of CO, beginning at temperatures as low as 323 K. As the in situ XAS study demonstrated, the evolution of nickel and cobalt coordination spheres occurs with intermediate formation of amorphous metal carbides, which subsequently decompose to the metal nanoparticles covered with carbon shells.     

Zirconium nitrides deposited by dual ion beam sputtering: physical properties and growth modelling

Zirconium nitrides reveal interesting optical and electrical properties which highly depend on the nitrogen stoichiometry. Indeed, the material exhibits a transition from the stable metallic ZrN (optical index for bulk at 633 nm: N=0.5−i3.2) to the metastable semi-transparent insulating Zr₃N₄ (N=3.2−i0.4). This work deals with the elaboration of homogeneous ZrN-like and Zr₃N₄-like coatings. These have been prepared using reactive Dual Ion Beam Sputtering (DIBS) using a Zr target and N₂ or N₂+Ar reactive gas. The influence of different elaboration parameters (ion energy, gas composition of the reactive beam and substrate temperature) on the nitrides composition and on their optical and electrical properties was particularly studied. A model was proposed to explain the influence of energy and temperature on the nitrogen composition. The nitrogen stoichiometry was shown to be controlled by a competitive mechanism between implantation of excess nitrogen amount in the subsurface and their elimination by exodiffusion. The first phenomenon is mainly controlled by the ion energy whereas the second one is enhanced by a high temperature and a high irradiation defects density. Therefore, the Zr₃N₄-like nitrides were obtained with low temperature and high energy (200 eV) conditions whereas high temperature and low energy led to ZrN-like materials.     

Trinuclear Cyanido-Bridged [Cr2Fe] Complexes: To Be or not to Be a Single-Molecule Magnet,a Matter of Straightness

Trinuclear systems of formula [{Cr(L^N3O2Ph)(CN)₂}₂M(H₂L^N3O2R)] (M=Mn^II and Fe^II, L^N3O2R stands for pentadentate ligands) were prepared in order to assess the influence of the bending of the apical M−N≡C linkages on the magnetic anisotropy of the Fe^II derivatives and in turn on their Single-Molecule Magnet (SMM) behaviors. The cyanido-bridged [Cr₂M] derivatives were obtained by assembling trans-dicyanido Cr^III complex [Cr(L^N3O2Ph)(CN)₂]⁻ and divalent pentagonal bipyramid complexes [M^II(H₂L^N3O2R)]²⁺ with various R substituents (R=NH₂, cyclohexyl, S,S-mandelic) imparting different steric demand to the central moiety of the complexes. A comparative examination of the structural and magnetic properties showed an obvious effect of the deviation from straightness of the M−N≡C alignment on the slow relaxation of the magnetization exhibited by the [Cr₂Fe] complexes. Theoretical calculations have highlighted important effects of the bending of the apical C−N−Fe linkages on both the magnetic anisotropy of the Fe^II center and the exchange interactions with the Cr^III units.     

Influence of argon-implantation on conventional and phototransferred thermoluminescence of synthetic quartz

Conventional and phototransferred thermoluminescence of crystalline synthetic quartz implanted with 70 keV Ar ions at fluences in the range 1?×?10¹⁴–5?×?10¹⁵?ions/cm² is reported. The glow curves, recorded at 5°C/s from beta-irradiated samples of similar mass, show a prominent peak between 100°C and 120°C. The thermoluminescence intensity of all implanted samples was greater than that of the unimplanted one. The increase in sensitivity is attributed to a corresponding increase in the concentration of point defects, as a result of the implantation, which act as electron traps or recombination centres. Kinetic analysis carried out using the peak shape, whole glow-peak and curve-fitting methods produced values of the activation energy, frequency factor and order of kinetics that are generally independent of implantation fluence. This result suggests that implantation did not necessarily affect the nature of the electron traps. With respect to phototransferred thermoluminescence, it was observed that it only appeared in the sample implanted at the highest fluence of 5?×?10¹⁵?ions/cm². This may be so because the concentration of deep traps produced as a result of implantation at low fluence is too low to give rise to phototransferred thermoluminescence. The intensity of the phototransferred thermoluminescence goes through a peak with illumination time. We attribute this behaviour to the relative concentration of holes at recombination centres and phototransferred electrons at shallow traps.     

Advanced preparation of functionalized triarylbismuths and triheteroaryl-bismuths: new scope and alternatives

A simple and versatile novel method for the preparation of triaryl- and trihetero-arylbismuths bearing electron withdrawing or electron donating groups was accomplished by the reaction of organozinc reagents with BiCl₃. Scope and limits of the process are investigated.     

