1,4-Phenylen-bis-diphenylderivate der Elemente der 5. Hauptgruppe des Periodensystems

Zusammenfassung Die Darstellung sämtlicher am mittleren Benzolkern p-substitutierten Verbindungen (C₆H₅)₂ MC₆H₄ M(C₆H₅)₂ mitM=N, P, As, Sb und Bi wird beschrieben. Für die bereits bekannte Stickstoff-bzw. Arsen-Verbindung konnte ein neuer Darstellungs-weg mit guten Ausbeuten gefunden werden, während die Antimon-und Wismutverbindung erstmals beschrieben werden. Durch Dipolmomentmessungen, UV- und IR-Aufnahmen ist ein Vergleich mit den einfachen Triphenylderivaten der genannten Elemente möglich.

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The compounds p-(C₆H₅)₂ MC₆H₄ M(C₆H₅)₂,M=N, P, As, Sb, and Bi, were prepared. New methods for the preparation of the N and As compound with good yields were found. The Sb and Bi compound were synthesized for the first time. Dipole moments, IR- and UV-spectra of these compounds were compared with those of the triphenyl derivates.

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Herrn Prof. Dr.F. Wessely zum 70. Geburtstag gewidmet.     

Characterization of modified low density lipoprotein subfractions by capillary isotachophoresis

Oxidative modification of low density lipoproteins (LDLs) is an important pathogenetic factor in atherosclerosis. The various steps in oxidative modifications of LDL can be monitored using different methodologies with varying degrees of complexity. In this study, we propose capillary isotachophoresis (CITP) as a suitable tool to detect and measure the degree of oxidation of LDL. LDL was isolated from pooled plasma of healthy volunteers by sequential ultracentrifugation, and oxidation was performed in vitro as well as in cell culture experiments. Native LDL and oxidatively modified LDL were characterized by apo B-100 fluorescence and conjugated diene formation. Samples were separated by CITP combined with sudan black B staining. To underline the inherent advantages of this approach, CITP was compared with classical lipoprotein electrophoresis using agarose gel. We demonstrate the CITP method to be highly sensitive, as changes in peak area of the separated LDL subfractions were detected after only 2 h of oxidation. The leading LDL peaks increased, while the terminating LDL peaks decreased in parallel throughout the duration of oxidation. The LDL samples, oxidized for 4-24 h, also exhibited an increased migration velocity of the fractions. In summary, we present the first study investigating LDL-subfractions separated by CITP and the alterations of these LDL-subfractions after gradual in vitro oxidation and after oxidative modification by monocyte-derived macrophages and vascular smooth muscle cells.     

Glassy dynamics of polymers confined to nanoporous glasses revealed by relaxational and scattering experiments

The glassy dynamics of poly(propylene glycol) (PPG) and poly(dimethyl siloxane) (PDMS) confined to a nanoporous host system revealed by dielectric spectroscopy, temperature-modulated DSC and neutron scattering is compared. For both systems the relaxation rates estimated from dielectric spectroscopy and temperature-modulated DSC agree quantitatively indicating that both experiments sense the glass transition. For PPG the segmental dynamics is determined by a counterbalance of adsorption and confinement effect. The former results form an interaction of the confined macromolecules with the internal surfaces. A confinement effect originates from an inherent length scale on which the underlying molecular motions take place. The increment of the specific-heat capacity at the glass transition vanishes at a finite length scale of 1.8 nm. Both results support the conception that a characteristic length scale is relevant for glassy dynamics. For PDMS only a confinement effect is observed which is much stronger than that for PPG. Down to a pore size of 7.5 nm, the temperature dependence of the relaxation times follows the Vogel-Fulcher-Tammann dependence. At a pore size of 5 nm this changes to an Arrhenius-like behaviour with a low activation energy. At the same pore size vanishes for PDMS. Quasielastic neutron scattering experiments reveal that also the diffusive character of the relevant molecular motions --found to be characteristic above the glass transition-- seems to disappear at this length scale. These results gives further strong support that the glass transition has to be characterised by an inherent length scale of the relevant molecular motions.Received: 1 January 2003, Published online: 14 October 2003PACS: 64.70.Pf Glass transitions - 77.22.Gm Dielectric loss and relaxation - 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling     

Segmental dynamics of poly(methyl phenyl siloxane) confined to nanoporous glasses

