Crystallization and second harmonic generation in thermally poled niobium borophosphate glasses

Crystallization of glasses with compositions (1−x)(0.95 NaPO₃+0.05 Na₂B₄O₇)+xNb₂O₅, x=0.4, 0.43, 0.45, 0.48 was investigated by differential scanning calorimetry and X-ray powder diffraction. Crystallization of two phases was observed in the glasses with x=0.43-0.48. First phase is a sodium niobate with the structure of tetragonal tungsten bronze () and second phase is Na₄Nb₈P₄O₃₂ (). The crystallization of sodium niobate is correlated with increasing of nonlinear optical efficiency reported for thermally poled glasses with x>0.4. The results of Raman spectroscopy show the formation of three-dimensional (3D) niobium oxide framework in the glasses with increase of niobium concentration. This framework is supposed to have tetragonal tungsten bronze structure and to be responsible for nonlinear optical properties of the glass. Second harmonic generation signals of as prepared and crystallized glass after thermal poling are compared. The nucleation and crystallization do not improve the NLO properties of the glasses under study.     

Electrocatalytic Proton Reduction by a Cobalt Complex Containing a Proton-Responsive Bis(alkylimdazole)methane Ligand: Involvement of a C−H Bond in H2 Formation

Homogeneous electrocatalytic proton reduction is reported using cobalt complex [ 1 ](BF₄)₂. This complex comprises two bis(1-methyl-4,5-diphenyl-1H-imidazol-2-yl)methane (HBMIM ) ligands that contain an acidic methylene moiety in their backbone. Upon reduction of [ 1 ](BF₄)₂ by either electrochemical or chemical means, one of its HBMIM ligands undergoes deprotonation under the formation of dihydrogen. Addition of a mild proton source (acetic acid) to deprotonated complex [ 2 ](BF₄) regenerates protonated complex [ 1 ](BF₄)₂. In presence of acetic acid in acetonitrile solvent [ 1 ](BF₄)₂ shows electrocatalytic proton reduction with a k_obs of ≈200 s⁻¹ at an overpotential of 590 mV. Mechanistic investigations supported by DFT (BP86) suggest that dihydrogen formation takes place in an intramolecular fashion through the participation of a methylene C−H bond of the HBMIM ligand and a Co^II−H bond through formal heterolytic splitting of the latter. These findings are of interest to the development of responsive ligands for molecular (base)metal (electro)catalysis.     

Potential bile acid metabolites. 1. The epimeric 3ϵ,7α,12β-trihydroxy-5β-cholanic acids. Raney nickel as an epimerizing catalyst.

The epimeric 3α,7α,12β- and 3β,7α,12β-trihydroxy-5β-cholanic acids have been prepared. Under ambient hydrogenation conditions with Raney nickel as catalyst the axial 3β-ester ($\text{4b}$) is epimerized to the 3α-compound ($\text{2b}$).     

Preparation,lithiation and transformation of N-(benzotriazol-1-ylmethyl) heterocycles

Indole, carbazole, pyrrole, imidazole, benzimidazole, 2-methyl- and 2-phenylbenzimidazole, and 1, 2, 4-triazole have each been converted into their N-(benzotriazol-1-ylmethyl) derivatives. The pyrrole, indole, and carbazole adducts undergo smooth lithiation at the inter-ring methylene group and subsequent reaction there with electrophiles. For the imidazole, benzimidazole, and triazole systems, lithiations at other molecular positions competed.     

Copper reagents: a new and efficient solution for the selective addition of metallated propargylic amines to aldehydes

[reaction: see text] Anti alpha-amino-homopropargylic alcohols are prepared by addition of metallated propargylic amines to aldehydes. Among the four organometallic (LI, Zn, Ti, Cu) derivatives used, the most effective are the copper reagents.     

Pressure pinched injection of nanolitre volumes in planar micro-analytical devices

A new method for injecting and driving fluids by means of a multi-port injection valve and syringe pumps in a micro-channel network is described. A structure composed of two micro-channels arranged as a cross is connected with capillary tubes to an external multi-port injection valve. The fluid flows are driven by pressure and the multi-port valve controls the direction of the flow within the different sections of the structure. The first position of the multi-port valve allows the preparation of the loading of the sample, which is pinched in the cross section of the two micro-channels. The second position allows the precise injection of nL volumes. No dead volume exists between injection and separation modes. The system can be used to prepare a sample plug by pressure in order to perform chromatography with a broad range of buffered or non-buffered solutions. Thanks to the insensitivity to the ionic strength of the sample, this injection method is useful for the injection of complex biological samples in microchip analysis. In order to demonstrate the feasibility of the method, different solutions of ionic or fluorescent molecules were injected and detected in a photoablated planar polymer device.     

Hybrid fluorocarbon-hydrocarbon CO2-philic surfactants. 2. formation and properties of water-in-CO2 microemulsions

Hybrid fluorocarbon-hydrocarbon (F-H) sulfate surfactants are shown to be efficient stabilizers in water-in-CO2 (w/c) microemulsions. The chain structure and F-H ratio affect the regions of P-T phase stability and aggregation structure in these w/c phases. High-pressure near-infrared spectroscopy and small-angle neutron scattering measurements of microemulsified water provide evidence for the stabilization of w/c microemulsion droplets. The relative lengths of the two chains were found to influence the favored aggregation structure: for symmetric chain surfactants (F8H8, F7H7) spherical reverse micelles are present, but for asymmetric chain surfactants (F7H4, F8H4) extended cylinder aggregates form. These changes in aggregation are consistent with different surfactant packing parameters owing to the controlled variations in molecular structure. Furthermore, the general order of w/c phase transition pressures (F8H8 < F7H7 and F8H4 < F7H4) is in line with estimations of surfactant fractional free volume, as proposed by Johnston et al. (J. Phys. Chem. B 2004, 108, 1962-1966). Studies of adsorption at the poly(dimethylsiloxane)-water interface are shown to be valuable for assessing the CO2-philicity of new surfactants. All in all, the symmetric F8H8 and F7H7 analogues are seen to be the most efficient compounds from this class for applications in CO2.     

Thermal analysis of some metal benzohydroxamates

The preparation and thermal analysis of metal chelates of benzohydroxarnic acid (BHA) with Al(III), Cd(II), Co(II), Cu(II) (two compounds), Fe(III), La(III), Pb(II), Mn(II), Ni(II), U(VI) and Zn(II) is discussed. The Al(III), La(III), Pb(II) and Mn(II) chelates are new compounds. DTA and TGA curves of the chelates and of BHA are presented, and the heats of decomposition of the chelates are estimated.