Ultrafast laser written active devices

Direct‐write optical waveguide device fabrication is probably the most widely studied application of femtosecond laser micromachining in transparent dielectrics at the present time. Devices such as buried waveguides, power splitters, couplers, gratings, optical amplifiers and laser oscillators have all been demonstrated. This paper reviews the application of the femtosecond laser direct‐write technique to the fabrication of active waveguide devices in bulk glass materials.     

Self-assembly of a confined rhodium catalyst for asymmetric hydroformylation of unfunctionalized internal alkenes

A chiral supramolecular ligand has been assembled and applied to the rhodium-catalyzed asymmetric hydroformylation of unfunctionalized internal alkenes. Spatial confinement of the metal center within a chiral pocket results in reversed regioselectivity and remarkable enantioselectivities.     

Complexation of divalent metal ions with diols in the presence of anion auxiliary ligands: zinc-induced oxidation of ethylene glycol to glycolaldehyde by consecutive hydride ion and proton shifts

Ternary complexes of the type AH???M(2+)???L(-) (AH?=?diol, including diethylene and triethylene glycol, M?=?Ca, Mn, Fe, Co, Ni, Cu and Zn and auxiliary anion ligand L(-) =?CH(3)COO(-), HCOO(-) and Cl(-)) have been generated in the gas phase by MALDI and ESI, and their dissociation characteristics have been obtained. Use of the auxiliary ligands enables the complexation of AH with the divalent metal ion without AH becoming deprotonated, although A(-)???M(2+) is often also generated in the ion source or after MS/MS. For M?=?Ca, dissociation occurs to AH?+?M(2+)???L(-) and/or to A(-)???M(2+) + LH, the latter being produced from the H-shifted isomer A(-) ???M(2+)???LH. For a given ligand L(-), the intensity ratio of these processes can be interpreted (barring reverse energy barriers) in terms of the quantity PA(A(-)) - Ca(aff) (A(-)), where PA is the proton affinity and Ca(aff) is the calcium ion affinity. Deuterium labeling shows that the complex ion HOCH(2)CH(2) OH???Zn(2+)???(-)OOCCH(3), in addition to losing acetic acid (60 Da), also eliminates glycolaldehyde (HOCH(2)CH=O, also 60 Da); it is proposed that these reactions commence with a hydride ion shift to produce the ion-dipole complex HOCH(2)CHOH(+)??? HZnOOCCH(3), which then undergoes proton transfer and dissociation to HOCH(2)CH=O?+?HZn(+)???O?=?C(OH)CH(3). In this reaction, ethylene glycol is oxidized by consecutive hydride ion and proton shifts. A minor process leads to loss of the isomeric species HOCH=CHOH.     

Complexation of divalent metal ions with diols in the presence of anion auxiliary ligands: zinc‐induced oxidation of ethylene glycol to glycolaldehyde by consecutive hydride ion and proton shifts

Ternary complexes of the type AH???M²⁺???L^– (AH = diol, including diethylene and triethylene glycol, M = Ca, Mn, Fe, Co, Ni, Cu and Zn and auxiliary anion ligand L^– = CH₃COO^–, HCOO^– and Cl^–) have been generated in the gas phase by MALDI and ESI, and their dissociation characteristics have been obtained. Use of the auxiliary ligands enables the complexation of AH with the divalent metal ion without AH becoming deprotonated, although A^–???M²⁺ is often also generated in the ion source or after MS/MS. For M = Ca, dissociation occurs to AH + M²⁺???L^– and/or to A^–???M²⁺ + LH, the latter being produced from the H‐shifted isomer A^–???M²⁺???LH. For a given ligand L^–, the intensity ratio of these processes can be interpreted (barring reverse energy barriers) in terms of the quantity PA(A^–) – Ca_aff(A^–), where PA is the proton affinity and Ca_aff is the calcium ion affinity. Deuterium labeling shows that the complex ion HOCH₂CH₂OH???Zn²⁺???^–OOCCH₃, in addition to losing acetic acid (60 Da), also eliminates glycolaldehyde (HOCH₂CH=O, also 60 Da); it is proposed that these reactions commence with a hydride ion shift to produce the ion–dipole complex HOCH₂CHOH⁺??? HZnOOCCH₃, which then undergoes proton transfer and dissociation to HOCH₂CH=O + HZn⁺???O = C(OH)CH₃. In this reaction, ethylene glycol is oxidized by consecutive hydride ion and proton shifts. A minor process leads to loss of the isomeric species HOCH=CHOH. Copyright © 2012 John Wiley & Sons, Ltd.     

