Generation of spatial subharmonic gratings in the absence of photorefractive beam coupling

Using a new experimental geometry, we have proved for the first time that the generation of spatial subharmonic gratings in photorefractive crystals is not dependent on optical nonlinearity. We present results which confirm that the subharmonic gratings result from a parametric excitation of ultra low-frequency eigenmodes of a crystal by a time modulated fundamental grating.

Influence of beam-coupling on photorefractive parametric oscillation in a dc-field-biased Bi12SiO20 crystal

The influence of beam coupling on photorefractive parametric oscillation generated in a Bi12SiO20 crystal is investigated experimentally by comparing two configurations with and without the presence of beam coupling. It is shown that beam coupling has a great influence; for example, the transversal split of the K/2 subharmonic grating is seen only in the beam-coupling geometry. A case that resembles K/4 subharmonic generation can, however, still be found in the absence of beam coupling.

Co-propagating cladding modes coupling assisted by tilted Bragg grating with large tilting angle

We report for the first time forward propagating cladding modes coupling by using tilted gratings. The spectral responses of these gratings were investigated and their thermal characteristics and sensitivity to environmental refractive index were evaluated.

Anisotropic model of kinetic roughening:he strong-coupling regime

We study the strong coupling (SC) limit of the anisotropic Kardar-Parisi-Zhang (KPZ) model. A systematic mapping of the continuum model to its lattice equivalent shows that in the SC limit, anisotropic perturbations destroy all spatial correlations but retain a temporal scaling which shows a remarkable crossover along one of the two spatial directions, the choice of direction depending on the relative strength of anisotropicity. The results agree with exact numerics and are expected to settle the long-standing SC problem of a KPZ model in the infinite range limit. © 2007 The American Physical Society.

The coupling mechanism of P-glycoprotein involves residue L339 in the sixth membrane spanning segment

The transmembrane (TM) domains in P-glycoprotein (P-gp) contain the drug binding sites and undergo conformational changes driven by nucleotide catalysis to effect translocation. However, our understanding of exactly which regions are involved in such events remains unclear. A site-directed labelling approach was used to attach thiol-reactive probes to cysteines introduced into transmembrane segment 6 (TM6) in order to perturb function and infer involvement of specific residues in drug binding and/or interdomain communication. Covalent attachment of coumarin-maleimide at residue 339C within TM6 resulted in impaired ATP hydrolysis by P-gp. The nature of the effect was to reduce the characteristic modulation of basal activity caused by transported substrates, modulators and the potent inhibitor XR9576. Photoaffinity labelling of P-gp with [(3)H]-azidopine indicated that residue 339C does not alter drug binding per se. However, covalent modification of this residue appears to prevent conformational changes that lead to drug stimulation of ATP hydrolysis.

Impact of linear mode coupling on the group delay spread in few-mode fibers

We report an investigation on the group delay spread in few-mode fibers operating in the weak and strong linear coupling regimes, and for the first time, we study the transition region between them. A single expression linking the group delay spread to the fiber correlation length is validated for any coupling regime, considering 3 guided modes.

Fundamental Pd0/PdII redox steps in cross-coupling reactions:homogeneous, hybrid homogeneous-heterogeneous to heterogeneous mechanistic pathways for C-C couplings

C–C bond-forming, cross-coupling reactions of organohalides with nucleophilic compounds, catalysed by palladium, are amongst the most important chemical reactions available to the synthetic chemist. The intimate mechanisms of these reactions, involving Pd0/PdII redox steps, have been of great historical interest and continue to be so. The myriad of possible mechanisms is reviewed in this chapter. The interplay of mononuclear Pd species with higher order Pd species, e.g. nanoclusters/nanoparticles are considered as being equally important in cross-coupling reaction mechanisms. A focus is placed on trichotomic behaviour of cross-coupling catalytic manifolds, from homogeneous to hybrid homogeneous–heterogeneous to truly heterogeneous behaviour. For the latter, surface chemistry and metal atom leaching (and various experimental techniques) are broadly discussed. It is now clear that mechanism for general cross‐coupling reactions, that is as presented to undergraduate students studying Chemistry degrees across the world, is undoubtedly more complex than first thought. New opportunities for catalyst design have therefore emerged in the area of Pd nanoparticles and nanocatalysis, with some wonderful applications especially in chemical biology, providing a snapshot of what the future might hold.

