Wendelin J Stark

University of Zurich, Zürich, Zurich, Switzerland

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Publications (184)696.35 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: Unprecedented magnetic borohydride exchange (mBER), magnetic Wang aldehyde (mWang) and magnetic amine resins were prepared from highly magnetic polymer-coated cobalt or iron nanoparticles. Microwave irradiation was used to obtain excellent degrees of functionalization (>95 %) and loadings (up to 3.0 mmol g(-1) ) in short reaction times of 15 min or less. A small library of ureas and thioureas was synthesized by the exclusive application of these magnetic resins. As a first step, a reductive amination of aromatic and aliphatic aldehydes was carried out with mBER. The excess of primary amine needed to complete the reaction was subsequently scavenged selectively by mWang. Simple magnetic decantation from the resins resulted in secondary amines in good to excellent yields and purities. The used magnetic resins were efficiently regenerated and reused for the next run. In a second step, the secondary amines were converted to trisubstituted (thio)ureas in excellent yields and purities by stirring with an excess of iso(thio)cyanate, which was scavenged by addition of the magnetic amine resin after completion of the reaction. The whole reaction sequence is carried out without any purification apart from magnetic decantation; moreover, conventional magnetic stirring can be used as opposed to the vortexing required for polystyrene resins.
    Chemistry 06/2013; · 5.93 Impact Factor
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    ABSTRACT: Magnetic separation-based blood purification enables rapid and selective removal of endotoxin and bacteria from human whole blood. Functional assays assessing key steps in host defense against bacteria show an attenuated inflammatory response in purified samples and less chemotactic activity. Beatrice Beck-Schimmer and co-workers introduce on page 829 this promising new approach for future sepsis treatment.
    Advanced healthcare materials. 06/2013; 2(6):828.
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    ABSTRACT: Magnetic nanomaterials find increasing application as separation agents to rapidly isolate target compounds from complex biological media (i.e., blood purification). The responsiveness of the used materials to external magnetic fields (i.e., their saturation magnetization) is one of the most critical parameters for a fast and thorough separation. In the present study, magnetite (Fe3O4) and non-oxidic cementite (Fe3C) based carbon-coated nanomagnets are characterized in detail and compared regarding their separation behavior from human whole blood. A quantification approach for iron-based nanomaterials in biological samples with strong matrix effects (here, salts in blood) based on platinum spiking is shown. Both materials are functionalized with polyethyleneglycol (PEG) to improve cytocompatibility (confirmed by cell toxicity tests) and dispersability. The separation performance is tested in two setups, namely under stationary and different flow-conditions using fresh human blood. The results reveal a superior separation behavior of the cementite based nanomagnets and strongly suggest the use of nanomaterials with high saturation magnetizations for magnetic retention under common blood flow conditions such as in veins.
    Advanced Functional Materials 04/2013; 23:4888. · 9.77 Impact Factor
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    ABSTRACT: Deinking is a fundamental part of paper recycling. As the global paper consumption rises and exceeds even the annual paper production, recycling of this raw material is of high importance. Magnetic ink based on carbon coated magnetic nanoparticles enables an alternative approach to state of the art paper deinking. Magnetic deinking comprises three steps (pre- selection, washing and magnetic separation of fibers). Pre-separation of printed from non-printed scraps of paper is feasible and reduces the paper mass which has to be fed into a deinking process. A consecutively washing process removes surficial magnetic ink that can be collected by application of a permanent magnet. Still printed parts are subjected to a further continuous magnetic deinking step, where magnetic and non- magnetic paper fibers can be separated. Magnetic deinking of a model print allows recovery of more than 80% of bright fibers without any harsh chemical treatment and the re- collection of more than 82% of magnetic ink.
