Photocycloaddition of Cyclohex‐2‐enones to Penta‐1,2,4‐triene

Dihydrothiinone 9a undergoes photocycloaddition regioselectively to all three C?C bonds of penta‐1,2,4‐triene ( 10 ), the relative stabilities of the biradical intermediates determining the product distribution. In contrast, cyclohexenone 9b and dihydropyranone 9c afford more complex mixtures of bicyclo[4.2.0]octanones, which also turn out to be less stable on chromatographic workup, reflecting the higher strain due to the shorter bond lengths (C? O and C? C vs. C? S) in the six‐membered rings, respectively.     

1,2,5,6-Tetrakis(guanidino)-Naphthalenes: Electron Donors,Fluorescent Probes and Redox-Active Ligands

New redox-active 1,2,5,6-tetrakis(guanidino)-naphthalene compounds, isolable and storable in the neutral and deep-green dicationic redox states and oxidisable further in two one-electron steps to the tetracations, are reported. Protonation switches on blue fluorescence, with the fluorescence intensity (quantum yield) increasing with the degree of protonation. Reactions with N-halogenosuccinimides or N-halogenophthalimides led to a series of new redox-active halogeno- and succinimido-/phthalimido-substituted derivatives. These highly selective reactions are proposed to proceed via the tri- or tetracationic state as the intermediate. The derivatives are oxidised reversibly at slightly higher potentials than that of the unsubstituted compounds to dications and further to tri- and tetracations. The integration of redox-active ligands in the transition-metal complexes shifts the redox potentials to higher values and also allows reversible oxidation in two potentially separated one-electron steps.     

Interplay and Competition Between Two Different Types of Redox-Active Ligands in Cobalt Complexes: How to Allocate the Electrons?

The field of molecular transition metal complexes with redox-active ligands is dominated by compounds with one or two units of the same redox-active ligand; complexes in which different redox-active ligands are bound to the same metal are uncommon. This work reports the first molecular coordination compounds in which redox-active bisguanidine or urea azine (biguanidine) ligands as well as oxolene ligands are bound to the same cobalt atom. The combination of two different redox-active ligands leads to mono- as well as unprecedented dinuclear cobalt complexes, being multiple (four or six) center redox systems with intriguing electronic structures, all exhibiting radical ligands. By changing the redox potential of the ligands through derivatisation, the electronic structure of the complexes could be altered in a rational way.     

Integrated optical cross strip polarizer concept

Passing across an abrupt junction from a thick vertically bimodal waveguide to a thinner single mode segment, guided light can undergo complete destructive interference, provided that the geometry and the phases of the modes in the initial segment are properly adjusted. We propose to employ this effect to realize a simple polarizer configuration, using a strip that is etched from a planar waveguide. A beam of light is made to pass the strip perpendicularly. The light enters from the single mode waveguide outside the strip into the strip segment, which is configured to support two modes. At the end of the strip, apart from reflections, the amount of power that is guided in the following lower segment depends on the local phases of the two modes. These phases are different for TE and TM light, hence we may expect a polarization dependent power transfer, resulting in polarizer performance for a properly selected geometry. The paper describes in detail the modeling of the device in terms of rigorous mode expansion. Design guidelines and tolerance requirements for geometric and material parameters are discussed. For typical Si₃N₄/SiO₂ materials, our calculations predict a peak performance of 34 dB polarization discrimination and 0.3 dB insertion loss for a device with a total length of about 12 m that selects TE polarization at a wavelength of 1.3 m.     

Determination of 13C/12C-Ratios in Rumen Produced Methane and CO2 of Cows,Sheep and Camels

Abstract

Naturally produced methane shows different δ¹³C-values with respect to its origin, e.g., geological or biological. Methane-production of ruminants is considered to be the dominant source from the animal kingdom. Isotopic values of rumen methane—given in literature—range between ?80‰ and -50‰ and are related to feed composition and also sampling techniques. Keeping cows, camels and sheep under identical feed conditions and sampling rumen gases via implanted fistulae we compared δ_PDB ¹³C-values of methane and CO₂ between the species. Referring to mean values obtained from 4 or 5 samples at different times of 11 animals (n = 47) we calculated δ_PDB ¹³C-medians resulting in small but not significant differences within and significant differences between the species for CO₂ and methane. The δ_PDB ¹³C-differences between methane and CO₂ were statistically equal within and also between the species. Therefore a linear regression of methane values on CO₂ is appropriate and leads to: δ_PDB ¹³C(methane)‰ = 1,57 * δ_PDB ¹³C(CO₂)‰-47‰ with a correlation coefficient of r = 0,87.     

Radiatively coupled waveguide polarization splitter simulated by wave-matching-based coupled mode theory

Coupled mode theory is applied to an arrangement of three raised strip waveguides with a multimode central strip. We use semivectorial numerically computed modes of the three single isolated waveguides as a basis for propagating supermode analysis of the entire structure. The pronounced polarization dependence of the raised strip guides allows for the design of a conveniently short polarization splitter. We discuss design guidelines and estimate the fabrication tolerances. The accuracy of the coupled mode approach is assessed by comparison with rigorously computed supermodes for comparable two waveguide couplers. Both types of structures indicate the limits in the applicability of the coupled mode model.     

Analysis of nonreciprocal light propagation in multimode imaging devices

We investigate a structure consisting of a magneto-optic multimode waveguide and two monomode waveguides serving as in- and outlets. The geometrical dimensions of the multimode waveguide can be adjusted such that the guided modes interfere constructively in forward direction and destructively for backward propagation. In this paper we present concepts for a circulator and two isolators based on multimode imaging.     

Mode expansion modeling of rectangular integrated optical microresonators

Two dielectric waveguides that are evanescently coupled to a square or rectangular region of increased refractive index can serve as a very compact integrated optical microresonator. We consider these devices in a spatial two-dimensional setting, where a rigorous mode expansion technique enables accurate and quite efficient numerical simulations of these configurations. The paper is concerned with single resonator units as well as with an add-drop filter constructed by cascading two square cavities. Besides calculating the power transmission spectra, we try to document as far as possible the characteristic electric field patterns that occur at major and minor resonance wavelengths. The influence of the various geometrical parameters on the resonator performance is investigated in detail.     

Mode expansion modeling of rectangular integrated optical microresonators

Two dielectric waveguides that are evanescently coupled to a square or rectangular region of increased refractive index can serve as a very compact integrated optical microresonator. We consider these devices in a spatial two-dimensional setting, where a rigorous mode expansion technique enables accurate and quite efficient numerical simulations of these configurations. The paper is concerned with single resonator units as well as with an add-drop filter constructed by cascading two square cavities. Besides calculating the power transmission spectra, we try to document as far as possible the characteristic electric field patterns that occur at major and minor resonance wavelengths. The influence of the various geometrical parameters on the resonator performance is investigated in detail.     

An improved design of an integrated optical isolator based on non-reciprocalMach–Zehnder interferometry

Non-reciprocal rib waveguide structures can be used to realize integrated optical isolators. In this paper, we propose a concrete design for a Mach–Zehnder interferometer type isolator for TM modes. Just one of the arms, which are of equal length, is a non-reciprocal magneto-optic waveguide. The rest of the interferometer is reciprocal. Required fabrication tolerances are estimated, and the entire isolator is simulated by applying a finite difference beam propagation method.