Darstellung und Eigenschaften spirocyclischer Titan(IV)-amide Ti[-NMe-SiMe2-Y-SiMe2-NMe-]2 mit Y = NMe,O und CH2

Preparation and Properties of Spirocyclic Ti(IV) Amides Ti( –NMe–SiMe₂–Y–Sime₂–NMe–)₂ with Y ? NMe, 0, and CH₂ The title compounds have been obtained from the reaction of TiBr₄ with the di-lithiated α, ω-bifunctional amines Y(SiMe₂NHMe)₂ in yields of about 50%. The compounds are monomeric, crystalline and of considerable stability. Their constitution has been proved by elemental analyses, ¹H n.m.r., i.r., and Raman spectra. A synthesis is described for the hitherto unknown diamine CH₂(SiMe₂NHMe)₂.     

Spiro- und monocyclische Zirkonium(IV)-amide Zr(L2)2 und L2ZrCl2 mit L2 = ( ? NMe ? SiMe2)2 Y (Y = NMe,O, CH2)

Spiro and Monocyclic Zr(IV) Amides Zr(L₂)₂ and L₂ZrCl₂ with L₂ = (? NMe? SiMe₂)₂ Y (Y = NMe, O, CH₂) The preparation of the spirocyclic Zr(IV) amides Zr[(NMeSiMe₂)₂Y]₂, Y = NMe, O, CH₂, by the reaction of ZrCl₄ with α, ω-dilithio diamines is reported. The monomeric spiranes are cleaved by ZrCl₄ to yield the monocyclic compounds Y(SiMe₂NMe)₂ZrCl₂. These are oligomeric or polymeric; the i.r. spectra suggest a structure consisting of edge-sharing [L₂ZrCl_4/2] octahedra.     

Zur infrarotspektroskopischen Erfassung kleiner Wassergehalte in Benzylalkohol, 1,4-Dioxan, Glykol und Glykolderivaten

Zusammenfassung Die bereits an aliphatischen Alkoholen und Ketonen mit Hilfe eines selbstregistrierenden Infrarotspektralphotometers durchgeführten Untersuchungen zur infrarotspektroskopischen Erfassung kleiner Wassergehalte wurden an den mit Wasser mischbaren organischen Lösungsmitteln Äthylenglykol, Äthylenglykolmonomethyläther, Äthylenchlorhydrin, Glycerin, 1,4-Dioxan und Benzylalkohol fortgesetzt. Für Wasserbestimmungen in diesen Lösungsmitteln erwies sich besonders die OH-Kombinationsschwingung des Wassers im Spektralbereich um 5200 cm^–1 geeignet. Mit Hilfe dieser OH-Absorptionsbande, die Messungen in Küvetten mit Glasfenstern gestattet, können im Direktverfahren Wassergehalte von etwa 1,0–10,0 Vol-% mit guter Genauigkeit, besser als 0,1 Vol-% bestimmt werden; im Kompensationsverfahren sind noch Konzentrationen von 0,1–2,0 Vol-% erfaßbar.Bei dem nicht hydroxylhaltigen 1,4-Dioxan lassen sich mittels dieser Bande Wassergehalte von 0,1–10,0 Vol-% im Direktverfahren bestimmen. Für die quantitative Erfassung sehr kleiner Wassergehalte im Dioxan eignet sich infolge günstiger Eigenabsorptionsverhältnisse besonders gut die OH-Valenzschwingung bei 3600 cm^–1, die hier Wasser-bestimmungen bis herab zu 0,02 Vol-% im Direktverfahren mit hinreichender Genauigkeit ermöglicht.Auch die OH-Deformationsschwingung bei 1600 cm^–1 erweist sich für Wassergehalte von 0,5–10 Vol-% zum qualitativen Nachweis und zur quantitativen Bestimmung verwendbar, soweit bei den betreffenden Lösungsmitteln nicht Fehler durch die Löslichkeit der Steinsalz-Küvettenfenster auftreten.Frühere Mitt.: Wiegel, E., u. H. H. Kirchner: diese Z. 178, 241 (1960/61).     

POLAR INTERACTIONS OF HYALURONIC ACID -EXPERIMENTS AND MOLECULAR DYNAMICS SIMULATIONS-

ABSTRACT

To study the polar interactions of the cartilage component hyaluronate (HA) contact angle measurements of polymer films of sodium hyaluronate and of the free hyaluronic acid with different probe liquids and theoretical investigations with molecular dynamics simulation (MD) on polymer segments in aqueous environment were performed. For the designation of contact angles water, formamid, glycerol and α-bromnaphthalene as probe liquids were used. The surface tension components were calculated on the basis of the theory of van Oss using the Young equation. Experimental investigations were done with air dried layers of the sodium salt of HA whose surface has been formed at the interface to the air resp. glass support. Whereas the surface polymer/air is characterized by small, but non-zero values for γ^? and γ^-the surface polymer/glass tends to have γ^-monopolar properties. In opposite to the salt form of HA a strong repulsion of chains and high γ^- monopolarity was measured for the protonated form.

