TY - JOUR A1 - Yuan, Jiayin A1 - ten Brummelhuis, Niels A1 - Junginger, Mathias A1 - Xie, Zailai A1 - Lu, Yan A1 - Taubert, Andreas A1 - Schlaad, Helmut T1 - Diversified applications of chemically modified 1,2-Polybutadiene JF - Macromolecular rapid communications N2 - 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. KW - emulsion polymerization KW - polybutadiene KW - polyelectrolytes KW - polymer modification KW - ring-opening polymerization Y1 - 2011 U6 - https://doi.org/10.1002/marc.201100254 SN - 1022-1336 VL - 32 IS - 15 SP - 1157 EP - 1162 PB - Wiley-Blackwell CY - Malden ER - TY - JOUR A1 - Xie, Zai-Lai A1 - White, Robin J. A1 - Weber, Jens A1 - Taubert, Andreas A1 - Titirici, Magdalena M. T1 - Hierarchical porous carbonaceous materials via ionothermal carbonization of carbohydrates JF - Journal of materials chemistry N2 - 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. Y1 - 2011 U6 - https://doi.org/10.1039/c1jm00013f SN - 0959-9428 VL - 21 IS - 20 SP - 7434 EP - 7442 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Xie, Zai-Lai A1 - Taubert, Andreas T1 - Thermomorphic behavior of the ionic liquids [C(4)mim][FeCl4] and [C(12)mim][FeCl4] JF - ChemPhysChem : a European journal of chemical physics and physical chemistry N2 - 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. KW - imidazolium KW - ionic liquids KW - phase transitions KW - Raman spectroscopy KW - thermomorphism Y1 - 2011 U6 - https://doi.org/10.1002/cphc.201000808 SN - 1439-4235 VL - 12 IS - 2 SP - 364 EP - 368 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Thiel, Kerstin A1 - Klamroth, Tillmann A1 - Strauch, Peter A1 - Taubert, Andreas T1 - On the interaction of ascorbic acid and the tetrachlorocuprate ion [CuCl4](2-) in CuCl nanoplatelet formation from an ionic liquid precursor (ILP) JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - 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. Y1 - 2011 U6 - https://doi.org/10.1039/c1cp20648f SN - 1463-9076 VL - 13 IS - 30 SP - 13537 EP - 13543 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Shkilnyy, Andriy A1 - Schöne, Stefanie A1 - Rumplasch, Claudia A1 - Uhlmann, Annett A1 - Hedderich, Annett A1 - Günter, Christina A1 - Taubert, Andreas T1 - Calcium phosphate mineralization with linear poly(ethylene imine) a time-resolved study JF - Colloid and polymer science : official journal of the Kolloid-Gesellschaft N2 - 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. KW - Calcium phosphate KW - Polyethylene imine KW - Mineralization KW - Kinetics Y1 - 2011 U6 - https://doi.org/10.1007/s00396-011-2403-2 SN - 0303-402X VL - 289 IS - 8 SP - 881 EP - 888 PB - Springer CY - New York ER - TY - JOUR A1 - Prieto, Susana A1 - Shkilnyy, Andriy A1 - Rumplasch, Claudia A1 - Ribeiro, Artur A1 - Javier Arias, F. A1 - Carlos Rodriguez-Cabello, Jose A1 - Taubert, Andreas T1 - Biomimetic calcium phosphate mineralization with multifunctional elastin-like recombinamers JF - Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences N2 - 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. Y1 - 2011 U6 - https://doi.org/10.1021/bm200287c SN - 1525-7797 VL - 12 IS - 5 SP - 1480 EP - 1486 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Marquardt, Dorothea A1 - Xie, Zailai A1 - Taubert, Andreas A1 - Thomann, Ralf A1 - Janiak, Christoph T1 - Microwave synthesis and inherent stabilization of metal nanoparticles in 1-methyl-3-(3-carboxyethyl)-imidazolium tetrafluoroborate JF - Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry N2 - 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. Y1 - 2011 U6 - https://doi.org/10.1039/c1dt10795j SN - 1477-9226 VL - 40 IS - 33 SP - 8290 EP - 8293 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Mantion, Alexandre A1 - Graf, Philipp A1 - Florea, Ileana A1 - Haase, Andrea A1 - Thuenemann, Andreas F. A1 - Masic, Admir A1 - Ersen, Ovidiu A1 - Rabu, Pierre A1 - Meier, Wolfgang P. A1 - Luch, Andreas A1 - Taubert, Andreas T1 - Biomimetic synthesis of chiral erbium-doped silver/peptide/silica core-shell nanoparticles (ESPN) JF - Nanoscale N2 - 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. Y1 - 2011 U6 - https://doi.org/10.1039/c1nr10930h SN - 2040-3364 VL - 3 IS - 12 SP - 5168 EP - 5179 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Löbbicke, Ruben A1 - Chanana, Munish A1 - Schlaad, Helmut A1 - Pilz-Allen, Christine A1 - Günter, Christina A1 - Möhwald, Helmuth A1 - Taubert, Andreas T1 - Polymer Brush Controlled Bioinspired Calcium Phosphate Mineralization and Bone Cell Growth JF - Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences N2 - 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. Y1 - 2011 U6 - https://doi.org/10.1021/bm200991b SN - 1525-7797 VL - 12 IS - 10 SP - 3753 EP - 3760 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kita-Tokarczyk, Katarzyna A1 - Junginger, Mathias A1 - Belegrinou, Serena A1 - Taubert, Andreas ED - Muller, AHE ED - Borisov, O T1 - Amphiphilic polymers at interfaces JF - Advances in polymer science JF - Advances in Polymer Science N2 - 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. KW - Amphiphilic polymers KW - Langmuir monolayers KW - Polymers on surfaces KW - Bio-inspired mineralization Y1 - 2011 SN - 978-3-642-22297-9 U6 - https://doi.org/10.1007/12_2010_58 SN - 0065-3195 VL - 242 IS - 1 SP - 151 EP - 201 PB - Springer CY - Berlin ER -