@article{UgwujaAdelowoOgunlajaetal.2019, author = {Ugwuja, Chidinma G. and Adelowo, Olawale O. and Ogunlaja, Aemere and Omorogie, Martins O. and Olukanni, Olumide D. and Ikhimiukor, Odion O. and Iermak, Ievgeniia and Kolawole, Gabriel A. and G{\"u}nter, Christina and Taubert, Andreas and Bodede, Olusola and Moodley, Roshila and Inada, Natalia M. and Camargo, Andrea S.S. de and Unuabonah, Emmanuel Iyayi}, title = {Visible-Light-Mediated Photodynamic Water Disinfection @ Bimetallic-Doped Hybrid Clay Nanocomposites}, series = {ACS applied materials \& interfaces}, volume = {11}, journal = {ACS applied materials \& interfaces}, number = {28}, publisher = {American Chemical Society}, address = {Washington, DC}, issn = {1944-8244}, doi = {10.1021/acsami.9b01212}, pages = {25483 -- 25494}, year = {2019}, abstract = {This study reports a new class of photocatalytic hybrid clay nanocomposites prepared from low-cost sources (kaolinite clay and Carica papaya seeds) doped with Zn and Cu salts via a solvothermal process. X-ray diffraction analysis suggests that Cu-doping and Cu/Zn-doping introduce new phases into the crystalline structure of Kaolinite clay, which is linked to the reduced band gap of kaolinite from typically between 4.9 and 8.2 eV to 2.69 eV for Cu-doped and 1.5 eV for Cu/Zn hybrid clay nanocomposites (Nisar, J.; Arhammar, C.; Jamstorp, E.; Ahuja, R. Phys. Rev. B 2011, 84, 075120). In the presence of solar light irradiation, Cu- and Cu/Zn-doped nanocomposites facilitate the electron hole pair separation. This promotes the generation of singlet oxygen which in turn improves the water disinfection efficiencies of these novel nanocomposite materials. The nanocomposite materials were further characterized using high-resolution scanning electron microscopy, fluorimetry, therrnogravimetric analysis, and Raman spectroscopy. The breakthrough times of the nanocomposites for a fixed bed mode of disinfection of water contaminated with 2.32 x 10(7) cfu/mL E. coli ATCC 25922 under solar light irradiation are 25 h for Zn-doped, 30 h for Cu-doped, and 35 h for Cu/Zn-doped nanocomposites. In the presence of multidrug and multimetal resistant strains of E. coli, the breakthrough time decreases significantly. Zn-only doped nanocomposites are not photocatalytically active. In the absence of light, the nanocomposites are still effective in decontaminating water, although less efficient than under solar light irradiation. Electrostatic interaction, metal toxicity, and release of singlet oxygen (only in the Cu-doped and Cu/Zn-doped nanocomposites) are the three disinfection mechanisms by which these nanocomposites disinfect water. A regrowth study indicates the absence of any living E. coli cells in treated water even after 4 days. These data and the long hydraulic times (under gravity) exhibited by these nanocomposites during photodisinfection of water indicate an unusually high potential of these nanocomposites as efficient, affordable, and sustainable point-of-use systems for the disinfection of water in developing countries.}, language = {en} } @article{TaoLiuWuetal.2020, author = {Tao, Lumi and Liu, Yuchuan and Wu, Dan and Wei, Qiao-Hua and Taubert, Andreas and Xie, Zailai}, title = {Luminescent Ionogels with Excellent Transparency, High Mechanical Strength, and High Conductivity}, series = {Nanomaterials}, volume = {10}, journal = {Nanomaterials}, number = {12}, publisher = {MDPI}, address = {Basel}, issn = {2079-4991}, doi = {10.3390/nano10122521}, pages = {11}, year = {2020}, abstract = {The paper describes a new kind of ionogel with both good mechanical strength and high conductivity synthesized by confining the ionic liquid (IL) 1-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide ([Bmim][NTf₂]) within an organic-inorganic hybrid host. The organic-inorganic host network was synthesized by the reaction of methyltrimethoxysilane (MTMS), tetraethoxysilane (TEOS), and methyl methacrylate (MMA) in the presence of a coupling agent, offering the good mechanical strength and rapid shape recovery of the final products. The silane coupling agent 3-methacryloxypropyltrimethoxysilane (KH-570) plays an important role in improving the mechanical strength of the inorganic-organic hybrid, because it covalently connected the organic component MMA and the inorganic component SiO₂. Both the thermal stability and mechanical strength of the ionogel significantly increased by the addition of IL. The immobilization of [Bmim][NTf₂] within the ionogel provided the final ionogel with an ionic conductivity as high as ca. 0.04 S cm⁻¹ at 50 °C. Moreover, the hybrid ionogel can be modified with organosilica-modified carbon dots within the network to yield a transparent and flexible ionogel with strong excitation-dependent emission between 400 and 800 nm. The approach is, therefore, a blueprint for the construction of next-generation multifunctional ionogels.}, language = {en} } @article{HeyneArltGessneretal.2020, author = {Heyne, Benjamin and Arlt, Kristin and Geßner, Andr{\´e} and Richter, Alexander F. and D{\"o}blinger, Markus and Feldmann, Jochen and Taubert, Andreas and Wedel, Armin}, title = {Mixed Mercaptocarboxylic Acid Shells Provide Stable Dispersions of InPZnS/ZnSe/ZnS Multishell Quantum Dots in Aqueous Media}, series = {Nanomaterials}, volume = {10}, journal = {Nanomaterials}, number = {9}, publisher = {MDPI}, address = {Basel}, issn = {2079-4991}, doi = {10.3390/nano10091858}, pages = {24}, year = {2020}, abstract = {Highly luminescent indium phosphide zinc sulfide (InPZnS) quantum dots (QDs), with zinc selenide/zinc sulfide (ZnSe/ZnS) shells, were synthesized. The QDs were modified via a post-synthetic ligand exchange reaction with 3-mercaptopropionic acid (MPA) and 11-mercaptoundecanoic acid (MUA) in different MPA:MUA ratios, making this study the first investigation into the effects of mixed ligand shells on InPZnS QDs. Moreover, this article also describes an optimized method for the correlation of the QD size vs. optical absorption of the QDs. Upon ligand exchange, the QDs can be dispersed in water. Longer ligands (MUA) provide more stable dispersions than short-chain ligands. Thicker ZnSe/ZnS shells provide a better photoluminescence quantum yield (PLQY) and higher emission stability upon ligand exchange. Both the ligand exchange and the optical properties are highly reproducible between different QD batches. Before dialysis, QDs with a ZnS shell thickness of ~4.9 monolayers (ML), stabilized with a mixed MPA:MUA (mixing ratio of 1:10), showed the highest PLQY, at ~45\%. After dialysis, QDs with a ZnS shell thickness of ~4.9 ML, stabilized with a mixed MPA:MUA and a ratio of 1:10 and 1:100, showed the highest PLQYs, of ~41\%. The dispersions were stable up to 44 days at ambient conditions and in the dark. After 44 days, QDs with a ZnS shell thickness of ~4.9 ML, stabilized with only MUA, showed the highest PLQY, of ~34\%.}, language = {en} } @article{ZehbeLangeTaubert2019, author = {Zehbe, Kerstin and Lange, Alyna and Taubert, Andreas}, title = {Stereolithography Provides Access to 3D Printed lonogels with High Ionic Conductivity}, series = {Energy Fuels}, volume = {33}, journal = {Energy Fuels}, number = {12}, publisher = {American Chemical Society}, address = {Washington}, issn = {0887-0624}, doi = {10.1021/acs.energyfuels.9b03379}, pages = {12885 -- 12893}, year = {2019}, abstract = {New ionogels (IGs) were prepared by combination of a series of sulfonate-based ionic liquids (ILs), 1-methyl-3-(4-sulfobutyl)imidazolium para-toluenesulfonate [BmimSO(3)][pTS], 1-methyl-1-butylpiperidiniumsulfonate para-toluenesul-fonate [BmpipSO(3)] [pTS], and 1-methyl-3-(4-sulfobutyl) imidazolium methylsulfonate [BmimSO(3)H][MeSO3] with a commercial stereolithography photoreactive resin. The article describes both the fundamental properties of the ILs and the resulting IGs. The IGs obtained from the ILs and the resin show high ionic conductivity of up to ca. 0.7.10(-4) S/cm at room temperature and 3.4-10(-3) S/cm at 90 degrees C. Moreover, the IGs are thermally stable to about 200 degrees C and mechanically robust. Finally, and most importantly, the article demonstrates that the IGs can be molded three-dimensionally using stereolithography. This provides, for the first time, access to IGs with complex 3D shapes with potential application in battery or fuel cell technology.