    Langmuir 03/2013; · 4.38 Impact Factor
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    ABSTRACT: An important aspect in risk assessment of nanoparticles (NPs) is to understand their environmental interactions. We used hydroponic plant cultures to study nanoparticle-plant-root interaction and translocation and exposed wheat and pumpkin to suspensions of uncoated CeO(2)-NP for 8d (primary particle size 17-100nm, 100mgL(-1)) in the absence and presence of fulvic acid (FA) and gum arabic (GA) as representatives of different types of natural organic matter. The behavior of CeO(2)-NPs in the hydroponic solution was monitored regarding agglomeration, sedimentation, particle size distribution, surface charge, amounts of root association, and translocation into shoots. NP-dispersions were stable over 8d in the presence of FA or GA, but with growing plants, changes in pH, particle agglomeration rate, and hydrodynamic diameter were observed. None of the plants exhibited reduced growth or any toxic response during the experiment. We found that CeO(2)-NPs translocated into pumpkin shoots, whereas this did not occur in wheat plants. The presence of FA and GA affected the amount of CeO(2) associated with roots (pure>FA>GA) but did not affect the translocation factor. Additionally, we could confirm via TEM and SEM that CeO(2)-NPs adhered strongly to root surfaces of both plant species.
    Chemosphere 01/2013; · 3.14 Impact Factor
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    ABSTRACT: The present study evaluates the effect of heat treatment on electrospun poly(lactide‐co‐glycolide) fibrous membranes. Both a temperature (75–150 °C) and a treatment time range (5–40 min) are tested. The effect on the fibrous structure is investigated in terms of morphology, showing that with increasing temperature or longer treatment time the fusion of fibres progresses continuously. Additionally, the tensile properties of the various scaffolds deliver results on the effect of increasing fibre‐to‐fibre linkages. Both modulus and yield increase within the heat treatment procedures. The elevated stiffness of the membranes accompanies a loss in porosity. These findings deliver insights into the tailoring of membranes that might be used in the fabrication of customised scaffolds intended for cell culture in tissue engineering.
    Macromolecular Materials and Engineering 01/2013; 298(11). · 2.34 Impact Factor
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    ABSTRACT: Movement is a key characteristic of higher organisms. During mammalian embryogenesis fetal movements have been found critical to normal tissue development. On the single cell level, however, our current understanding of stem cell differentiation concentrates on inducing factors through cytokine mediated biochemical signaling. In this study, human mesenchymal stem cells and chondrogenesis were investigated as representative examples. We show that pressureless, soft mechanical stimulation precipitated by the cyclic deformation of soft, magnetic hydrogel scaffolds with an external magnetic field, can induce chondrogenesis in mesenchymal stem cells without any additional chondrogenesis transcription factors (TGF-β1 and dexamethasone). A systematic study on the role of movement frequency revealed a classical dose-response relationship for human mesenchymal stem cells differentiation towards cartilage using mere mechanical stimulation. This effect could even be synergistically amplified when exogenous chondrogenic factors and movement were combined.
    PLoS ONE 01/2013; 8(11):e81362. · 3.73 Impact Factor
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    ABSTRACT: This work describes a magnetic separation-based approach using polymyxin B-functionalized metal alloy nanomagnets for the rapid elimination of endotoxins from human blood in vitro and functional assays to evaluate the biological relevance of the blood purification process. Playing a central role in gram-negative sepsis, bacteria-derived endotoxins are attractive therapeutic targets. However, both direct endotoxin detection in and removal from protein-rich fluids remains challenging. We present the synthesis and functionalization of ultra-magnetic cobalt/iron alloy nanoparticles and a magnetic separation-based approach using polymyxin B-functionalized nanomagnets to remove endotoxin from human blood in vitro. Conventional chromogenic Limulus Amebocyte Lysate assays confirm decreased endotoxin activity in purified compared to untreated samples. Functional assays assessing key steps in host defense against bacteria show an attenuated inflammatory mediator expression from human primary endothelial cells in response to purified blood samples compared to untreated blood and less chemotactic activity. Exposing Escherichia coli-positive blood samples to polymyxin B-functionalized nanomagnets even impairs the ability of gram-negative bacteria to form colony forming units, thus making magnetic separation based blood purification a promising new approach for future sepsis treatment.
