Synthese und Circulardichroismus optisch aktiver Carotinoidmodelle

Synthesis and Circular Dichroism of Optically Active Carotenoid Models The synthesis of the following optically active carotenoidic model compounds are described: (—)-(3,S,3′S)-3,3′-diisopropenyl-16,17,18,16′,17,18′-hexanor-β,β-carotene ( 1 ), (3R,3′R)-19,20,19′,20′-Metranor-zeaxanthin ( 2 ) and (6R,6′R)-19,20, 19′,20′-tetranor-ε,ε-carotene ( 3 ). These compounds were synthesized for the following reasons: (1) the presence of methyl groups at C(1), C(1′), C(5), C(5′) of cyclic carotenoids profoundly affects the torsional angle of the C(6), C(7)- and C(6′), C(7′)-bonds. Sign and magnitude of this angle are, according to recent theories [4] [5], responsible for a helical chromophore and for strong conservative [4] Cotton effects. CD. measurements of 1 give experimental support to these state- 1 exhibits weaker and less temperature dependent Cotton effects. Of more significance, the shape of the curve is no longer conservative, as expected. This constitutes experimental evidence for the contention that the β-endgroups and the polyene chain indeed form an inherently dissymmetric chromophore in optically active β, β-carotene derivatives; (2) the slightly S-shaped form of the polyene chain of carotenoids, shown by X-ray analyses [12] [13], is mainly ascribed to the presence of the methyl groups in the chain. Models 2 and 3 therefore are assumed to be linear. CD. studies of these compounds should consequently give information about the influence of deviation from Linearity and planarity of the polyene on the CD. spectra of carotenoids. CD measurements of 2 and 3 show that the lack of methyl groups does not alter the general type of the curve. Only the intensity and to some extent the position of the Cotton effects are influenced. Carotenoids with the ε-endgroup possess inherently symmetric but asymmetrically distorted chromophores. The assumption that non-conservative CD. spectra could become conservative upon cooling [4] is experimentally confirmed by model 3 . The rule stating that pairs of all-(E) and mono-(Z) isomers of carotenoids with only one cyclic endgroup should have CD. spectra with the same sign [5] is disproved by the CD. spectra of four stereoisomeric rubixanthins (s. Fig. 5). The UV./VIS. spectrum of 3, λ_max 447 (ε 216000), 418 (ε 189000) exhibits the highest molecular extinction ever reported for a carotenoid.     

Measurement of electrical conductivity of low-temperature alkali plasma by weak probing signals

A method for measuring the real component of the electrical conductivity in a plasma diode is described. The phase — sensitive detection enables to use extremely low probing signal down to 10 V.     

Comparison of Experimental Methods and Theoretical Calculations on Crystal Energies of ‘Isoenergetic’ Polymorphs of Cimetidine

The thermodynamic energy relationship between two crystal modifications of cimetidine was investigated and compared with differences in their processing properties with respect to transformation from one modification to the other.The crystal energies of the two modifications A and D were found to be almost identical and therefore the polymorphs are regarded as virtually isoenergetic crystals. This statement is based on DSC measurements of the melting points and of the enthalpies of fusion for the two crystal forms, which enable the calculation of the Gibbs free energy functions. Furthermore, the statement is supported by measurements of the enthalpies of solution in two different solvents. Both DSC and solution experiments reveal a slightly higher stability of the D modification with respect to the A form. In addition, tribomechanical treatment also indicates modification D to be the more stable one, as well as the higher density of the D form. No transformation during DSC at low heating rate was found which could be used in a stability consideration.As the explicit crystal structures of the two modifications are resolved, it was possible to calculate crystal energies theoretically as well. The theoretical results showed a remarkable difference in the crystal energies at zero degree Kelvin. Furthermore, they were just contradicting experimental findings by stating A being more stable than D. Possible reasons for this discrepancy and the feasibility of today's calculation methods with respect to prediction of stability properties are discussed.This revised version was published online in November 2005 with corrections to the Cover Date.     

