Synthesis and magnetic properties of new mono- and binuclear iron complexes with salicyloylhydrazono dithiolane ligand

We report here experimental evidence for the formation in the solid state of a new binuclear Fe (III) 2(mu-OMe) 2(HL) 4 complex (H 2L is 2-salicyloylhydrazono-1,3-dithiolane). The isostructural Mn (III) 2(mu-OMe) 2(HL) 4 complex has provided the strongest ferromagnetic interaction value (J approximately 20 cm (-1)) between Mn (III) ions to date. The new iron binuclear compound presented in this study shows antiferromagnetic intramolecular coupling, which agrees with the theoretical study that we previously proposed. During our synthetic work, we also observed an unexpected spontaneous reduction of the new Fe (III)(HL) 2Cl,S complex to the new Fe (II)(H 2L) 2Cl 2 high-spin mononuclear complex. This process has been checked by cyclo-voltammetry as well as pseudosteady voltammetry.     

Electronic communication in "chain-like" trimetallic ruthenium complexes with two C7 carbon-rich conjugated bridges

This paper describes the synthesis and properties of the first homotrinuclear metal complexes with large carbon-rich ligands that provide unique extended conduits for electron mobility.     

Preparation and characterization of polypyrrole with dispersed metallic rhodium particles

Polypyrrole (PPy) with dispersed metallic Rh particles has been prepared by all‐chemical route, i.e. reduction of Rh³⁺ ions existing in RhCl₃ aqueous solutions with sodium borohydride (NaBH₄) carried out in the presence of the previously obtained PPy doped with chloride ions (PPyCl). PPy–Rh composites thus formed have been characterized using X‐ray diffraction (XRD), scanning and transmission electron microscopies (SEM, TEM) combined with energy dispersive X‐ray (EDX) microanalysis, Rh3d X‐ray photoelectron (XPS), and IR spectroscopies. This has made it possible to find out that metallic Rh nanoparticles, mainly of sizes below 10 nm, have been present in the composites. Agglomerates, with sizes up to 0.7 µm, have been formed in the systems containing higher amounts of Rh. PPy serving as the matrix in the composites has been doped. However, its doping level has been lower than that of the starting PPyCl. This has been explained by partial reduction of the polymer occurring during preparation of the composites. Catalytic properties of the PPy–Rh systems have been investigated using isopropyl alcohol conversion as a test reaction. It has been established that the composites are active redox catalysts. This makes them promising materials for applications as catalysts of various redox processes. Copyright © 2010 John Wiley & Sons, Ltd.     

Resolution of conformer-specific all-trans-1,6-diphenyl-1,3,5-hexatriene UV absorption spectra

All-trans-1,6-diphenyl-1,3,5-hexatriene (ttt-DPH) exists in solution as a mixture of s-trans,s-trans and s-cis,s-trans conformers. The latter is higher in energy, and its contribution increases with increasing temperature. ttt-DPH UV absorption spectra broaden with increasing temperature and undergo blue shifts with decreasing polarizability. We describe here the resolution of two spectrothermal matrices of ttt-DPH UV absorption spectra into two conformer-specific components. The first matrix consists of DPH spectra measured in n-dodecane in the 283 to 374 K T range and the second of ttt-DPH absorption spectra measured in the even numbered n-alkanes (n-C(8)-n-C(16)) at temperatures selected to achieve isopolarizability (284-372 K). Principal component analysis (PCA) treatments showed that reasonable two-component systems are attained by compensation for T-induced broadening and shifting in the pure conformer spectra. The self-modeling (SM) method used to resolve the n-C(12) matrix is successfully tested on a simulated matrix closely mimicking ttt-DPH experimental spectra in n-C(12). Compensation for nonlinear effects yields robust two-component matrices from the experimental spectra. Their resolution into pure component spectra is based on the application of the Lawton and Sylvestre (LS) non-negativity criterion at the spectral onset to define the spectrum of the low energy s-trans-conformer and the optimum linearity van't Hoff (vH) plot criterion to find the spectrum of the higher-energy s-cis-conformer. Resolved spectra are somewhat sensitive to the choice of the spectral region in which the LS criterion is applied. The surprising result is that both resolutions lead to the conclusion that the molar fraction of the s-cis-conformer equals, or even exceeds, the molar fraction of the s-trans-conformer as the highest T's employed in our study are approached.     