    Advanced healthcare materials. 12/2012;
  • Fabian M Koehler, Wendelin J Stark
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    ABSTRACT: Graphene is a two-dimensional crystalline carbon allotrope that has fascinated researchers worldwide and has extended the interest in carbon structures such as fullerenes and nanotubes. In this Account, we use electrical characterization tools to study chemistry on supported graphene. These experiments elucidate the way covalently bound phenyl units can change graphene's physical properties. Can we use chemistry to control electronic properties of graphene? What can we learn from well-known carbon allotropes like fullerenes? The surfaces of fullerenes and graphene show distinct differences in reactivity because of the high strain of sp(2) carbon in fullerenes compared with the complete lack of strain in graphene. Diazonium chemistry provides a versatile tool for attaching phenyl units covalently to carbon to produce advanced materials and electronic components, but diazonium-based carbon chemistry is strongly influenced by strain. Although fullerenes are highly reactive, graphite (stacks of graphene) remains relatively inert. We chemically introduce n- and p-like doping patterns in two-dimensional graphene using photolithography and extend the ability to chemically control doping to the chemical design of conducting and insulating areas. Thereby we can shape graphene surfaces into functional electronic devices. This Account also describes multistep synthesis on graphene-coated nanoparticles and the introduction of various functional groups on graphene surfaces. Only few functional groups can be produced directly via diazonium chemistry. To overcome this issue, we used these functional groups as starting points for more demanding organic reactions. We covalently attached chelating agents, catalysts, or polymers on the carbon surface. These more complex reactions facilitate the design of electronic modifications, intergraphene connections, and anchors for polymer incorporation. Diazonium chemistry forms strong covalent bridges between graphene and other areas of chemistry.
    Accounts of Chemical Research 12/2012; · 20.83 Impact Factor
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    ABSTRACT: Living materials: Artificial biological niches are loaded with the penicillin-producing mold Penicillium chrysogenum. This living material consumes food through a nanoporous top layer and releases the antibiotic on-site. No reloading of the active compound is needed. Gram-positive bacteria were efficiently killed if nearby, whereas Gram-negative bacteria (control experiment, not sensitive to penicillin) were not affected.
    Angewandte Chemie International Edition 10/2012; · 11.34 Impact Factor
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    ABSTRACT: Graphene-coated cobalt nanoparticles surface-functionalized with benzylamine groups (CoC-NH(2) nanomagnets) were shown to effectively enrich analytes for surface-assisted laser desorption/ionization mass spectrometry (affinity SALDI-MS) analysis. These CoC-NH(2) nanomagnets are highly suited for use with affinity SALDI-MS because their mean diameter of 30 nm, high specific surface area of 15 m(2) g(-1), and high-strength saturation magnetization of 158 emu g(-1) led to efficient extraction of analytes by magnetic separation, which in turn enabled excellent SALDI-MS performance. Surface modification of CoC nanomagnets with benzylamine groups increased the yield of peptide ions and decreased fragmentation of benzylpyridinium ions, so-called "thermometer ions" formed through soft ionization. The CoC-NH(2) nanomagnets were used to extract perfluorooctanesulfonate from large volumes of aqueous solutions by magnetic separation, which was identified directly by SALDI-MS analysis with high sensitivity even at the sub-part-per-trillion level (∼0.1 ng/L). The applicability of CoC-NH(2) nanomagnets in conjunction with SALDI-MS for the enrichment and detection of pentachlorophenol, bisphenol A, and polyfluorinated compounds (PFCs) with varying chain length, which are environmentally significant compounds, as well as small drugs, was also evaluated.