}, language = {en} } @article{TaubertLerouxRabuetal.2019, author = {Taubert, Andreas and Leroux, Fabrice and Rabu, Pierre and de Zea Bermudez, Veronica}, title = {Advanced hybrid nanomaterials}, series = {Beilstein journal of nanotechnology}, volume = {10}, journal = {Beilstein journal of nanotechnology}, publisher = {Beilstein-Institut zur F{\"o}rderung der Chemischen Wissenschaften}, address = {Frankfurt am Main}, issn = {2190-4286}, doi = {10.3762/bjnano.10.247}, pages = {2563 -- 2567}, year = {2019}, language = {en} } @article{PehLiedelTaubertetal.2017, author = {Peh, Eddie and Liedel, Clemens and Taubert, Andreas and Tauer, Klaus}, title = {Composition inversion to form calcium carbonate mixtures}, series = {CrystEngComm}, volume = {19}, journal = {CrystEngComm}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1466-8033}, doi = {10.1039/c7ce00433h}, pages = {3573 -- 3583}, year = {2017}, abstract = {Composition inversion takes place in equimolar solid mixtures of sodium or ammonium carbonate and calcium chloride with respect to the combination of anions and cations leading to the corresponding chloride and calcite in complete conversion. The transformation takes place spontaneously under a variety of different situations, even in a powdery mixture resting under ambient conditions. Powder X-ray diffraction data and scanning electron microscopy micrographs are presented to describe the course of the reaction and to characterize the reaction products. The incomplete reaction in the interspace between two compressed tablets of pure starting materials leads to an electric potential due to the presence of uncompensated charges.}, language = {en} } @article{ZhangWillaSunetal.2017, author = {Zhang, Weiyi and Willa, Christoph and Sun, Jian-Ke and Guterman, Ryan and Taubert, Andreas and Yuan, Jiayin}, title = {Polytriazolium poly(ionic liquid) bearing triiodide anions: Synthesis, basic properties and electrochemical behaviors}, series = {Polymer : the international journal for the science and technology of polymers}, volume = {124}, journal = {Polymer : the international journal for the science and technology of polymers}, publisher = {Elsevier}, address = {Oxford}, issn = {0032-3861}, doi = {10.1016/j.polymer.2017.07.059}, pages = {246 -- 251}, year = {2017}, abstract = {4-Methyl-1-vinyl-1,2,4-triazolium triiodide ionic liquid and its polymer poly(4-methyl-1-vinyl-1,2,4-triazolium) triiodide were prepared for the first time from their iodide precursors via the reaction of iodide (I-) with elemental iodine (I-2). The change from iodide to triiodide (I-3(-)) was found to introduce particular variations in the physical properties of these two compounds, including lower melting point/glass transition temperature and altered solubility. The compounds were characterized by single-crystal X-ray diffraction, elemental analysis, and their electrochemical properties examined in solution and in the solid-state. Compared with their iodide analogues, the triiodide salts exhibited lower electrical impedance and higher current in the cyclic voltammetry. We found that poly(4-methyl-1,2,4-triazolium triiodide) was proven to be a promising solid polymer electrolyte candidate. (C) 2017 Elsevier Ltd. All rights reserved.}, language = {en} } @article{HentrichBrezesinskiKuebeletal.2017, author = {Hentrich, Doreen and Brezesinski, Gerald and Kuebel, Christian and Bruns, Michael and Taubert, Andreas}, title = {Cholesteryl Hemisuccinate Monolayers Efficiently Control Calcium Phosphate Nucleation and Growth}, series = {Crystal growth \& design : integrating the fields of crystal engineering and crystal growth for the synthesis and applications of new materials}, volume = {17}, journal = {Crystal growth \& design : integrating the fields of crystal engineering and crystal growth for the synthesis and applications of new materials}, publisher = {American Chemical Society}, address = {Washington}, issn = {1528-7483}, doi = {10.1021/acs.cgd.7b00753}, pages = {5764 -- 5774}, year = {2017}, abstract = {The article describes the phase behavior of cholesteryl hemisuccinate at the air-liquid interface and its effect on calcium phosphate (CP) mineralization. The amphiphile forms stable monolayers with phase transitions at the air-liquid interface from a gas to a tilted liquid-condensed (TLC) and finally to an untilted liquid-condensed (ULC) phase. CP mineralization beneath these monolayers leads to crumpled CP layers made from individual plates. The main crystal phase is octacalcium phosphate (OCP) along with a minor fraction of hydroxyapatite (HAP), as confirmed by X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy, bright field transmission electron microscopy, and electron diffraction.}, language = {en} } @article{AbouserieZehbeMetzneretal.2017, author = {Abouserie, Ahed and Zehbe, Kerstin and Metzner, Philipp and Kelling, Alexandra and G{\"u}nter, Christina and Schilde, Uwe and Strauch, Peter and K{\"o}rzd{\"o}rfer, Thomas and Taubert, Andreas}, title = {Alkylpyridinium Tetrahalidometallate Ionic Liquids and Ionic Liquid Crystals: Insights into the Origin of Their Phase Behavior}, series = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, journal = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-1948}, doi = {10.1002/ejic.201700826}, pages = {5640 -- 5649}, year = {2017}, abstract = {Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry.}, language = {en} } @article{AbouserieZehbeMetzneretal.2017, author = {Abouserie, Ahed and Zehbe, Kerstin and Metzner, Philipp and Kelling, Alexandra and G{\"u}nter, Christina and Schilde, Uwe and Strauch, Peter and K{\"o}rzd{\"o}rfer, Thomas and Taubert, Andreas}, title = {Alkylpyridinium Tetrahalidometallate Ionic Liquids and Ionic Liquid Crystals: Insights into the Origin of Their Phase Behavior}, series = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, journal = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-1948}, doi = {10.1002/ejic.201700826}, pages = {5640 -- 5649}, year = {2017}, abstract = {Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry.}, language = {en} } @article{GoebelStoltenbergKrehletal.2016, author = {G{\"o}bel, Ronald and Stoltenberg, Marcus and Krehl, Stefan and Biolley, Christine and Rothe, Regina and Schmidt, Bernd and Hesemann, Peter and Taubert, Andreas}, title = {A Modular Approach towards Mesoporous Silica Monoliths with Organically Modified Pore Walls: Nucleophilic Addition, Olefin Metathesis, and Cycloaddition}, series = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, volume = {6}, journal = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-1948}, doi = {10.1002/ejic.201500638}, pages = {2088 -- 2099}, year = {2016}, abstract = {We have synthesized mesoporous silica (monoliths) with defined surface chemistry by means of a number of addition reactions: (i) coupling of an isocyanate to a surface-immobilized thiol, (ii) addition of an epoxide to a surface-immobilized thiol, (iii) cross-metathesis between two olefins, and (iv) Huisgen [2+3] cycloaddition of an alkyne-functionalized silica monolith with an azide. Functionalization of the mesopores was observed, but there are significant differences between individual approaches. Isocyanate and epoxide additions lead to high degrees of functionalization, whereas olefin metathesis and [2+3] cycloaddition are less effective. We further show that the efficiency of the modification is about twice as high in mesoporous silica particles than in macroscopic silica monoliths.}, language = {en} } @article{KirchheckerTroegerMuellerBakeetal.2015, author = {Kirchhecker, Sarah and Tr{\"o}ger-M{\"u}ller, Steffen and Bake, Sebastian and Antonietti, Markus and Taubert, Andreas and Esposito, Davide}, title = {Renewable pyridinium ionic liquids from the continuous hydrothermal decarboxylation of furfural-amino acid derived pyridinium zwitterions}, series = {Green chemistry : an international journal and green chemistry resource}, volume = {17}, journal = {Green chemistry : an international journal and green chemistry resource}, number = {8}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9262}, doi = {10.1039/c5gc00913h}, pages = {4151 -- 4156}, year = {2015}, abstract = {Fully renewable pyridinium ionic liquids were synthesised via the hydrothermal decarboxylation of pyridinium zwitterions derived from furfural and amino acids in flow. The functionality of the resulting ionic liquid (IL) can be tuned by choice of different amino acids as well as different natural carboxylic acids as the counter-ions. A representative member of this new class of ionic liquids was successfully used for the synthesis of ionogels and as a solvent for the Heck coupling.