Styrene polymerization catalyzed by metal porphyrin complex/MAO for in situ synthesizing polystyrene containing air stable pi cation radicals

A novel catalyst system based on nickel(II) tetraphenylporphyrin (Ni(II)TPP) and methylaluminoxane for styrene polymerization was developed. This catalyst system has a high thermal stability and show fairly good activity. The obtained polystyrene (PS) was isotactic-rich atactic polymer by C-13 NMR analysis, and its molecular weight distribution was rather narrow (M-w/M-n approximate to 1.6, by GPC analysis). ESR revealed that Ni(II)TPP pi cation radicals were formed in the polymerization and could remain in the resulting PS stably. The mechanism of the polymerization was discussed and a special coordination mechanism was proposed. The PS product containing Ni(II)TPP pi cation radicals can be used as a potential functional material.

Strengthening Mechanisms And Dislocation Dynamics In Twinned Metal Nanowires

Microtwins are frequently observed in face-centered-cubic (fcc) metal nanowires with low stacking fault energy. The authors have previously reported that the tensile Yield strength of copper nanowires can be increased by, the presence of twin boundaries. lit this work, simulations are carried out under both uniaxial tension and compression loading, to demonstrate that the strengthening effects are inherent to these nanowires, independent of the loading condition (tensile/compressive). It appears that the strengthening mechanism of the twinned nanowires can be attributed to stress redistribution due to the change of crystallographic orientations across twin boundaries, which requires larger external stress to make them Yield as compared to the twin-free wire.

Alternating Starvation Of Dislocations During Plastic Yielding In Metallic Nanowires

Using molecular dynamics simulations, we show that the mechanical deformation behaviors of single-crystalline nickel nanowires are quite different from their bulk counterparts. Correlation between the obtained stress-strain curves and the visualized defect evolution during deformation processes clearly demonstrates that a sequence of complex dislocation slip events results in a state of dislocation starvation, involving the nucleation and propagation of dislocations until they finally escape from the wires, so that the wires deform elastically until new dislocations are generated. (C) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Deformation mechanisms of face-centered-cubic metal nanowires with twin boundaries

This letter addresses the issue of deformation mechanisms and mechanical tensile behavior of the twinned metal nanowires using atomistic simulations. Free surfaces are always the preferential dislocation nucleation sites in the initial inelastic deformation stage, while with further plastic deformation, twin boundary interfaces will act as sources of dislocations with the assistance of the newly formed defects. The smaller the twin boundary spacing, the higher the yielding stresses of the twinned nanowires. Twin boundaries, which serve both as obstacles to dislocation motion and dislocation sources, can lead to hardening effects and contribute to the tensile ductility. This work illustrates that the mechanical properties of metal nanowires could be controlled by tailoring internal growth twin structures. (c) 2007 American Institute of Physics.

Reduced deep-tissue image degradation in three-dimensional multiphoton microscopy with concentric two-color two-photon fluorescence excitation

We theoretically demonstrate that enhanced penetration depth in three-dimensional multiphoton microscopy can be achieved using concentric two-color two-photon (C2C2P) fluorescence excitation in which the two excitation beams are separated in space before reaching their common focal spot. Monte Carlo simulation shows that, in comparison with the one-color two-photon excitation scheme, the C2C2P fluorescence microscopy provides a significantly greater penetration depth for imaging into a highly scattering medium. (C) 2008 Optical Society of America.

Two-color two-photon excitation of indole using a femtosecond laser regenerative amplifier

The fluorescence emission from indole resulting from two-color two-photon (2C2P) excitation with 400 and 800 nm wavelengths is observed, using the second harmonic and fundamental wavelength of a 800 nm 40 fs pulsed Ti:Sapphire femtosecond (fs) regenerative amplifier operating at a repetition rate of 1 kHz. By delaying one fs laser pulse relative to the other, the cross correlation of fluorescence is observed, which indicates the generation of 2C2P fluorescence signal in the experiment. The strongest 2C2P fluorescence emission characterized by the peak of cross correlation curve suggests optimal temporal overlap of the two fs laser pulses. The 2C2P fluorescence signal is linearly dependent on the total excitation intensity. The fluorescence signals with 400 nm and 800 nm irradiation alone are also demonstrated and discussed in this paper. (C) 2008 Elsevier B.V. All rights reserved.

Three-photon absorption-induced fluorescence and optical limiting effects in a fluorene derivative

This paper reports on the steady-state fluorescence, three- photon absorption-induced fluorescence emission and subsequently induced optical limiting behaviour of a fluorene derivative with D-pi-D structural motifs. The lifetime of the steady-state fluorescence is 0.903 ns. Large optical limiting behaviour induced by 3PA has also been demonstrated, and the nonlinear absorption coefficient gamma derived from 3PA fitting curves is 5.92 x 10(-20) cm(3)/W-2 and the corresponding molecular 3PA cross-section sigma(3)' is 1.14 x 10(-76) cm(6) s(2).