Quantum Decoherence of Neutrino Oscillation and Weak Measurement about Its Group Velocity

We theoretically explore the possibility of observing the quantum decoherence of neutrino oscillation due to the vacuum dispersion, that the wave-packet of neutrino spatially splits according to the different velocities of two mass eigenstates. We find that if this decoherence could be observed and the range of values of the mixing angle is known, then the superluminal neutrino phenomena could occur for some mixing angles as the consequence of a weak measurement about flavor mixing in the neutrino propagation. Our calculation gives the explicit dependence of group velocity shift to the decoherence factor and the weak value of neutrino's pre and post-selected states. We also study the related problems for the neutrino oscillation with three generations.     

Microstructural identification of Cu in solar cells sensitive to light‐induced degradation

Light‐induced degradation (mc‐LID or LeTID) can lead to a severe efficiency loss in multi‐crystalline solar cells. The underlying mechanism clearly distinguishes from known mechanisms as B‐O‐LID and Fe‐B‐LID. Various defect models have been suggested for mc‐LID mainly based on metal impurities, including Cu which is known to cause light‐induced degradation. We investigate mc‐LID sensitive PERC cells that show an efficiency degradation of 15%_rel. The weaker degradation of the grain boundaries (GBs) typical for mc‐LID is identified and further investigated from front and rear side with respect to recombination activities. The combination of local electrical measurements (LBIC), target preparation (REM, FIB) and element analysis (EDX, TEM) unveil Cu‐containing precipitates at the rear side of the solar cells. They accumulate at grain boundaries and at the rear surface of the Si‐bulk material where the passivation stack is damaged. We conclude that Cu originates from the cell material and discuss its relation to mc‐LID.

LBIC mapping (EQE at fixed wavelength) of a degraded mc‐Si PERC cell from front and rear side results in qualitatively different appearance of GBs.     

Photoactive Analogs of Farnesyl Pyrophosphate Containing Benzoylbenzoate Esters: Synthesis and Application to Photoaffinity Labeling of Yeast Protein Farnesyltransferase

Farnesyl pyrophosphate (FPP) is involved in a large number of cellular processes including the prenylation of transforming mutants of Ras proteins implicated in cancer. Photoactive analogs could provide useful information about enzyme active sites that bind farnesyl pyrophosphate; however, the availability of such compounds is extremely limited. Molecules that incorporate benzophenone moieties are attractive photoaffinity labeling reagents because of their useful photochemical properties. Here, the syntheses of two compounds, 3a and 3b, containing para- and meta-substituted benzoylbenzoates are described. Compounds 3a and 3b are competitive inhibitors (with respect to FPP) of yeast protein farnesyltransferase (PFTase) with K(i) values of 910 and 380 nM, respectively. Both compounds inactivate PFTase upon photolysis, resulting in as much as 44% inactivation of enzyme activity. Photolysis of PFTase in the presence of [(32)P]3a or of [(32)P]3b results in preferential labeling of the beta subunit, suggesting that this subunit is involved in prenyl group recognition. These compounds should be valuable tools for studying enzymes that utilize FPP as a substrate.     

Synthesis and multitopic complex formation of a photochromic bis(crown ether) based on benzobis(thiazole)

2,7-Bis[2-(6,7,9,10,12,13,15,16-octahydro-5,8,11,14,17-pentaoxabenzocyclopentadecen-2-yl)vinyl]-benzo[1,2-d;3,4-d']bisthiazole, 2, with crown ether styryl moieties substituted on a heterocyclic core, was synthesized and its complex forming ability with several metal cations was evaluated in acetonitrile by absorption and fluorescence spectroscopy. The results are compared to those for the analogous ligand possessing a single crown ether styryl moiety. Selective binding of the metal cation at the heterocyclic core of both ligands was observed only for Hg2+. Alkali and alkaline earth cations bind selectively at the crown ether moieties. Stability constants and pure spectra of defined stoichiometry were determined with the use of HYPERQUAD, a least-squares fitting program, and the results were validated in one case by subjecting the titration spectral matrix to singular value decomposition with self-modeling (SVD-SM). The multitopic ligand 2 forms relatively strong 2:2 stoichiometric complexes with K+, among the alkali metal cations, and Ba2+, among the alkaline earth metal cations, and is a promising selective optical sensor for these ions.