@article{YuantenBrummelhuisJungingeretal.2011, author = {Yuan, Jiayin and ten Brummelhuis, Niels and Junginger, Mathias and Xie, Zailai and Lu, Yan and Taubert, Andreas and Schlaad, Helmut}, title = {Diversified applications of chemically modified 1,2-Polybutadiene}, series = {Macromolecular rapid communications}, volume = {32}, journal = {Macromolecular rapid communications}, number = {15}, publisher = {Wiley-Blackwell}, address = {Malden}, issn = {1022-1336}, doi = {10.1002/marc.201100254}, pages = {1157 -- 1162}, year = {2011}, abstract = {Commercially available 1,2-PB was transformed into a well-defined reactive intermediate by quantitative bromination. The brominated polymer was used as a polyfunctional macroinitiator for the cationic ring-opening polymerization of 2-ethyl-2-oxazoline to yield a water-soluble brush polymer. Nucleophilic substitution of bromide by 1-methyl imidazole resulted in the formation of polyelectrolyte copolymers consisting of mixed units of imidazolium, bromo, and double bond. These copolymers, which were soluble in water without forming aggregates, were used as stabilizers in the heterophase polymerization of styrene and were also studied for their ionic conducting properties.}, language = {en} } @article{XieWhiteWeberetal.2011, author = {Xie, Zai-Lai and White, Robin J. and Weber, Jens and Taubert, Andreas and Titirici, Magdalena M.}, title = {Hierarchical porous carbonaceous materials via ionothermal carbonization of carbohydrates}, series = {Journal of materials chemistry}, volume = {21}, journal = {Journal of materials chemistry}, number = {20}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {0959-9428}, doi = {10.1039/c1jm00013f}, pages = {7434 -- 7442}, year = {2011}, abstract = {We report on the ionothermal synthesis of porous carbon materials from a variety of carbohydrate precursors (i.e. D-glucose, D-fructose, D-xylose, and starch) using 1-butyl-3-methylimidazolium tetrachloroferrate(III), [Bmim][FeCl(4)] as a reusable solvent and catalyst. The carbon materials derived from these different carbohydrates are similar in terms of particle size and chemical composition, possessing relatively high surface areas from 44 to 155 m(2) g(-1) after ionothermal processing, which can be significantly increased to > 350 m(2) g(-1) by further thermal treatment (e. g. post-carbonization at 750 degrees C). CO(2) and N(2) sorption analysis, combined with Hg intrusion porosimetry, reveals a promising hierarchical pore structuring to these carbon materials. The ionic liquid [Bmim][FeCl(4)] has a triple role: it acts as both a soft template to generate the characterized pore structuring, solvent and as a catalyst resulting in enhanced ionothermal carbon yields. Importantly from a process point of view, the ionic liquid can be successfully recovered and reused. The current work shows that ionothermal synthesis has the potential to be an effective, low cost, and green reusable synthetic route towards sustainable porous carbon materials.}, language = {en} } @article{XieTaubert2011, author = {Xie, Zai-Lai and Taubert, Andreas}, title = {Thermomorphic behavior of the ionic liquids [C(4)mim][FeCl4] and [C(12)mim][FeCl4]}, series = {ChemPhysChem : a European journal of chemical physics and physical chemistry}, volume = {12}, journal = {ChemPhysChem : a European journal of chemical physics and physical chemistry}, number = {2}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1439-4235}, doi = {10.1002/cphc.201000808}, pages = {364 -- 368}, year = {2011}, abstract = {The iron-containing ionic liquids 1-butyl-3-methylimidazolium tetrachloroferrate(III) [C(4)mim][FeCl4] and 1-dodecyl-3-methylimidazolium tetrachloroferrate(III) [C(12)mim][FeCl4] exhibit a thermally induced demixing with water (thermomorphism). The phase separation temperature varies with IL weight fraction in water and can be tuned between 100 degrees C and room temperature. The reversible lower critical solution temperature (LCST) is only observed at IL weight fractions below ca. 35\% in water. UV/Vis, IR, and Raman spectroscopy along with elemental analysis prove that the yellow-brown liquid phase recovered after phase separation is the starting IL [C(4)mim][FeCl4] and [C(12)mim][FeCl4], respectively. Photometry and ICP-OES show that about 40\% of iron remains in the water phase upon phase separation. Although the process is thus not very efficient at the moment, the current approach is the first example of an LCST behavior of a metal-containing IL and therefore, although still inefficient, a prototype for catalyst removal or metal extraction.}, language = {en} } @article{ThielKlamrothStrauchetal.2011, author = {Thiel, Kerstin and Klamroth, Tillmann and Strauch, Peter and Taubert, Andreas}, title = {On the interaction of ascorbic acid and the tetrachlorocuprate ion [CuCl4](2-) in CuCl nanoplatelet formation from an ionic liquid precursor (ILP)}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {13}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, number = {30}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/c1cp20648f}, pages = {13537 -- 13543}, year = {2011}, abstract = {The formation of CuCl nanoplatelets from the ionic liquid precursor (ILP) butylpyridinium tetrachlorocuprate [C4Py](2)[CuCl4] using ascorbic acid as a reducing agent was investigated. In particular, electron paramagnetic resonance (EPR) spectroscopy was used to evaluate the interaction between ascorbic acid and the Cu(II) ion before reduction to Cu(I). EPR spectroscopy suggests that the [CuCl4](2-) ion in the neat IL is a distorted tetrahedron, consistent with DFT calculations. Addition of ascorbic acid leads to the removal of one chloride from the [CuCl4](2-) anion, as shown by DFT and the loss of symmetry by EPR. DFT furthermore suggests that the most stable adduct is formed when only one hydroxyl group of the ascorbic acid coordinates to the Cu(II) ion.