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.

Coupling in silico and in vitro analysis of peptide-MHC binding:a bioinformatic approach enabling prediction of superbinding peptides and anchorless epitopes

The ability to define and manipulate the interaction of peptides with MHC molecules has immense immunological utility, with applications in epitope identification, vaccine design, and immunomodulation. However, the methods currently available for prediction of peptide-MHC binding are far from ideal. We recently described the application of a bioinformatic prediction method based on quantitative structure-affinity relationship methods to peptide-MHC binding. In this study we demonstrate the predictivity and utility of this approach. We determined the binding affinities of a set of 90 nonamer peptides for the MHC class I allele HLA-A*0201 using an in-house, FACS-based, MHC stabilization assay, and from these data we derived an additive quantitative structure-affinity relationship model for peptide interaction with the HLA-A*0201 molecule. Using this model we then designed a series of high affinity HLA-A2-binding peptides. Experimental analysis revealed that all these peptides showed high binding affinities to the HLA-A*0201 molecule, significantly higher than the highest previously recorded. In addition, by the use of systematic substitution at principal anchor positions 2 and 9, we showed that high binding peptides are tolerant to a wide range of nonpreferred amino acids. Our results support a model in which the affinity of peptide binding to MHC is determined by the interactions of amino acids at multiple positions with the MHC molecule and may be enhanced by enthalpic cooperativity between these component interactions.

Biconical-taper-assisted fiber interferometer with modes coupling enhancement for high-sensitive curvature measurement

A modal interferometer based on multimode-singlemode-multimode fiber structure built with a biconical taper for fiber curvature measurement is proposed and experimentally demonstrated. Due to the tapered singlemode fiber acting as a high-efficient mode power converter to enhance the modes coupling, curvature sensor with improved sensitivity is achieved by monitoring the defined fringe visibility of the interference spectrum. The measuring range can be tuned by changing the waist diameter of the fiber taper. Meanwhile, the sensor shows an intrinsic ability to overcome the influence of temperature cross-sensitivity and the power fluctuation of light source. The advantages of easy fabrication, high-quality spectrum with improved sensitivity, and small hysteresis will provide great potential for practical applications of the sensor. © 2013 Springer-Verlag Berlin Heidelberg.

Polarisation mode coupling of excessively tilted fibre Bragg gratings with directional transverse loading

We report a distinctive polarisation mode coupling behaviour of tilted fibre Bragg gratings (TFBGs) with tilted angle exceeding 45°. The ex-45° TFBGs exhibit pronounced polarisation mode splitting resulted from grating structure asymmetry induced birefringence. We have studied and analysed the property of ex-45° TFBGs under transverse load applied to their equivalent fast- and slow-axis. The results show that the coupling between the orthogonally polarised modes takes place only when the load is applied to its fast-axis, giving a prominent directional loading response. This transverse load related polarisation property may be exploitable for implementation of optical fibre vector sensors capable of measuring the magnitude and orientation of the applied transverse load.

Low thermal sensitivity grating devices based on ex-45° tilting structure capable of forward-propagating cladding modes coupling

The authors describe a detailed investigation on tilted fiber Bragg grating (TFBG) structures with tilted angles exceeding 45°. In contrast to the backward mode coupling mechanism of Bragg gratings with normal and small tilting structures, the ex-45° TFBGs facilitate the light coupling to the forward-propagating cladding modes. The authors have also theoretically and experimentally examined the mode coupling transition of TFBGs with small, medium, and large tilt angles. In particular, experiments are conducted to investigate the spectra and far-field distribution, as well as temperature, strain, and refractive-index sensitivities of ex-45° devices. It has been revealed that these ex-45° gratings exhibit ultralow thermal sensitivity. As in-fiber devices, they may be superior to conventional Bragg and long-period gratings when the low thermal cross sensitivity is required. © 2006 IEEE.

