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Two different approaches. with an unsaturated carbohydrate as a radical acceptor and a carbohydrate derived aldehyde as a radical precursor, led to key intermediates in the synthesis of 3-deoxy-D-oct-2-ulosonic acids (KDO). Manganese(III) acetate and cerium(IV) ammonium nitrate were the reagents of choice for the oxidative generation of radicals, whereas samarium(II) iodide was employed for reductive couplings. Both strategies were realized by using easily available starting materials, with acetic acid as C-2 and ethyl acrylate as C-3 building blocks, respectively
In this paper we report dynamical simulations of laser-driven, coupled nuclear-electron dynamics for a molecule- surface system. Specifically, the laser desorption of a small molecule (NO) from a metal slab (Pt) in the so-called DIET limit (Desorption Induced by Electronic Transitions), is studied. The excitation of the metal electrons by a laser pulse followed by the formation of a negative ion resonance, its subsequent decay, and the simultaneous desorption of the molecule are all treated within a single quantum mechanical model. This model is based on an earlier theory of Harris and others [S. M. Harris, S. Holloway, and G. R. Darling, J. Chem. Phys. 102, 8235 (1995)], according to which a nuclear degree of freedom is coupled to an electronic one, both propagated on a single non-Born-Oppenheimer potential energy surface. The goals of the present contribution are (i) to make a conceptual connection of this model to the frequently adopted nonadiabatic "multi-state" models of photodesorption, (ii) to understand details of the desorption mechanism, (iii) to explicitly account for the laser pulse, and (iv) to study the photodesorption as a function of the thickness of the metal film, and the laser parameters. As an important methodological aspect we also present a highly efficient numerical scheme to propagate the wave packet in a problem-adapted diabatic basis
Conformational equilibria for a number of methyl substituted 1,3-dioxanes 1, 1,3-oxathianes 2 and 1,3-dithianes 3 were calculated at the HF and DFT levels of theory. In addition to the chair conformers also the energetically adjacent twist conformers were considered and the positions of the corresponding conformational equilibria estimated. On the basis of the global energy minima of conformers, participating in the conformational equilibria, the 1J(C,Hax,equ) coupling constants were calculated using the GIAO method and compared with the experimental values obtained from C-13, H- 1 coupled C-13 NMR spectra. The Perlin effect, the influence of the solvent and the suitability of this NMR parameter for assigning the conformational equilibria present are critically discussed. (c) 2005 Elsevier Ltd. All rights reserved
The quotient of the occupation numbers of pi bonding and pi* antibonding orbitals of the central C=C partial double bond, pi*(C=C)/pi(C=C), proved to be a useful parameter to quantify the push-pull effect completely for the first time in substituted alkenes by examination of a comprehensive set of compounds. (c) 2005 Elsevier Ltd. All rights reserved
[GRAPHICS] Amino-substituted thio(seleno)acrylamides 1-4 were synthesized and their H-1 and C-13 NMR spectra assigned. Both the NMR data and the results of theoretical calculations at the ab initio level of theory were employed to elucidate the adopted structures of the compounds in terms of E/Z isomerism and s-cis/s-trans configuration. In the case of the asymmetrically N(Me)Ph-substituted compounds, ab initio GIAO-calculated ring current effects of the N-phenyl group were applied to successfully determine the preferred conformer bias. The restricted rotations about the two C-N partial double bonds were studied by DNMR and the barriers to rotation (Delta G(c)(double dagger)) determined at the coalescence temperatures, and these were discussed with respect to the structural differences between the compounds. The barriers to rotation were also calculated at the ab initio level of theory where the best results (R-2 = 0.8746) were obtained only with inclusion of the solvent at the SCIPCMHF/6-31G* level of theory. The calculations also provided means of assessing structural influences which were not available due to inaccessible rotation barriers. By means of natural bond orbital (NBO) analysis of 1-4, the occupation numbers of nitrogen lone pairs and bonding/antibonding pi/pi* orbitals were shown to quantitatively describe thio(seleno)amide/vinylogous thio(seleno)amide "resonance". Finally, the thio(seleno)carbonyl anisotropic effect was quantitatively calculated by the GIRO method and visualized by isochemical shielding surfaces (ICSS). Only marginal differences between the two anisotropic effects were calculated and are therefore of questionable utility for previous and future applications with respect to stereochemical assignments