    Analytical Chemistry 09/2012; · 5.70 Impact Factor
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    ABSTRACT: Polyethylene is widely used as a component of implants in medicine. Composites made of high-density polyethylene (HDPE) containing different amounts of amorphous calcium phosphate nanoparticles were investigated concerning their in vitro biomedical performance. The nanoparticles were produced by flame spray synthesis and extruded with HDPE, the latter complying with Food and Drug Administration regulations. Mechanical properties such as Young's modulus and contact angle as well as in vitro biomineralization of the nanocomposites hot-pressed into thin films were evaluated. The deposition of a hydroxyapatite layer occurred upon immersion in simulated body fluid. Additionally, a cell culture study with human mesenchymal stem cells for six weeks allowed a primary assessment of the cytocompatibility. Viability assays (alamarBlue and lactate dehydrogenase detection) proved the absence of cytotoxic effects of the scaffolds. Microscopic images after hematoxylin and eosin staining confirmed typical growth and morphology. A preliminary experiment analyzed the alkaline phosphatase activity after two weeks. These findings motivate further investigations on bioactive HDPE in bone tissue engineering.
    Biomedical Materials 09/2012; 7(5):054103. · 2.17 Impact Factor
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    ABSTRACT: BACKGROUND: Predominantly, studies of nanoparticle (NPs) toxicology in vitro are based upon the exposure of submerged cell cultures to particle suspensions. Such an approach however, does not reflect particle inhalation. As a more realistic simulation of such a scenario, efforts were made towards direct delivery of aerosols to air-liquid-interface cultivated cell cultures by the use of aerosol exposure systems.This study aims to provide a direct comparison of the effects of zinc oxide (ZnO) NPs when delivered as either an aerosol, or in suspension to a triple cell co-culture model of the epithelial airway barrier. To ensure dose--equivalence, ZnO-deposition was determined in each exposure scenario by atomic absorption spectroscopy. Biological endpoints being investigated after 4 or 24h incubation include cytotoxicity, total reduced glutathione, induction of antioxidative genes such as heme-oxygenase 1 (HO--1) as well as the release of the (pro)-inflammatory cytokine TNFalpha. RESULTS: Off-gasses released as by-product of flame ZnO synthesis caused a significant decrease of total reduced GSH and induced further the release of the cytokine TNFalpha, demonstrating the influence of the gas phase on aerosol toxicology. No direct effects could be attributed to ZnO particles. By performing suspension exposure to avoid the factor "flame-gases", particle specific effects become apparent. Other parameters such as LDH and HO--1 were not influenced by gaseous compounds: Following aerosol exposure, LDH levels appeared elevated at both timepoints and the HO--1 transcript correlated positively with deposited ZnO-dose. Under submerged conditions, the HO--1 induction scheme deviated for 4 and 24h and increased extracellular LDH was found following 24h exposure. CONCLUSION: In the current study, aerosol and suspension-exposure has been compared by exposing cell cultures to equivalent amounts of ZnO. Both exposure strategies differ fundamentally in their dose--response pattern. Additional differences can be found for the factor time: In the aerosol scenario, parameters tend to their maximum already after 4h of exposure, whereas under submerged conditions, effects appear most pronounced mainly after 24h. Aerosol exposure provides information about the synergistic interplay of gaseous and particulate phase of an aerosol in the context of inhalation toxicology. Exposure to suspensions represents a valuable complementary method and allows investigations on particle-associated toxicity by excluding all gas--derived effects.
    Particle and Fibre Toxicology 08/2012; 9(1):33. · 9.18 Impact Factor
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    ABSTRACT: For tissue engineering of critical size bone grafts, nanocomposites are getting more and more attractive due to their controllable physical and biological properties. We report in vitro and in vivo behaviour of an electrospun nanocomposite based on poly-lactic-co-glycolic acid and amorphous calcium phosphate nanoparticles (PLGA/a-CaP) seeded with human adipose-derived stem cells (ASC) compared to PLGA. Major findings were that cell attachment, three-dimensional ingrowth and proliferation were very good on both materials. Cell morphology changed from a spindle-shaped fibroblast-like form to a more roundish type when ASC were seeded on PLGA, while they retained their morphology on PLGA/a-CaP. Moreover, we found ASC differentiation to a phenotype committed towards osteogenesis when a-CaP nanoparticles were suspended in normal culture medium without any osteogenic supplements, which renders a-CaP nanoparticles an interesting osteoinductive component for the synthesis of other nanocomposites than PLGA/a-CaP. Finally, electrospun PLGA/a-CaP scaffold architecture is suitable for a rapid and homogenous vascularisation confirmed by a complete penetration by avian vessels from the chick chorioallantoic membrane (CAM) within one week.