}, language = {en} } @article{HentrichJungingerBrunsetal.2015, author = {Hentrich, Doreen and Junginger, Mathias and Bruns, Michael and Boerner, Hans G. and Brandt, Jessica and Brezesinski, Gerald and Taubert, Andreas}, title = {Interface-controlled calcium phosphate mineralization: effect of oligo(aspartic acid)-rich interfaces}, series = {CrystEngComm}, volume = {17}, journal = {CrystEngComm}, number = {36}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1466-8033}, doi = {10.1039/c4ce02274b}, pages = {6901 -- 6913}, year = {2015}, abstract = {The phase behavior of an amphiphilic block copolymer based on a poly(aspartic acid) hydrophilic block and a poly(n-butyl acrylate) hydrophobic block was investigated at the air-water and air-buffer interface. The polymer forms stable monomolecular films on both subphases. At low pH, the isotherms exhibit a plateau. Compression-expansion experiments and infrared reflection absorption spectroscopy suggest that the plateau is likely due to the formation of polymer bi- or multilayers. At high pH the films remain intact upon compression and no multilayer formation is observed. Furthermore, the mineralization of calcium phosphate beneath the monolayer was studied at different pH. The pH of the subphase and thus the polymer charge strongly affects the phase behavior of the film and the mineral formation. After 4 h of mineralization at low pH, atomic force microscopy shows smooth mineral films with a low roughness. With increasing pH the mineral films become inhomogeneous and the roughness increases. Transmission electron microscopy confirms this: at low pH a few small but uniform particles form whereas particles grown at higher pH are larger and highly agglomerated. Energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy confirm the formation of calcium phosphate. The levels of mineralization are higher in samples grown at high pH.}, language = {en} } @article{MaiBoyeYuanetal.2015, author = {Mai, Tobias and Boye, Susanne and Yuan, Jiayin and Voelkel, Antje and Graewert, Marlies and G{\"u}nter, Christina and Lederer, Albena and Taubert, Andreas}, title = {Poly(ethylene oxide)-based block copolymers with very high molecular weights for biomimetic calcium phosphate mineralization}, series = {RSC Advances}, volume = {5}, journal = {RSC Advances}, number = {125}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2046-2069}, doi = {10.1039/c5ra20035k}, pages = {103494 -- 103505}, year = {2015}, abstract = {The present article is among the first reports on the effects of poly(ampholyte)s and poly(betaine) s on the biomimetic formation of calcium phosphate. We have synthesized a series of di- and triblock copolymers based on a non-ionic poly(ethylene oxide) block and several charged methacrylate monomers, 2-(trimethylammonium) ethyl methacrylate chloride, 2-((3-cyanopropyl)-dimethylammonium)ethyl methacrylate chloride, 3-sulfopropyl methacrylate potassium salt, and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide. The resulting copolymers are either positively charged, ampholytic, or betaine block copolymers. All the polymers have very high molecular weights of over 10(6) g mol(-1). All polymers are water-soluble and show a strong effect on the precipitation and dissolution of calcium phosphate. The strongest effects are observed with triblock copolymers based on a large poly(ethylene oxide) middle block (nominal M-n = 100 000 g mol(-1)). Surprisingly, the data show that there is a need for positive charges in the polymers to exert tight control over mineralization and dissolution, but that the exact position of the charge in the polymer is of minor importance for both calcium phosphate precipitation and dissolution.}, language = {en} } @article{LerouxRabuSommerdijketal.2015, author = {Leroux, Fabrice and Rabu, Pierre and Sommerdijk, Nico A. J. M. and Taubert, Andreas}, title = {Two-Dimensional Hybrid Materials: Transferring Technology from Biology to Society}, series = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, journal = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, number = {7}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-1948}, doi = {10.1002/ejic.201500153}, pages = {1089 -- 1095}, year = {2015}, abstract = {Hybrid materials are at the forefront of modern research and technology; hence a large number of publications on hybrid materials has already appeared in the scientific literature. This essay focuses on the specifics and peculiarities of hybrid materials based on two-dimensional (2D) building blocks and confinements, for two reasons: (1) 2D materials have a very broad field of application, but they also illustrate many of the scientific challenges the community faces, both on a fundamental and an application level; (2) all authors of this essay are involved in research on 2D materials, but their perspective and vision of how the field will develop in the future and how it is possible to benefit from these new developments are rooted in very different scientific subfields. The current article will thus present a personal, yet quite broad, account of how hybrid materials, specifically 2D hybrid materials, will provide means to aid modern societies in fields as different as healthcare and energy.}, language = {en} } @article{WinterThielZabeletal.2014, author = {Winter, Alette and Thiel, Kerstin and Zabel, Andre and Klamroth, Tillmann and Poeppl, Andreas and Kelling, Alexandra and Schilde, Uwe and Taubert, Andreas and Strauch, Peter}, title = {Tetrahalidocuprates(II) - structure and EPR spectroscopy. Part 2: tetrachloridocuprates(II)}, series = {New journal of chemistry}, volume = {38}, journal = {New journal of chemistry}, number = {3}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1144-0546}, doi = {10.1039/c3nj01039b}, pages = {1019 -- 1030}, year = {2014}, abstract = {We present and discuss the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of five tetrachloridocuprate(II) complexes to supply a useful tool for the structural characterisation of the [CuCl4](2-) moiety in the liquid state, for example in ionic liquids, or in solution. Bis(benzyltriethylammonium)-, bis(trimethylphenylammonium)-, bis(ethyltriphenylphosphonium)-, bis(benzyltriphenylphosphonium)-, and bis(tetraphenylarsonium) tetrachloridocuprate(II) were synthesised and characterised by elemental, IR, EPR and X-ray analyses. The results of the crystallographic analyses show distorted tetrahedral coordination geometry of all [CuCl4](2-) anions in the five complexes and prove that all investigated complexes are stabilised by hydrogen bonds of different intensities. Despite the use of sterically demanding ammonium, phosphonium and arsonium cations to obtain the separation of the paramagnetic Cu(II) centres for EPR spectroscopy no hyperfine structure was observed in the EPR spectra but the principal values of the electron Zeeman tensor, g(parallel to) and g(perpendicular to), could be determined. With these EPR data and the crystallographic parameters we were able to carry out a correlation study to anticipate the structural situation of tetrachloridocuprates in different physical states. This correlation is in good agreement with DFT calculations.}, language = {en} } @article{XieHuangTitiricietal.2014, author = {Xie, Zai-Lai and Huang, Xing and Titirici, Maria-Magdalena and Taubert, Andreas}, title = {Mesoporous graphite nanoflakes via ionothermal carbonization of fructose and their use in dye removal}, series = {RSC Advances}, volume = {4}, journal = {RSC Advances}, number = {70}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2046-2069}, doi = {10.1039/c4ra05146g}, pages = {37423 -- 37430}, year = {2014}, abstract = {The large-scale green synthesis of graphene-type two-dimensional materials is still challenging. Herein, we describe the ionothermal synthesis of carbon-based composites from fructose in the iron-containing ionic liquid 1-butyl-3-methylimidazolium tetrachloridoferrate(III), [Bmim][FeCl4] serving as solvent, catalyst, and template for product formation. The resulting composites consist of oligo-layer graphite nanoflakes and iron carbide particles. The mesoporosity, strong magnetic moment, and high specific surface area of the composites make them attractive for water purification with facile magnetic separation. Moreover, Fe3Cfree graphite can be obtained via acid etching, providing access to fairly large amounts of graphite material. The current approach is versatile and scalable, and thus opens the door to ionothermal synthesis towards the larger-scale synthesis of materials that are, although not made via a sustainable process, useful for water treatment such as the removal of organic molecules.