TY - JOUR A1 - Engelhardt, Ulrike A1 - Linker, Torsten T1 - 1,4-cyclohexadienes as mechanistic probes for the Jacobsen epoxidation : evidence for radical pathways N2 - 1,4-Cyclohexadienes allow a direct comparison of epoxidation and C - H oxidation within the same molecule and give evidence for radical pathways during the Jacobsen epoxidation Y1 - 2005 ER - TY - JOUR A1 - Yenesew, Abiy A1 - Mushibe, E. K. A1 - Induli, M. A1 - Derese, Solomon A1 - Midiwo, Jacob O. A1 - Kabaru, Jacques M. A1 - Heydenreich, Matthias A1 - Koch, Andreas A1 - Peter, Martin G. T1 - 7a-O-methyldeguelol, a modified rotenoid with an open ring-C, from the roots of Derris trifoloata N2 - From the acetone extract of the roots of Derris trifoliata an isollavonoid derivative, named 7a-O- methyldeguelol, a modified rotenoid with an open ring-C, representing a new sub-class of isollavonoids (the sub-class is here named as rotenoloid), was isolated and characterised. In addition, the known rotenoids, rotenone, deguelin and alpha-toxicarol, were identified. The structures were determined on the basis of spectroscopic evidence. Rotenone and deguelin were identified as the larvicidal principles of the acetone extract of the roots of Derris trifoliata. (c) 2005 Elsevier Ltd. All rights reserved Y1 - 2005 SN - 0031-9422 ER - TY - JOUR A1 - Thomas, Steffen A1 - Kleinpeter, Erich T1 - A novel empirical approach for the structure elucidation of disilanes by empirical estimation of their Si-29 chemical shifts N2 - In C-13 NMR spectroscopy, there are many empirical methods for fast and exact computation of C-13 chemical shifts; comparable procedures for Si-29 NMR chemical shifts are not existing or are older than 20 years. On basis of the largest database of Si-29 chemical shifts available, along this paper a relatively simple procedure for the similarly exact calculation of the Si-29 chemical shifts of disilanes (average margin of error ca. 3.7 ppm) is given. (c) 2005 Elsevier B.V. All rights reserved Y1 - 2005 SN - 0022-2860 ER - TY - JOUR A1 - Neuvonen, Helmi A1 - Neuvonen, Kari A1 - Koch, Andreas A1 - Kleinpeter, Erich T1 - Ab initio study of the substituent effects on the relative stability of the E and Z conformers of phenyl esters : Stereoelectronic effects on the reactivity of the carbonyl group N2 - Equilibria between the Z (tau(1) = 0 degrees) and E (tau(1) = 180 degrees) conformers of p-substituted phenyl acetates 4 and trifluoroacetates 5 (X = OMe, Me, H, Cl, CN, NO2) were studied by ab initio calculations at the HF/6-31G* and MP2/6-31G* levels of theory. The preference for the Z conformer, Delta E(HF), was calculated to be 5.36 kcal mol(-1) and 7.50 kcal mot(-1) for phenyl acetate and phenyl trifluoroacetate (i.e., with X = H), respectively. The increasing electron-withdrawing ability of the phenyl substituent X increases the preference of the Z conformer. An excellent correlation with a negative slope was observed for both series between Delta E of the E-Z equilibrium and the Hammett sigma constant. By using an appropriate isodesmic reaction, it was shown that electron-withdrawing substituents decrease the stability of both conformers, but the effect is higher with the E conformer. Electron-withdrawing phenyl substituents decrease the delocalization of the lone pair of the ether oxygen to the C=O antibonding orbital (n(O) -> pi*(C=O)) in both the E and Z forms and in both series studied; this effect is higher in the E conformer than in the Z conformer. The n(O) -> pi*(C=O) electron donation has a minimum value with tau(1) = 90 degrees and a maximum value with tau(1) = 90 degrees (the Z conformer), the value with tau(1) = 180 degrees (the E conformer) being between these two values, obviously due to steric hindrance. The effects of the phenyl substituents on the reactivity of the esters studied are discussed in terms of molecular orbital interactions. ED/EW substituents adjust the availability of the pi*(C=O) antibonding orbital to interact with the lone pair orbital of the attacking nucleophile and therefore affect the reactivity: EW substituents increase and ED substituents decrease it. Excellent correlations were observed between the rate coefficients of nucleophilic acyl substitutions and pi*(C=O) occupancies of the ester series 4 and Y1 - 2005 SN - 1089-5639 ER - TY - THES A1 - Asfaw, Mesfin T1 - Adhesion of multi-component membbranes and strings Y1 - 2005 CY - Potsdam ER - TY - GEN A1 - Schmälzlin, Elmar A1 - Dongen, Joost T. van A1 - Klimant, Ingo A1 - Marmodée, Bettina A1 - Steup, Martin A1 - Fishahn, Joachim