TY - JOUR A1 - Abdissa, Negera A1 - Induli, Martha A1 - Akala, Hoseah M. A1 - Heydenreich, Matthias A1 - Midiwo, Jacob O. A1 - Ndakala, Albert A1 - Yenesew, Abiy T1 - Knipholone cyclooxanthrone and an anthraquinone dimer with antiplasmodial activities from the roots of Kniphofia foliosa JF - Phytochemistry letters N2 - A new phenylanthrone, named knipholone cyclooxanthrone and a dimeric anthraquinone, 10-methoxy-10,7'-(chrysophanol anthrone)-chrysophanol were isolated from the roots of Kniphofia foliosa together with the rare naphthalene glycoside, dianellin. The structures were determined by NMR and mass spectroscopic techniques. The compounds showed antiplasmodial activities against the chloroquine-resistant (W2) and chloroquine-sensitive (D6) strains of Plasmodium falciparum with 10-methoxy-10,7'-(chrysophanol anthrone)-chrysophanol being the most active with IC50 values of 1.17 +/- 0.12 and 4.07 +/- 1.54 mu g/ml, respectively. KW - Kniphofia foliosa KW - Asphodelaceae KW - Roots KW - Anthraquinone KW - Knipholone cyclooxanthrone KW - 10-Methoxy-10,7 '-(chrysophanol anthrone)-chrysophanol KW - Dianellin KW - Malaria Y1 - 2013 U6 - https://doi.org/10.1016/j.phytol.2013.02.005 SN - 1874-3900 VL - 6 IS - 2 SP - 241 EP - 245 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Adelsberger, Joseph A1 - Grillo, Isabelle A1 - Kulkarni, Amit A1 - Sharp, Melissa A1 - Bivigou Koumba, Achille Mayelle A1 - Laschewsky, André A1 - Müller-Buschbaum, Peter A1 - Papadakis, Christine M. T1 - Kinetics of aggregation in micellar solutions of thermoresponsive triblock copolymers - influence of concentration, start and target temperatures JF - Soft matter N2 - In aqueous solution, symmetric triblock copolymers with a thermoresponsive middle block and hydrophobic end blocks form flower-like core-shell micelles which collapse and aggregate upon heating through the cloud point (CP). The collapse of the micellar shell and the intermicellar aggregation are followed in situ and in real-time using time-resolved small-angle neutron scattering (SANS), while heating micellar solutions of a poly((styrene-d(8))-b-(N-isopropyl acrylamide)-b-(styrene-d(8))) triblock copolymer in D2O rapidly through their CP. The influence of polymer concentration as well as of the start and target temperatures is addressed. In all cases, the micellar collapse is very fast. The collapsed micelles immediately form small clusters which contain voids. They densify which slows down or even stops their growth. For low concentrations and target temperatures just above the CP, i.e. shallow temperature jumps, the subsequent growth of the clusters is described by diffusion-limited aggregation. In contrast, for higher concentrations and/or higher target temperatures, i.e. deep temperature jumps, intermicellar bridges dominate the growth. Eventually, in all cases, the clusters coagulate which results in macroscopic phase separation. For shallow temperature jumps, the cluster surfaces stay rough; whereas for deep temperature jumps, a concentration gradient develops at late stages. These results are important for the development of conditions for thermal switching in applications, e.g. for the use of thermoresponsive micellar systems for transport and delivery purposes. Y1 - 2013 U6 - https://doi.org/10.1039/c2sm27152d SN - 1744-683X VL - 9 IS - 5 SP - 1685 EP - 1699 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Ali, Mostafa A1 - Homann, Thomas A1 - Khalil, Mahmoud A1 - Kruse, Hans-Peter A1 - Rawel, Harshadrai Manilal T1 - Milk whey protein modification by coffee-specific phenolics effect on structural and functional properties JF - Journal of agricultural and food chemistry : a publication of the American Chemical Society N2 - A suitable vehicle for integration of bioactive plant constituents is proposed. It involves modification of proteins using phenolics and applying these for protection of labile constituents. It dissects the noncovalent and covalent interactions of beta-lactoglobulin with coffee-specific phenolics. Alkaline and polyphenol oxidase modulated covalent reactions were compared. Tryptic digestion combined with MALDI-TOF-MS provided tentative allocation of the modification type and site in the