}, language = {en} } @article{XieHuangTaubert2014, author = {Xie, Zai-Lai and Huang, Xing and Taubert, Andreas}, title = {DyeIonogels: proton-responsive ionogels based on a dye-ionic liquid exhibiting reversible color change}, series = {Advanced functional materials}, volume = {24}, journal = {Advanced functional materials}, number = {19}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1616-301X}, doi = {10.1002/adfm.201303016}, pages = {2837 -- 2843}, year = {2014}, abstract = {Transparent, ion-conducting, and flexible ionogels based on the room temperature ionic liquid (IL) 1-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl) imide [Bmim][N(Tf)(2)], the dye-IL (DIL) 1-butyl-3-methylimidazolium methyl orange [Bmim][MO], and poly(methylmethacrylate) (PMMA) are prepared. Upon IL incorporation the thermal stability of the PMMA matrix significantly increases from 220 to 280 degrees C. The ionogels have a relatively high ionic conductivity of 10(-4) S cm(-1) at 373 K. Most importantly, the ionogels exhibit a strong and reversible color change when exposed to aqueous or organic solutions containing protons or hydroxide ions. The resulting material is thus a prototype of soft multifunctional matter featuring ionic conductivity, easy processability, response to changes in the environment, and a strong readout signal, the color change, that could be used in optical data storage or environmental sensing.}, language = {en} } @article{SalamaNeumannGuenteretal.2014, author = {Salama, Ahmed and Neumann, Mike and G{\"u}nter, Christina and Taubert, Andreas}, title = {Ionic liquid-assisted formation of cellulose/calcium phosphate hybrid materials}, series = {Beilstein journal of nanotechnology}, volume = {5}, journal = {Beilstein journal of nanotechnology}, publisher = {Beilstein-Institut zur F{\"o}rderung der Chemischen Wissenschaften}, address = {Frankfurt, Main}, issn = {2190-4286}, doi = {10.3762/bjnano.5.167}, pages = {1553 -- 1568}, year = {2014}, abstract = {Cellulose/calcium phosphate hybrid materials were synthesized via an ionic liquid-assisted route. Scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis/differential thermal analysis show that, depending on the reaction conditions, cellulose/hydroxyapatite, cellulose/ chlorapatite, or cellulose/monetite composites form. Preliminary studies with MC3T3-E1 pre-osteoblasts show that the cells proliferate on the hybrid materials suggesting that the ionic liquid-based process yields materials that are potentially useful as scaffolds for regenerative therapies.}, language = {en} } @article{MaiRakhmatullinaBleeketal.2014, author = {Mai, Tobias and Rakhmatullina, Ekaterina and Bleek, Katrin and Boye, Susanne and Yuan, Jiayin and Voelkel, Antje and Graewert, Marlies and Cheaib, Zeinab and Eick, Sigrun and G{\"u}nter, Christina and Lederer, Albena and Lussi, Adrian and Taubert, Andreas}, title = {Poly(ethylene oxide)-b-poly(3-sulfopropyl methacrylate) block copolymers for calcium phosphate mineralization and biofilm inhibition}, series = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, volume = {15}, journal = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, number = {11}, publisher = {American Chemical Society}, address = {Washington}, issn = {1525-7797}, doi = {10.1021/bm500888q}, pages = {3901 -- 3914}, year = {2014}, abstract = {Poly(ethylene oxide) (PEO) has long been used as an additive in toothpaste, partly because it reduces biofilm formation on teeth. It does not, however, reduce the formation of dental calculus or support the remineralization of dental enamel or dentine. The present article describes the synthesis of new block copolymers on the basis of PEO and poly(3-sulfopropyl methacrylate) blocks using atom transfer radical polymerization. The polymers have very large molecular weights (over 10(6) g/mol) and are highly water-soluble. They delay the precipitation of calcium phosphate from aqueous solution but, upon precipitation, lead to relatively monodisperse hydroxyapatite (HAP) spheres. Moreover, the polymers inhibit the bacterial colonization of human enamel by Streptococcus gordonii, a pioneer bacterium in oral biofilm formation, in vitro. The formation of well-defined HAP spheres suggests that a polymer-induced liquid precursor phase could be involved in the precipitation process. Moreover, the inhibition of bacterial adhesion suggests that the polymers could be utilized in caries prevention.}, language = {en} } @article{TentschertJungnickelReichardtetal.2014, author = {Tentschert, Jutta and Jungnickel, Harald and Reichardt, Philipp and Leube, Peter and Kretzschmar, Bernd and Taubert, Andreas and Luch, A.}, title = {Identification of nano clay in composite polymers}, series = {Surface and interface analysis : an international journal devoted to the development and application of techniques for the analysis surfaces, interfaces and thin films}, volume = {46}, journal = {Surface and interface analysis : an international journal devoted to the development and application of techniques for the analysis surfaces, interfaces and thin films}, publisher = {Wiley-Blackwell}, address = {Hoboken}, issn = {0142-2421}, doi = {10.1002/sia.5546}, pages = {334 -- 336}, year = {2014}, abstract = {Industrialized food production is in urgent search for alternative packaging materials, which can serve the requirements of a globalized world in terms of longer product shelf lives, reduced freight weight to decrease transport costs, and better barrier functionality to preserve its freshness. Polymer materials containing organically modified nano clay particles as additives are one example for a new generation of packaging materials with specific barrier functionality to actually hit the market. Clay types used for these applications are aluminosilicates, which belong to the mineral group of phyllosilicates. These consist of nano-scaled thin platelets, which are organically modified with quaternary ammonium compounds acting as spacers between the different clay layers, thereby increasing the hydrophobicity of the mineral additive. A variety of different organically modified clays are already available, and the use as additive for food packaging materials is one important application. To ensure valid risk assessments of emerging nano composite polymers used in the food packaging industry, exact analytical characterization of the organically modified clay within the polymer matrix is of paramount importance. Time-of-flight SIMS in combination with multivariate statistical analysis was used to differentiate modified clay reference materials from another. Time-of-flight SIMS spectra of a reference polymer plate, which contained one specific nano clay composite, were acquired. For each modified clay additive, a set of characteristic diagnostic ions could be identified, which then was used to successfully assign unknown clay additives to the corresponding reference material. Thus, the described methodology could be used to define and characterize nano clay within polymer matrices. Copyright (c) 2014 John Wiley \& Sons, Ltd.}, language = {en} } @article{GoebelHesemannFriedrichetal.2014, author = {Goebel, Ronald and Hesemann, Peter and Friedrich, Alwin and Rothe, Regina and Schlaad, Helmut and Taubert, Andreas}, title = {Modular thiol-ene chemistry approach towards mesoporous silica monoliths with organically modified pore walls}, series = {Chemistry - a European journal}, volume = {20}, journal = {Chemistry - a European journal}, number = {52}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201403982}, pages = {17579 -- 17589}, year = {2014}, abstract = {The surface modification of mesoporous silica monoliths through thiol-ene chemistry is reported. First, mesoporous silica monoliths with vinyl, allyl, and thiol groups were synthesized through a sol-gel hydrolysis-poly-condensation reaction from tetramethyl orthosilicate (TMOS) and vinyltriethoxysilane, allyltriethoxysilane, and (3-mercaptopropyl) trimethoxysilane, respectively. By variation of the molar ratio of the comonomers TMOS and functional silane, mesoporous silica objects containing different amounts of vinyl, allyl, and thiol groups were obtained. These intermediates can subsequently be derivatized through radical photoaddition reactions either with a thiol or an olefin, depending on the initial pore wall functionality, to yield silica monoliths with different pore-wall chemistries. Nitrogen sorption, small-angle X-ray scattering, solid-state NMR spectroscopy, elemental analysis, thermogravimetric analysis, and redox titration demonstrate that the synthetic pathway influences the morphology and pore characteristics of the resulting monoliths and also plays a significant role in the efficiency of functionalization. Moreover, the different reactivity of the vinyl and allyl groups on the pore wall affects the addition reaction, and hence, the degree of the pore-wall functionalization. This report demonstrates that thiol-ene photoaddition reactions are a versatile platform for the generation of a large variety of organically modified silica monoliths with different pore surfaces.