Interrogation of a sonogashira cross-coupling of 8-bromoguanosine with phenylacetylene on amberlite:evidence for Pd/Cu ion binding and propagation of Pd/Cu nanoparticles

The reactivity of Amberlite (IRA-67) base "heterogeneous" resin in Sonogashira cross-coupling of 8-bromoguanosine 1 with phenylacetylene 3 to give 2 has been examined. Both 1 and 2 coordinate to Pd and Cu ions, which explains why at equivalent catalyst loadings, the homogeneous reaction employing triethylamine base is poor yielding. X-ray photo-electron spectroscopy (XPS) has been used to probe and quantify the active nitrogen base sites of the Amberlite resin, and postreaction Pd and Cu species. The Pd2Cl3(PPh)2 precatalyst and CuI cocatalyst degrade to give Amberlite-supported metal nanoparticles (average size ∼2.7 nm). The guanosine product 2 formed using the Amberlite Pd/Cu catalyst system is of higher purity than reactions using a homogeneous Pd precatalyst, a prerequisite for use in biological applications. Copyright © Taylor and Francis Group, LLC.

Surface catalysed Suzuki-Miyaura cross-coupling by Pd nanoparticles:an operando XAS study

Size-controlled, catalytically active PVP-stabilised Pd nanoparticles have been studied by operando liquid phase XAS during the Suzuki cross-coupling of iodonanisole and phenylboronic acid in MeOH-toluene using KOMe base. XAS reveals nanoparticles are stable to metal leaching throughout the reaction, with surface density Pd defect sites directly implicated in the catalytic cycle. The efficacy of popular selective chemical and structural poisons for distinguishing heterogeneous and homogeneous contributions in Pd catalysed cross-couplings is also explored. © 2010 The Royal Society of Chemistry.

Coupling of Heck and hydrogenation reactions in a continuous compact reactor

A continuous multi-step synthesis of 1,2-diphenylethane was performed sequentially in a structured compact reactor. This process involved a Heck C-C coupling reaction followed by the addition of hydrogen to perform reduction of the intermediate obtained in the first step. Both of the reactions were catalysed by microspherical carbon-supported Pd catalysts. Due to the integration of the micro-heat exchanger, the static mixer and the mesoscale packed-bed reaction channel, the compact reactor was proven to be an intensified tool for promoting the reactions. In comparison with the batch reactor, this flow process in the compact reactor was more efficient as: (i) the reaction time was significantly reduced (ca. 7 min versus several hours), (ii) no additional ligands were used and (iii) the reaction was run at lower operational pressure and temperature. Pd leached in the Heck reaction step was shown to be effectively recovered in the following hydrogenation reaction section and the catalytic activity of the system can be mostly retained by reverse flow operation. © 2009 Elsevier Inc. All rights reserved.

CuII chain compound showing a ferromagnetic coupling through triple N1,N2-1,2,4-triazole bridges

[Cu(hyetrz)3](CF3SO3)2·H2O [hyetrz = 4-(2′-hydroxyethyl)-1,2,4-triazole] represents the first structurally characterised ferromagnetically coupled CuII chain compound containing triple N1,N2-1,2,4-triazole bridges. catena-[μ-Tris{4-(2′-hydroxyethyl)-1,2,4-triazole-N1,N2}copper(II)] bis(trifluoromethanesulfonate) hydrate (C14H23F6S2O10CuN9) crystallises in the triclinic space group Pl, a = 13.54(3), b = 14.37(3), c = 15.61(4) Å, α = 95.9(1), β = 104.9(1), γ = 106.5(1)°, V = 2763(11) Å3, Z = 4 (CuII units). The CuII ions are linked by triple N1,N2-1,2,4-triazole bridges yielding an alternating chain with Cu1−Cu2 = 3.8842(4) Å and Cu2−Cu3 = 3.9354(4) Å. Analysis of the magnetic data according to a high-temperature series expansion gives a J value of +1.45(3) cm−1. The nature and the magnitude of the ferromagnetic exchange have been discussed on the basis of the structural features. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

Side detection of strong radiation-mode out-coupling from blazed FBGs in single-mode and multimode fibers

We report on the effective side detection of radiation-mode out-coupling from blazed fiber Bragg gratings (BFBGs) fabricated in single-mode fiber (SMF) and multimode fiber (MMF). The far-field radiation power distribution from BFBGs have been measured achieving a high spatial-spectral resolution (0.17 mm/nm). We have also investigated comparatively the transmission-loss characteristics of BFBGs in both fiber types, fabricated using phase-mask and holographic inscription techniques. Our results reveal clearly that the radiation out-coupling from BFBGs is significantly stronger and spectrally more confined in MMF than in SMF.

Suppression of cladding-mode coupling loss in Bragg grating using standard single-mode fiber

We present a technique for suppressing cladding-mode coupling loss in fiber Bragg grating fabrication. Suppression of cladding-modes down to 0.2 dB in a Bragg grating of 18dB reflectivity has been achieved in hydrogen-loaded standard single-mode fiber.