Development of an optical membrane for humidity

4-(N,N-dioctylamino)-4-trifluoroacetyl-azobenzene (ETH^T 4001), together with the catalyst tridodecylmethylammonium chloride, is dissolved in the hydrophilic polymer polyurethane Tecoflex. The resulting membrane layers show high sensitivity toward water vapour and allow the application of the membranes for humidity measurements. Upon exposure to humid air, the membrane exhibits a decrease in absorbance at a wavelength around 490 nm and an increase at around 430 nm. This signal change is caused by the conversion of the trifluoroacetyl group of the reactand into a diol, thus changing the electron delocalisation of the reactand. The sensor layer exhibits a dynamic range from 1% to 100% RH with highest sensitivity in the 5%–40% RH range. The limit of detection is 0.5% RH. The amount of added catalyst enables the sensitive range to be tailored. The selectivity over ethanol and carbonate is sufficient for the membrane to be used for long-term measurements of air. The change in colour of the humidity-sensitive membrane from red to yellow also means it can be used as an optical test strip.     

Anordnung und Orientierung kationischer Tenside auf ebenen Silicatoberflächen

Zusammenfassung Die n-Alkylammoniumderivate der glimmerartigen Schichtsilicate können als Modellsubstanzen für die Anordnung kationischer Tenside an Festkörpergrenzflächen herangezogen werden. Im ersten Teil der Arbeit wird die Darstellung durch Kationenaustausch aus den natürlichen Schichtsilicaten beschrieben. Es wird ausführlich auf die Fehlerquellen hingewiesen, die reproduzierbare Messungen erschweren.

---

Summary The n-alkylammonium derivatives of mica-type layer silicates are suitable models for studies about the arrangement of cationic tensides at solid interfaces. Part I of the paper deals with the preparation of these compounds by a simple cation exchange reaction. Sources for errors in obtaining reproducible data are discussed in detail.

---

---

Mit 1 Abbildung in 3 Einzeldarstellungen und 3 Tabellen     

Elektronenmangelverbindungen des Galliums Zur Kenntnis von Ca3Ga5

Electron Deficient Compounds of Gallium: Crystal Structure of Ca₃Ga₅ The stoichiometry of the formerly described compound Ca₂Ga₃ is corrected to Ca₃Ga₅. This compound crystallizes in the orthorhombic system, space group Cmcm (No. 63) with the lattice constants see ?Inhaltsübersicht”?. In the structure there is a Ga framework for which on the basis of the Gillespie/Nyholm conception and by calculating the bond numbers according to Pauling a characteristic electron concentration can be derived.     

Fabrication of magnetically separable mesostructured silica with an open pore system

Magnetically separable mesostructured silica with an unobstructed pore system was fabricated through the deposition of cobalt nanoparticles on the outer surface of the submicron-sized silica particles. These cobalt nanoparticles were further protected by a nanometer-thick carbon shell against acid erosion. Due to the fact that the magnetic particles are grafted on the outer surface of the porous silica, the pores are still accessible for further modification, which could widen the application range of porous silica.     

Evaluation of methods to measure differential 15N labeling of soil and root N pools for studies of root exudation

To study patterns of root exudation, the effectiveness of different techniques for in situ 15N labeling of Brassica napus, Centaurea jacea and Lolium perenne with ammonium nitrate was tested. Stem infiltration was found to effectively label plants with thicker stems, whereas, for grass species, cutting and immersing the leaf tips into 15N solution proved to be most effective. A microdiffusion technique to isolate ammonium, combined with conventional cation-exchange chromatography to separate nitrate from amino-N compounds thereafter, was found suitable for separation of the N fractions of plant and soil extracts for 15N determination. All three species were then cultivated in nutrient solution and labeled with 15NH4 15NO3 by stem feeding for 42 hours. Kinetics of 15N labeling of bulk roots and shoots as well as hot water extractable material were assessed, and up to 1.1 at% 15N excess (APE) was found in nutrient solutions. The main amino acids exuded by L. perenne were glycine, serine, alanine and aspartic acid. To assess the suitability of this set of methods to study root exudation in field settings, L. perenne was grown without fertiliser addition in pots containing low-nutrient soil. Plants were 15N labeled via tip immersion and 15N and N concentrations were analysed in shoots, roots and soils during a 48-h interval. Shoots reached 1.25 APE, roots and soil 0.10 and 0.005 APE, respectively. Between 4% (48 h) and 6% (24 h) of total plant 15N was exuded by roots into the soil. In roots amino acids comprised the largest proportion of the soluble 15N pool, whereas soil 15N levels were similar for amino acids and ammonium, exceeding those of nitrate. Mechanisms for the shift within N fractions from roots to soils are briefly discussed.     

Hierarchical dynamics in allostery following ATP hydrolysis monitored by single molecule FRET measurements and MD simulations

We report on a study that combines advanced fluorescence methods with molecular dynamics (MD) simulations to cover timescales from nanoseconds to milliseconds for a large protein. This allows us to delineate how ATP hydrolysis in a protein causes allosteric changes at a distant protein binding site, using the chaperone Hsp90 as test system. The allosteric process occurs via hierarchical dynamics involving timescales from nano- to milliseconds and length scales from Ångstroms to several nanometers. We find that hydrolysis of one ATP is coupled to a conformational change of Arg380, which in turn passes structural information via the large M-domain α-helix to the whole protein. The resulting structural asymmetry in Hsp90 leads to the collapse of a central folding substrate binding site, causing the formation of a novel collapsed state (closed state B) that we characterise structurally. We presume that similar hierarchical mechanisms are fundamental for information transfer induced by ATP hydrolysis through many other proteins.

We report on a study that combines advanced fluorescence methods with molecular dynamics simulations to cover timescales from nanoseconds to milliseconds for a large protein, the chaperone Hsp90.     

Exploring CH-activation pathways in bifunctional zirconocene/borane systems

The dimethylsilanediyl-bridged ansa-zirconocene dichloride 1, that contains a pendent allyl substituent at a Cp-ring, adds HB(C(6)F(5))(2) to the vinyl group to yield the bifunctional zirconocene/borane complex 2. Substituted benzimidazoles were added to the strongly electrophilic borane moiety as protective groups, which allowed subsequent chloride versus -CH(2)SiMe(3) exchange at zirconium to take place by treatment with the respective alkyllithium reagent. Alternatively, the introduction of active sigma-ligands at zirconium is carried out first, followed by the hydroboration reaction. This route was followed for the synthesis of the diphenyl-ansa-zirconocene/borane complex 12. Complex 12 reacts slowly in solution by intramolecular electrophilic attack of the borane at its adjacent Cp-ring, followed by deprotonation using a [Zr]-Ph group to yield the zwitterionic complex 14 featuring a borata-tetrahydroindenyl moiety as part of the ansa-metallocene framework. Complex 14 was characterized by X-ray diffraction. It adds PMe(3) at zirconium to yield 15. Thermolysis of 12 with excess PMe(3) leads to the formation of the (aryne)zirconocene complex 18, which is stabilized by PMe(3) coordination to zirconium and PMe(3) addition to boron. N-Methylbenzimidazole adds to the -B(C(6)F(5))(2) unit of 12 to give the 1:1 adduct 19. Thermolysis of 19 at 80 degrees C in benzene solution in the presence of one additional equivalent of N-methylbenzimidazole results in deprotonation of the substrate to yield the sigma-N-methylbenzimidazolyl zirconium complex 20 (as a mixture of two diastereoisomers). An additional N-methylbenzimidazole ligand is bonded to the B(C(6)F(5))(2) unit in this product.