High spin level structure of 63 143 Eu80

The level scheme of ¹⁴³ Eu has been extended to I=75/2 in an experiment with the NORDBALL Compton-suppressed Ge detector array and the ¹¹⁰ Pd(³⁷ Cl, 4n) reaction. Most of the scheme shows irregular structure of multiparticle excitations. A strongly populated straight cascade of more than 10 stretched E2 transitions suggests the onset of collectivity.     

EFFECTS OF MUTAGENETIC SUBSTITUTION OF PROLINES ON THE RATE OF DEPROTONATION and REPROTONATION OF THE SCHIFF BASE DURING THE PHOTOCYCLE OF BACTERIORHODOPSIN

Abstract— Membrane-buried proline residues are found in many transport proteins. To study their roles in the structure and function of bacteriorhodopsin (bR), effects of the individual substitutions ofPro–50,Pro–91 andPro–186 on the deprotonation and reprotonation kinetics of the Schiffbase (SB) were determined by flash photolysis. The obtained rate constants and the amplitudes of the slow and fast components were compared with those of ebR (wild-type bR, the native protein that is expressed in Escherichia coli). The deprotonation rates of PSB were found to be 10 times faster than that of ebR for P50A, P91A and P91G mutants, and 4 times faster for the P50G mutant. These mutations also increased the initial reprotonation rate of the SB, although the overall change in the reprotonation rate is not as significant as that in the deprotonation rate. Our results indicate thatPro–50 andPro–91, as well asPro–186, are important for the proton-pumping function of bR.     

Optimisation of 40 Gb/s wavelength converters based on four-wave mixing in a semiconductor optical amplifier

The optimum operating powers and wavelengths for a 40 Gb/s wavelength converter based on four-wave mixing in a semiconductor optical amplifier are inferred from experimental results. From these measurements, some general rules of thumb are derived for this kind of devices. Generally, the optimum signal power should be 10 dB lower than the pump power (−16 dB conversion efficiency) whereas the wavelength separation between the signal and the pump carrier should not be lower than about four times the signal bitrate (1.3 nm for 40 Gb/s RZ signals).     

Synthetic magnetic opals

We present studies of novel nanocomposites of BiNi impregnated into the structure of opals as well as inverse opals. Atomic force microscopy and high resolution elemental analyses show a highly ordered structure and uniform distribution of the BiNi filler in the matrix. These BiNi-based nanocomposites are found to exhibit distinct ferromagnetic-like ordering with transition temperature of about 675 K. As far as we know there exists no report in literature on any BiNi compound which is magnetic.     

Proton shock acceleration in laser-plasma interactions

The formation of strong, high Mach number (2-3), electrostatic shocks by laser pulses incident on overdense plasma slabs is observed in one- and two-dimensional particle-in-cell simulations, for a wide range of intensities, pulse durations, target thicknesses, and densities. The shocks propagate undisturbed across the plasma, accelerating the ions (protons). For a dimensionless field strength parameter a(0)=16 (Ilambda(2) approximately 3 x 10(20) W cm(-2) microm(2), where I is the intensity and lambda the wavelength), and target thicknesses of a few microns, the shock is responsible for the highest energy protons. A plateau in the ion spectrum provides a direct signature for shock acceleration.     

Analysis of adiabatic coupling between photonic crystal single-line-defect and coupled-resonator optical waveguides

A detailed analysis of adiabatic coupling between conventional photonic crystal single-line-defect and coupled-resonator optical waveguides is reported. Adiabatic coupling by progressive variation of the radii of the spacing defects between cavities is investigated. Flat transmission spectra with coupling efficiencies greater than 90% are achieved in a broad frequency range with short coupling lengths. Moreover, we find that flat transmission at low frequencies requires longer coupling lengths partly because the requirements imposed for adiabatic transmission in photonic crystals are violated.