TY - JOUR A1 - Machumi, Francis A1 - Yenesew, Abiy A1 - Midiwo, Jacob O. A1 - Heydenreich, Matthias A1 - Kleinpeter, Erich A1 - Tekwani, Babu L. A1 - Khan, Shabana I. A1 - Walker, Larry A. A1 - Muhammad, Ilias T1 - Antiparasitic and anticancer carvotacetone derivatives of Sphaeranthus bullatus JF - Natural product communications : an international journal for communications and reviews N2 - The CH2Cl2-MeOH (1:1) extract of the aerial parts of Sphaeranthus bullatus, an annual herb native to tropical East Africa, showed activity against chloroquine sensitive D6 (IC50 9.7 mu g/mL) and chloroquine resistant W2 (IC50 15.0 mu g/mL) strains of Plasmodium falciparum. Seventeen secondary metabolites were isolated from the extract through conventional chromatographic techniques and identified using various spectroscopic methods. The compounds were evaluated for their in vitro antiplasmodial, antileishmanial and anticancer activities revealing activity of four carvotacetone derivatives, namely 3-acetoxy-7-hydroxy-5-tigloyloxycarvotacetone (1) 3,7-dihydroxy-5-tigloyloxycarvotacetone (2), 3-acetoxy-5,7-dihydroxycarvotacetone (3) and 3,5,7-trihydroxycarvotacetone (4); with antiplasmodial IC50 values of 1.40, 0.79, 0.60 and 3.40 mu g/mL, respectively, against chloroquine sensitive D6 strains of P. falciparum; antiplasmodial activity of IC50 2.00, 0.90, 0.68 and 2.80 mu g/mL respectively, against chloroquine resistant W2 strains of P. falciparum, antileishmanial IC50, values of 0.70, 3.00, 0.70 and 17.00 mu g/mL, respectively, against the parasite L. donovanii promastigotes, and anticancer activity against human SK-MEL, KB, BT-549 and SK-OV-3 tumor cells, with IC50 values between <1.1 - 5.3 mu g/mL, for 1-3. In addition, cytotoxic effects of the active compounds were evaluated against monkey kidney fibroblasts (VERO) and pig kidney epithelial cells (LLC-PK11). The structures of carvotacetone derivatives were determined by ID and 2D NMR spectroscopy; the absolute stereochemical configuration of 3-acetoxy-7-hydroxy-5-tigloyloxycarvotacetone (I) was determined as 3R, 4R, 5S by circular dichroism, specific rotation, H-1 NMR and 2D NMR ROESY and NOESY experiments. KW - Sphaeranthus bullatus KW - Asteraceae KW - Antiplasmodial KW - Antileishmanial KW - Anticancer KW - Carvotacetones Y1 - 2012 SN - 1934-578X VL - 7 IS - 9 SP - 1123 EP - 1126 PB - NPC CY - Westerville ER - TY - JOUR A1 - Induli, Martha A1 - Cheloti, Michael A1 - Wasuna, Antonina A1 - Wekesa, Ingrid A1 - Wanjohi, John M. A1 - Byamukama, Robert A1 - Heydenrich, Matthias A1 - Makayoto, Moses A1 - Yenesew, Abiy T1 - Naphthoquinones from the roots of Aloe secundiflora JF - Phytochemistry letters N2 - Two new naphthoquinones, 5-hydroxy-3,6-dimethoxy-2-methylnaphthalene-1,4-dione and 5,8-dihydroxy-3-methoxy-2-methylnaphthalene-1,4-dione, were isolated from the roots of Aloe secundiflora together with the known compounds chrysophanol, helminthosporin, isoxanthorin, ancistroquinone C, aloesaponarins I and II, aloesaponols I and II, laccaic acid D methyl ester and asphodelin. The structures were elucidated based on spectroscopic evidence. This appears to be the first report on the occurrence of naphthoquinones in the genus Aloe. Aloesaponarin I and 5-hydroxy-3,6-dimethoxy-2-methylnaphthalene-1,4-dione showed anti-bacterial activity against Mycobacterium tuberculosis with MIC values of 21-23 mu g/mL in the Microplate Alamar Blue Assay (MABA) and Low Oxygen Recovery Assay (LORA); 5-hydroxy-3,6-dimethoxy-2-methylnaphthalene-1,4-dione also showed cytotoxicity against the Vero cell line (IC50 = 10.2 mu g/mL). KW - Aloe secundiflora KW - Asphodelaceae KW - Roots KW - Naphthoquinone KW - 5-Hydroxy-3,6-dimethoxy-2-methylnaphthalene-1,4-dione 5,8-Dihydroxy-3-methoxy-2-methylnaphthalene-1,4-dione KW - Anthraquinone KW - Aloesaponarin I KW - Mycobacterium tuberculosis Y1 - 2012 U6 - https://doi.org/10.1016/j.phytol.2012.04.014 SN - 1874-3900 VL - 5 IS - 3 SP - 506 EP - 509 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Gumula, Ivan A1 - Heydenreich, Matthias A1 - Derese, Solomon A1 - Ndiege, Isaiah O. A1 - Yenesew, Abiy T1 - Four isoflavanones from the stem bark of Platycelphium voense JF - Phytochemistry letters N2 - From the stem bark of Platycelphium voense (Leguminosae) four new isoflavanones were isolated and characterized as (S)-5,7-dihydroxy-2 ',4 '-dimethoxy-3 '-(3 ''-methylbut-2 ''-enyl)-isoflavanone (trivial name platyisoflavanone A), (+)-5,7,2 '-trihydroxy-4 '-methoxy-3 '-(3 ''-methylbut-2 ''-enyl)-isoflavanone (platyisoflavanone B), 5,7-dihydroxy-4 '-methoxy-2 ''-(2 '''-hydroxyisopropyl)-dihydrofurano-[4 '',5 '':3 ',2 ']-isoflavanone (platyisoflavanone C) and 5,7,2 ',3 ''-tetrahydroxy-2 '',2 ''-dimethyldihydropyrano-[5 '',6 '':3 ',4 ']-isoflavanone (platyisoflavanone D). In addition, the known isoflavanones, sophoraisoflavanone A and glyasperin F; the isoflavone, formononetin; two flavones, kumatakenin and isokaempferide; as well as two triterpenes, betulin and beta-amyrin were identified. The structures were elucidated on the basis of spectroscopic evidence. Platyisoflavanone A showed antibacterial activity against Mycobacterium tuberculosis in the microplate alamar blue assay (MABA) with MIC = 23.7 mu M, but also showed cytotoxicity (IC50 = 21.1 mu M) in the vero cell test. KW - Platycelphium voense KW - Stem bark KW - Leguminosae KW - Isoflavanones KW - Platyisoflavanone KW - Mycobacterium tuberculosis Y1 - 2012 U6 - https://doi.org/10.1016/j.phytol.2011.11.012 SN - 1874-3900 VL - 5 IS - 1 SP - 150 EP - 154 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Munzke, Dorit A1 - Saunders, John A1 - Omrani, Hengameh A1 - Reich, Oliver A1 - Loock, Hans-Peter T1 - Modeling of fiber-optic fluorescence probes for strongly absorbing samples JF - Applied optics N2 - The dynamic range of fiber-optic fluorescent probes such as single fibers and fiber bundles is calculated for strongly absorbing samples, such as process liquids, foodstuffs, and lubricants. The model assumes an excitation beam profile based on a Lambertian light source and uses analytical forms of the collection efficiency, followed by an Abel transformation and numerical integration. It is found that the effect of primary absorption of the excitation light and secondary absorption of the fluorescence is profound. For fiber bundles and bifurcated fiber probes, the upper accessible concentration limit is roughly given by the absorption length of the primary and secondary absorption. Fluorescence detectors that are placed at right angles to the excitation beam axis or collinear to the beam axis are equally strongly affected by secondary absorption. A probe in which the same fiber is used for excitation and for collection of the fluorescence emerges as the fiber probe with the largest accessible concentration range. Y1 - 2012 U6 - https://doi.org/10.1364/AO.51.006343 SN - 1559-128X SN - 2155-3165 VL - 51 IS - 26 SP - 6343 EP - 6351 PB - Optical Society of America CY - Washington ER - TY - JOUR A1 - Ruiz, Salome Vargas A1 - Hass, Roland A1 - Reich, Oliver T1 - Optical monitoring of milk fat phase transition within homogenized fresh milk by Photon Density Wave spectroscopy JF - International dairy journal N2 - Photon Density Wave (PDW) spectroscopy was applied for temperature dependent monitoring of melting and crystallization of milk fat within homogenized fresh milk. As an in-line process analytical technique, PDW spectroscopy quantifies continuously the optical properties of turbid material, providing an insight into its structural processes. Here, the measured absorption coefficients reflect temperature as well as fat content of milk and the reduced scattering coefficients probe physical changes of the light scattering fat droplets and casein micelles. Thermal processing reveals breakpoints within the temperature trend of the reduced scattering coefficient of fat containing milk. Found at 16 degrees C and 24 degrees C while cooling and heating, respectively, they are associated to the phase transitions of milk fat. Continuous isothermal measurement of the optical coefficients showed that the crystallization process requires several hours. The strongly changing reduced scattering coefficient implies that the thermal history of milk will have a major impact on any method based on light scattering as quantitative analytical technique. Y1 - 2012 U6 - https://doi.org/10.1016/j.idairyj.2012.03.012 SN - 0958-6946 VL - 26 IS - 2 SP - 120 EP - 126 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Wöhl-Bruhn, Stefanie