The effect of a nanometer confinement on the molecular dynamics of poly(methyl phenyl siloxane) (PMPS) was studied by dielectric spectroscopy (DS), temperature modulated DSC (TMDSC) and neutron scattering (NS). Nanoporous glasses with pore sizes of 2.5–20 nm have been used. DS and TMDSC experiments show that for PMPS in 7.5 nm pores the molecular dynamics is faster than in the bulk which originates from an inherent length scale of the underlying molecular motions. For high temperatures the temperature dependence of the relaxation rates for confined PMPS crosses that of the bulk state. Besides finite states effects also the thermodynamic state of nano-confined PMPS is different from that of the bulk. At a pore size of 5 nm the temperature dependence of the relaxation times changes from a Vogel/Fulcher/Tammann like to an Arrhenius behavior where the activation energy depends on pore size. This is in agreement with the results obtained by NS. The increment of the specific heat capacity at the glass transition depends strongly on pore size and vanishes at a finite length scale between 3 and 5 nm which can be regarded as minimal length scale for glass transition to appear in PMPS.     

Global optimization of general nonconvex problems with intermediate polynomial substructures

This work considers the global optimization of general nonconvex nonlinear and mixed-integer nonlinear programming problems with underlying polynomial substructures. We incorporate linear cutting planes inspired by reformulation-linearization techniques to produce tight subproblem formulations that exploit these underlying structures. These cutting plane strategies simultaneously convexify linear and nonlinear terms from multiple constraints and are highly effective at tightening standard linear programming relaxations generated by sequential factorable programming techniques. Because the number of available cutting planes increases exponentially with the number of variables, we implement cut filtering and selection strategies to prevent an exponential increase in relaxation size. We introduce algorithms for polynomial substructure detection, cutting plane identification, cut filtering, and cut selection and embed the proposed implementation in BARON at every node in the branch-and-bound tree. A computational study including randomly generated problems of varying size and complexity demonstrates that the exploitation of underlying polynomial substructures significantly reduces computational time, branch-and-bound tree size, and required memory.     

Preparation of P-rich InP surfaces via MOCVD and surface characterization in UHV

For the first time direct contamination-free transfer to UHV was achieved for the P-rich InP(100) surface that is the easiest to prepare and control in the MOCVD environment. To avoid contamination during transfer a commercial MOCVD apparatus was modified to allow for transfer of samples to the 10^-9 mbar UHV range within a very short time (less than 20 s) [1]. Epitaxial InP(100) films were prepared with TBP (tertiarybutylphosphine) and TMIn (trimethylindium) as precursors. In situ reflectance anisotropy spectroscopy (RAS) was carried out in the MOCVD environment. After transfer of the sample to UHV the same RAS spectrum was recovered. Auger-electron spectra (AES) confirmed the P-termination of the surface reconstructions suggested by RAS. Received: 19 October 1998 / Accepted: 21 April 1999 / Published online: 14 July 1999     

Transformation of macromonomers into ring‐opening polymerization macroinitiators: A detailed initiation efficiency study

In the present study, n‐butyl acrylate macromonomer (BAMM) (M_n = 1900 g mol^?1; PDI = 1.96) has been synthesized via a high‐temperature polymerization process. Subsequently, the olefinic termini of the BAMM have been transformed into a diol via a dihydroxylation process using KMnO₄ as an oxidizing agent. The OH‐terminated macroinitiator pBA(OH)₂ has subsequently been employed for the ring‐opening polymerization (ROP) of ε‐caprolactone via various catalytic systems, that is, organo‐(1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene), metal (tin(II) 2‐ethylhexanoate), and enzymatic catalysis (Novozym® 435). The obtained pBA‐b‐pCL block copolymers and the initiation efficiency of the BAMM macroinitiator have been investigated via size exclusion chromatography (SEC), electrospray ionization–mass spectrometry (ESI‐MS) hyphenated with SEC and liquid chromatography at the critical conditions of both poly(ε‐caprolactone) (pCL) and pBA. The in vitro enzyme catalysis (eROP) approach proved to be the most efficient catalysis system due to minor transesterification side reactions during the polymerization process. However, side reactions such as transesterifications occur in each catalytic system and—while they cannot be suppressed—they can be minimized. The species generated during the eROP process include the desired block copolymer pBA‐b‐pCL as main species as well as pCL homopolymer and residual macroinitiator pBA(OH)₂. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012