Über die grenzflächenenergetische Zustandsfunktion

Zusammenfassung Im Anschluß an vorangehende Untersuchungen, die ergeben hatten, daß zwischen den drei grenzflächenenergetischen Grundgrößen Festkörperoberflächenspannung, Flüssigkeitsoberflächenspannung und Grenzflächenspannung fest/flüssig eine Beziehung in der Art einer Zustandsgieichung besteht, werden in der vorliegenden Untersuchung mögliche Formulierungen dieser Zustandsgieichung diskutiert. Es wird gezeigt, daß der Quotient aus Adhäsionsarbeit und geometrischem Mittel der beiden Kohäsionsarbeiten in dem bisher zugänglichen Bereich von Festkörpern und Flüssigkeiten eine eindeutige Funktion der Grenzflächenspannung ist.Es wird diskutiert, ob diese Zustandsgieichung unabhängig vom Aggregatzustand ist, d. h. also insbesondere auch Systeme flüssig/flüssig beschreibt.Aus dem bisher vorliegenden Meßmaterial an Systemen fest/flüssig wurde die grenzflächenenergetische Zustandsfläche konstruiert.Wir danken dem Fonds der Chemischen Industrie für die Unterstützung der vorliegenden Untersuchung.     

Composition and thermal stability of SiO2-based hybrid materials TEOS-MTEOS system

Hybrid materials with different amounts of organics permanently bound on the inorganic network obtained in the TEOS-MTEOS (tetraethoxysilan-methyltriethoxysilan) system are used for obtaining coatings with different optical and mechanical properties. To study the thermal stability of the mentioned materials, compositions with different molar ratios of the precursors were prepared. The influence of the solvent and water amounts on the gelation process was also investigated. The gels obtained were characterised by IR spectrometry and their decomposition temperatures were determined by DTA/TG. Thermal stability of the gels is rather influenced by their composition than the conditions of the gelation process. This revised version was published online in July 2006 with corrections to the Cover Date.     

The mass spectra of substituted 2-methylbenzophenones

The mass spectra of some methoxy and methyl derivatives of 2-methylbenzophenone have been examined. Loss of a substituents from 3′-and 4′-positions as well as the previously known loss from 2′-positions are important fragmentation processes. Thus, these fragmentations are of little use in locating substituents on benzophenones of unknown structure. Deuterium labelling shows the [M - 1]⁺ ion from 3′,4,4′,5,5′-pentamethoxy-2-methyl benzophenone to be due largely to loss of hydrogen from 2′- and 6′-positions.     

Radiation dose contribution from coal-slags used as structural building material

A significant dose contribution on the population could be derived from coal slags used as isolation material. Extremely high natural activities are measured in the coal slag, derived from the region of the settlement Ajka, Hungary. In some buildings monitored, the elevated -doses were nearly 5–10 times higher than the world average ones. The annual average indoor radon concentrations from the slag exceeded 400 Bq/m³ and in some cases up to 1200 Bq/m³. Due to the elevated exposure and the radon concentrations in the dwellings the annual dose was estimated to 8–24 mSv/y more than 5–10 times of the world average one.     

Light‐Driven Coordination‐Induced Spin‐State Switching: Rational Design of Photodissociable Ligands

The bistability of spin states (e.g., spin crossover) in bulk materials is well investigated and understood. We recently extended spin‐state switching to isolated molecules at room temperature (light‐driven coordination‐induced spin‐state switching, or LD‐CISSS). Whereas bistability and hysteresis in conventional spin‐crossover materials are caused by cooperative effects in the crystal lattice, spin switching in LD‐CISSS is achieved by reversibly changing the coordination number of a metal complex by means of a photochromic ligand that binds in one configuration but dissociates in the other form. We present mathematical proof that the maximum efficiency in property switching by such a photodissociable ligand (PDL) is only dependent on the ratio of the association constants of both configurations. Rational design by using DFT calculations was applied to develop a photoswitchable ligand with a high switching efficiency. The starting point was a nickel–porphyrin as the transition‐metal complex and 3‐phenylazopyridine as the photodissociable ligand. Calculations and experiments were performed in two iterative steps to find a substitution pattern at the phenylazopyridine ligand that provided optimum performance. Following this strategy, we synthesized an improved photodissociable ligand that binds to the Ni–porphyrin with an association constant that is 5.36 times higher in its trans form than in the cis form. The switching efficiency between the diamagnetic and paramagnetic state is efficient as well (72 % paramagnetic Ni–porphyrin after irradiation at 365 nm, 32 % paramagnetic species after irradiation at 440 nm). Potential applications arise from the fact that the LD‐CISSS approach for the first time allows reversible switching of the magnetic susceptibility of a homogeneous solution. Photoswitchable contrast agents for magnetic resonance imaging and light‐controlled magnetic levitation are conceivable applications.     

Primary Amine‐Initiated Polymerizations of α–Amino Acid N‐Thiocarbonic Acid Anhydrosulfide

The N‐thiocarbonic acid anhydrosulfides NTAs of D,L‐leucine, D,L‐phenylalanine and sarcosine were polymerized in dioxane by addition of n‐hexylamine as initiator. Despite variation of the monomer‐initiator ratio (M/I) only low yields of oligopeptides were obtained from D,L‐Leu‐ and D,L‐Phe‐NTA. Both yields and molecular weights were almost twice as high for polymerizations of Sar‐NTA. MALDI‐TOF mass spectra confirmed that the isolated oligo‐and polypeptides possess the expected structure with one reactive amino end group. Therefore, it is surprising that the polymerizations stopped at low conversions. Two hypotheses explaining this phenomenon are discussed.     

Carbocyclization of E,E-1,4-Diphenyl-1,3-butadiene with Dichloroalkanes Mediated by Rieke Metals

The Rieke metal complexes of barium and strontium readily react with E,E-1,4-diphenyl-1,3-butadiene to form metal-diene reagents. Upon treatment with l .n-dichloroalkanes, these metallocycles are transformed into ring derivatives in excellent chemical yield.     

CIRCULAR DICHROISM SPECTRA OF SYSTEM I PARTICLES FROM NORMAL CHLOROPLASTS AND CAROTENOID-DEFICIENT MUTANTS OF MAIZE

Abstract— Circular dichroism (CD) spectra were studied in System I particles prepared by digitonin fragmentation of chloroplasts of normal maize and carotenoid-deficient mutants. CD bands of pigment molecules were found to be higher in particles than in solutions. This phenomenon was most pronounced for the particles containing the carotenoid composition of normal chloroplast lamellae. The CD signal of chlorophylls bound to particles of carotenoid-deficient chloroplasts was closer to that found in solutions. This indicates that aggregation and/or binding of chlorophylls in carotenoid-deficient mutants may be less extensive than in normal chloroplasts.