New functionalized polyesters to achieve controlled architectures

Following our continued interest in the production of bioerodible and biodegradable functional polymers for biomedical applications, we synthesized and characterized new unsaturated polyesters. The presence of functional groups in the polymer backbone provided sites for chemical modification, and through a variation in the structure, the physical properties, such as the hydrophilicity and solubility, could be affected. With 1,1-di-n-butyl-stanna-2,7-dioxacyclo-4-heptene as the initiator in the ring-opening polymerization of polyesters, a new set of functionalized polyesters was created. The polymerization of ϵ-caprolactone resulted in poly(ϵ-caprolactone) with a double bond incorporated into the structure. The polymers were obtained in a controlled manner with low molecular dispersities. The double bond was previously incorporated into L -lactide polymers, and the two reactions were compared in this study. The conversion of ϵ-caprolactone, with a degree of polymerization of 50, was completed within 140 min, whereas for L -lactide, only a 45% conversion took place in the same period of time. The dispersities were somewhat higher with ϵ-caprolactone because of the higher reaction rate and, therefore, lower selectivity. The incorporated CC double bond in the polyesters provided a variety of opportunities for further modifications. In this case, the double bond of the L -lactide macromonomers was oxidized into epoxides. Epoxidation was carried out with m-chloroperoxybenzoic acid as a chemical reagent. The conversion of the double bonds into epoxides was completed, and the obtained yields were good (>95%). As a result of the mild reaction conditions, the epoxidation of the double bond was carried out quantitatively without any side reactions. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 444–452, 2004     

Synthesis of Organic-Inorganic Hybrid Particles by Sol-Gel Chemistry

The synthesis of ORganically MOdified SILica (ORMOSIL) particles has been carried out using both the hydrolytic and non-hydrolytic sol-gel routes. The hybrid (nano)composites are organically modified with an alkyl or aryl group covalently bonded to silicon. Hybrids have been synthesised in an aqueous sol-gel process by a modified Stöber route, producing spherical nanoparticles with diameters in the range 50–300 nm. The size of the particles can be controlled by control of certain reaction parameters. Smaller ormosil nanoparticles can be synthesised by a base-catalysed emulsion polymerisation route, by varying the type and concentration of surfactant and precursor feed rate. In this case, particles in the size range 3.5–10 nm can be obtained. Hybrids have been synthesised from hyperbranched polyesters by encapsulation in a silica matrix using the hydrolytic sol-gel route. Optimisation of the reaction conditions allows the hybrids to be produced as isolated sub-micron spherical particles. Ormosil particles have also been synthesised using the non-hydrolytic sol-gel route, which may lead to products of different morphologies because of the different polarity of the reaction medium. Different reaction conditions were studied in order to optimise the size and shape of the particles, including choice of solvent, use of surfactants and addition of polystyrene. Dimethylsulfoxide acts as a novel oxygen donor for the catalyst-free formation of colourless silsesquioxanes.     

On division rings with algebraic commutators of bounded degree

We shall answer several questions concerning additive or multiplicative commutators in a division ring which are algebraic of bounded degree over its center.     

Seizure warning algorithm based on optimization and nonlinear dynamics

There is growing evidence that temporal lobe seizures are preceded by a preictal transition, characterized by a gradual dynamical change from asymptomatic interictal state to seizure. We herein report the first prospective analysis of the online automated algorithm for detecting the preictal transition in ongoing EEG signals. Such, the algorithm constitutes a seizure warning system. The algorithm estimates STL_max, a measure of the order or disorder of the signal, of EEG signals recorded from individual electrode sites. The optimization techniques were employed to select critical brain electrode sites that exhibit the preictal transition for the warning of epileptic seizures. Specifically, a quadratically constrained quadratic 0-1 programming problem is formulated to identify critical electrode sites. The automated seizure warning algorithm was tested in continuous, long-term EEG recordings obtained from 5 patients with temporal lobe epilepsy. For individual patient, we use the first half of seizures to train the parameter settings, which is evaluated by ROC (Receiver Operating Characteristic) curve analysis. With the best parameter setting, the algorithm applied to all cases predicted an average of 91.7% of seizures with an average false prediction rate of 0.196 per hour. These results indicate that it may be possible to develop automated seizure warning devices for diagnostic and therapeutic purposes.Mathematics Subject Classification (1991):20E28, 20G40, 20C20     

On Einstein four-manifolds with <Emphasis Type="Italic">S</Emphasis><Superscript>1</Superscript>-actions

We study closed Einstein 4-manifolds which admit S¹ actions of a certain type, i.e., warped products. In particular, we classify them up to isometry when the fixed point of the S¹ action satisfies certain natural geometric conditions. The proof uses the Bochner-Weitzenböck formula for 1-forms and the theory of minimal surfaces in 3-manifolds.in final form: 22 January 2003     

Kinetic Models for Chemotaxis and their Drift-Diffusion Limits

Kinetic models for chemotaxis, nonlinearly coupled to a Poisson equation for the chemo-attractant density, are considered. Under suitable assumptions on the turning kernel (including models introduced by Othmer, Dunbar and Alt), convergence in the macroscopic limit to a drift-diffusion model is proven. The drift-diffusion models derived in this way include the classical Keller-Segel model. Furthermore, sufficient conditions for kinetic models are given such that finite-time-blow-up does not occur. Examples are given satisfying these conditions, whereas the macroscopic limit problem is known to exhibit finite-time-blow-up. The main analytical tools are entropy techniques for the macroscopic limit as well as results from potential theory for the control of the chemo-attractant density.Present address: Centro de Matemática e Aplicações Fundamentais, Universidade de Lisboa, Av. Prof. Gama Pinto 2, 1649-003, Lisboa, Portugal     

Bounded Positive Solutions of Schrödinger Equations in Two-Dimensional Exterior Domains

We prove under quite general assumptions the existence of a bounded positive solution to the semilinear Schrödinger equation in a two-dimensional exterior domain.     

On a Definitizable Analog of the Trigonometric Moment Problem Generating an Indefinite Toeplitz Form

We prove the existence of an integro-polynomial representation for a sequence of numbers such that there exists a difference operator mapping this sequence to a sequence that generates the solvable trigonometric moment problem. A similar result related to the power moment problem was given in [12].