}, 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{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{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{DelahayeXieSchaeferetal.2011, author = {Delahaye, Emilie and Xie, Zailai and Sch{\"a}fer, Andreas and Douce, Laurent and Rogez, Guillaume and Rabu, Pierre and G{\"u}nter, Christina and Gutmann, Jochen S. and Taubert, Andreas}, title = {Intercalation synthesis of functional hybrid materials based on layered simple hydroxide hosts and ionic liquid guests - a pathway towards multifunctional ionogels without a silica matrix?}, 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 = {39}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1477-9226}, doi = {10.1039/c1dt10841g}, pages = {9977 -- 9988}, year = {2011}, abstract = {Functional hybrid materials on the basis of inorganic hosts and ionic liquids (ILs) as guests hold promise for a virtually unlimited number of applications. In particular, the interaction and the combination of properties of a defined inorganic matrix and a specific IL could lead to synergistic effects in property selection and tuning. Such hybrid materials, generally termed ionogels, are thus an emerging topic in hybrid materials research. The current article addresses some of the recent developments and focuses on the question why silica is currently the dominating matrix used for (inorganic) ionogel fabrication. In comparison to silica, matrix materials such as layered simple hydroxides, layered double hydroxides, clay-type substances, magnetic or catalytically active solids, and many other compounds could be much more interesting because they themselves may carry useful functionalities, which could also be exploited for multifunctional hybrid materials synthesis. The current article combines experimental results with some arguments as to how new, advanced functional hybrid materials can be generated and which obstacles will need to be overcome to successfully achieve the synthesis of a desired target material.}, 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{FarraThielWinteretal.2011, author = {Farra, Ramzi and Thiel, Kerstin and Winter, Alette and Klamroth, Tillmann and Poeppl, Andreas and Kelling, Alexandra and Schilde, Uwe and Taubert, Andreas and Strauch, Peter}, title = {Tetrahalidocuprates(II)-structure and EPR spectroscopy Part 1: Tetrabromidocuprates(II)}, series = {New journal of chemistry}, volume = {35}, journal = {New journal of chemistry}, number = {12}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1144-0546}, doi = {10.1039/c1nj20271e}, pages = {2793 -- 2803}, year = {2011}, abstract = {Tetrahalidocuprates(II) show a high degree of structural flexibility. We present the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of four new tetrabromidocuprate(II) compounds and compare the results with previously reported data. The cations in the new compounds are the sterically demanding benzyltriphenylphosphonium, methyltriphenylphosphonium, tetraphenylphosphonium, and hexadecyltrimethylammonium ions; they were used to achieve a reasonable separation of the paramagnetic Cu(II) ions for EPR spectroscopy. X-Ray crystallography shows that in all four complexes the [CuBr4](2-) units have a distorted tetrahedral coordination geometry which is in agreement with DFT calculations. The EPR hyperfine structure was not resolved. This is due to the exchange broadening resulting from still incomplete separation of the paramagnetic Cu(II) centres. Nevertheless, the principal values of the electron Zeemann tensor (g(parallel to) and g(perpendicular to)) of the complexes could be determined. A correlation of structural (X-ray) parameters with the spin density at the copper centres (DFT) is well reflected in the EPR spectra of the bromidocuprates. This enables the correlation of X-ray and EPR parameters to predict the structure of tetrabromidocuprates in physical states other than the crystalline state. As a result, we provide a method to structurally characterize [CuBr4](2-) in, for example, ionic liquids or in solution, which has important implications for e.g. catalysis or materials science.}, language = {en} } @article{GrafMantionHaaseetal.2011, author = {Graf, Philipp and Mantion, Alexandre and Haase, Andrea and Thuenemann, Andreas F. and Masic, Admir and Meier, Wolfgang P. and Luch, Andreas and Taubert, Andreas}, title = {Silicification of peptide-coated silver nanoparticles-A biomimetic soft chemistry approach toward chiral hybrid core-shell materials}, series = {ACS nano}, volume = {5}, journal = {ACS nano}, number = {2}, publisher = {American Chemical Society}, address = {Washington}, issn = {1936-0851}, doi = {10.1021/nn102969p}, pages = {820 -- 833}, year = {2011}, abstract = {Silica and silver nanoparticles are relevant materials for new applications in optics, medicine, and analytical chemistry. We have previously reported the synthesis of pH responsive, peptide-templated, chiral silver nanoparticles. The current report shows that peptide-stabilized nanoparticles can easily be coated with a silica shell by exploiting the ability of the peptide coating to hydrolyze silica precursors such as TEOS or TMOS. The resulting silica layer protects the nanoparticles from chemical etching, allows their inclusion in other materials, and renders them biocompatible. Using electron and atomic force microscopy, we show that the silica shell thickness and the particle aggregation can be controlled simply by the reaction time. Small-angle X ray scattering confirms the Ag/peptide@silica core-shell structure. UV-vis and circular dichroism spectroscopy prove the conservation of the silver nanoparticle chirality upon silicification. Biological tests show that the biocompatibility in simple bacterial systems is significantly improved once a silica layer is deposited on the silver particles.}, 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{HaaseArlinghausTentschertetal.2011, author = {Haase, Andrea and Arlinghaus, Heinrich F. and Tentschert, Jutta and Jungnickel, Harald and Graf, Philipp and Mantion, Alexandre and Draude, Felix and Galla, Sebastian and Plendl, Johanna and Goetz, Mario E. and Masic, Admir and Meier, Wolfgang P. and Thuenemann, Andreas F. and Taubert, Andreas and Luch, Andreas}, title = {Application of Laser Postionization Secondary Neutral Mass Spectrometry/Time-of-Flight Secondary Ion Mass Spectrometry in Nanotoxicology: Visualization of Nanosilver in Human Macrophages and Cellular Responses}, series = {ACS nano}, volume = {5}, journal = {ACS nano}, number = {4}, publisher = {American Chemical Society}, address = {Washington}, issn = {1936-0851}, doi = {10.1021/nn200163w}, pages = {3059 -- 3068}, year = {2011}, abstract = {Silver nanoparticles (SNP) are the subject of worldwide commercialization because of their antimicrobial effects. Yet only little data on their mode of action exist. Further, only few techniques allow for visualization and quantification of unlabeled nanoparticles inside cells. To study SNP of different sizes and coatings within human macrophages, we introduce a novel laser postionization secondary neutral mass spectrometry (Laser-SNMS) approach and prove this method superior to the widely applied confocal Raman and transmission electron microscopy. With time-of-flight secondary ion mass spectrometry (TOF-SIMS) we further demonstrate characteristic fingerprints in the lipid pattern of the cellular membrane indicative of oxidative stress and membrane fluidity changes. Increases of protein carbonyl and heme oxygenase-1 levels in treated cells confirm the presence of oxidative stress biochemically. Intriguingly, affected phagocytosis reveals as highly sensitive end point of SNP-mediated adversity In macrophages. The cellular responses monitored are. hierarchically linked, but follow individual kinetics and are partially reversible.