The molecular dynamics simulation (MD) on HA in water were carried out employing the force field CHARMM and the water model TIP3P. MD trajectories of HA tetramer subunit surrounded by approximately 950 water molecules were produced up to 3 ns. The interaction energies of HA and water, hydrogen bonding, and the orientation of water molecules at different solute atom groups were calculated. On the basis of energy and geometry criteria, the number of hydrogen bonds between the water molecules and the polymer acceptor atoms was determined to be between 10 and 15 per dimer unit.     

Distribution of pore-size in an exactly solvable two-dimensional biomembrane model

A model for a two-dimensional lipid bilayer in which both short range repulsive forces and long range attractive forces play a role, and which can be solved exactly, is discussed. It is shown that the bilayer consists of long stretches of relatively densely packed lipids separated by small pores. The statistical distributions of number and size of the pores are calculated from first principles.     

Probability of knots in a polymer ring

We generate equilibrium configurations of a ring polymer in an infinite space, or confined to the interior of a sphere. Using a new algorithm, the a priori probability for the occurence of a knot is determined numerically. The results are compatible with power laws and scaling laws of striking simplicity.     

Calibration of a Bonner sphere extension (BSE) for high-energy neutron spectrometry

In a recent work, we constructed modular multisphere system which expands upon the design of an existing, commercially available Bonner sphere system by adding concentric shells of copper, tungsten, or lead. Our modular multisphere system is referred to as the Bonner Sphere Extension (BSE). The BSE was tested in a high energy neutron beam (thermal to 800 MeV) at Los Alamos Neutron Science Center and provided improvement in the measurement of the neutron spectrum in the energy regions above 20 MeV when compared to the standard BSS (Burgett, 2008 and Howell et al., 2009).However, when the initial test of the system was carried-out at LANSCE, the BSE had not yet been calibrated. Therefore the objective of the present study was to perform calibration measurements. These calibration measurements were carried out using monoenergetic neutron ISO 8529-1 reference beams at the Physikalisch-Technische Bundesanstalt (PTB), Braunschweig, Germany. The following monoenergetic reference beams were used for these experiments: 14.8 MeV, 1.2 MeV, 565 keV, and 144 keV. Response functions for the BSE were calculated using the Monte Carlo N-Particle Code, eXtended (MCNPX). The percent difference between the measured and calculated responses was calculated for each sphere and energy. The difference between measured and calculated responses for individual spheres ranged between 7.9 % and 16.7 % and the arithmetic mean for all spheres was (10.9 ± 1.8) %. These sphere specific correction factors will be applied for all future measurements carried-out with the BSE.     

The simulated workplace field with a high-energy neutron component produced by irradiating a Fe-target with 200 MeV/u 12C-ions

Recent developments in accelerator physics have led to new challenges for radiation protection dosimetry. Doses have to be determined for workplace fields which are characterized by high-energy radiation, a dominant contribution from neutrons, high intensities and pulsed time structure This may present problems for active measuring devices. As is well known, the ambient dose equivalent is often underestimated by area monitors operating in high-energy neutron fields behind shielding. Therefore, it is desirable to calibrate survey monitors in a characterized neutron field with the type of spectral fluence distribution that is expected behind shielding, i.e. where the main dose from neutrons arises from two peaks with mean energies of about 1 MeV and 100 MeV, respectively. Such a neutron fluence distribution is produced by the irradiation of a Fe-target with 200 MeV/u ¹²C-ions. Measurements with the extended range Bonner sphere spectrometer NEMUS of PTB were performed at two positions inside the experimental area Cave A of the heavy-ion synchrotron SIS at GSI. The measured neutron spectra show different fluence contributions for the two peaks at the two positions. The results were compared to Monte Carlo Simulations with MCNPX and FLUKA.     

Ueber Bildungsweise und Teilchenstruktur einer neuen Art Silbersole von ausgeprägtester Buntfarbigkeit II

Ohne Zusammenfassung Zum Schlu? m?chte ich auch hier Herrn Prof.Dr. H. Freundlich für sein reges Interesse und die stete F?rderung dieser Arbeiten meinen herzlichsten Dank aussprechen. Der Notgemeinschaft derDeutschenWissenschaft bin ich für die Unterstutzung dieser Untersuchungen ebenfalls zu gro?em Dank verpflichtet.