}, language = {en} } @article{ShkilnyySchoeneRumplaschetal.2011, author = {Shkilnyy, Andriy and Sch{\"o}ne, Stefanie and Rumplasch, Claudia and Uhlmann, Annett and Hedderich, Annett and G{\"u}nter, Christina and Taubert, Andreas}, title = {Calcium phosphate mineralization with linear poly(ethylene imine) a time-resolved study}, series = {Colloid and polymer science : official journal of the Kolloid-Gesellschaft}, volume = {289}, journal = {Colloid and polymer science : official journal of the Kolloid-Gesellschaft}, number = {8}, publisher = {Springer}, address = {New York}, issn = {0303-402X}, doi = {10.1007/s00396-011-2403-2}, pages = {881 -- 888}, year = {2011}, abstract = {We have earlier shown that linear poly(ethylene imine) (LPEI) is an efficient growth modifier for calcium phosphate mineralization from aqueous solution (Shkilnyy et al., Langmuir, 2008, 24 (5), 2102). The current study addresses the growth process and the reason why LPEI is such an effective additive. To that end, the solution pH and the calcium and phosphate concentrations were monitored vs. reaction time using potentiometric, complexometric, and photometric methods. The phase transformations in the precipitates and particle morphogenesis were analyzed by X-ray diffraction and transmission electron microscopy, respectively. All measurements reveal steep decreases of the pH, calcium, and phosphate concentrations along with a rapid precipitation of brushite nanoparticles early on in the reaction. Brushite transforms into hydroxyapatite (HAP) within the first 2 h, which is much faster than what is reported, for example, for calcium phosphate precipitated with poly(acrylic acid). We propose that poly(ethylene imine) acts as a proton acceptor (weak buffer), which accelerates the transformation from brushite to HAP by taking up the protons that are released from the calcium phosphate precipitate during the phase transformation.}, language = {en} } @article{PrietoShkilnyyRumplaschetal.2011, author = {Prieto, Susana and Shkilnyy, Andriy and Rumplasch, Claudia and Ribeiro, Artur and Javier Arias, F. and Carlos Rodriguez-Cabello, Jose and Taubert, Andreas}, title = {Biomimetic calcium phosphate mineralization with multifunctional elastin-like recombinamers}, series = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, volume = {12}, journal = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, number = {5}, publisher = {American Chemical Society}, address = {Washington}, issn = {1525-7797}, doi = {10.1021/bm200287c}, pages = {1480 -- 1486}, year = {2011}, abstract = {Biomimetic hybrid materials based on a polymeric and an inorganic component such as calcium phosphate are potentially useful for bone repair. The current study reports on a new approach toward biomimetic hybrid materials using a set of recombinamers (recombinant protein materials obtained from a synthetic gene) as crystallization additive for calcium phosphate. The recombinamers contain elements from elastin, an elastic structural protein, and statherin, a salivary protein. Via genetic engineering, the basic elastin sequence was modified with the SN(A)15 domain of statherin, whose interaction with calcium phosphate is well-established. These new materials retain the biocompatibility, "smart" nature, and desired mechanical behavior of the elastin-like recombinamer (ELR) family. Mineralization in simulated body fluid (SBF) in the presence of these recombinamers reveals surprising differences. Two of the polymers inhibit calcium phosphate deposition (although they contain the statherin segment). In contrast, the third polymer, which has a triblock structure, efficiently controls the calcium phosphate formation, yielding spherical hydroxyapatite (HAP) nanoparticles with diameters from 1 to 3 nm after 1 week in SBF at 37 degrees C. However, at lower temperatures, no precipitation is observed with any of the polymers. The data thus suggest that the molecular design of ELRs containing statherin segments and the selection of an appropriate polymer structure are key parameters to obtain functional materials for the development of intelligent systems for hard tissue engineering and subsequent in vivo applications.