Förster energy transfer from poly(arylene–ethynylene)s to an erbium–porphyrin complex

We study the infrared emission at 1.54 μm of an organolanthanide complex, Er(III)-tetraphenylporphyrin [Er(TPP)acac], both as a result of direct optical excitation and via energy transfer from host π-conjugate polymers of type poly(arylene–ethynylene) [PAE]. In the first case, the emission of the neat complex is characterized in inert transparent materials and a value of the quantum yield at 1.54 μm φ_IR=4×10⁻⁴ is measured. Then, fluorescence resonance transfer is investigated in blends of Er(TPP)acac with PAEs by monitoring the quenching of the polymer fluorescence along with the enhancement of both the visible emission of the ligand and the near-infrared band of Er³⁺. These different procedures allow a detailed analysis of the transfer efficiency within a specific implementation of the Förster model for polymeric donors. The experimental values of the critical radius R₀, ranging from 1.3 to 2.5 nm for the different blends, are in good agreement with theory for a wide interval of the physical and spectroscopic parameters. This suggests that other mechanisms for excitation transfer do not play a significant role in these materials.     

Ordered states and structural transitions in a system of Abrikosov vortices with periodic pinning

A system of Abrikosov vortices in a quasi-two-dimensional HTSC plate is considered for various periodic lattices of pinning centers. The magnetization and equilibrium configurations of the vortex density for various values of external magnetic field and temperature are calculated using the Monte Carlo method. It is found that the interaction of the vortex system with the periodic lattice of pinning centers leads to the formation of various ordered vortex states through which the vortex system passes upon an increase or a decrease in the magnetic field. It is shown that ordered vortex states, as well as magnetic field screening processes, are responsible for the emergence of clearly manifested peaks on the magnetization curves. Extended pinning centers and the effect of multiple trapping of vortices on the behavior of magnetization are considered. Melting and crystallization of the vortex system under the periodic pinning conditions are investigated. It is found that the vortex system can crystallize upon heating in the case of periodic pinning.     

Sulfobetaine‐containing diblock and triblock copolymers via reversible addition‐fragmentation chain transfer polymerization in aqueous media

A novel bifunctional acrylamido‐based reversible addition–fragmentation chain transfer (RAFT) chain‐transfer agent (CTA), N,N′‐ethylenebis[2‐(thiobenzoylthio)propionamide] (CTA2), has been synthesized and used for the controlled free‐radical polymerization of N,N‐dimethylacrylamide (DMA). A comparative study of CTA2 and the monofunctional CTA N,N‐dimethyl‐s‐thiobenzoylthiopropionamide (CTA1) has been conducted. Polymerizations mediated by CTA1 result in poly(N,N‐dimethylacrylamide) (PDMA) homopolymers with unimodal molecular weight distributions, whereas CTA2 yields unimodal, bimodal, and trimodal distributions according to the extent of conversion. The multimodal nature of the PDMAs has been attributed to termination events and/or chains initiated by primary radicals. The RAFT polymerization of DMA with CTA2 also results in a prolonged induction period that may be attributed to the higher local concentration of dithioester functionalities early in the polymerization. A series of ω‐ and α,ω‐dithioester‐capped PDMAs have been prepared in organic media and subsequently employed as macro‐CTAs for the synthesis of diblock and triblock copolymers in aqueous media with the zwitterionic monomer 3‐[2‐(N‐methylacrylamido)‐ethyldimethylammonio] propane sulfonate (MAEDAPS). Additionally, an ω‐dithioester‐capped MAEDAPS homopolymer has been used as a macro‐CTA for the block polymerization of DMA. To our knowledge, this is the first example of a near‐monodisperse, sulfobetaine‐containing block copolymer prepared entirely in aqueous media. The diblock and triblock copolymers form aggregates in pure water that can be dissociated by the addition of salt, as determined by ¹H NMR spectroscopy and dynamic light scattering. In pure water, highly uniform, micellelike aggregates with hydrodynamic diameters of 71–93 nm are formed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1262–1281, 2003     

Lein?l, Lein?lfirniss und Oelfarben

Ohne Zusammenfassung     

The mechanism of emission in the red photoluminescence band of porous silicon

Porous silicon (PS) exhibits several photoluminescence (PL) bands, whose spectral position and intensity depend strongly on the actual conditions of preparation of PS, its treatment, and subsequent use. The PS PL band peaking at about 1.8 eV and usually assigned to the intrinsic emission of silicon nanocrystals was studied. It was shown that the temperature-induced variation of the PL kinetics in the 80 to 300-K interval follows a complex pattern and depends noticeably on the actual point on the band profile. The temperature behavior of PL decay in the 1.8-eV band is determined by the electron-hole recombination rate within a nanocrystal and the cascade carrier transitions from small to large nanocrystals, with an attendant decrease in energy.     

Numerical study of the effects of the rupture process of a secondary diaphragm in expansion tubes

The results of a numerical study are described in which the interactions of a primary shock wave with a secondary diaphragm in expansion tubes are taken into account. The developing wave pattern in the interacting process of the shock with a secondary diaphragm are visualized by many kinds of figures (e.g., the time-distance diagrams of the wave phenomena on the axis, the acoustic impedance contours, and the time histories of the pitot pressure on the axis), and the influences of the shape and rupture process of the diaphragm on the quality of the test gas are explored.     

An algorithm to locate perinatal facilities in the municipality of Rio de Janeiro

In order to reduce infant mortality in the municipality of Rio de Janeiro it is desired to encourage all mothers-to-be to attend the appropriate health care facilities. A 3-level hierarchical prenatal–neonatal health care system is described together with a basic model for optimising accessibility to facilities. A genetic algorithm to solve the basic model is developed and some numerical experience reported. Extensions to the basic model and planned future research are briefly indicated.     

Inversion of adjunction for non-degenerate hypersurfaces

 We prove a precise inversion of adjunction formula for the log variety (ℂ ^{d +1},X), where X is a non-degenerate hypersurface. As a corollary, the minimal log discrepancies of non-degenerate normal hypersurface singularities are bounded by dimension. Received: 17 September 2002 / Revised version: 22 November 2002 Published online: 14 February 2003 Current address: DPMMS, CMS, University of Cambridge, Wilberforce Road, Cambridge CB3 0WB, England. e-mail: f.ambro@dpmms.cam.ac.uk Mathematics Subject Classification (2000): Primary 14B05; Secondary 14M25, 52B20