protein, and an in silico modeling of modified beta-lactoglobulin is proposed. The modification delivers proteins with enhanced antioxidative properties. Changed structural properties and differences in solubility, surface hydrophobicity, and emulsification were observed. The polyphenol oxidase modulated reaction provides a modified beta-lactoglobulin with a high antioxidative power, is thermally more stable, requires less energy to unfold, and, when emulsified with lutein esters, exhibits their higher stability against UV light. Thus, adaptation of this modification provides an innovative approach for functionalizing proteins and their uses in the food industry. KW - coffee phenolic compounds KW - whey proteins KW - antioxidants KW - protein-phenol interactions KW - modeling KW - functionalizing proteins Y1 - 2013 U6 - https://doi.org/10.1021/jf402221m SN - 0021-8561 VL - 61 IS - 28 SP - 6911 EP - 6920 PB - American Chemical Society CY - Washington ER - TY - THES A1 - Ast, Cindy T1 - Design and photophysical characterization of single fluorophore-based ammonium sensors Y1 - 2013 CY - Potsdam ER - TY - JOUR A1 - Ast, Sandra A1 - Fischer, Tobias A1 - Müller, Holger A1 - Mickler, Wulfhard A1 - Schwichtenberg, Mathias A1 - Rurack, Knut A1 - Holdt, Hans-Jürgen T1 - Integration of the 1,2,3-Triazole "Click" Motif as a potent signalling element in metal ion responsive fluorescent probes JF - Chemistry - a European journal N2 - In a systematic approach we synthesized a new series of fluorescent probes incorporating donoracceptor (D-A) substituted 1,2,3-triazoles as conjugative -linkers between the alkali metal ion receptor N-phenylaza-[18]crown-6 and different fluorophoric groups with different electron-acceptor properties (4-naphthalimide, meso-phenyl-BODIPY and 9-anthracene) and investigated their performance in organic and aqueous environments (physiological conditions). In the charge-transfer (CT) type probes 1, 2 and 7, the fluorescence is almost completely quenched by intramolecular CT (ICT) processes involving charge-separated states. In the presence of Na+ and K+ ICT is interrupted, which resulted in a lighting-up of the fluorescence in acetonitrile. Among the investigated fluoroionophores, compound 7, which contains a 9-anthracenyl moiety as the electron-accepting fluorophore, is the only probe which retains light-up features in water and works as a highly K+/Na+-selective probe under simulated physiological conditions. Virtually decoupled BODIPY-based 6 and photoinduced electron transfer (PET) type probes 35, where the 10-substituted anthracen-9-yl fluorophores are connected to the 1,2,3-triazole through a methylene spacer, show strong ion-induced fluorescence enhancement in acetonitrile, but not under physiological conditions. Electrochemical studies and theoretical calculations were used to assess and support the underlying mechanisms for the new ICT and PET 1,2,3-triazole fluoroionophores. KW - charge transfer KW - click chemistry KW - electron transfer KW - fluorescent probes KW - metal ions Y1 - 2013 U6 - https://doi.org/10.1002/chem.201201575 SN - 0947-6539 VL - 19 IS - 9 SP - 2990 EP - 3005 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Ast, Sandra A1 - Schwarze, Thomas A1 - Müller, Holger A1 - Sukhanov, Aleksey A1 - Michaelis, Stefanie A1 - Wegener, Joachim A1 - Wolfbeis, Otto S. A1 - Körzdörfer, Thomas A1 - Dürkop, Axel A1 - Holdt, Hans-Jürgen T1 - A highly K+-Selective Phenylaza-[18]crown-6-Lariat-Ether-Based Fluoroionophore and its application in the sensing of K+ Ions with an optical sensor film and in cells JF - Chemistry - a European journal N2 - Herein, we report the synthesis of two phenylaza-[18]crown-6 lariat ethers with a coumarin fluorophore (1 and 2) and we reveal that compound 1 is an excellent probe for K+ ions under simulated physiological conditions. The presence of a 2-methoxyethoxy lariat group at the ortho position of the anilino moiety is crucial to the substantially increased stability of compounds 1 and 2 over their lariat-free phenylaza-[18] crown-6 ether analogues. Probe 1 shows a high K+/Na+ selectivity and a 2.5-fold fluorescence enhancement was observed in the presence of 100 mm K+ ions. A fluorescent membrane sensor, which