Quasi-solitonic behavior of self-written waveguides created by photopolymerization

We investigated the condition of unique self-written channel and multichannel propagation inside bulk photopolymerizable materials. Light was introduced in the medium by a single-mode optical fiber. At a very low beam power of 5 muW , a unique uniform-channel waveguide without any broadening was obtained by polymerization. When the input power is increased to 100 muW , the guide becomes chaotic and multichannel. We connected two fibers separated by a 1-cm distance. The results open the door to studies of the optical and electro-optical properties of photopolymerized guides doped by nonlinear optical chromophores and to possible applications in integrated optical devices.     

Richness of isomerism in labile octahedral Werner-type cobalt(II) complexes demonstrated by 19F NMR spectroscopy: structure and stability

The cobalt(II) complexes [CoL2(R2-Py)2] (1-4) where HLA = 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, R2-Py = 4-methylpyridine (1), HLB = 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione, R2-Py = 4-methylpyridine (2), 4-phenylpyridine (3) and S-(-)-1-(4-pyridyl)ethanol (4) were prepared by two-step reactions. X-ray structure analysis of [CoLA2(CH3-Py)2] revealed the {trans(N)-trans(CF3)-trans} configuration for the complex obtained by crystallization from ethanol. A dynamic equilibrium between the five possible stereoisomers was observed for each complex 1-4 in solution by 19F NMR spectroscopy. The criteria used for full NMR assignment (180-265 K) include comparison of integral ratios, cis(N) and trans(N) differentiation in presence of the chiral amine [S-(-)-1-(4-pyridyl)ethanol], effect of solvent polarity on the relative stabilities of the five isomers and observation of trans influences in a mixture of complexes. Thermodynamic parameters for the equilibria between the isomers of 2 in CD2Cl2 (DeltaHi,j, DeltaSi,j and Ki,j) were obtained from signal integrals. The two trans(N) isomers are slightly more stable than the three cis(N) isomers at low temperature [DeltaGdegreesi,j (max) = 2.8 kJ mol(-1) at 179.8 K], but this stability difference almost vanishes with increasing temperature [DeltaGdegreesi,j (max) = 1.0 kJ mol(-1) at 265.0 K]. The values found for DeltaHdegreesi,j are relatively small and largely entropy compensated.     

Redox-triggered molecular movement in a multicomponent metal complex in solution and in the solid state

The Cu(I) and Cu(II) complexes of the new 1,8-diferro-cenylmethyl-4,11-dimethyl-1,4,8,11-tetraazacyclotetra-decane ligand (denoted L) have been isolated and characterized by X-ray structure determination and electrochemical studies. The Cu(I) complex presents an unprecedented stability toward dioxygen. The two complexes adopt two energetically distinct and stable geometries, which differ mainly by the relative positioning of the substituents above or below the cyclam plane. Triggered by a copper-centered electron transfer, a fast and reversible motion of the noncoordinating subunits is obtained in homogeneous solution and in the solid state.     

Heterogeneity of the surface energy on unused C18-chromolith adsorbents in reversed-phase liquid chromatography

Single-component adsorption isotherm data were acquired by frontal analysis (FA) for phenol and caffeine on a new C18-Chromolith column (Merck, Darmstadt, Germany), using a water-rich mobile phase (methanol/water, 15/85, v/v). These data were modeled for best agreement between the experimental data points and the adsorption isotherm model. The adsorption-energy distributions, based on the expectation-maximization (EM) procedure, were also derived and used for the selection of the best isotherm model. The adsorption energy distributions (AEDs) for phenol and caffeine converged toward a trimodal and a quadrimodal distribution, respectively. Energy distributions with more than two modes had not been reported before for the adsorption of these compounds on packed columns. The third high energy mode observed for both phenol and caffeine seems to be specific of the surface of the monolithic column while the first and second low energy modes have the same physical origin as the two modes detected on packed columns. These results suggest significant differences between the structures of the porous silica in these different materials.     

Effect of pressure and temperature upon tin alkoxide-promoted ring-opening polymerisation of epsilon-caprolactone in supercritical carbon dioxide

Ring-opening polymerisation of epsilon-caprolactone in supercritical carbon dioxide is slowed down by a carbonation reaction, resulting in a positive volume of activation and a higher energy of activation as compared to polymerisation in a regular hydrocarbon solvent.     

Scattering on Reissner-Nordstrøm Metric for Massive Charged Spin 1/2 Fields

We consider massive charged Dirac fields on the Reissner-Nordstrøm metric. We prove the existence and asymptotic completeness of wave operators, classical at horizon and modified at infinity. Communicated by Piotr Chrusciel submitted 24/05/02, accepted: 14/02/03     

Sensitivity indices for multivariate outputs

We define and study a generalization of Sobol sensitivity indices for the case of a vector output.     

Removal of the PsaF Polypeptide Biases Electron Transfer in Favor of the PsaB Branch of Cofactors in Triton X‐100 Photosystem I Complexes from Synechococcus sp. PCC 7002†

Continuous wave (CW) and transient electron paramagnetic resonance studies have implied that when PsaF is removed genetically, the double reduction of A_1A is facile, the lifetime of A_1A^? is shorter and the ratio of fast to slow kinetic phases increases in PS I complexes isolated with Triton X‐100 (Van der Est, A., A. I. Valieva, Y. E. Kandrashkin, G. Shen, D. A. Bryant and J. H. Golbeck [2004] Biochemistry 43 , 1264–1275). Changes in the lifetimes of A_1A^? and A_1B^? are characteristic of mutants involving the quinone binding sites, but changes in the relative amplitudes of A_1A^? and A_1B^? are characteristic of mutants involving the primary electron acceptors, A_0A and A_0B. Here, we measured the fast and slow phases of electron transfer from A_1B^? and A_1A^? to F_X in psaF and psaE psaF null mutants using time‐resolved CW and pump‐probe optical absorption spectroscopy. The lifetime of the fast kinetic phase was found to be unaltered, but the lifetime of the slow kinetic phase was shorter in the psaF null mutant and even more so in the psaE psaF null mutant. Concomitantly, the amplitude of the fast kinetic phase increased by a factor of 1.8 and 2.0 in the psaF and psaE psaF null mutants, respectively, at the expense of the slow kinetic phase. The change in ratio of the fast to slow kinetic phases is explained as either a redirection of electron transfer through A_1B at the expense of A_1A, or a shortening of the lifetime of A_1A^? to become identical to that of A_1B^?. The constant lifetime and the characteristics of the near‐UV spectrum of the fast kinetic phase favor the former explanation. A unified hypothesis is presented of a displacement of the A‐jk(1) α‐helix and switchback loop, which would weaken the H‐bond from Leu₇₂₂ to A_1A, accounting for the acceleration of the slow kinetic phase, as well as weaken the H‐bond from Tyr₆₉₆ to A_0A, accounting for the bias of electron transfer in favor of the PsaB branch of cofactors.