A1 - Badar, Muhammad A1 - Bertz, Andreas A1 - Tiersch, Brigitte A1 - Koetz, Joachim A1 - Menzel, Henning A1 - Müller, Peter P. A1 - Bunjes, Heike T1 - Comparison of in vitro and in vivo protein release from hydrogel systems JF - Journal of controlled release N2 - Hydrogel systems based on hydroxyethyl starch-polyethylene glycol methacrylate (HES-P(EG)(6)MA) or hydroxyethyl starch methacrylate (HES-MA) were used to assess the protein release behavior. Here, we analyzed the in vitro release of FITC-anti-human antibodies incorporated in either HES-P(EG)(6)MA or HES-MA hydrogel delivery systems in PBS or human serum. In addition, hydrogel disks and microparticles prepared from the two polymers were subcutaneously implanted in BALB/c mice. The in vivo release of FITC-IgG was non-invasively monitored by an in vivo imaging system (IVIS 200) over a time period of up to 3 months. The imaging system allowed to asses individual animals over time, therefore only a small number of animals was required to obtain high quality data. The reduction in fluorescence intensity at the site of administration was compared to in vitro release profiles. These investigations demonstrated a sustained release from HES-MA hydrogel disks compared to rapidly degrading HES-P(EG)(6)MA disks and microparticles. The sustained release from HES-MA disks could be further optimized by using increased polymer concentrations. Human serum as in vitro release medium reflected better the in vivo release from HES-P(EG)(6)MA systems than PBS, suggesting that the presence of organic substances like proteins or lipids may play a significant role for the release kinetics. KW - In vivo imaging system (IVIS) KW - Hydrogel disks KW - Hydrogel microparticles KW - Release KW - In vivo-in vitro correlation KW - Hydroxyethyl starch (HES) Y1 - 2012 U6 - https://doi.org/10.1016/j.jconrel.2012.05.049 SN - 0168-3659 VL - 162 IS - 1 SP - 127 EP - 133 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Koeth, Anja A1 - Tiersch, Brigitte A1 - Appelhans, Dietmar A1 - Gradzielski, Michael A1 - Cölfen, Helmut A1 - Koetz, Joachim T1 - Synthesis of Core-Shell Gold Nanoparticles with Maltose-Modified Poly(Ethyleneimine) JF - Journal of dispersion science and technology N2 - The synthesis of ultrafine gold nanoparticles in presence of maltose-modified hyperbranched poly(ethyleneimines) (PEI) is described. The polymer acted as both a reducing and stabilising agent in the particle formation process. The nanoparticles were characterized by means of dynamic light scattering (DLS), transmission electron microscopy (TEM), analytical ultracentrifugation (AUC), small-angle x-ray scattering (SAXS), and small-angle neutron scattering (SANS). The mechanism of nanoparticle formation can be described in two steps. The reduction process of the Au3+ ions located in the inner coil region of the hyperbranched PEI led to the formation of a compact gold core, and is accompanied by a collapse of the polymer coil. Therefore, in the subsequent reduction process a gold-polymer hybrid shell is formed. By using the PEI of higher molar mass, core-shell gold nanoparticles of about 3.6 nm size with a more narrow size distribution and special fluorescence behavior could be synthesized. KW - Gold nanoparticles KW - gold-polymer hybrid shell KW - maltose-modified poly(ethyleneimine) Y1 - 2012 U6 - https://doi.org/10.1080/01932691.2010.530084 SN - 0193-2691 VL - 33 IS - 1-3 SP - 52 EP - 60 PB - Taylor & Francis Group CY - Philadelphia ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Shainyan, Bagrat A. A1 - Kirpichenko, Svetlana V. A1 - Shlykov, Sergei A. T1 - Structure and Conformational Properties of 1,3,3-Trimethyl-1,3-Azasilinane : Gas Electron Diffraction, Dynamic NMR, and Theoretical Study. Y1 - 2012 SN - 1089-5639 ER - TY - THES A1 - Mucic, Nenad T1 - Thermodynamics, kinetics and rheology of surfactant adsorption layers at water/oil interfaces Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Debatin, Franziska T1 - Eine isoretikulare Serie mikroporöser, metall-organischer Netzwerke basierend auf 2-substituierten Imidazolat-4-amid-5-imidaten und Zink- oder Cobalt-Zentren: Synthesen, Strukturen und Eigenschaften Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Dorff, Giselher