was prepared by incorporating probe 1 into a hydrogel, showed a fully reversible response, a response time of 150 s, and a signal change of 7.8% per 1 mm K+ within the range 1-10 mm K+. The membrane was easily fabricated (only a single sensing layer on a solid polyester support), yet no leaching was observed. Moreover, compound 1 rapidly permeated into cells, was cytocompatible, and was suitable for the fluorescent imaging of K+ ions on both the extracellular and intracellular levels. KW - crown compounds KW - fluorescence KW - gels KW - potassium KW - sensors Y1 - 2013 U6 - https://doi.org/10.1002/chem.201302350 SN - 0947-6539 SN - 1521-3765 VL - 19 IS - 44 SP - 14911 EP - 14917 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Awasthi, Neha A1 - Ritschel, Thomas A1 - Lipowsky, Reinhard A1 - Knecht, Volker T1 - Standard gibbs energies of formation and equilibrium constants from ab-initio calculations covalent dimerization of NO2 and synthesis of NH3 JF - The journal of chemical thermodynamics N2 - Standard quantum chemical methods are used for accurate calculation of thermochemical properties such as enthalpies of formation, entropies and Gibbs energies of formation. Equilibrium reactions are widely investigated and experimental measurements often lead to a range of reaction Gibbs energies and equilibrium constants. It is useful to calculate these equilibrium properties from quantum chemical methods in order to address the experimental differences. Furthermore, most standard calculation methods differ in accuracy and feasibility of the system size. Hence, asystematic comparison of equilibrium properties calculated with different numerical algorithms would provide a useful reference. We select two well-known gas phase equilibrium reactions with small molecules: covalent dimer formation of NO2 (2NO(2) reversible arrow N2O4) and the synthesis of NH3 (N-2 + 3 H-2 reversible arrow 2NH(3)). We test four quantum chemical methods denoted by G3B3, CBS-APNO, W1 and CCSD(T) with aug-cc-pVXZ basis sets (X = 2, 3, and 4), to obtain thermochemical data for NO2, N2O4, and NH3. The calculated standard formation Gibbs energies Delta(f)G degrees are used to calculate standard reaction Gibbs energies Delta(r)G degrees and standard equilibrium constants K-eq for the two reactions. Standard formation enthalpies Delta H-f degrees are calculated in a more reliable way using high-level methods such as W1 and CCSD(T). Standard entropies S degrees for the molecules are calculated well within the range of experiments for all methods, however, the values of standard formation Gibbs energies Delta(f)G degrees show some dependence on the choice of the method. High-level methods perform better for the calculation of molecular energies, however, simpler methods such as G3B3 and CBS-APNO perform quite well in the calculation of total reaction energies and equilibrium constants, provided that the chemical species involved do not exhibit molecular geometries that are difficult to handle by the applied method. The temperature dependence of standard reaction Gibbs energy Delta(r)G degrees for the NH3 reaction is discussed by using the calculated standard formation Gibbs energies Delta(f)G degrees of the reaction species at 298.15 K. The corresponding equilibrium constant K-eq as a function of temperature is found to be close to experimental values. KW - Equilibrium constants KW - Thermochemical properties KW - Ab-initio calculations Y1 - 2013 U6 - https://doi.org/10.1016/j.jct.2013.03.011 SN - 0021-9614 VL - 62 IS - 3 SP - 211 EP - 221 PB - Elsevier CY - London ER - TY - JOUR A1 - Bagdahn, Christian A1 - Taubert, Andreas T1 - Ionogel fiber mats - functional materials via electrospinning of PMMA and the ionic liquid bis(1-butyl-3-methyl-imidazolium) Tetrachloridocuprate(II), [Bmim](2)[CuCl4] JF - Zeitschrift für Naturforschung : B, Chemical sciences N2 - Ionogel fiber mats were made by electrospinning poly(methylmethacrylate) (PMMA) and the ionic liquid (IL) bis(1-butyl-3-methyl-imidazolium) tetrachloridocupraten, [Bmim](2)[CuCl4], from acetone. The morphology of the electrospun ionogels strongly depends on the spinning parameters. Dense and uniform fiber mats were only obtained at