Octa- and nonanuclear nickel(II) polyoxometalate clusters: synthesis and electrochemical and magnetic characterizations

Three high-nuclearity NiII-substituted polyoxometalate compounds functionalized by exogenous ligands have been synthesized and characterized. The octanuclear complexes in Na15[Na{(A-R-SiW9O34)Ni4(CH3COO)3(OH)3}2] . 4NaCl . 36H2O (1) and Na15[Na{(A-R-SiW9O34)Ni4(CH3COO)3(OH)2(N3)}2] . 32H2O (2) can be described as two {Ni4} subunits connected via a {Na(CH3COO)6} group, with the acetato ligands also ensuring in each subunit the connection between the paramagnetic centers. In 2, two azido groups replace two of the six mu-hydroxo ligands present in 1. The nonanuclear complex K7Na7[(A-R-SiW9O34)2Ni9(OH)6(H2O)6(CO3)3] . 42H2O (3) exhibits a double cubanestructure with two [(A-R-SiW9O34)Ni4(OH)3]5- subunits linked by three carbonato ligands. A ninth NiII center connected to one subunit via a carbonato ligand and a O=W group completes this asymmetric polyoxometalate.Electronic spectroscopy and electrochemical studies indicate that, while compounds 1-3 decompose in a pure aqueous medium, these complexes are very stable in a pH 6 acetate medium. The cyclic voltammetry pattern of each complex is constituted by a first eight-electron reduction wave followed by a second large-current intensity wave. The characteristics of the first waves of the complexes are clearly distinct from those obtained for their lacunary precursor [A-R-SiW9O34]10-, a feature that is due to the Ni centers in the complexes. Such observations of electroactive, stable, and highly nickel-rich polyoxometalates are not common. Measurements of the magnetic susceptibility revealed the occurrence of concomitant ferromagnetic and antiferromagnetic interactions in 1 and 3.For both of these compounds, the extension of the magnetic exchange has been determined by means of a spin Hamiltonian with three and four J constants, respectively.     

Novel neutral imidazole-lipophosphoramides for transfection assays

New helper lipids, possessing an imidazole polar head, have been synthesized and included in formulations for transfection assays; these new helper lipids can improve the transfection by a factor of up to 100 compared to the use of DOPE as co-lipid.     

Cyanido-bridged one-dimensional systems assembled from [ReIVCl4(CN)2]2? and [MII(cyclam)]2+ (M = Ni, Cu) precursors

Three new cyanido-bridged heterometallic Re^IVNi^II and Re^IVCu^II one-dimensional systems were synthesized and extensively characterized both structurally and magnetically. Single-crystal X-ray diffraction analysis revealed that these compounds display a common topology, with chains composed of alternating [Re^IVCl₄(CN)₂]^2? and [M^II(cyclam)]²⁺ (M = Ni in 1, Cu in 2) or [Cu^II(N,N??-dimethylcyclam)]²⁺ (in 3) building units. Two different chain orientations with a tilt angle of ca. 51° to 55° are present in the crystal packing of these compounds. The magnetic susceptibility measurements suggest the presence of intrachain ferromagnetic interactions between the S = 3/2 Re^IV centers and the 3d metal ions: S = 1 Ni^II or S = 1/2 Cu^II. At low temperature, a three-dimensional ordered magnetic phase induced by interchain antiferromagnetic interactions (antiferromagnetic for 1 and 2; canted antiferromagnetic for 3) is detected for the three compounds.     

Solid-phase extraction using molecularly imprinted polymers for selective extraction of a mycotoxin in cereals

The aim of this work was to develop a method for the clean-up of a mycotoxin, i.e. Ochratoxin A (OTA), from cereal extracts employing a new molecularly imprinted polymer (MIP) as selective sorbent for solid-phase extraction (SPE) and to compare with an immunoaffinity column. A first series of experiments was carried out in pure solvents to estimate the potential of the imprinted sorbent in terms of selectivity studying the retention of OTA on the MIP and on a non-imprinted polymer using conventional crushed monolith. The selectivity of the MIP was also checked by its application to wheat extracts. Then, after this feasibility study, two different formats of MIP: crushed monolith and micro-beads were evaluated and compared. Therefore an optimization procedure was applied to the selective extraction from wheat using the MIP beads. The whole procedure was validated by applying it to wheat extract spiked by OTA at different concentration levels and then to a certified contaminated wheat sample. Recoveries close to 100% were obtained. The high selectivity brought by the MIP was compared to the selectivity by an immunoaffinity cartridge for the clean-up of the same wheat sample. The study of capacity of both showed a significant higher capacity of the MIP.