T1 - Eigenschaftsverbesserung von Polylactid durch Copolymerisation mit anderen Thermoplasten Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Bettenbühl, Mario T1 - Microsaccades: symbols in fixational eye movements Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Rojas Carillo, Oscar Mario T1 - Versatile uses of halogen-free Ionic Liquids for the formulation of non-aqueous microemulsion and synthesis of gold nanoparticles Y1 - 2012 CY - Potsdam ER - TY - JOUR A1 - Shainyan, Bagrat A. A1 - Suslova, Elena N. A1 - Kleinpeter, Erich T1 - Conformational analysis of 4,4-dimethyl-1-(trifluoromethylsulfonyl)-1,4-azasilinane and 2,2,6,6-tetramethyl-4- (trifluoromethylsulfonyl)-1,4,2,6-oxazadisilinane N2 - 4,4-Dimethyl-1-(trifluoromethylsulfonyl)-1,4-azasilinane 1 and 2,2,6,6-tetramethyl-4-(trifluoromethylsulfonyl)- 1,4,2,6-oxazadisilinane 2 were studied by variable temperature dynamic 1H, 13C, 19F NMR spectroscopy and theoretical calculations at the DFT (density functional theory) and MP2 (Moller-Plesset 2) levels of theory. Both kinetic (barriers to ring inversion) and thermodynamic data (frozen conformational equilibria) could be obtained for the two compounds. The computations revealed two minima on the potential energy surface for molecules 1 and 2 corresponding to the rotamers with the CF3SO2 group directed inward and outward the ring, the latter being 0.20.4 kcal/mol (for 1) and 1.1 kcal/mol (for 2) more stable than the former. The vibrational calculations at the DFT and MP2 levels of theory give the values of the free energy difference Delta G degrees for the 'inward' reversible arrow 'outward' equilibrium consistent with those determined from the experimentally measured ratio of the rotamers. The structure of crystalline compound 2 was ascertained by X-ray diffraction analysis. Y1 - 2012 ER - TY - JOUR A1 - Lazareva, Nataliya F. A1 - Albanov, Alexander I. A1 - Shainyan, Bagrat A. A1 - Kleinpeter, Erich T1 - Synthesis and conformational properties of substituted 1,4,2-oxazasilinanes: low temperature NMR study and quantum chemical calculations Y1 - 2012 UR - http://www.sciencedirect.com/science/article/pii/S0040402011018321 U6 - https://doi.org/10.1016/j.tet.2011.11.077 ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Stojanovic, Milovan A1 - Markovic, Rade A1 - Baranac-Stojanovic, Marija T1 - Synthesis of thiazolidine-fused heterocycles via exo-mode cyclizations of vinylogous N-acyliminium ions N2 - Syntheses of thiazolidine-fused heterocycles via exo-mode cyclizations of vinylogous N-acyliminium ions incorporating heteroatom-based nucleophiles have been examined and discussed. The formation of (5,6)-membered systems was feasible with all nucleophiles tried (O, S and N), while the closing of the five-membered ring was restricted to O- and S-nucleophiles. The closure of a four-membered ring failed. Instead, the bicyclic (5,6)-membered acetal derivative and the tricyclic system with an eight-membered central ring were obtained from the substrates containing O and S nucleophilic moieties, respectively. The reaction outcome and stereochemistry are rationalized using quantum chemical calculations at B3LYP/6-31G(d) level. The exclusive cis-stereoselectivity in the formation of (5,6)- and (5,5)-membered systems results from thermodynamic control, whereas the formation of the eight-membered ring was kinetically controlled. Y1 - 2012 SN - 1477-0520 ER - TY - THES A1 - Kuke, Stefanie T1 - Lanthanoide(III) in Komplexen mit niedermolekularen Säuren : Spektroskopische Betrachtung kompexer- spezifischer Löschmechanis,men in Eu(III)- und TB(III)-Komplexen Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Steinbrück, Dörte T1 - Faseroptische Sauerstoff- und ph-Sensorik mittels Phasenmodulationsspektroskopie Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Hahn, Simone T1 - Extration von Hexachloroplatinat(IV) mit phoshorylierten Merrifield-Harzen aus salzsauren Lösungen Y1 - 2012 CY - Potsdam ER - TY - JOUR A1 - Shainyan, Bagrat A. A1 - Kleinpeter, Erich T1 - Conformational preferences of Si-Ph,H and Si-Ph,Me silacyclohexanes and 1,3-thiasilacyclohexanes : Additivity of conformational energies in 1,1-disubstituted heterocyclohexanes N2 - The conformational