TY - JOUR A1 - Yin, Jian A1 - Linker, Torsten T1 - Stereodivergent syntheses at the glucose backbone N2 - Both diastereomers of 2-C-branched carbohydrates with various functional groups are selectively available from the same malonate precursor in good yields in only a few steps. Y1 - 2009 UR - http://www.rsc.org/Publishing/Journals/OB/index.asp U6 - https://doi.org/10.1039/B918893m SN - 1477-0520 ER - TY - JOUR A1 - Yin, Jian A1 - Linker, Torsten T1 - Convenient synthesis of bicyclic carbohydrate 1,2-lactones and their stereoselective opening to 1- functionalized glucose derivatives N2 - Closed and re-opened for business: C-2 branched carbohydrates 1 cyclize under conditions of decarboxylation to the hitherto unknown carbohydrate 1,2-lactones 2 in high yields. The gluco isomer can be opened at the anomeric position with various nuceophiles in the presence of Sc(OTf)3, which allows the stereoselective synthesis of 1-functionalized glucose derivatives 3. Thus, 1,2-bis-C-branched saccharides become available in only a few steps starting from glycals. Y1 - 2009 UR - http://www3.interscience.wiley.com/cgi-bin/jhome/26293/ U6 - https://doi.org/10.1002/chem.200802178 SN - 0947-6539 ER - TY - JOUR A1 - Wischerhoff, Erik A1 - Glatzel, Stefan A1 - Uhlig, Katja A1 - Lankenau, Andreas A1 - Lutz, Jean-Francois A1 - Laschewsky, André T1 - Tuning the thickness of polymer brushes grafted from nonlinearly growing multilayer assemblies N2 - A new versatile method for tuning the thickness of surface-tethered polymer brushes is introduced. It is based on the combination of polyelectrolyte multilayer deposition and surface-initiated atom transfer radical polymerization. To control the thickness of the brushes, the nonlinear growth of certain polyelectrolyte multilayer systems is exploited. The method is demonstrated to work with different polyelectrolytes and different monomers. The relevance for applications is demonstrated by cell adhesion experiments oil grafted thermoresponsive polymer layers with varying thickness. Y1 - 2009 UR - http://pubs.acs.org/journal/langd5 U6 - https://doi.org/10.1021/La804197j SN - 0743-7463 ER - TY - JOUR A1 - von Berlepsch, Hans A1 - Boettcher, Christoph A1 - Skrabania, Katja A1 - Laschewsky, André T1 - Complex domain architecture of multicompartment micelles from a linear ABC triblock copolymer revealed by cryogenic electron tomography N2 - Cryo-electron tomography of raspberry-like multicompartment micelles formed by a linear ABC triblock copolymer in water revealed that the fluorocarbon domains may be dispersed all over the hydrocarbon core. Y1 - 2009 UR - http://xlink.rsc.org/jumptojournal.cfm?journal_code=CC U6 - https://doi.org/10.1039/B903658j SN - 1359-7345 ER - TY - JOUR A1 - Vazhappilly, Tijo A1 - Klamroth, Tillmann A1 - Saalfrank, Peter A1 - Hernandez, Rigoberto T1 - Femtosecond-laser desorption of H-2 (D-2) from Ru(0001) : quantum and classical approaches N2 - The femtosecond-laser-induced, substrate-mediated associative desorption of molecular hydrogen and deuterium from a Ru(0001) surface in the so-called DIMET limit is studied theoretically. Two widely used models, a "quantum nonadiabatic" approach and a "classical adiabatic" one are employed and compared to each other. The quantum model is realized by the Monte Carlo wave packet (MCWP) method in the framework of open-system density matrix theory: The classical approach is realized with the help of (frictional) Langevin dynamics with stochastic forces. For both models the same ground-state potential energy surface is used and the same two-temperature model adopted to describe the hot- electron-driven desorption dynamics. Apart from these common features both models are different. Still, both account well for the main experimental findings (Wagner et al. Phys. Rev. B 2005, 72, 205404). In particular, an isotope effect in desorption probabilities, the energy content of the desorbing molecules, and the scaling