Functional Carbazole Liquid‐Crystal Block Codendrimers with Optical and Electronic Properties

The synthesis and characterisation of a family of block codendrimers consisting of highly versatile mesogenic and carbazole‐containing 2,2‐bis(hydroxymethyl)propionic acid (bis‐MPA) dendrons are reported. The liquid‐crystal behaviour was investigated by means of differential scanning calorimetry, polarised‐light optical microscopy and X‐ray diffraction. Depending on the chemical structure of the constituent dendrons, the codendrimers show lamellar or columnar mesophases. On the basis of the experimental results, models both at the molecular level and in the mesophase are proposed. The physical properties of the block codendrimers derived from the presence of the carbazole moiety in their structure were investigated: photoluminescence in solution and in the mesophase, electrochemical behaviour and hole transport. Electrodeposition of carbazole dendrons afforded a globular supramolecular conformation in which the mesogenic molecular side plays a key role.     

Diblock copolymers based on allyl methacrylate: Synthesis,characterization, and chemical modification

Different diblock copolymers constituted by one segment of a monomer supporting a reactive functional group, like allyl methacrylate (AMA), were synthesized by atom transfer radical polymerization (ATRP). Bromo‐terminated polymers, like polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(butyl acrylate) (PBA) were employed as macroinitiators to form the other blocks. Copolymerizations were carried out using copper chloride with N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as the catalyst system in benzonitrile solution at 70 °C. At the early stage, the ATRP copolymerizations yielded well‐defined linear block copolymers. However, with the polymerization progress a change in the macromolecular architecture takes place due to the secondary reactions caused by the allylic groups, passing to a branched and/or star‐shaped structure until finally yielding gel at monomer conversion around 40% or higher. The block copolymers were characterized by means of size exclusion chromatography (SEC), ¹H NMR spectroscopy, and differential scanning calorimetry (DSC). In addition, one of these copolymers, specifically P(BA‐b‐AMA), was satisfactorily modified through osmylation reaction to obtain the subsequent amphiphilic diblock copolymer of P(BA‐b‐DHPMA), where DHPMA is 2,3‐dihydroxypropyl methacrylate; demonstrating the feasibility of side‐chain modification of the functional obtained copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3538–3549, 2007     

Residual currents and corridor of flow in the Rio de la Plata

The Rio de la Plata is a large and shallow water body that discharges onto the Atlantic Ocean. The main driving forces for the river flow are the bathymetry, tides, the outflow from the Paraná and Uruguay rivers and the winds. A numerical model covering the entire river was set up with the objective of increasing our understanding of the hydrographical features and morphological dynamics in the Estuary. The simulations revealed a counter-clockwise residual circulation in the Samborombón Bay and an eastward net flow near the Uruguayan coast. The residual flow is forced by both the tides and the bathymetry. The residence time for the entire river ranges from 40 to 80 days. However, residence times above 120 days was found in the Samborombón Bay. Three corridors of flow have been identified.     

Analysis of Antennas with PBG Substrate

The use of photonic materials has been used in the theory of optical waves. The PBG (Photonic Band Gap) theory and material, was developed recently for optical frequencies and can be easily applied to millimeter waves, microwaves and planar antenna frequencies. The presence of photonic materials as substrate in antennas has some good characteristics such as, supression of light spontaneous emission and suppression of surface waves, allowing the application in planar antenna array. In this work an elaborate analysis using the full wave Transverse Transmission Line - TTL method, that provides efficient and concise results is applied to the planar antennas array with PBG substrate.     

UPML formulation for truncating conductive media in curvilinear coordinates

This work presents a formulation based on UPML for truncating conductive media by using a local and non-orthogonal coordinate system to solve Maxwell’s equations by the FDTD method. The detailed procedure for obtaining the UPML equations for this case is shown and the complete equation set is provided.     

The first total synthesis of (R)-convolutamydine A

The first total synthesis of (R)-convolutamydine A has been achieved by the organocatalytic addition of acetone to 4,6-dibromoisatin. The absolute configuration was determined by single crystal X-ray diffraction. DFT studies were used to model the transition states for the aldol reaction and equilibrium geometries of the post-aldol reaction intermediates. The DFT study revealed that the aldol bond forming reaction was considerably endothermic.     

On the evolution of sharp fronts for the quasi‐geostrophic equation

We consider the problem of the evolution of sharp fronts for the surface quasi‐geostrophic (QG) equation. This problem is the analogue to the vortex patch problem for the two‐dimensional Euler equation. The special interest of the quasi‐geostrophic equation lies in its strong similarities with the three‐dimensional Euler equation, while being a two‐dimen‐sional model. In particular, an analogue of the problem considered here, the evolution of sharp fronts for QG, is the evolution of a vortex line for the three‐dimensional Euler equation. The rigorous derivation of an equation for the evolution of a vortex line is still an open problem. The influence of the singularity appearing in the velocity when using the Biot‐Savart law still needs to be understood. We present two derivations for the evolution of a periodic sharp front. The first one, heuristic, shows the presence of a logarithmic singularity in the velocity, while the second, making use of weak solutions, obtains a rigorous equation for the evolution explaining the influence of that term in the evolution of the curve. Finally, using a Nash‐Moser argument as the main tool, we obtain local existence and uniqueness of a solution for the derived equation in the C^∞ case. © 2004 Wiley Periodicals, Inc.     

Synthesis and characterization of functional gradient copolymers of allyl methacrylate and butyl acrylate

Functional spontaneous gradient copolymers of allyl methacrylate (A) and butyl acrylate (B) were synthesized via atom transfer radical polymerization. The copolymerization reactions were carried out in toluene solutions at 100 °C with methyl 2‐bromopropionate as the initiator and copper bromide with N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the catalyst system. Different aspects of the statistical reaction copolymerizations, such as the kinetic behavior, crosslinking density, and gel fraction, were studied. The gel data were compared with Flory's gelation theory, and the sol fractions of the synthesized copolymers were characterized by size exclusion chromatography and nuclear magnetic resonance spectroscopy. The copolymer composition, demonstrating the gradient character of the copolymers, and the microstructure were analyzed. The experimental data agreed well with data calculated with the Mayo–Lewis terminal model and Bernoullian statistics, with monomer reactivity ratios of 2.58 ± 0.37 and 0.51 ± 0.05 for A and B, respectively, an isotacticity parameter for A of 0.24, and a coisotacticity parameter of 0.33. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5304–5315, 2006     

The radiative return at small angles: virtual corrections

Virtual corrections for electron-positron annihilation into one real and one off-shell photon of invariant mass are evaluated. Special attention is paid to those configurations where the real photon is collinear with the beam direction. This calculation is an important ingredient of a Monte Carlo program, which simulates events with tagged photons from initial-state radiation, including NLO corrections. Received: 24 April 2002 / Published online: 12 July 2002     

On boundary conditions in three-dimensional AdS gravity

A finite action principle for three-dimensional gravity with negative cosmological constant, based on a boundary condition for the asymptotic extrinsic curvature, is considered. The bulk action appears naturally supplemented by a boundary term that is one half the Gibbons–Hawking term, that makes the Euclidean action and the Noether charges finite without additional Dirichlet counterterms. The consistency of this boundary condition with the Dirichlet problem in AdS gravity and the Chern–Simons formulation in three dimensions, and its suitability for the higher odd-dimensional case, are also discussed.