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.     

Study of Experimental Methods for Interface Problems Based on Virtual Testing

The effective properties of fiber reinforced materials depend strongly on the properties of the interface between the phases. In the particular case of glass fiber reinforced thermoplastics, this bonding is inherently weak and needs to be improved, e.g., by addition of compatibilyzers. Reliable experimental setups are needed in order to investigate the effects of such additives on the interface properties. In this contribution, the sensitivity of push out experiments with respect to the microstructure and test setup are examined in order to find such an experimental configuration. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

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...     

Guided waves for autonomous online identification of structural defects under ambient temperature variations

Ultrasonic guided waves that are excited by piezoelectric transducers can be used for the autonomous online identification of structural defects in thin structures. The proposed technique in this paper continuously analyzes a damage metric which is defined as the maximum residual amplitude of the differential signal. A special focus is on the decision making to discriminate the undamaged from the damaged state of the structure where the appropriate detection thresholds are derived statistically from the inverse cumulative distribution function of the damage metric during an initial training phase. An integrated trend analysis by means of the moving average mitigates the impact of statistical outliers and reduces the probability of erroneous identifications.Long-term measurements under ambient temperature variations have been conducted on an aluminum and a composite plate to study the properties of the proposed novelty detection framework. In this process the temperature effect was compensated by the well-known combination of optimal baseline selection (OBS) and baseline signal stretch (BSS). In case of the aluminum structure two artificial cracks with different sizes have been identified reliably. Consistent results were found on the composite specimen where an impact damage was identified for different excitation frequencies.     

HERBRAND’s Fundamental Theorem in the Eyes of JEAN VAN HEIJENOORT

Using Heijenoort??s unpublished generalized rules of quantification, we discuss the proof of Herbrand??s Fundamental Theorem in the form of Heijenoort??s correction of Herbrand??s ??False Lemma?? and present a didactic example. Although we are mainly concerned with the inner structure of Herbrand??s Fundamental Theorem and the questions of its quality and its depth, we also discuss the outer questions of its historical context and why Bernays called it ??the central theorem of predicate logic?? and considered the form of its expression to be ??concise and felicitous??.     

Surface Functionalization at Atmospheric Pressure by DBD-Based Pulsed Plasma Polymerization

Dielectric barrier discharge (DBD)-based plasma deposition at atmospheric pressure, using glycidyl methacrylate (GMA, methacrylic acid-[2,3-epoxy-propyl ester]) as a prototype precursor was investigated in order to evaluate the applicability of dielectric barrier discharges to obtain plasma polymers with a high degree of structural retention of the starting precursor. Using pulsed excitation of the discharge, up to about 90% of the epoxy groups of GMA can be retained in plasma polymers obtainableat deposition rates in the order of 3–5nm/s. Preliminary investigations of the mechanism of film formation under pulsed plasma conditions indicate that the reaction of intact monomer molecules withsurface radicals generated during the pulses play a prominent role.