of these observables with laser fluence are reproduced and explained. The similarity of the results obtained with both models is traced back to the fact that, in the present case, the photodynamics takes place dominantly in the ground electronic state because the electronically excited state is rapidly quenched. The short lifetime of the excited state has also the effect that photoreaction cross sections are typically very small. An IR+vis hybrid scheme, by which the adsorbate is vibrationally excited by IR photons prior to the heating of metal electrons with the vis pulse, is shown to successfully promote the reaction even for strongly coupled adsorbate-surface systems. Y1 - 2009 UR - http://pubs.acs.org/journal/jpccck U6 - https://doi.org/10.1021/Jp810709k SN - 1932-7447 ER - TY - JOUR A1 - Tremblay, Jean Christophe A1 - Saalfrank, Peter T1 - Selective subsurface absorption of hydrogen in palladium using laser distillation N2 - A theoretical model for the selective subsurface absorption of atomic hydrogen in a Pd(111) surface by infrared (IR) laser pulses is presented. The dynamics of the adsorbate is studied within the reduced density matrix approach. Energy and phase relaxation of the hydrogen atom are treated using the semigroup formalism. The vibrational excitation leading to subsurface absorption is performed using rationally designed pulses as well as IR laser pulses optimized on- the-fly. It is shown that dissipation can be used as a tool to transfer population to an otherwise inaccessible state via a mechanism known as "laser distillation." We demonstrate that when the reaction path is generalized from a reduced one-dimensional to full three-dimensional treatment of the system, the laser control strategy can prove very different. Y1 - 2009 UR - http://jcp.aip.org/ U6 - https://doi.org/10.1063/1.3212695 SN - 0021-9606 ER - TY - JOUR A1 - Strehmel, Veronika A1 - Wishart, James F. A1 - Polyansky, Dmitry E. A1 - Strehmel, Bernd T1 - Recombination of photogenerated lophyl radicals in imidazolium-based ionic liquids N2 - Laser flash photolysis is applied to study the recombination reaction of lophyl radicals in ionic liquids in comparison with dimethylsulfoxide as an example of a traditional organic solvent. The latter exhibits a similar micropolarity as the ionic liquids. The ionic liquids investigated are 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (1), 1-hexyl-3-methylimidazolium hexafluorophosphate (2), and 1-butyl-3- methylimidazolium tetafluoroborate (3). The recombination of the photolytic generated lophyl radicals occur significantly faster in the ionic liquids than expected from their macroscopic viscosities and is a specific effect of these ionic liquids. On the other hand, this reaction can be compared with the macroscopic viscosity in the case of dimethylsulfoxide. Activation parameters obtained for lophyl radical recombination suggest different, anion-dependent mechanistic effects. Quantum chemical calculations based on density functional theory provide a deeper insight of the molecular properties of the lophyl radical and its precursor. Thus, excitation energies, spin densities, molar volumes, and partial charges are calculated. Calculations show a spread of spin density over the three carbon atoms of the imidazolyl moiety, while only low spin density is calculated for the nitrogens. Y1 - 2009 UR - http://www3.interscience.wiley.com/cgi-bin/jhome/72514732/ U6 - https://doi.org/10.1002/cphc.200900594 SN - 1439-4235 ER - TY - JOUR A1 - Skrabania, Katja A1 - Laschewsky, André A1 - von Berlepsch, Hans A1 - Boettcher, Christoph T1 - Synthesis and micellar self-assembly of ternary hydrophilic-lipophilic-fluorophilic block copolymers with a linear PEO chain N2 - Linear amphiphilic diblock and ternary triblock copolymers were synthesized by the RAFT method in two successive steps using a poly(ethylene oxide) (PEO) macrochain transfer agent, butyl or 2-ethylhexyl