Biomimetic oxygen reduction by cofacial porphyrins at a liquid-liquid interface

Oxygen reduction catalyzed by cofacial metalloporphyrins at the 1,2-dichlorobenzene-water interface was studied with two lipophilic electron donors of similar driving force, 1,1'-dimethylferrocene (DMFc) and tetrathiafulvalene (TTF). The reaction produces mainly water and some hydrogen peroxide, but the mediator has a significant effect on the selectivity, as DMFc and the porphyrins themselves catalyze the decomposition and the further reduction of hydrogen peroxide. Density functional theory calculations indicate that the biscobaltporphyrin, 4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene, Co(2)(DPX), actually catalyzes oxygen reduction to hydrogen peroxide when oxygen is bound on the "exo" side ("dock-on") of the catalyst, while four-electron reduction takes place with oxygen bound on the "endo" side ("dock-in") of the molecule. These results can be explained by a "dock-on/dock-in" mechanism. The next step for improving bioinspired oxygen reduction catalysts would be blocking the "dock-on" path to achieve selective four-electron reduction of molecular oxygen.     

Optimizing millisecond time scale near-infrared emission in polynuclear chrome(III)-lanthanide(III) complexes

This work illustrates a simple approach for optimizing long-lived near-infrared lanthanide-centered luminescence using trivalent chromium chromophores as sensitizers. Reactions of the segmental ligand L2 with stoichiometric amounts of M(CF(3)SO(3))(2) (M = Cr, Zn) and Ln(CF(3)SO(3))(3) (Ln = Nd, Er, Yb) under aerobic conditions quantitatively yield the D(3)-symmetrical trinuclear [MLnM(L2)(3)](CF(3)SO(3))(n) complexes (M = Zn, n = 7; M = Cr, n = 9), in which the central lanthanide activator is sandwiched between the two transition metal cations. Visible or NIR irradiation of the peripheral Cr(III) chromophores in [CrLnCr(L2)(3)](9+) induces rate-limiting intramolecular intermetallic Cr→Ln energy transfer processes (Ln = Nd, Er, Yb), which eventually produces lanthanide-centered near-infrared (NIR) or IR emission with apparent lifetimes within the millisecond range. As compared to the parent dinuclear complexes [CrLn(L1)(3)](6+), the connection of a second strong-field [CrN(6)] sensitizer in [CrLnCr(L2)(3)](9+) significantly enhances the emission intensity without perturbing the kinetic regime. This work opens novel exciting photophysical perspectives via the buildup of non-negligible population densities for the long-lived doubly excited state [Cr*LnCr*(L2)(3)](9+) under reasonable pumping powers.     

The nature of black stains in Lascaux Cave,France, as revealed by surface‐enhanced Raman spectroscopy

We used surface‐enhanced Raman spectroscopy to investigate the chemical composition of the black stains threatening the rock‐art paintings of Lascaux Cave, Montignac, France. The stains are mainly composed of melanin from the fungus Ochroconis sp. and the faecal pellets of the collembolan Folsomia candida. Surface‐enhanced Raman spectroscopy is a useful technique for revealing the structure of unknown macromolecules in cultural heritage research. Copyright © 2011 John Wiley & Sons, Ltd.     

N-Heterocyclic tridentate aromatic ligands bound to [Ln(hexafluoroacetylacetonate)3] units: thermodynamic, structural, and luminescent properties

Herein, we discuss how, why, and when cascade complexation reactions produce stable, mononuclear, luminescent ternary complexes, by considering the binding of hexafluoroacetylacetonate anions (hfac(-)) and neutral, semi-rigid, tridentate 2,6-bis(benzimidazol-2-yl)pyridine ligands (Lk) to trivalent lanthanide atoms (Ln(III)). The solid-state structures of [Ln(Lk)(hfac)(3)] (Ln=La, Eu, Lu) showed that [Ln(hfac)(3)] behaved as a neutral six-coordinate lanthanide carrier with remarkable properties: 1) the strong cohesion between the trivalent cation and the didentate hfac anions prevented salt dissociation; 2) the electron-withdrawing trifluoromethyl substituents limited charge-neutralization and favored cascade complexation with Lk; 3) nine-coordination was preserved for [Ln(Lk)(hfac)(3)] for the complete lanthanide series, whilst a counterintuitive trend showed that the complexes formed with the smaller lanthanide elements were destabilized. Thermodynamic and NMR spectroscopic studies in solution confirmed that these characteristics were retained for solvated molecules, but the operation of concerted anion/ligand transfers with the larger cations induced subtle structural variations. Combined with the strong red photoluminescence of [Eu(Lk)(hfac)(3)], the ternary system Ln(III)/hfac(-)/Lk is a promising candidate for the planned metal-loading of preformed multi-tridentate polymers.     

Electronic fine structure calculation of [Gd(DOTA)(H2O)]– using LF-DFT: The zero field splitting

Zerfo field splitting plays an important role in determining the electron spin relaxation of Gd(III) in solution. We understand the ZFS as an effect depending on the f electron structure and treat it in the framework of ligand field-density functional theory (LF-DFT). We apply this theory to calculate the ZFS of [Gd(DOTA)(H₂O)]^? from first principles, having an insight concerning the contributions determining the ZFS.     

Coherence and polarization properties in speckle of totally depolarized light scattered by totally depolarizing media

When a totally unpolarized light is scattered by a medium that spatially totally depolarizes incident polarized light, the scattered field presents an increase of the order described by the temporal degree of polarization. We analyze the behavior of some polarization and coherence properties in such a physical situation.     

High-fidelity single-photon source based on a Type II optical parametric oscillator

Using a continuous-wave Type II optical parametric oscillator below threshold, we have demonstrated a novel source of heralded single photons with high fidelity. The generated state is characterized by homodyne detection and exhibits a 79% fidelity with a single-photon Fock state (91% after correction of detection loss). The low admixture of vacuum and the well-defined spatiotemporal mode are critical requirements for their subsequent use in quantum information processing.     

Current understanding of ultra-high cycle fatigue

The fatigue life of numerous aerospace, locomotive, automotive and biomedical structures may go beyond 10⁸ cycles. Determination of long life fatigue behavior becomes extremely important for better understanding and design of the components and structures. Initially, before the invention of ultrasonic fatigue testing, most of the engineering materials were supposed to exhibit fatigue life up to 10⁷ cycles or less. This paper reviews current understanding of some fundamental aspects on the development of accelerated fatigue testing method and its application in ultra-high cycle fatigue, crack initiation and growth mechanisms of internal fracture, S-N diagram, fatigue limit and life prediction, etc.