equilibria of 1-phenyl-1-silacyclohexane 1, 3-phenyl-1,3-thiasilacyclohexane 2, 1-methyl-1- phenyl-1-silacyclohexane 3, and 3-methyl-3-phenyl-1,3-thiasilacyclohexane 4 have been studied for the first time by low temperature C-13 NMR spectroscopy at 103 K. Predominance of the equatorial conformer of compound 1 (Ph-eq/Ph-ax=78%:22%) is much less than in its carbon analog, phenylcyclohexane (nearly 100% of Ph-eq). And in contrast to 1-methyl-1- phenylcyclohexane, the conformers with the equatorial Ph group are predominant for compounds 3 and 4: at 103 K, Ph-eq/Ph- ax ratios are 63%:37% (3) and 68%:32% (4). As the Si-C bonds are elongated with respect to C-C bonds, the barriers to ring inversion are only between 5.2-6.0 (ax -> eq) and 5.4-6.0 (eq -> ax) kcal mol(-1). Parallel calculations at the DFT and MP2 level of theory (as well as the G2 calculations for compound 1) show qualitative agreement with the experiment. The additivity/nonadditivity of conformational energies of substituents on cyclohexane and silacyclohexane derivatives is analyzed. The geminally disubstituted cyclohexanes containing a phenyl group show large deviations from additivity, whereas in 1-methyl-1-phenyl-1-silacyclohexane and 3-methyl-3-phenyl-1,3-thiasilacyclohexane the effects of the methyl and phenyl groups are almost additive. The reasons for the different conformational preferences in carbocyclic and heterocyclic compounds are analyzed using the homodesmotic reactions approach. Y1 - 2012 UR - http://www.sciencedirect.com/science/article/pii/S0040402011016620 (25.11.2013) SN - 0040-4020 ER - TY - THES A1 - Schneider, Julia T1 - Characterisation of single and multibubble cavitation through analysis of molecular, atomic and ionic line emissions Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Kupstat, Annette T1 - Förster resonance energy transfer (FRET)-based detection of molecular binding interactions - from fundamental research to application in life science Y1 - 2012 CY - Potsdam ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Heydenreich, Matthias A1 - Koch, Andreas A1 - Linker, Torsten T1 - Synthesis and NMR spectroscopic conformational analysis of esters of 4-hydroxy-cyclohexanone-the more polar the molecule the more stable the axial conformer N2 - The esters of 4-hydroxy-cyclohexanone and a series of carboxylic acids R-COOH with R of different electronic and steric influence (R=Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, sec-Bu, t-Bu, CF3, CH2Cl, CHCl2, CCl3, CH2Br, CHBr2, and CBr3) were synthesized and the conformational equilibria studied by 1H and 13C NMR spectroscopy at 103 K and at 295 K, respectively. The geometry of optimized structures of the axial/equatorial chair conformers was computed at the ab initio MO and DFT levels of theory. Only one preferred conformation was obtained for the axial and the equatorial conformer as well. When comparing the conformational equilibria of the cyclohexanone esters with those of the corresponding cyclohexyl esters a certain polarity contribution of the cyclohexanone framework was revealed, which is independent of the substituent effects and increases the stability of the axial conformers by a constant amount. Y1 - 2012 SN - 0040-4020 ER - TY - THES A1 - von Rüsten-Lange, Maik T1 - Improving Hemocompatibility of poly(ether imide) by surface functionalization with polyethers Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Techen, Anne T1 - Fluoreszenzspektroskopische Untersuchungen von Arzneimittel-Träger-Wechselwirkungen am Beispiel von Xanthenfarbstoff-markierten CTAB-Mizellen Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Flehr, Roman T1 - Design and development of novel three color-FRET systems in synthetic peptides and oligonucleotides Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Geißler, Daniel T1 - Multiplexing in homogenen FRET-Immunoassays : Detektion von Lungenkrebs-Tumormarkern mittels zeitaufgelöster Laserspektoskopie durch Förster-Resonanzenergietransfer (FRET) Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Su, Fangzheng T1 - Graphitic carbon nitride as a metal-free catalyst for photosynthesis, Amine oxidation and base-mediated reactions Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Lahn, Mattes T1 - Investigation