concentrations of 60 to 70 g of polymer and IL mass combined. Lower concentrations led to a low number of poorly defined fibers. High voltages of 20 to 25 kV led to well-defined and uniform fibers; voltages between 15 and 20 kV again led to less uniform and less dense fibers. At 10 kV and lower, no spinning could be induced. Finally, PMMA fibers electrospun without IL show a less well-defined morphology combining fibers and oblong droplets indicating that the IL has a beneficial effect on the electrospinning process. The resulting materials are prototypes for new functional materials, for example in sterile filtration. KW - Ionic Liquid KW - Ionogel KW - Electrospinning KW - Fiber KW - Hydrogen Production KW - Filtration Y1 - 2013 U6 - https://doi.org/10.5560/ZNB.2013-3195 SN - 0932-0776 SN - 1865-7117 VL - 68 IS - 10 SP - 1163 EP - 1171 PB - De Gruyter CY - Tübingen ER - TY - JOUR A1 - Baier, Heiko A1 - Kelling, Alexandra A1 - Jackstell, Ralf A1 - Holdt, Hans-Jürgen T1 - Rhodium(I) and Silver(I) Complexes of 4,5-Dicyano-1,3-dimesityl- and 4,5-Dicyano-1,3-dineopentylimidazol-2-ylidene JF - Zeitschrift für anorganische und allgemeine Chemie N2 - The new N-heterocyclic carbene (NHC) precursors 4,5-dicyano-1, -dimesityl- (9) and 4, 5-dicyano-1, 3-dineopentyl-2-(pentafluorophenyl)imidazoline (14) were synthesized. 9 could be determined by X-ray crystallography. With the 2-pentafluorophenyl-substituted imidazolines 9 and 14, the [AgCl(NHC)], [RhCl(COD)(NHC)], and [RhCl(CO)(2)(NHC)] complexes [NHC = 4, 5-dicyano-1, 3-dimesitylimidazol-2-ylidene (3) and 4, 5-dicyano-1, 3-dineopentylimidazol-2-ylidene (4)] were obtained. Crystal structures of [AgCl(3)] (15), [RhCl(COD)(3)] (17), [RhCl(COD)(4)] (18), and [RhCl(CO)(2)(3)] (19) were solved and with the crystal data of 19, the percent buried volume (%V-bur) of 31.8(+/- 0.1)% was determined for NHC 3. Infrared spectra of the imidazolines 9 and 14 and of the complexes 15-20 were recorded and the CO stretching frequencies of complexes 19 and 20 were used to determine the 3 ( (-1)) and 4 ( (-1)), thus proving that 1, 3-substitution of maleonitrile-NHCs does not have a significant effect for the high -acceptor strength of these carbenes. KW - Carbenes KW - Rhodium KW - Silver KW - Crystal structure KW - Diaminomaleonitrile Y1 - 2013 U6 - https://doi.org/10.1002/zaac.201300250 SN - 0044-2313 SN - 1521-3749 VL - 639 IS - 10 SP - 1731 EP - 1739 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Bertz, Andreas A1 - Wöhl-Bruhn, Stefanie A1 - Miethe, Sebastian A1 - Tiersch, Brigitte A1 - Koetz, Joachim A1 - Hust, Michael A1 - Bunjes, Heike A1 - Menzel, Henning T1 - Encapsulation of proteins in hydrogel carrier systems for controlled drug delivery influence of network structure and drug size on release rate JF - Journal of biotechnology N2 - Novel hydrogels based on hydroxyethyl starch modified with polyethylene glycol methacrylate (HES-P(EG)(6)MA) were developed as delivery system for the controlled release of proteins. Since the drug release behavior is supposed to be related to the pore structure of the hydrogel network the pore sizes were determined by cryo-SEM, which is a mild technique for imaging on a nanometer scale. The results showed a decreasing pore size and an increase in pore homogeneity with increasing polymer concentration. Furthermore, the mesh sizes of the hydrogels were calculated based on swelling data. Pore and mesh size were significantly different which indicates that both structures are present in the hydrogel. The resulting structural model was correlated with release data for bulk hydrogel cylinders loaded with FITC-dextran and hydrogel microspheres loaded with FITC-IgG and FITC-dextran of different molecular size. The initial release depended much on the relation between hydrodynamic diameter and pore size while the long term release of the incorporated substances was predominantly controlled by degradation of the network of the much smaller meshes. KW - Hydrogel KW - Hydrogel microspheres KW - Network structure KW - Release studies KW - Protein delivery KW - Mesh size Y1 - 2013 U6 - https://doi.org/10.1016/j.jbiotec.2012.06.036 SN - 0168-1656 VL - 163 IS - 2 SP - 243 EP - 249 PB - Elsevier CY - Amsterdam ER -