Unusual emissions from low-concentrated porphyrin solutions

This contribution presents fluorescence measurements from highly diluted tetratolylporphyrin (TTP) solutions where acetone has been chosen as solvent. The concentrations of the solutions ranged from 10(-8) to 10(-14) M. Apart the normal S1-S0 fluorescence a new broad emission was recorded below 10(-8) M. This new emission blue-shifted to the S1-S0 fluorescence covered the spectral range between 19000 and 14000 cm(-1). Within the dilution series, both the S1-S0 porphyrin fluorescence and the new emission exhibited a remarkably non-linear concentration-dependence. In the case in which the aggregate emission was strong, little S1-S0 emission could be detected and vice versa. The intensity maximum of the broad emission was detected from a 10(-13) M solution. The supplementary fluorescence was attributed to the presence of assembled molecules. This assumption was established by comparing the measurements with those obtained from 1:1 acetone water solvent mixtures in which the formation of aggregates had been formerly proven. The emission originating from the formation of aggregates was interpreted by a qualitative model considering the energy levels of J-aggregated porphyrins.     

Metallorganische Verbindungen des Kupfers XIII. Kupfer(I)-chlorid-Komplexe winkelgespannter Cycloheptine Synthesen und Röntgenstrukturanalysen

The strained cycloheptynes 2a, 2b and 2c react with copper(I) chloride to form the dinuclear complexes [CuCl(cycloheptyne)]₂ 3a, 3b and 3c respectively. X-ray diffraction studies on all three compounds 3 show an increase in strength of the copper-alkyne bond with increasing deformation of the alkyne moiety from the ideal 180°. Thus going from the least strained alkyne (2c) to the most strained one (2a), the Cu-C bond lengths in the corresponding complexes decrease from 197.5 pm (3c) to 194.9 pm (3a). The C≡C-C angles increase from 145.6° (3a) over 147.4° (3b) to 151.6° (3c).

Zusammenfassung

Die gespannten Cycloheptine 2a, 2b und 2c reagieren mit Kupfer(I)—chlorid unter Bildung der zweikernigen Komplexe [CuCl(cycloheptin)]₂ 3a, 3b und 3c. Röntgenstrukturanalysen von allen drei Verbindungen 3 zeigen, daβ die Stärke der Kupfer—Alkin-Bindung zunimmt je mehr das ganze Alkinsystem vom idealen 180°-Winkel abweicht. Geht man vom am wenigsten gespannten Alkin (2c) zum gespanntesten (2a), so nehmen die Cu-C-Bindungslängen in den entsprechenden Komplexen von 197.5 pm (3c) auf 194.9 pm (3a) ab. Die C≡C-C-Winkel werden von 145.6° (3a) über 147.4° (3b) nach 151.6° (3c) hin gröβer.     

Modeling of Atmospheric-Pressure Dielectric Barrier Discharges in Argon with Small Admixtures of Tetramethylsilane

Plasma Chemistry and Plasma Processing - A time-dependent, spatially one-dimensional fluid-Poisson model is applied to analyze the impact of small amounts of tetramethylsilane (TMS) as precursor on...     

Polarisation und differentieller Wirkungsquerschnitt der Neutronen aus der Reaktion9Be(α,n)12C

The differential cross section and the angular distribution of the polarization of neutrons from the reaction⁹Be(α, n) leading to the ground state of¹²C have been determined at 1.75 and 1.96 MeV energy of theα-particles. The polarization was measured by left-right asymmetry induced by elastic scattering from⁴He. From Blatt, Biedenharn and Simon, Welton theory analysis a set of spectroscopic data has been obtained for five states of the compound nucleus¹³C.     

Spatiotemporal dynamics of bumblebees foraging under predation risk

We analyze 3D flight paths of bumblebees searching for nectar in a laboratory experiment with and without predation risk from artificial spiders. For the flight velocities we find mixed probability distributions reflecting the access to the food sources while the threat posed by the spiders shows up only in the velocity correlations. The bumblebees thus adjust their flight patterns spatially to the environment and temporally to predation risk. Key information on response to environmental changes is contained in temporal correlation functions, as we explain by a simple emergent model.