of ion concentrations in biological tissue using FLIM and 2P-microscopy Y1 - 2012 CY - Potsdam ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Neuvonen, Kari A1 - Neuvonen, Helmi A1 - Koch, Andreas T1 - Taft equation in the light of NBO computations : Introduction of a novel polar computational substituent constant scale for alkyl groups Y1 - 2012 SN - 2210-271X ER - TY - THES A1 - Pick, Charlotte Hildegard T1 - Die Photo-Dehydro-Diels-Alder-Reaktion als potentielle Methode zur Ligandendarstellung: Untersuchungen zur atropselektiven Synthese von Biarylen und Synthese von Naphthylpryridinen Y1 - 2012 SN - 978-3-8439-0337-0 PB - Dr. Hut CY - München ER - TY - THES A1 - Glatzel, Stefan T1 - Cellulose based transition metal nano-composites : structuring and development Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Ast, Sandra T1 - Integration of the 1,2,3-Triazole "Click" motif as a potent signalling element into metal ion responsive fluorescent probes for physiological cations Y1 - 2012 CY - Potsdam ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Lazareva, Nataliya F. A1 - Shainyan, Bagrat A. A1 - Schilde, Uwe A1 - Chipania, Nina N. T1 - Synthesis, Molecular Structure, Conformational Analysis, and Chemical Properties of Silicon-Containing Derivatives of Quinolizidine Y1 - 2012 SN - 0022-3263 ER - TY - THES A1 - Möllnitz, Kristian T1 - Synthese und Untersuchung von molekularen Stäben basierend auf Oligospiroketalen Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Junginger, Mathias T1 - Interface-controlled calcium phosphate mineralization Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Marmodée, Bettina T1 - Fluorenscence Line-Narrowing-Spektroskopie zur Charakterisierung von Eu(III) in Komplexen mit kleinen organischen Liganden Y1 - 2012 CY - Potsdam ER - TY - GEN A1 - Krehl, Stefan T1 - Entwicklung von Ruthenium-katalysierten Tandem-Reaktionssequenzen Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Wilke, Antje T1 - Synthese und Charakterisierung von mesoporösen Polymernetzwerken Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Xie, Zai-Lai T1 - Functional materials in metal-containing ionic liquids Y1 - 2012 CY - Potsdam ER - TY - THES A1 - Luzi, Manja T1 - Kinetic studies of mixed gas hydrates Y1 - 2012 CY - Potsdam ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Koch, Andreas T1 - Spatial magnetic properties subject to lone pair and pi electron delocalization in benzenoid and quinoid structures : are quinoid tautomers really nonaromatic? N2 - The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of benzenoid and quinoid tautomeric structures such as benzodifurantrione and phenazine-type molecules have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept of Paul von Rague Schleyer and visualized as iso- chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values were employed to quantify and visualize the partial aromaticity of the studied compounds. In the case of the surprisingly more stable quinoid tautomers, the aromaticity-synonymous with stability due to the conjugation of p electrons and lone pairs-was not found to be particularly reduced. Y1 - 2012 SN - 1551-7004 ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Modarresi-Alam, Ali Reza A1 - Inaloo, Iman Dindarloo T1 - Synthesis of primary thiocarbamates by silica sulfuric acid as effective reagent under solid-state and solution conditions N2 - A simple and efficient method for the conversion of alcohols and phenols to primary O-thiocarbamates and S- thiocarbamates in the absence of solvent (solvent-free condition) using silica sulfuric acid (SiO2OSO3H) as a solid acid is described. The products are easily distinguished by IR, NMR and X-ray data. X-ray data of the compounds reveal a planar trigonal orientation of the NH2 nitrogen atom with the partial C,N double-bond character and the CS or CO groups in synperiplanar position with CarylO and CalkylS moieties, respectively. Moreover, the OCSNH2 group which is perpendicular to the plane of the benzene ring in 1c and the central thiocarbamate SCONH2 group in 2b are essentially planar. Y1 - 2012 SN - 0022-2860 ER - TY - JOUR A1 - Kleinpeter, Erich T1 - Are lithium and sodium salts of N-(2-hydroxyphenyl)-salicylaldimine aromatic