Anionic iron(II) alkoxides as initiators for the controlled ring‐opening polymerization of lactide

Hetero‐bimetallic Fe(II) alkoxide/aryloxides were evaluated as initiators for the ring‐opening polymerization of rac‐lactide. [(THF)NaFe(O^tBu)₃]₂ ( 1 ) and [(THF)₄Na₂Fe(2,6‐diisopropylphenolate)₄] ( 2 ) (THF = tetrahydrofuran) both polymerized lactide efficiently at room temperature, with complex 1 affording better control over the molecular weight parameters of the resultant polymer. At conversions below 70%, a linear increase in molecular weight with conversion was observed, indicative of a well‐controlled polymerization process. Complex 2 is the first example of a dianionic Fe(II) alkoxide and has been structurally characterized to reveal a distorted square planar FeO₄ array in which both Na counterions bridge two aryloxide ligands and are further complexed by two THF ligands. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3798–3803, 2003     

effect of surface modification on the properties of hydrogen-sensitive GaAs-based Schottky diodes

The surface of hydrogen-sensitive GaAs Schottky diodes is modified by nonpolishing etching and by producing quantum wells and quantum dots in the space-charge region of the semiconductor. The sensitivity to hydrogen is found to increase by a factor of 8–37 after the etching and by two or three orders of magnitude after the introduction of quantum wells and dots. It is shown that the increased sensitivity is associated with the lowering of the barrier at the Pd/GaAs interface, the retardation of hydrogen diffusion into GaAs due to the presence of strained quantum-size layers, and an increase in the recombination current. The presence of the recombination component is supported by luminescence from the quantum wells and quantum dots, as well as from the GaAs substrate. The etch composition is shown to be a decisive factor in raising the sensitivity.     

Rapid and efficient synthesis of optically active pyrazoles under solvent-free conditions

2-Formyl glycals undergo rapid condensation with arylhydrazines under solvent-free conditions to give the corresponding optically pure 4-substituted pyrazoles in good yields with high selectivity. The stereochemistry of the products was assigned by various NMR experiments.     

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     

Some applications of polarized inelastic neutron scattering in magnetism

A brief account of applications of polarized inelastic neutron scattering in condensed matter research is given. We show that full polarization analysis is the only tool allowing to discriminate unambiguously between different magnetic modes in various magnetic materials. We show by means of recent results in the Heisenberg ferromagnet EuS that the effects of dipolar interactions can be studied on a microscopic scale. Moreover, we have found for the first time indications for the divergence of the longitudinal fluctuations belowT _c. In the itinerant antiferromagnet chromium we demonstrate that the dynamics of the longitudinal and transverse excitations are very different, resolving a long standing puzzle concerning the slope of their dispersion. Finally, we show that a measurement of the polarization-dependent part of the cross section of non-centrosymmetric MnSi proves directly that the chirality of the magnetic fluctuations is left-handed.     

What Oxidation State of Iron Determines the Amethyst Colour?

A colourless quartz crystal doped with ⁵⁷Fe³⁺ was obtained by hydrothermal synthesis in an NH₄F solution. The crystal was transformed into violet amethyst by gamma-irradiation. The change in colour was accompanied by changes in the Mössbauer spectrum that can be interpreted as the conversion of trivalent iron into the tetravalent state: Fe³⁺→Fe⁴⁺.

     

Mechanisms for the SAR Imaging of the Ocean

We perform a comparative analysis of two mechanisms for the formation of a synthetic aperture radar (SAR) image of the ocean, which are related to orbital velocities on the surface. It is shown that the mechanism of fluctuations of the effective density of scatterers, which is commonly accepted at present as the physical basis for the SAR diagnostics of roughness, actually works only in the case of a sufficiently flat swell. In the presence of wind roughness, the dominant role is played by another mechanism, namely, fluctuations of the number of surface elements whose images are randomly shifted and superimposed in the image plane due to orbital velocities. In the case of a developed wind roughness propagated in the azimuthal direction, the power contributions of two above-mentioned mechanisms to the SAR imaging of the ocean differ by about two orders of magnitude.     

On a Result of R. Turner

We study the similarity of perturbed compact operators to operators of block-diagonal structure with respect to some family of orthogonal projection operators, which allows us to refine and essentially strengthen results due to R. Turner. We obtain information about the operator realizing the similarity transformation, present estimates for the eigenvalues and eigenvectors of the perturbed operator, and also study the inverse problem of spectral analysis.     

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.