The configuration and dynamic behavior of O-allyl-S-methyl-N-(acridin-9-yl)iminothiocarbonate (1) and its S- allyl-O-methyl regioisomer (2) were studied using quantum chemical calculations and by applying a novel graphical method to scatter maps obtained from MD simulations for evaluation of an NOE-weighted internuclear distance (r(NOE)). Energy calculations indicated that the Z configuration was predominant for each compound and, further, this was supported both by the calculated chemical shifts and the rNOE. Both N-inversion- and rotation-type transition-state structures were also calculated for the E/Z isomerization process, the results indicating that the preferred interconversion mechanism for 1 is N-inversion, but contrastingly, interconversion via rotation is equally as probable as N-inversion for 2. This supports the notion that one or the other or both pathways can be active and each system needs to be assessed on a case- by-case basis. Copyright (c) 2005 John Wiley & Sons, Ltd
This paper focuses on the characterization and use of polymer-modified phosphatidylcholine (PC)/sodium dodecyl sulfate (SDS)-based inverse microemulsions as a template phase for BaSO4 nanoparticle formation. The area of the optically clear inverse microemulsion phase in the isooctane/hexanol/water/PC/SDS system is not significantly changed by adding polyelectrolytes, i.e., poly(diallyldimethylammonium chloride) (PDADMAC), or amphoteric copolymers of diallyldimethylammonium chloride and maleamid acid to the SDS-modified inverse microemulsion. Shear experiments show non- Newtonian flow behavior and oscillation experiments show a frequency-dependent viscosity increase (dilatant behavior) of the microemulsions. Small amounts of bulk water were identified by means of differential scanning calorimetry. One can conclude that the macromolecules are incorporated into the individual droplets, and polymer-filled microemulsions are formed. The polymer-filled microemulsions were used as a template phase for the synthesis of BaSO4 nanoparticles. After solvent evaporation the nanoparticles were redispersed in water and isooctane, respectively. The polymers incorporated into the microemulsion are involved in the redispersion process and influence the size and shape of the redispersed BaSO4 particles in a specific way. The crystallization process mainly depends on the type of solvent and the polymer component added. In the presence of the cationic polyelectrolyte PDADMAC the crystallization to larger cubic crystals is inhibited, and layers consisting of polymer-stabilized spherical nanoparticles of BaSO4 (6 nm in size) will be observed. (c) 2004 Elsevier Inc. All rights reserved
Polymere sind zweifelsohne der Werkstoff in unserer Zeit. Ein bedeutender Anteil der heute industriell produzierten Polymere wird durch Emulsionspolymerisation hergestellt. Obwohl die Emulsionspolymerisation breite Anwendung findet, sind die involvierten Mechanismen von Teilchenbildung und -wachstum noch heute Gegenstand heftiger Kontroversen. Ein Spezialfall der Emulsionspolymerisation ist die emulgatorfreie Emulsionspolymerisation. Hierbei handelt es sich um ein scheinbar einfacheres System der Emulsionspolymerisation, weil diese Methode ohne Zusatz von Emulgatoren auskommt. Die Teilchenbildung ist ein fundamentaler Vorgang im Verlauf der Emulsionspolymerisation, da sie zur Ausbildung der polymeren Latexphase führt. Detaillierte Kenntnisse zum Mechanismus der Nukleierung ermöglichen eine bessere Kontrolle des Reaktionsverlaufes und damit der Eigenschaften des Endproduktes der Emulsionspolymerisation, dem Polymer-Latex. Wie bereits vorangegangene Arbeiten auf dem Gebiet der emulgatorfreien Emulsionspolymerisation von Styrol sowie Methylmethacrylat und Vinylacetat zeigen konnten, verläuft die Teilchenbildung in diesen Systemen über den Mechanismus der aggregativen Nukleierung. Im Zusammenhang mit den Ergebnissen der genannten Arbeiten tauchte dabei immer wieder ein interessanter Effekt im Bereich der Partikelnukleierung auf. Dieses als JUMBO-Effekt bezeichnete Phänomen zeigte sich reproduzierbar in einem Anstieg der Transmission im Bereich der Teilchenbildung von emulgatorfreien Emulsionspolymerisationen von Styrol, MMA und VAc. Nach der Initiierung der Polymerisation in einer wässrigen Monomerlösung durch Kaliumperoxodisulfat steigt die Durchlässigkeit bei 546 nm auf über 100 % an. Für diese „Abnahme der optischen Dichte“ wurden verschiedene Erklärungsmöglichkeiten vorgeschlagen, jedoch