Emissive Annular Digold(I) Compounds Containing Diphosphine and Dithiolate Ligands

Molecular structures of three emissive annular digold compounds [Au₂(dmpm)(dtc)]Cl (dmpm = Me₂PCH₂PMe_2,dtc = S₂CNEt₂), 1 , [Au₂(dppm)(dtc)]PF₆, (dppm = Ph₂PCH₂PPh₂),₂,and [Au₂(dppe)(dtc)]-(PF₂) (dppe = Ph₂P(CH₂)₂PPh₂), 3, were determined. All three compounds are dimetallacycles having two gold atoms bridged by a dithiolate ligand and a diphosphine ligand, the geometry around each gold atom being almost linear. All the dimetal lacy die rings are slightly distorted from planarity with intramolecular Au-Au distances shorter than 3.0 Å. Compound 1 forms a polymeric chain through intermolecular Au-Au contacts (3.061 ? 3.135 Å). Compound 2 forms a tetramer through intermolecular Au-Au interactions (Au-Au distances ranging from 3.086 to 3.222 ). Compound 3 is monomeric. All of the compounds luminesce at 77 K in the solid state. Emissions originating from ³LMCT from dtc ligand to Au excited states are assigned. The emission maxima of 1 ? 3 are at 541,535 and 520 nm respectively and are blue shifted as the number of Au-Au interactions is decreased.     

Comparative study on conventional and low-flow nebulizers for arsenic speciation by means of microbore liquid chromatography with inductively coupled plasma mass spectrometry

The performance of conventional and low-flow nebulizer systems with liquid chromatography in differentiating four arsenic species in urine was evaluated. Two low-flow (DIN and MCN) chamber assemblies and a conventional (CFN) nebulizer-spray chamber assembly were compared in the hyphenation of anion-exchange microbore liquid chromatography with inductively coupled plasma mass spectrometry. Under optimal analytical conditions, the detection limits of the four arsenic species were 0.2-0.6 ng ml(-1) for all the nebulizer systems tested. The chromatographic resolution was best in the case of DIN due to its minimal off-column dead volume and superior transport efficiency. Four arsenic species were determined in the certified reference materials NIST SRM 2670E and 2670N.     

Voltage-controlled optical switch in planar nematic liquid crystal film

This study presents an integrated device that consists of a directional coupler and an electro-optic switch. The device is designed to include a nematic liquid crystal cell, comprising a grating-like electrode. Applying the appropriate voltage to the cell yields a periodically distributed refractive index. An incident polarized beam will couple to an adjacent channel if it is parallel to the channel. The coupling efficiency is controlled by applied voltage. An obliquely injected polarized beam will be reflected and refracted in the channel, and propagated along a curved path. The route of the beam can be controlled by applying the voltage. A multiport routing was achieved for voltage modulation. In addition, the distribution of refractive index is also investigated by employing conoscopic technique experimentally and numerically.     

Nanoscale Material Heterogeneity of Glowworm Capture Threads Revealed by AFM

Adhesive materials used by many arthropods for biological functions incorporate sticky substances and a supporting material that operate synergistically by exploiting substrate attachment and energy dissipation. While there has been much focus on the composition and properties of the sticky glues of these bio-composites, less attention has been given to the materials that support them. In particular, as these materials are primarily responsible for dissipation during adhesive pull-off, little is known of the structures that give rise to functionality, especially at the nano-scale. In this study we used tapping mode atomic force microscopy (TM-AFM) to analyze unstretched and stretched glowworm (Arachnocampa tasmaniensis) capture threads and revealed nano-scale features corresponding to variation in surface structure and elastic modulus near the surface of the silk. Phase images demonstrated a high resolution of viscoelastic variation and revealed mostly globular and elongated features in the material. Increased vertical orientation of 11–15 nm wide fibrillar features was observed in stretched threads. Fast Fourier transform analysis of phase images confirmed these results. Relative viscoelastic properties were also highly variable at inter- and intra-individual levels. Results of this study demonstrate the practical usefulness of TM-AFM, especially phase angle imaging, in investigating the nano-scale structures that give rise to macro-scale function of soft and highly heterogeneous materials of both natural and synthetic origins.     