acrylate, and 1H, 1H, 2H, 2H-perfluorodecyl acrylate. The diblock and the triblock copolymers, which consist of a hydrophilic, a lipophilic, and a short fluorophilic block, self-assemble in water into spherical micellar aggregates. Imaging by cryogenic transmission electron microscopy (cryo-TEM) revealed that the micellar cores of the aggregates made from these "triphilic" copolymers can undergo local phase separation to form a unique ultrastructure. In these multicompartment micelles, it appears that extended nonspherical domains, presumably made of nanocrystallites of the fluorocarbon block, are embedded in the hydrocarbon matrix forming the spherical micellar core. This novel internal structure of a micellar core is attributed to the mutual incompatibility of the fluorocarbon and hydrocarbon side chains in combination with the tendency of the used fluorocarbon acrylate monomer to undergo side-chain crystallization. Y1 - 2009 UR - http://pubs.acs.org/journal/langd5 U6 - https://doi.org/10.1021/La900253j SN - 0743-7463 ER - TY - JOUR A1 - Shkilnyy, Andriy A1 - Gräf, Ralph A1 - Hiebl, Bernhard A1 - Neffe, Axel T. A1 - Friedrich, Alwin A1 - Hartmann, Juergen A1 - Taubert, Andreas T1 - Unprecedented, low cytotoxicity of spongelike calcium phosphate/poly(ethylene imine) hydrogel composites N2 - Covalently crosslinked PEI hydrogels are efficient templates for calcium phosphate mineralization in SBF. In contrast to the PEI hydrogels, non-crosslinked PEI does not lead to calcium phosphate nucleation and growth in SBF. The precipitate is a mixture of brushite and hydroxyapatite. The PEI/calcium phosphate composite material exhibits a sponge like morphology and a chemical composition that is interesting for implants. Cytotoxicity tests using Dictyostelium discoideum amoebae show that both the non-mineralized and mineralized hydrogels have a very low cytotoxicity. This suggests that next generation PEI hydrogels, where also the degradation products are non-toxic, could be interesting for biomedical applications. Y1 - 2009 UR - http://www3.interscience.wiley.com/cgi-bin/jhome/77002860 U6 - https://doi.org/10.1002/mabi.200800266 SN - 1616-5187 ER - TY - JOUR A1 - Shkilnyy, Andriy A1 - Brandt, Jessica A1 - Mantion, Alexandre A1 - Paris, Oskar A1 - Schlaad, Helmut A1 - Taubert, Andreas T1 - Calcium phosphate with a channel-like morphology by polymer templating N2 - Calcium phosphate mineralization from aqueous solution in the presence of organic growth modifiers has been intensely studied in the recent past. This is mostly due to potential applications of the resulting composites in the biomaterials field. Polymers in particular are efficient growth modifiers. As a result, there has been a large amount of work on polymeric growth modifiers. Interestingly, however, relatively little work has been done on polycationic additives. The current paper shows that poly(ethylene oxide)b-poly(L-lysine) block copolymers lead to an interesting morphology of calcium phosphate precipitated at room temperature and subjected to a mild heat treatment at 85 degrees C. Electron microscopy, synchrotron X-ray diffraction, and porosity analysis show that a (somewhat) porous material with channel-like features forms. Closer inspection using transmission electron microscopy shows that the channels are probably not real channels. Much rather the morphology is the result of the aggregation of ca. 100-nm-sized rodlike primary particles, which changes upon drying to exhibit the observed channel-like features. Comparison experiments conducted in the absence of polymer and with poly(ethylene oxide)-b-poly(L-glutamate) show that these features only form in the presence of the polycationic poly(L-lysine) block, suggesting a distinct interaction of the polycation with either the crystal or the phosphate ions prior to mineralization. Y1 - 2009 UR - http://pubs.acs.org/journal/cmatex U6 - https://doi.org/10.1021/Cm803244z SN - 0897-4756 ER -