}, language = {en} } @article{MarquardtXieTaubertetal.2011, author = {Marquardt, Dorothea and Xie, Zailai and Taubert, Andreas and Thomann, Ralf and Janiak, Christoph}, title = {Microwave synthesis and inherent stabilization of metal nanoparticles in 1-methyl-3-(3-carboxyethyl)-imidazolium tetrafluoroborate}, series = {Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry}, volume = {40}, journal = {Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry}, number = {33}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1477-9226}, doi = {10.1039/c1dt10795j}, pages = {8290 -- 8293}, year = {2011}, abstract = {The synthesis of Co-NPs and Mn-NPs by microwave-induced decomposition of the metal carbonyls Co-2(CO)(8) and Mn-2(CO)(10), respectively, yields smaller and better separated particles in the functionalized IL 1-methyl-3-(3-carboxyethyl)-imidazolium tetrafluoroborate [EmimCO(2)H][BF4] (1.6 +/- 0.3 nm and 4.3 +/- 1.0 nm, respectively) than in the non-functionalized IL 1-n-butyl-3-methylimidazolium tetrafluoroborate [Bmim][BF4]. The particles are stable in the absence of capping ligands (surfactants) for more than six months although some variation in particle size could be observed by TEM.}, language = {en} } @article{MantionGrafFloreaetal.2011, author = {Mantion, Alexandre and Graf, Philipp and Florea, Ileana and Haase, Andrea and Thuenemann, Andreas F. and Masic, Admir and Ersen, Ovidiu and Rabu, Pierre and Meier, Wolfgang P. and Luch, Andreas and Taubert, Andreas}, title = {Biomimetic synthesis of chiral erbium-doped silver/peptide/silica core-shell nanoparticles (ESPN)}, series = {Nanoscale}, volume = {3}, journal = {Nanoscale}, number = {12}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2040-3364}, doi = {10.1039/c1nr10930h}, pages = {5168 -- 5179}, year = {2011}, abstract = {Peptide-modified silver nanoparticles have been coated with an erbium-doped silica layer using a method inspired by silica biomineralization. Electron microscopy and small-angle X-ray scattering confirm the presence of an Ag/peptide core and silica shell. The erbium is present as small Er(2)O(3) particles in and on the silica shell. Raman, IR, UV-Vis, and circular dichroism spectroscopies show that the peptide is still present after shell formation and the nanoparticles conserve a chiral plasmon resonance. Magnetic measurements find a paramagnetic behavior. In vitro tests using a macrophage cell line model show that the resulting multicomponent nanoparticles have a low toxicity for macrophages, even on partial dissolution of the silica shell.}, language = {en} } @article{LoebbickeChananaSchlaadetal.2011, author = {L{\"o}bbicke, Ruben and Chanana, Munish and Schlaad, Helmut and Pilz-Allen, Christine and G{\"u}nter, Christina and M{\"o}hwald, Helmuth and Taubert, Andreas}, title = {Polymer Brush Controlled Bioinspired Calcium Phosphate Mineralization and Bone Cell Growth}, series = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, volume = {12}, journal = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, number = {10}, publisher = {American Chemical Society}, address = {Washington}, issn = {1525-7797}, doi = {10.1021/bm200991b}, pages = {3753 -- 3760}, year = {2011}, abstract = {Polymer brushes on thiol-modified gold surfaces were synthesized by using terminal thiol groups for the surface initiated free radical polymerization of methacrylic acid and dimethylaminotheyl methacrylate, respectively. Atomic force microscopy shows that the resulting poly(methacrylic acid (PMAA) and poly(dimethylaminothyl methacrylate) (PDM- AEMA) brushes are homogeneous. Contact angle measurements show that the brushes are pH responsive and can reversibly be protonated and deprotonated. Mineralization of the brushes with calcium phosphate at different pH yields homogeneously mineralized surfaces, and preosteoblastic cells proliferate-on be number of living cells on the mineralized hybrid surface is ca. 3 times (P corresponding nonmineralized brushes.}, language = {en} } @misc{KitaTokarczykJungingerBelegrinouetal.2011, author = {Kita-Tokarczyk, Katarzyna and Junginger, Mathias and Belegrinou, Serena and Taubert, Andreas}, title = {Amphiphilic polymers at interfaces}, series = {Advances in polymer science}, volume = {242}, journal = {Advances in polymer science}, number = {1}, editor = {Muller, AHE and Borisov, O}, publisher = {Springer}, address = {Berlin}, isbn = {978-3-642-22297-9}, issn = {0065-3195}, doi = {10.1007/12_2010_58}, pages = {151 -- 201}, year = {2011}, abstract = {Self-assembly phenomena in block copolymer systems are attracting considerable interest from the scientific community and industry alike. Particularly interesting is the behavior of amphiphilic copolymers, which can self-organize into nanoscale-sized objects such as micelles, vesicles, or tubes in solution, and which form well-defined assemblies at interfaces such as air-liquid, air-solid, or liquid-solid. Depending on the polymer chemistry and architecture, various types of organization at interfaces can be expected, and further exploited for applications in nanotechnology, electronics, and biomedical sciences. In this article, we discuss the formation and characterization of Langmuir monolayers from various amphiphilic block copolymers, including chargeable and thus pH-responsivematerials. Solid-supported polymer films are reviewed in the context of alteration of surface properties by ultrathin polymer layers and the possibilities for application in tissue engineering, sensors and biomaterials. Finally, we focus on how organic and polymer monolayers influence the growth of inorganic materials. This is a truly biomimetic approach since Nature uses soft interfaces to control the nucleation, growth, and morphology of biominerals such as calcium phosphate, calcium carbonate, and silica.}, language = {en} }