metalla-hetero[10]annulenes? An answer given by spatial magnetic properties (through space NMR shieldings-TSNMRS) N2 - The spatial magnetic properties (through space NMR shieldings-TSNMRS) of the enol tautomer of N-(2- hydroxyphenyl)-salicylaldimine, the lithium and sodium salts in comparison with cyclodecapentaene and pyrano[2,3- b]pyrrole were studied to answer this question. Y1 - 2012 SN - 1463-9076 ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Branac-Stojanovi, Marija A1 - Koch, Andreas T1 - Is the Conventional Interpretation of the Anisotropic Effects of CC Double Bonds and Aromatic Rings in NMR Spectra in Terms of the -Electron Shielding/Deshielding Contributions Correct? N2 - Based on the nucleus-independent chemical shift (NICS) concept, isotropic magnetic shielding values have been computed along the three Cartesian axes for ethene, cyclobutadiene, benzene, naphthalene, and benzocyclobutadiene, starting from the molecular/ring center up to 10;Å away. These through-space NMR spectroscopic shielding (TSNMRS) values, which reflect the anisotropic effects, have been broken down into contributions from localized- and canonical molecular orbitals (LMOs and CMOs); these contributions revealed that the proton NMR spectroscopic chemical shifts of nuclei that are spatially close to the C=C double bond or the aromatic ring should not be explained in terms of the conventionally accepted ;-electron shielding/deshielding effects. In fact, these effects followed the predictions only for the antiaromatic cyclobutadiene ring. Y1 - 2012 SN - 1521-3765 ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Balci, Kubilay A1 - Yapar, G. A1 - Akkaya, S. A1 - Akyuz, S. A1 - Koch, Andreas T1 - A conformational analysis and vibrational spectroscopic investigation on 1,2-bis(o-carboxyphenoxy) ethane molecule N2 - The minima on the potential energy surface of 1,2-bis(o-carboxyphenoxy) ethane (CPE) molecule in its electronic ground state were searched by a molecular dynamics simulation performed with MM2 force field. For each of the found minimum-energy conformers, the corresponding equilibrium geometry, charge distribution, HOMO-LUMO energy gap, force field, vibrational normal modes and associated IR and Raman spectral data were determined by means of the density functional theory (DFT) based electronic structure calculations carried out by using B3LYP method and various Pople- style basis sets. The obtained theoretical data confirmed the significant effects of the intra- and inter-molecular hydrogen bonding interactions on the conformational structure, force field, and group vibrations of the molecule. The same data have also revealed that two of the determined stable conformers, both of which exhibit pseudo-crown structure, are considerably more favorable in energy to the others and accordingly provide the major c ntribution to the experimental spectra of CPE. In the light of the improved vibrational spectral data obtained within the "SQM FF" methodology and "Dual Scale Factors" approach for the monomer and dimer forms of these two conformers, a reliable assignment of the fundamental bands observed in the experimental room-temperature IR and Raman spectra of the molecule was given, and the sensitivities of its group vibratb20s to conformation, substitution and dimerization were discussed. Y1 - 2012 ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Schainyan, Bagrat A. A1 - Kirpichenko, Svetlane V. T1 - Synthesis and conformational properties of 1,3-dimethyl-3-phenyl-1,3-azasilinane : low temperature dynamic NMR and computational study N2 - 1,3-Dimethyl-3-phenyl-1,3-azasilinane was synthesized and its conformational behavior was studied by the low temperature NMR spectroscopy and quantum chemical calculations. The compound was shown to exist as an equilibrium mixture of the PhaxMeeq and PheqMeax chair conformers with the N-methyl substituent in equatorial position. The barrier to ring inversion was also determined. Y1 - 2012 SN - 1551-7004 ER - TY - JOUR A1 - Awad, Duha Jawad A1 - Koch, Andreas A1 - Mickler, Wulfhard A1 - Schilde, Uwe A1 - Strauch, Peter T1 - EPR spectroscopy of 4, 4 '-Bis(tert-butyl)-2, 2 '-bipyridine-1, 2-dithiolatocuprates(II) in host lattices with different coordination geometries