Reorientational optical nonlinearity of nematic liquid-crystal cells near the nematic-isotropic phase transition temperature

We address the reorientational optical nonlinearity of homogeneously aligned neamtic liquid-crystal (NLC) cells. The propagation of light in NLC cells depend strongly on temperature. At a temperature approaching the clearing point, an undulating beam and multifocal points are observed in the NLC cell by use of a polarizing optical microscope. Using a conoscopic technique, we observed novel consecutive concentric and parabolic patterns projected onto a screen. Optical energy is considered to compete with thermal energy to affect NLC's orientation and to generate singularities in the steady state. A model of the configuration of the liquid crystal's orientation is proposed.     

Synthesis of 7-oxo-8-aza-10a-homoprost-13-enoic acid

The synthesis of a prostaglandin E₁ analog, 7-oxo-8-aza-10a-homoprost-13-enoic acid, is reported.     

Experimental observation of chaotic phase synchronization of a periodically pump-modulated multimode microchip Nd:YVO4 laser

In this Letter we demonstrate the experimental observation of chaotic phase synchronization (CPS) in a periodically pump-modulated multimode microchip Nd:YVO₄ laser. PS transition is displayed via the stroboscopic technique. We apply the recurrence probability and correlation probability of recurrence to estimate the degree of PS. The degree of PS is studied taking into account the modulation amplitude and modulation frequency. We also propose an experimental compatible numerical simulation to reflect the fact that the Arnold tongues are experimentally and numerically exhibited in the periodically pump-modulated multimode microchip Nd:YVO₄ laser.     

Electroactive self-assembled biferrocenyl alkanethiol monolayers on Au(111) surface and on gold nanoclusters

The spectroscopic and electrochemical characterizations of electrochemically stable biferrocene-modified Au clusters and chemisorbed biferrocenylalkanethiols on Au(111) surface were studied. The characterizations of biferrocene-modified Au cluster using TEM, UV-vis, and NMR techniques are also reported. Two successive reversible one-electron redox waves were observed for the biferrocenylalkanethiol Au nanoclusters and biferrocenylalkanethiol monolayers on Au(111) surface in the cyclic voltammetry. Furthermore, the positive and negative current peaks for each redox wave occur at almost the same potential, and the peak current increases almost linearly with the sweep rate. Repeat scanning does not change the voltammograms, demonstrating that these monolayers are stable to electrochemical cycling. The coverages of electroactive biferrocene in the monolayers were calculated from the cyclic voltammograms. The standard electron-transfer rate constant was calculated from the splitting between the oxidation and reduction peaks.     

Boundary element method for thermoelastic analysis of three-dimensional transversely isotropic solids

Thermal effects are well known to manifest themselves as additional volume integral terms in the direct formulation of the boundary integral equation (BIE) for linear elastic solids when using the boundary element method (BEM). This domain integral has been successfully transformed in an exact manner to surface ones only in isotropy and in 2D anisotropy, thereby restoring the BEM as a truly boundary solution technique. The difficulties with extending it to 3D general anisotropic solids lie in the mathematical complexity of the Green’s function and its derivatives for such materials. These quantities are required items in the BEM formulation. In this paper, the exact, analytical transformation of the volume integral associated with thermal effects to surface ones is achieved for a transversely isotropic material using a similar approach which the authors have previously employed for the same task in BEM for 2D general anisotropy. A numerical scheme, however, needs to be employed to evaluate some of the new terms introduced in the surface integrals that arise from this process here. The mathematical soundness of the formulation is demonstrated by a few examples; the numerical results obtained are checked by alternative means, including those obtained from the commercial FEM code, ANSYS.     

Distinguishing a driver from a response system

This study presents an approach for distinguishing a driver from a response system. The proposed method can be applied to both unidirectional or bidirectional interactions, and to identical or structurally different systems. Compared with most previously proposed schemes, the present method is so "simple" that the driver-response relationships can generally be detected using a direct graphic way. On the other hand, quantitative estimation is also developed using the idea of the correlation dimension.