Investigating the role of capacitive coupling between the operating table and the return electrode of an electrosurgery unit in the modification of the current density distribution within the patients’ body

Background: Electrosurgery units are widely employed in modern surgery. Advances in technology have enhanced the safety of these devices, nevertheless, accidental burns are still regularly reported. This study focuses on possible causes of sacral burns as complication of the use of electrosurgery. Burns are caused by local densifications of the current, but the actual pathway of current within patient's body is unknown. Numerical electromagnetic analysis can help in understanding the issue. Methods: To this aim, an accurate heterogeneous model of human body (including seventy-seven different tissues), electrosurgery electrodes, operating table and mattress was build to resemble a typical surgery condition. The patient lays supine on the mattress with the active electrode placed onto the thorax and the return electrode on his back. Common operating frequencies of electrosurgery units were considered. Finite Difference Time Domain electromagnetic analysis was carried out to compute the spatial distribution of current density within the patient's body. A differential analysis by changing the electrical properties of the operating table from a conductor to an insulator was also performed. Results: Results revealed that distributed capacitive coupling between patient body and the conductive operating table offers an alternative path to the electrosurgery current. The patient's anatomy, the positioning and the different electromagnetic properties of tissues promote a densification of the current at the head and sacral region. In particular, high values of current density were located behind the sacral bone and beneath the skin. This did not occur in the case of non-conductive operating table. Conclusion: Results of the simulation highlight the role played from capacitive couplings between the return electrode and the conductive operating table. The concentration of current density may result in an undesired rise in temperature, originating burns in body region far from the electrodes. This outcome is concordant with the type of surgery-related sacral burns reported in literature. Such burns cannot be immediately detected after surgery, but appear later and can be confused with bedsores. In addition, the dosimetric analysis suggests that reducing the capacity coupling between the return electrode and the operating table can decrease or avoid this problem. © 2013 Bifulco et al.; licensee BioMed Central Ltd.

Facile synthesis of polymer-peptide conjugates via direct amino acid coupling chemistry

Polymer-peptide conjugates (also known as biohy-brids) are attracting considerable attention as injectable materials owing to the self-assembling behavior of the peptide and the ability to control the material properties using the polymer component. To this end, a simple method for preparing poly(ethylene oxide)-oligophenylalanine polymer-peptide conjugates (mPEOm-F n-OEt) using isobutylchloroformate as the activating reagent has been identified and developed. The synthetic approach reported employs an industrially viable route to produce conjugates with high yield and purity. Moreover, the approach allows judicious selection of the precursor building blocks to produce libraries of polymer-peptide conjugates with complete control over the molecular composition. Control over the molecular make-up of the conjugates allows fine control of the physicochemical properties, which will be exploited in future studies into the prominent self-assembling behavior of such materials. © 2013 Wiley Periodicals, Inc.

Few-mode fibre group-delays with intermediate coupling

We study the probability density function of the group-delay in few-mode fibres, validating for the first time an analytical estimation for the maximum group-delay spread as a function of linear mode coupling for fibres with more than three LP modes.

Advantages of strong mode coupling for suppression of nonlinear distortion in few-mode fibers

Nonlinear distortion in few-mode fibers for intermediate coupling is studied for the first time. Coupling strengths beyond -20 dB/100m give suppression of nonlinear distortion below the isolated mode without mode coupling.

Sonogashira cross-coupling and homocoupling on a silver surface:chlorobenzene and phenylacetylene on Ag(100)

Scanning tunneling microscopy, temperature-programmed reaction, near-edge X-ray absorption fine structure spectroscopy, and density functional theory calculations were used to study the adsorption and reactions of phenylacetylene and chlorobenzene on Ag(100). In the absence of solvent molecules and additives, these molecules underwent homocoupling and Sonogashira cross-coupling in an unambiguously heterogeneous mode. Of particular interest is the use of silver, previously unexplored, and chlorobenzene—normally regarded as relatively inert in such reactions. Both molecules adopt an essentially flat-lying conformation for which the observed and calculated adsorption energies are in reasonable agreement. Their magnitudes indicate that in both cases adsorption is predominantly due to dispersion forces for which interaction nevertheless leads to chemical activation and reaction. Both adsorbates exhibited pronounced island formation, thought to limit chemical activity under the conditions used and posited to occur at island boundaries, as was indeed observed in the case of phenylacetylene. The implications of these findings for the development of practical catalytic systems are considered.

On the group delay statistics of few-mode fibres with intermediate linear mode coupling

We report an investigation on the statistics of group delay for few-mode fibres operating in the weak and strong linear coupling regimes as well as in the intermediate coupling regime. A single expression linking the standard deviation of the group delay spread to the fibre linear mode coupling is validated for any coupling regime, considering up to six linearly polarized guided modes. Furthermore, the study of the probability density function of the group delays allowed deriving and validating an analytical estimation for the maximum group delay spread as a function of linear mode coupling.