JF - Zeitschrift für anorganische und allgemeine Chemie N2 - A series of new heteroleptic MN2S2 transition metal complexes with M = Cu2+ for EPR measurements and as diamagnetic hosts Ni2+, Zn2+, and Pd2+ were synthesized and characterized. The ligands are N2 = 4, 4'-bis(tert-butyl)-2, 2'-bipyridine (tBu2bpy) and S2 =1, 2-dithiooxalate, (dto), 1, 2-dithiosquarate, (dtsq), maleonitrile-1, 2-dithiolate, or 1, 2-dicyanoethene-1, 2-dithiolate, (mnt). The CuII complexes were studied by EPR in solution and as powders, diamagnetically diluted in the isostructural planar [NiII(tBu2bpy)(S2)] or[PdII(tBu2bpy)(S2)] as well as in tetrahedrally coordinated[ZnII(tBu2bpy)(S2)] host structures to put steric stress on the coordination geometry of the central CuN2S2 unit. The spin density contributions for different geometries calculated from experimental parameters are compared with the electronic situation in the frontier orbital, namely in the semi-occupied molecular orbital (SOMO) of the copper complex, derived from quantum chemical calculations on different levels (EHT and DFT). One of the hosts, [NiII(tBu2bpy)(mnt)], is characterized by X-ray structure analysis to prove the coordination geometry. The complex crystallizes in a square-planar coordination mode in the monoclinic space group P21/a with Z = 4 and the unit cell parameters a = 10.4508(10) angstrom, b = 18.266(2) angstrom, c = 12.6566(12) angstrom, beta = 112.095(7)degrees. Oxidation and reductions potentials of one of the host complexes, [Ni(tBu2bpy)(mnt)], were obtained by cyclovoltammetric measurements. KW - 1 KW - 2-Dithiosquarate KW - 1 KW - 2-Dithiooxalate KW - 1 KW - 2-Dicyanoethene-1 KW - 2-dithiolate KW - 4 KW - 4'-Bis(tert-butyl)-2 KW - 2'-bipyridine KW - X-ray structure KW - EPR KW - Copper KW - Nickel KW - Zinc Y1 - 2012 U6 - https://doi.org/10.1002/zaac.201100517 SN - 0044-2313 VL - 638 IS - 6 SP - 965 EP - 975 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Primus, Philipp-A. A1 - Kumke, Michael Uwe T1 - Flash photolysis study of complexes between salicylic acid and lanthanide ions in water JF - The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory N2 - In the natural environment humic substances (HS) represent a major factor determining the speciation of metal ions, e.g., in the context of radionuclide migration. Here, due to their intrinsic sensitivity and selectivity, spectroscopic methods are often applied, requiring a fundamental understanding of the photophysical processes present in such HS-metal complexes. Complexes with different metal ions were studied using 2-hydroxybenzoic acid (2HB) as a model compound representing an important part of the chelating substructures in HS. In flash photolysis experiments under direct excitation of 2HB in the absence and the presence of different lanthanide ions, the generation and the decay of the 2HB triplet state, of the phenoxy radical, and of the solvated electron were monitored. Depending on the lanthanide ion different intracomplex processes were observed for these transient species including energy migration to and photoreduction of the lanthanide ion. The complexity of the intracomplex photophysical processes even for small molecules such as 2HB underlines the necessity to step-by-step approach the photochemical reactivity of HS by using suitable model compounds. Y1 - 2012 U6 - https://doi.org/10.1021/jp2043575 SN - 1089-5639 VL - 116 IS - 4 SP - 1176 EP - 1182 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Shainyan, Bagrat A. A1 - Tolstikova, Ljudmila L. A1 - Schilde, Uwe T1 - Simple methods for the preparation of N-triflyl guanidines and the structure of compounds with the CF3SO2N=C-N fragment JF - Journal of fluorine chemistry N2 - Two novel and simple approaches to N-triflyl guanidines are elaborated. Owing to very strong conjugation the formally double C=N bond of TIN=C(NHR)(2) is longer than the formally single N-C bonds. Energetic effect of the triflylgroup on the conjugation in the N-C=N moiety is estimated to be >= 150 kcal/mol. KW - N-triflyl guanidines KW - Synthesis KW - Structure KW - X-ray KW - MP2 calculations Y1 - 2012 U6 - https://doi.org/10.1016/j.fluchem.2011.12.004 SN - 0022-1139 VL - 135 IS - 1 SP - 261 EP - 264 PB - Elsevier CY - Lausanne ER -