}, 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{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{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{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} } @article{XieXuGessneretal.2012, author = {Xie, Zai-Lai and Xu, Hai-Bing and Gessner, Andre and Kumke, Michael Uwe and Priebe, Magdalena and Fromm, Katharina M. and Taubert, Andreas}, title = {A transparent, flexible, ion conductive, and luminescent PMMA ionogel based on a Pt/Eu bimetallic complex and the ionic liquid [Bmim][N(Tf)(2)]}, series = {Journal of materials chemistry}, volume = {22}, journal = {Journal of materials chemistry}, number = {16}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {0959-9428}, doi = {10.1039/c2jm15862k}, pages = {8110 -- 8116}, year = {2012}, abstract = {Transparent, ion-conducting, luminescent, and flexible ionogels based on the room temperature ionic liquid (IL) 1-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl) imide [Bmim][N(Tf)(2)], a PtEu2 chromophore, and poly(methylmethacrylate) (PMMA) have been prepared. The thermal stability of the PMMA significantly increases with IL incorporation. In particular, the onset weight loss observed at ca. 229 degrees C for pure PMMA increases to 305 degrees C with IL addition. The ionogel has a high ionic conductivity of 10(-3) S cm(-1) at 373 K and exhibits a strong emission in the red with a long average luminescence decay time of tau = 890 mu s. The resulting material is a new type of soft hybrid material featuring useful thermal, optical, and ion transport properties.}, language = {en} } @article{GoebelWhiteTitiricietal.2012, author = {Goebel, Ronald and White, Robin J. and Titirici, Maria-Magdalena and Taubert, Andreas}, title = {Carbon-based ionogels tuning the properties of the ionic liquid via carbon-ionic liquid interaction}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {14}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, number = {17}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/c2cp23929a}, pages = {5992 -- 5997}, year = {2012}, abstract = {The behavior of two ionic liquids (ILs), 1-ethyl-3-methylimidazolium dicyanamide [Emim][DCA] and 1-ethyl-3-methylimidazolium triflate [Emim][TfO], in (meso) porous carbonaceous hosts was investigated. Prior to IL incorporation into the host, the carbon matrix was thermally annealed between 180 and 900 degrees C to control carbon condensation and surface chemistry. The resulting materials have an increasing "graphitic'' carbon character with increasing treatment temperature, reflected in a modified behavior of the ILs when impregnated into the carbon host. The two ILs show significant changes in the thermal behavior as measured from differential scanning calorimetry; these changes can be assigned to anion-pi interaction between the IL anions and the pore wall surfaces of these flexible carbonaceous support materials.}, language = {en} } @article{NeumannNoeskeTaubertetal.2012, author = {Neumann, Mike and Noeske, Robert and Taubert, Andreas and Tiersch, Brigitte and Strauch, Peter}, title = {Highly structured, biomorphous beta-SiC with high specific surface area from Equisetaceae}, series = {Journal of materials chemistry}, volume = {22}, journal = {Journal of materials chemistry}, number = {18}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {0959-9428}, doi = {10.1039/c2jm30253e}, pages = {9046 -- 9051}, year = {2012}, abstract = {Mesoporous, highly structured silicon carbide (beta-SiC) was synthesised from renewable plant materials (two Equisetaceae species) in a one-step carbothermal process at remarkably low temperatures down to 1200 degrees C. The SiC precursor is a silicon-carbon mixture with finely dispersed carbon prepared by pyrolysis of the organic plant matrix. Yields are 3 to 100\% (omega(Si/Si) related to the silicon deposited in the plant material), depending on reaction temperature and time. IR spectroscopy, X-ray diffraction, and nitrogen sorption prove the formation of high-purity beta-SiC with minor inorganic impurities after purification and a high specific surface area of up to 660 m(2) g(-1). Scanning electron microscopy shows that the plant morphology is maintained in the final SiC. Sedimentation analysis finds a mean particle size (diameters d(50)) of 20 mu m.}, language = {en} } @article{SiTaubertMantionetal.2012, author = {Si, Satyabrata and Taubert, Andreas and Mantion, Alexandre and Rogez, Guillaume and Rabu, Pierre}, title = {Peptide-intercalated layered metal hydroxides effect of peptide chain length and side chain functionality on structural, optical and magnetic properties}, series = {Chemical science}, volume = {3}, journal = {Chemical science}, number = {6}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2041-6520}, doi = {10.1039/c2sc01087a}, pages = {1945 -- 1957}, year = {2012}, abstract = {New hybrid materials have been prepared by grafting synthetic peptides in the interlayer spacing of Cu(II) and Co(II) layered simple hydroxides (LSHs). The interlayer spacing of the hybrids depends on the peptide chain length; the dependence is specific for the copper and cobalt-based hybrids. This suggests a metal-or LSH-specific interaction of the peptides with the respective inorganic layers. When tyrosine is present in the peptide, its fluorescence is quenched after grafting the peptide to the LSH. Studies of the luminescence vs. pH indicate deprotonation of the tyrosine moieties to tyrosinate at high pH, accompanied by the onset of luminescence. The luminescence increases with increasing OH- concentration, suggesting an application of the hybrids as chemical sensors. Moreover, the peptides influence the magnetic properties of the hybrids. The copper-based hybrids behave antiferromagnetically and the cobalt-based hybrids are ferrimagnets.}, language = {en} } @article{DelahayeGoebelLoebbickeetal.2012, author = {Delahaye, Emilie and Goebel, Ronald and Loebbicke, Ruben and Guillot, Regis and Sieber, Christoph and Taubert, Andreas}, title = {Silica ionogels for proton transport}, series = {Journal of materials chemistry}, volume = {22}, journal = {Journal of materials chemistry}, number = {33}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {0959-9428}, doi = {10.1039/c2jm00037g}, pages = {17140 -- 17146}, year = {2012}, abstract = {A number of ionogels - silica-ionic liquid (IL) hybrid materials - were synthesized and studied for their ionic conductivity. The materials are based on a sulfonated IL, 1-methyl-3-(3-sulfopropyl-)-imidazolium p-toluenesulfonate, [PmimSO(3)H][PTS], which contains a sulfonic acid/sulfonate group both in the IL anion and in the side chain of the IL cation. By way of the sulfonate-sulfonic acid proton transfer, the IL imparts the ionogel with a high ionic conductivity of ca. 10(-2) S cm(-1) in the as-synthesized state at 120 degrees C and 10(-3) S cm(-1) in the dry state at 120 degrees C. The ionogels are stable up to ca. 150 degrees C in dynamic thermogravimetric analysis. This suggests that these materials, which are relatively cheap and easily fabricated, could find application in fuel cells in intermediate temperature ranges where many other membrane materials are not suitable.}, language = {en} } @article{TaubertStangeLietal.2012, author = {Taubert, Andreas and Stange, Franziska and Li, Zhonghao and Junginger, Mathias and G{\"u}nter, Christina and Neumann, Mike and Friedrich, Alwin}, title = {CuO nanoparticles from the Strongly Hydrated Ionic Liquid Precursor (ILP) Tetrabutylammonium Hydroxide evaluation of the Ethanol Sensing Activity}, series = {ACS applied materials \& interfaces}, volume = {4}, journal = {ACS applied materials \& interfaces}, number = {2}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/am201427q}, pages = {791 -- 795}, year = {2012}, abstract = {The sensing potential of CuO nanoparticles synthesized via. precipitation from a water/ionic liquid precursor (ILP) mixture was investigated. The particles have a moderate surface area of 66 m(2)/g after synthesis, which decreases upon thermal treatment to below 5 m(2)/g. Transmission electron microscopy confirms crystal growth upon annealing, likely due to sintering effects. The as-synthesized particles can be used for ethanol sensing. The respective sensors show fast response and recovery times of below 10 s and responses greater than 2.3 at 100 ppm of ethanol at 200 degrees C, which is higher than any CuO-based ethanol sensor described so far.