Ruthenium tris(bipyridine) complexes with sulfur substituents: model studies for PEG coupling

Ruthenium polypyridyl complexes are incorporated into polymers for sensing and light emitting materials applications. Coupling reactions between metal complexes and polymers are one route to polymeric metal complexes. In an effort to increase conjugation efficiency, tune materials properties, and introduce a responsive crosslink, ruthenium tris(bipyridine) derivatives with sulfur substituents were synthesized and compared to oxygen analogues. Difunctional thiols, thioesters, thioethers, and disulfides, as well as hexafunctional nonpolymeric model systems, were explored. Upon exposure to oxygen, the thiol derivative was readily oxidized. These studies guided Ru(bpy)3 PEG coupling reactions with disulfide and thioether linkages, which proceeded to approximately 80% and approximately 60% yield, respectively. The luminescence properties of the Ru PEG derivatives and model systems were investigated. The emission spectra and lifetimes for all complexes in CH3CN under an inert atmosphere are comparable to [Ru(bpy)3]Cl2. Lifetime data for nonpolymeric analogues fit to a single exponential decay indicating heterogeneity, suggesting sample homogeneity, whereas data for polymers fit to a multiexponential decay. In contrast to certain [Ru(bpy)3](2+)/thiol mixtures, no intramolecular quenching by the sulfide is observed for [Ru(bpy)2{bpy(CH2SH)2}](PF6)2. Emission spectra red shift and multiexponential decay are noted for the oxidized Ru thiol product. The rates of oxygen quenching are slower for Ru PEG derivatives than those for nonpolymeric analogues, which may be attributed to shielding effects of the polymer chain.     

GaAs integrated quantum photonics: Towards compact and multi‐functional quantum photonic integrated circuits

The recent progress in integrated quantum optics has set the stage for the development of an integrated platform for quantum information processing with photons, with potential applications in quantum simulation. Among the different material platforms being investigated, direct‐bandgap semiconductors and particularly gallium arsenide (GaAs) offer the widest range of functionalities, including single‐ and entangled‐photon generation by radiative recombination, low‐loss routing, electro‐optic modulation and single‐photon detection. This paper reviews the recent progress in the development of the key building blocks for GaAs quantum photonics and the perspectives for their full integration in a fully‐functional and densely integrated quantum photonic circuit.

     

Geometrical Tools for Quantum Euclidean Spaces

We apply one of the formalisms of noncommutative geometry to ℝ ^N _q , the quantum space covariant under the quantum group SO _q (N). Over ℝ ^N _q there are two SO _q (N)-covariant differential calculi. For each we find a frame, a metric and two torsion-free covariant derivatives which are metric compatible up to a conformal factor and which have a vanishing linear curvature. This generalizes results found in a previous article for the case of ℝ³ _q . As in the case N=3, one has to slightly enlarge the algebra ℝ ^N _q ; for N odd one needs only one new generator whereas for N even one needs two. As in the particular case N=3 there is a conformal ambiguity in the natural metrics on the differential calculi over ℝ ^N _q . While in our previous article the frame was found “by hand”, here we disclose the crucial role of the quantum group covariance and exploit it in the construction. As an intermediate step, we find a homomorphism from the cross product of ℝ ^N _q with U _q so(N) into ℝ ^N _q , an interesting result in itself. Received: 4 March 2000 / Accepted: 11 October 2000     

Corrigendum: Organometallic complexes with biological molecules: VII. Diorgano– and triorgano–tin(IV)[meso–tetra(4–carboxyphenyl)porphinate] derivatives: solid–state,solution–phase structural aspects and in vivo effects

The title of this paper, published in Applied Organometallic Chemistry 11 , 499–511 (1977), was incorrect. The correct version is as above.     

Alginate Bioconjugate and Graphene Oxide in Multifunctional Hydrogels for Versatile Biomedical Applications

In this work, we combined electrically-conductive graphene oxide and a sodium alginate-caffeic acid conjugate, acting as a functional element, in an acrylate hydrogel network to obtain multifunctional materials designed to perform multiple tasks in biomedical research. The hybrid material was found to be well tolerated by human fibroblast lung cells (MRC-5) (viability higher than 94%) and able to modify its swelling properties upon application of an external electric field. Release experiments performed using lysozyme as the model drug, showed a pH and electro-responsive behavior, with higher release amounts and rated in physiological vs. acidic pH. Finally, the retainment of the antioxidant properties of caffeic acid upon conjugation and polymerization processes (Trolox equivalent antioxidant capacity values of 1.77 and 1.48, respectively) was used to quench the effect of hydrogen peroxide in a hydrogel-assisted lysozyme crystallization procedure.     

Non-linear BFKL dynamics: Color screening vs. gluon fusion

A feasible mechanism of unitarization of amplitudes of deep inelastic scattering at small values of Bjorken x is the gluon fusion. However, its efficiency depends crucially on the vacuum color screening effect which accompanies the multiplication and the diffusion of BFKL gluons from small to large distances. From the fits to lattice data on field strength correlators the propagation length of perturbative gluons is R _c ? (0.2–0.3) fm. The probability to find a perturbative gluon with short propagation length at large distances is suppressed exponentially. It changes the pattern of (dif)fusion dramatically. The magnitude of the fusion effect appears to be controlled by the new dimensionless parameter ～ R _c ² /8B, with the diffraction cone slope B standing for the characteristic size of the interaction region. It should slowly ∝ 1/lnQ ₂ decrease at large Q ². Smallness of the ratio R _c ² /8B makes the non-linear effects rather weak even at lowest Bjorken x available at HERA. We report the results of our studies of the non-linear BFKL equation which has been generalized to incorporate the running coupling and the screening radius, R _c as the infrared regulator.     

Liquid crystal orientation in elliptic droplets in nematic emulsions

Elliptic droplets of nematic liquid crystal dispersed in a fluid organic monomer were obtained by phase separation from an isotropic mixture consisting of an organic monomer and a nematic liquid crystal contained in a poly(ethylene terephthalate) cell with inner surfaces treated with rubbed polyimide. The elliptic shape is a consequence of the constraint upon droplet growth along the direction perpendicular to the cell surfaces owing to the small thickness. Then, the resulting droplets will have a contact area with the inner surfaces of the cell treated with polyimide, which will impart a planar orientation on the liquid crystal in the droplet. By means of an optical microscope, using a simple pin hole of 5 μm, we have selected single droplets for a series of samples having different contact areas. By polarized infrared spectroscopy we have also studied the liquid crystal orientation in selected areas of the droplets. We then report the dependence of the order parameter of the liquid crystal on different contact areas with the alignment surface of the cell. The good degree of planar alignment of the liquid crystal in the elliptic droplets allows the use of such a technique for realizing electro-optical films operating in the reverse mode. We report the electro-optical transmission of reverse mode films with different sizes of elliptic droplet.