Turbulence temperature spectra: Scaling theory

Grand canonical Monte Carlo, histogram reweighting and finite-size scaling methods are used to determine the phase transitions of bulk (three-dimensional) and confined (quasi-two-dimensional) neutral colloid–polymer systems. The colloids are modeled as hard spheres and the polymer molecules as hard chains, and the only attractive forces are effective ones induced by depletion effects. In contrast to the predictions of mean field and other approximate theories, the nature of the coexistence phases is found to not depend solely on the polymer-to-colloid size ratio, q, but on the colloid diameter, the polymer radius of gyration, and the polymer monomer size. The threshold values of q for the onset of liquid–liquid phase separation differ significantly from earlier predictions, and depend strongly on the dimensionality of space. Extrapolation to the “protein limit” of very small colloid and very long polymer indicates that immiscibility persists at this limit in three dimensions, while it does not always do so for confined systems.     

On the relation between algebraic stability andB-convergence for Runge-Kutta methods

Summary This paper is concerned with the numerical solution of stiff initial value problems for systems of ordinary differential equations using Runge-Kutta methods. For these and other methods Frank, Schneid and Ueberhuber [7] introduced the important concept ofB-convergence, i.e. convergence with error bounds only depending on the stepsizes, the smoothness of the exact solution and the so-called one-sided Lipschitz constant . Spijker [19] proved for the case <0 thatB-convergence follows from algebraic stability, the well-known criterion for contractivity (cf. [1, 2]). We show that the order ofB-convergence in this case is generally equal to the stage-order, improving by one half the order obtained in [19]. Further it is proved that algebraic stability is not only sufficient but also necessary forB-convergence.This study was completed while this author was visiting the Oxford University Computing Laboratory with a stipend from the Netherlands Organization for Scientific Research (N.W.O.)     

Stability of linear multistep methods on the imaginary axis

The stability of linear multistep methods of order higher than one is investigated for hyperbolic equations. By means of the Routh array and the Hermite-Biehler theorem, the stability boundary on the imaginary axis is expressed in terms of the error constant of the third order term. As a corollary we state the result that the stability boundary for methods of order higher than two, is at most 3, and this value is attained by the Milne-Simpson method.This work was done during the author's stay at the Mathematical Centre Amsterdam, and the University of Technology, Eindhoven.     

PHOTOREACTIVATING ENZYME FROM STREPTOMYCES GRISEUS—IV. ON THE NATURE OF THE CHROMOPHORIC COFACTOR IN STREPTOMYCES GRISEUS PHOTOREACTIVATING ENZYME

Abstract— A structure for the chromophoric part of the intrinsic cofactor of Streptomyces griseus photo-reactivating enzyme is suggested on the basis of absorption and fluorescence spectra of cofactor and reference compounds at various pH. The essential chromogenic part of this cofactor is proposed to be a 7,8-didemethy]-8-hydroxy-5-deazaflavin derivative (Ia).
From whole S. griseus cells a compound SF420 (Ic) was isolated which contains the same chromophoric group. This compound sensitizes the splitting of thymine dimers when irradiated with blue light, supporting the structure proposed for the photoreactivating enzyme cofactor.     

Developing shift problems to foster geometrical proof and understanding

Meaningful learning of formal mathematics in regular classrooms remains a problem in mathematics education. Research shows that instructional approaches in which students work collaboratively on tasks that are tailored to problem solving and reflection can improve students’ learning in experimental classrooms. However, these sequences involve often carefully constructed reinvention route, which do not fit the needs of teachers and students working from conventional curriculum materials. To help to narrow this gap, we developed an intervention—‘shift problem lessons’. The aim of this article is to discuss the design of shift problems and to analyze learning processes occurring when students are working on the tasks. Specifically, we discuss three paradigmatic episodes based on data from a teaching experiment in geometrical proof. The episodes show that is possible to create a micro-learning ecology where regular students are seriously involved in mathematical discussions, ground their mathematical understanding and strengthen their relational framework.