}, language = {en} } @article{HaaseRottMantionetal.2012, author = {Haase, Andrea and Rott, Stephanie and Mantion, Alexandre and Graf, Philipp and Plendl, Johanna and Th{\"u}nemann, Andreas F. and Meier, Wolfgang P. and Taubert, Andreas and Luch, Andreas and Reiser, Georg}, title = {Effects of silver nanoparticles on primary mixed neural cell cultures: Uptake, oxidative stress and acute calcium responses}, series = {Toxicological sciences}, volume = {126}, journal = {Toxicological sciences}, number = {2}, publisher = {Oxford Univ. Press}, address = {Oxford}, issn = {1096-6080}, doi = {10.1093/toxsci/kfs003}, pages = {457 -- 468}, year = {2012}, abstract = {In the body, nanoparticles can be systemically distributed and then may affect secondary target organs, such as the central nervous system (CNS). Putative adverse effects on the CNS are rarely investigated to date. Here, we used a mixed primary cell model consisting mainly of neurons and astrocytes and a minor proportion of oligodendrocytes to analyze the effects of well-characterized 20 and 40 nm silver nanoparticles (SNP). Similar gold nanoparticles served as control and proved inert for all endpoints tested. SNP induced a strong size-dependent cytotoxicity. Additionally, in the low concentration range (up to 10 mu g/ml of SNP), the further differentiated cultures were more sensitive to SNP treatment. For detailed studies, we used low/medium dose concentrations (up to 20 mu g/ml) and found strong oxidative stress responses. Reactive oxygen species (ROS) were detected along with the formation of protein carbonyls and the induction of heme oxygenase-1. We observed an acute calcium response, which clearly preceded oxidative stress responses. ROS formation was reduced by antioxidants, whereas the calcium response could not be alleviated by antioxidants. Finally, we looked into the responses of neurons and astrocytes separately. Astrocytes were much more vulnerable to SNP treatment compared with neurons. Consistently, SNP were mainly taken up by astrocytes and not by neurons. Immunofluorescence studies of mixed cell cultures indicated stronger effects on astrocyte morphology. Altogether, we can demonstrate strong effects of SNP associated with calcium dysregulation and ROS formation in primary neural cells, which were detectable already at moderate dosages.}, language = {en} } @article{CasseShkilnyyLindersetal.2012, author = {Casse, Olivier and Shkilnyy, Andriy and Linders, J{\"u}rgen and Mayer, Christian and H{\"a}ussinger, Daniel and V{\"o}lkel, Antje and Th{\"u}nemann, Andreas F. and Dimova, Rumiana and C{\"o}lfen, Helmut and Meier, Wolfgang P. and Schlaad, Helmut and Taubert, Andreas}, title = {Solution behavior of double-hydrophilic block copolymers in dilute aqueous solution}, series = {Macromolecules : a publication of the American Chemical Society}, volume = {45}, journal = {Macromolecules : a publication of the American Chemical Society}, number = {11}, publisher = {American Chemical Society}, address = {Washington}, issn = {0024-9297}, doi = {10.1021/ma300621g}, pages = {4772 -- 4777}, year = {2012}, abstract = {The self-assembly of double-hydrophilic poly(ethylene oxide)-poly(2-methyl-2-oxazoline) diblock copolymers in water has been studied. Isothermal titration calorimetry, small-angle X-ray scattering, and analytical ultracentrifugation suggest that only single polymer chains are present in solution. In contrast, light scattering and transmission electron microscopy detect aggregates with radii of ca. 100 nm. Pulsed field gradient NMR spectroscopy confirms the presence of aggregates, although only 2\% of the polymer chains undergo aggregation. Water uptake experiments indicate differences in the hydrophilicity of the two blocks, which is believed to be the origin of the unexpected aggregation behavior (in accordance with an earlier study by Ke et al. [Macromolecules 2009, 42, 5339-5344]). The data therefore suggest that even in double-hydrophilic block copolymers, differences in hydrophilicity are sufficient to drive polymer aggregation, a phenomenon that has largely been overlooked or ignored so far.}, language = {en} } @article{HaaseMantionGrafetal.2012, author = {Haase, A. and Mantion, A. and Graf, P. and Plendl, J. and Th{\"u}nemann, Andreas F. and Meier, Wolfgang P. and Taubert, Andreas and Luch, A.}, title = {A novel type of silver nanoparticles and their advantages in toxicity testing in cell culture systems}, series = {Archives of toxicology : official journal of EUROTOX}, volume = {86}, journal = {Archives of toxicology : official journal of EUROTOX}, number = {7}, publisher = {Springer}, address = {Heidelberg}, issn = {0340-5761}, doi = {10.1007/s00204-012-0836-0}, pages = {1089 -- 1098}, year = {2012}, abstract = {Silver nanoparticles (SNPs) are among the most commercialized nanoparticles worldwide. Often SNP are used because of their antibacterial properties. Besides that they possess unique optic and catalytic features, making them highly interesting for the creation of novel and advanced functional materials. Despite its widespread use only little data exist in terms of possible adverse effects of SNP on human health. Conventional synthesis routes usually yield products of varying quality and property. It thus may become puzzling to compare biological data from different studies due to the great variety in sizes, coatings or shapes of the particles applied. Here, we applied a novel synthesis approach to obtain SNP of well-defined colloidal and structural properties. Being stabilized by a covalently linked small peptide, these particles are nicely homogenous, with narrow size distribution, and form monodisperse suspensions in aqueous solutions. We applied these peptide-coated SNP in two different sizes of 20 or 40 nm (Ag20Pep and Ag40Pep) and analyzed responses of THP-1-derived human macrophages while being exposed against these particles. Gold nanoparticles of similar size and coating (Au20Pep) were used for comparison. The cytotoxicity of particles was assessed by WST-1 and LDH assays, and the uptake into the cells was confirmed via transmission electron microscopy. In summary, our data demonstrate that this novel type of SNP is well suited to serve as model system for nanoparticles to be tested in toxicological studies in vitro.}, language = {en} } @article{ZiolkowskiBleekTwamleyetal.2012, author = {Ziolkowski, Bartosz and Bleek, Katrin and Twamley, Brendan and Fraser, Kevin J. and Byrne, Robert and Diamond, Dermot and Taubert, Andreas}, title = {Magnetic ionogels (MagIGs) based on iron oxide nanoparticles, poly(N-isopropylacrylamide), and the ionic liquid trihexyl(tetradecyl)phosphonium dicyanamide}, series = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, journal = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, number = {32}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-1948}, doi = {10.1002/ejic.201200597}, pages = {5245 -- 5251}, year = {2012}, abstract = {Magnetic ionogels (MagIGs) were prepared from organosilane-coated iron oxide nanoparticles, N-isopropylacrylamide, and the ionic liquid trihexyl(tetradecyl)phosphonium dicyanamide. The ionogels prepared with the silane-modified nanoparticles are more homogeneous than ionogels prepared with unmodified magnetite particles. The silane-modified particles are immobilized in the ionogel and are resistant tonanoparticle leaching. The modified particles also render the ionogels mechanically more stable than the ionogels synthesized with unmodified nanoparticles. The ionogels respond to external permanent magnets and are therefore prototypes of a new soft magnetic actuator.}, language = {en} } @article{TentschertDraudeJungnickeletal.2013, author = {Tentschert, J. and Draude, F. and Jungnickel, H. and Haase, A. and Mantion, Alexandre and Galla, S. and Thuenemann, Andreas F. and Taubert, Andreas and Luch, A. and Arlinghaus, H. F.