A1 - Geigenberger, Peter A1 - Löhmannsröben, Hans-Gerd T1 - An optical multifrequency phase-modulation method using microbeads for measuring intracellular oxygen concentrations in plants N2 - A technique has been developed to measure absolute intracellular oxygen concentrations in green plants. Oxygen-sensitive phosphorescent microbeads were injected into the cells and an optical multifrequency phase-modulation technique was used to discriminate the sensor signal from the strong autofluorescence of the plant tissue. The method was established using photosynthesis-competent cells of the giant algae Chara corallina L., and was validated by application to various cell types of other plant species. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 007 Y1 - 2005 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-12232 ER - TY - JOUR A1 - Yenesew, Abiy A1 - Derese, Solomon A1 - Midiwo, Jacob O. A1 - Bii, Christine C. A1 - Heydenreich, Matthias A1 - Peter, Martin G. T1 - Antimicrobial flavonoids from the stem bark of Erythrina burttii N2 - The chloroform extract of the stem bark of Erythrina burttii showed antifungal and antibacterial activities using the disk diffusion method. Flavonoids were identified as the active principles. Activities were observed against fungi and Gram(+) bacteria, but the Gram(-) bacteria Escherichia coli was resistant. (c) 2005 Elsevier B.V. All rights reserved Y1 - 2005 SN - 0367-326X ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Koch, Andreas A1 - Pihlaja, Kalevi T1 - Application of (1)J(C,H) coupling constants in conformational analysis N2 - 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 Y1 - 2005 SN - 0040-4020 ER - TY - JOUR A1 - Rickert, D A1 - Lendlein, Andreas A1 - Kelch, S A1 - Franke, R. P. A1 - Moses, M. A. T1 - Cell proliferation and cellular activity of primary cell cultures of the oral cavity after cell seeding on the surface of a degradable, thermoplastic block copolymer N2 - Using standard cell biological and biochemical methods we were able to test the ability of a degradable, thermoplastic block copolymer to support the adhesion, proliferation, and the cellular activity of primary cell cultures of the oral cavity in vitro. The delicate balance between a group of endogenous enzymes, Matrix Metalloproteinases (MMPs), and their inhibitors (Tissue Inhibitor of MMPs, TIMPs) have a decisive function in the remodeling of the extracellular matrix during processes like wound healing or the integration of biomaterials in surrounding tissues after implantation. Recently developed, biodegradable thermoplastic elastomers with shape-memory properties may be the key to develop new therapeutical options in head and neck surgery. Primary cell cultures of the oral cavity of Sprague-Dawley rats were seeded on the surface of a thermoplastic block copolymer and on a polystyrene surface as control. Conditioned media of the primary cells were analyzed for MMPs and TIMPs after different periods of cell growth. The MMP and TIMP expression was analysed by zymography and a radiometric enzyme assay. No statistically significant differences in the appearance and the kinetic of MMP-1, MMP-2, MMP-9 and TIMPs were detected between cells grown on the polymer surface compared to the control. An appropriate understanding of the molecular processes that regulate cellular growth and integration of a biomaterial in surrounding tissue is the requirement for an optimal adaptation of biodegradable, polymeric biomaterials to the physiological, anatomical, and surgical conditions in vivo to develop new therapeutic options in otolaryngology and head and neck surgery Y1 - 2005 ER - TY - JOUR A1 - Szczubialka, K. A1 - Moczek, Lukasz A1 - Goliszek, A. A1 - Nowakowska, M. A1 - Kotzev, Anton A1 - Laschewsky, André T1 - Characterization of hydrocarbon and fluorocarbon microdomains formed in aqueous solution of associative polymers : a molecular probe technique N2 - Fluorocarbon associative polymers of the polysoap type were studied using two fluorescent probes, 1- octanoylpyrene (OcPyH) and 1-perfluorooctanoylpyrene (OcPyF). In aqueous solution the polymers formed hydrophobic domains composed of hydrocarbon, fluorocarbon or both types of polymeric side chains, which could solubilize the probes. This resulted in the appearance of new fluorescence emission bands and changes in the fluorescence polarization of the probes. The differences in the solubilization properties of the polymers are discussed. (c) 2005 Elsevier B.V. All rights reserved Y1 - 2005 SN - 0022-1139 ER -