blieb ein Nachweis der Ursache für den JUMBO-Effekt bisher aus. Dieser Mangel an Aufklärung eines offenbar grundlegenden Phänomens in der emulgatorfreien Emulsionspolymerisation bildet den „Nukleus“ für die vorlie¬gende Arbeit. Durch die vorliegende Dissertation konnte das Verständnis für Phänomene der Teilchenbildung in der emulgatorfreien Emulsionspolymerisation von Styrol mit KPS erweitert werden. In diesem Rahmen wurde das Online-Monitoring des Polymerisationsvorganges verbessert und um verschiedene Methoden erweitert: Zur simultanen Erfassung von Trübungsdaten bei verschiedenen Wellenlängen konnte ein modernes Spektrometer in Kombination mit einer Lichtleitersonde in die Reaktionsapparatur integriert werden. Es wurde ein verbesserter Algorithmus zur Datenbearbeitung für die Partikelgrößenbestimmung mittels faseroptischer dynamischer Lichtstreuung entwickelt. Es wurden Online-Partikelgrößenanalysen mittels statischer Vielwinkellichtstreuung bei Polymerisationen direkt in entsprechenden Lichtstreuküvetten durchgeführt. Diese zur Beschreibung des untersuchten Systems eingeführten Methoden sowie ein zeitlich vollständiges Monitoring des gesamten Polymerisationsverlaufes, beginnend mit der Zugabe von Monomer zu Wasser, führten zu neuen Erkenntnissen zur emulgatorfreien Emulsionspolymerisation. Es wurden große Monomeraggregate, die sog. Nanotröpfchen, in wässriger Lösung (emulgatorfrei) nachgewiesen. Diese Aggregate bilden sich spontan und treten verstärkt in entgastem Wasser auf. Die Existenz von Nanotröpfchen in Verbindung mit Trübungs- und gaschromatografischen Messungen lässt auf eine molekular gelöste „Wirkkonzentration“ von Styrol in Wasser schließen, die bedeutend geringer ist als die absolute Sättigungskonzentration. Es konnten Hinweise auf eine Reaktion höherer Ordnung im System Wasser/Styrol/KPS gefunden werden. Es konnte gezeigt werden, dass eine präzise Einstellung der Nukleierungsdauer über die Zeit der Equilibrierung von Wasser mit Styrol möglich ist. Der JUMBO-Effekt, dem in dieser Arbeit ein besonderes Interesse galt, konnte in gewisser Weise entmystifiziert werden. Es konnte gezeigt werden, dass die Durchlässigkeit der Reaktionsmischung bereits beim Lösen von Styrol in Wasser durch Bildung von Styrolaggregaten abnimmt. Der darauf folgende kurzzeitige Transmissionsanstieg im Zusammenhang mit der Nukleierung erreicht dabei nicht mehr 100 % des Referenzwertes von reinem Wasser. Alle experimentellen Daten sprechen für die Nanotröpfchen als Ursache des JUMBO-Effekts. Wie die Ergebnisse dieser Arbeit zeigen, ist selbst das relativ „einfache“ System der emulgatorfreien Emulsionspolymerisation komplizierter als angenommen. Die Existenz von großen Styrolaggregaten in wässriger Lösung erfordert eine neue Betrachtungsweise des Reaktionssystems, in die auch der Lösungszustand des Monomers mit einbezogen werden muss.
In order to elucidate the interactions of copper with wood, three mononuclear copper(II) coordination compounds with a vanillinate anion, cis-[Cu(C8H7O3)(2)(H2O)(2)] (1), trans-[Cu(C8H7O3)(2)(H2O)(2)].2H(2)O (2), and trans- [Cu(C8H7O3)(2)(H2O)(2)] (3), have been characterized. X-ray structure analysis of the cis isomer 1 reveals two bidentate vanillinate ions coordinated via methoxy (Cu-O1 2.260(2) angstrom) and deprotonated hydroxy oxygen atoms (Cu-O2 1.909(2) angstrom), and two water molecules (Cu-O1w 2.087(2) angstrom) in the octahedral CuO6 chromophore. Two axes O1-Cu- O1w' in the octahedron have the same length, while the third axis O2-Cu-O2' is shorter. This is in agreement with the room temperature EPR spectrum of 1, showing two signals (g(12) 2.302, g(3) 2.005), but interestingly, three signals (g(1) 2.393, g(2) 2.214, g(3) 2.010) in the 115 K spectrum were found. The same coordination atoms were found also in the trans isomer 2 (Cu-O2 1.950(2), Cu-O1w 1.994(2), Cu-O1 2.334(2) angstrom), however here, two axes of almost equal length are short (O2-Cu-O2' O1w-Cu-O1w'), while the third axis is longer (O1-Cu-O1'). On the other hand, three (rhombic) signals (g(1) 2.289, g(2) 2.163, g(3) 2.086) in the room temperature EPR spectrum of 2 suggest three different axes in the coordination octahedron. In the EPR spectrum, of the second trans complex 3, a slightly rhombically distorted elongated axial spectrum is found. The 115 K EPR spectra of the two trans complexes 2 and 3 do not differ significantly from the features observed at room temperature. These results indicate that there is not always a straightforward correlation between the results of XRD structure analysis and EPR spectroscopy. Nevertheless, both methods can act also complementarily and give a deeper insight into the nature of copper(II) chromophores