}, title = {TOF-SIMS analysis of cell membrane changes in functional impaired human macrophages upon nanosilver treatment}, series = {Surface and interface analysis : an international journal devoted to the development and application of techniques for the analysis surfaces, interfaces and thin films}, volume = {45}, journal = {Surface and interface analysis : an international journal devoted to the development and application of techniques for the analysis surfaces, interfaces and thin films}, number = {1}, publisher = {Wiley-Blackwell}, address = {Hoboken}, issn = {0142-2421}, doi = {10.1002/sia.5155}, pages = {483 -- 485}, year = {2013}, abstract = {Silver nanoparticles (SNP) are among the most commercialized nanoparticles. Here, we show that peptide-coated SNP cause functional impairment of human macrophages. A dose-dependent inhibition of phagocytosis is observed after nanoparticle treatment, and pretreatment of cells with N-acetyl cysteine (NAC) can counteract the phagocytosis disturbances caused by SNP. Using the surface-sensitive mode of time-of-flight secondary ion mass spectrometry, in combination with multivariate statistical methods, we studied the composition of cell membranes in human macrophages upon exposure to SNP with and without NAC preconditioning. This method revealed characteristic changes in the lipid pattern of the cellular membrane outer leaflet in those cells challenged by SNP. Statistical analyses resulted in 19 characteristic ions, which can be used to distinguish between NAC pretreated and untreated macrophages. The present study discusses the assignments of surface cell membrane phospholipids for the identified ions and the resulting changes in the phospholipid pattern of treated cells. We conclude that the adverse effects in human macrophages caused by SNP can be partially reversed through NAC administration. Some alterations, however, remained.}, language = {en} } @article{DraudeGallaPelsteretal.2013, author = {Draude, F. and Galla, S. and Pelster, Axel and Tentschert, J. and Jungnickel, H. and Haase, Alfred and Mantion, Alexandre and Thuenemann, Andreas F. and Taubert, Andreas and Luch, A. and Arlinghaus, H. F.}, title = {ToF-SIMS and Laser-SNMS analysis of macrophages after exposure to silver nanoparticles}, series = {Surface and interface analysis : an international journal devoted to the development and application of techniques for the analysis surfaces, interfaces and thin films}, volume = {45}, journal = {Surface and interface analysis : an international journal devoted to the development and application of techniques for the analysis surfaces, interfaces and thin films}, number = {1}, publisher = {Wiley-Blackwell}, address = {Hoboken}, issn = {0142-2421}, doi = {10.1002/sia.4902}, pages = {286 -- 289}, year = {2013}, abstract = {Silver nanoparticles (SNPs) are among the most commercialized nanoparticles because of their antibacterial effects. Besides being employed, e. g. as a coatingmaterial for sterile surfaces in household articles and appliances, the particles are also used in a broad range of medical applications. Their antibacterial properties make SNPs especially useful for wound disinfection or as a coating material for prostheses and surgical instruments. Because of their optical characteristics, the particles are of increasing interest in biodetection as well. Despite the widespread use of SNPs, there is little knowledge of their toxicity. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and laser post-ionization secondary neutral mass spectrometry (Laser-SNMS) were used to investigate the effects of SNPs on human macrophages derived from THP-1 cells in vitro. For this purpose, macrophages were exposed to SNPs. The SNP concentration ranges were chosen with regard to functional impairments of the macrophages. To optimize the analysis of the macrophages, a special silicon wafer sandwich preparation technique was employed; ToF-SIMS was employed to characterize fragments originating from macrophage cell membranes. With the use of this optimized sample preparation method, the SNP-exposed macrophages were analyzed with ToF-SIMS and with Laser-SNMS. With Laser-SNMS, the three-dimensional distribution of SNPs in cells could be readily detected with very high efficiency, sensitivity, and submicron lateral resolution. We found an accumulation of SNPs directly beneath the cell membrane in a nanoparticular state as well as agglomerations of SNPs inside the cells.}, language = {en} } @article{JungingerKuebelSchacheretal.2013, author = {Junginger, Mathias and K{\"u}bel, Christian and Schacher, Felix H. and M{\"u}ller, Axel H. E. and Taubert, Andreas}, title = {Crystal structure and chemical composition of biomimetic calcium phosphate nanofibers}, series = {RSC Advances}, volume = {3}, journal = {RSC Advances}, number = {28}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2046-2069}, doi = {10.1039/c3ra23348k}, pages = {11301 -- 11308}, year = {2013}, abstract = {Calcium phosphate nanofibers with a diameter of only a few nanometers and a cotton-ball-like aggregate morphology have been reported several times in the literature. Although fiber formation seems reproducible in a variety of conditions, the crystal structure and chemical composition of the fibers have been elusive. Using scanning transmission electron microscopy, low dose electron (nano) diffraction, energy-dispersive X-ray spectroscopy, and energy-filtered transmission electron microscopy, we have assigned crystal structures and chemical compositions to the fibers. Moreover, we demonstrate that the mineralization process yields true polymer/calcium phosphate hybrid materials where the block copolymer template is closely associated with the calcium phosphate.}, language = {en} } @article{UnuabonahOluOwolabiTaubertetal.2013, author = {Unuabonah, Emmanuel Iyayi and Olu-Owolabi, Bamidele I. and Taubert, Andreas and Omolehin, Elizabeth B. and Adebowale, Kayode O.}, title = {SAPK a novel composite resin for water treatment with very high Zn2+, Cd2+, and Pb2+ adsorption capacity}, series = {Industrial \& engineering chemistry research}, volume = {52}, journal = {Industrial \& engineering chemistry research}, number = {2}, publisher = {American Chemical Society}, address = {Washington}, issn = {0888-5885}, doi = {10.1021/ie3024577}, pages = {578 -- 585}, year = {2013}, abstract = {A new sulfonated aniline-modified poly(vinyl alcohol)/K-feldspar (SAPK) composite was prepared. The cation-exchange capacity of the composite was found to be S times that of neat feldspar. The specific surface area and point of zero charge also changed significantly upon modification, from 15.6 +/- 0.1 m(2)/g and 2.20 (K-feldspar) to 73.6 +/- 0.3 m(2)/g and 1.91 (SAPK). Zn2+, Cd2+, and Pb2+ adsorption was found to be largely independent of pH, and the metal adsorption rate on SAPK was higher than that on neat feldspar. This particularly applies to the initial adsorption rates. The adsorption process involves both film and pore diffusion; film diffusion initially controls the adsorption. The Freundlich and Langmuir models were found to fit metal-ion adsorption on SAPK most accurately. Adsorption on neat feldspar was best fitted with a Langmuir model, indicating the formation of adsorbate monolayers. Both pure feldspar and SAPK showed better selectivity for Pb2+ than for Cd2+ or Zn2+.}, language = {en} } @article{UnuabonahGuenterWeberetal.2013, author = {Unuabonah, Emmanuel Iyayi and G{\"u}nter, Christina and Weber, Jens and Lubahn, Susanne and Taubert, Andreas}, title = {Hybrid Clay - a new highly efficient adsorbent for water treatment}, series = {ACS sustainable chemistry \& engineering}, volume = {1}, journal = {ACS sustainable chemistry \& engineering}, number = {8}, publisher = {American Chemical Society}, address = {Washington}, issn = {2168-0485}, doi = {10.1021/sc400051y}, pages = {966 -- 973}, year = {2013}, abstract = {New hybrid clay adsorbent based on kaolinite clay and Carica papaya seeds with improved cation exchange capacity (CEC), rate of heavy metal ion uptake, and adsorption capacity for heavy metal ions were prepared. The CEC of the new material is ca. 75 meq/100 g in spite of the unexpectedly low surface area (approximate to 19 m(2)/g). Accordingly, the average particle size of the hybrid clay adsorbent decreased from over 200 to 100 pm. The hybrid clay adsorbent is a highly efficient adsorbent for heavy metals. With an initial metal concentration of 1 mg/L, the hybrid clay adsorbent reduces the Cd2+, Ni2+, and Pb2+ concentration in aqueous solution to <= 4, <= 7 and <= 20 mu g/L, respectively, from the first minute to over 300 min using a fixed bed containing 2 g of adsorbent and a flow rate of approximate to 7 mL/min. These values are (with the exception of Pb2+) in line with the WHO permissible limits for heavy metal ions. In a cocktail solution of Cd2+, and Ni2+, the hybrid clay shows a reduced rate of uptake but an increased adsorption capacity. The CEC data suggest that the adsorption of Pb2+, Cd2+, and Ni2+ on the hybrid clay adsorbent is essentially due to ion exchange. This hybrid clay adsorbent is prepared from materials that are abundant and by a simple means that is sustainable, easily recovered from aqueous solution, nonbiodegradable (unlike numerous biosorbent), and easily regenerated and is a highly efficient alternative to activated carbon for water treatment.}, language = {en} }