    Injury 07/2012; 43(10):1689-97. · 1.93 Impact Factor
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    ABSTRACT: A simple structuring method for graphitic structures based on the catalytic properties of cerium oxide nanoparticles under oxidizing conditions is presented. Highly oriented pyrolytic graphite chips were impregnated with well-dispersed ceria nanoparticles and then treated at elevated temperatures for several hours. Oxidation activities on the particle surface appeared as crystallographically independent traces that were formed on the graphite and provide a simple method to manufacture nanogrooves at large scale. By altering treatment durations and temperatures, the optimal conditions and activity parameters of the particles were determined. A systematic AFM evaluation allowed formulating of a mechanism of the etching process. The findings provide a simple procedure for the patterning of graphitic structures, formation of nanogrooves and thereby a basic tool for material science with respect to the manufacturing of atmospheric nanofilters and ion-selective membranes.
    The Journal of Physical Chemistry C. 06/2012; 116(25):13693–13698.
  • ChemistryOpen. 06/2012; 1(3):125-9.
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    ABSTRACT: Magnetic nanoparticle dispersions are traditionally made from superparamagnetic materials since the absence of magnetic particle–particle attraction under normal conditions (no external field) easily allows preparation of stable dispersions. For inductive heating in medicinal chemistry or material science, however, the much higher magnetization of ferromagnetic metals over the currently used oxides is attractive. Traditional attempts to prepare stable dispersions of ferromagnetic particles, however, failed since the strong magnetic particle–particle attraction usually overcomes repulsive effects from surfactants or steric stabilizers (typically polymers). In the present work, we demonstrate how the direct, covalent attachment of highly charged polymers can circumvent stabilizer detachment and loss, and permits preparation of stable dispersions of ferromagnetic particles. More specifically, carbon-coated metal nanoparticles were covalently functionalized with positively charged polymer brushes via surface initiated atom transfer radical polymerization (SI-ATRP). Particle size distributions with an average diameter of 24 nm provided a ferromagnetic liquid with unprecedented stability in water over several months. The stability was discussed by comparison of the potentials of non-functionalized and modified nanomagnets within a modified Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. Measurements for inductive heating at different frequencies and various field strengths showed an average specific absorption rate of 360 W g−1. Altogether, this suggests that efficiently stabilized dispersions of ferromagnetic nanoparticles could be an alternative to superparamagnetic iron oxide particles in a number of applications.
    Journal of Materials Chemistry 05/2012; 22(24):12064-12071. · 5.97 Impact Factor
  • Alexander Schaetz, Martin Zeltner, Wendelin J. Stark
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    ABSTRACT: Carbon is anything but a new material, yet ubiquitously applicable for many catalytic transformations in modern organic chemistry. It is highly versatile, as it occurs as modifications abundantly available as 1–3D carbonaceous materials due to technical progress. In addition, materials such as activated charcoal, ordered mesoporous carbon (OMC), graphite and graphene (oxide), carbon nanotubes (CNTs), nanospheres (nano-onions, fullerenes), and many others are no “innocent” supports, as demonstrated by many recent publications within the revitalized field of “carbocatalysis”. By nature, carbon scaffolds offer a perfect link between nanoscaled matter and organic molecules, which makes them an ideal cornerstone for molecular catalysts. Apart from this inherent chemical significance, the physical properties (e.g., different conductivity) are equally important for the performance of heterogeneous or immobilized homogeneous catalysts. Careful selection of the carbon scaffold enables control of reactivity by tuning the electronic interactions of active sites with the support or among each other. Moreover, separation and recycling of “heterogenized” catalysts can be further improved by rendering carbon “magnetic”, that is, by incorporation of magnetic particles or by coating metal nanomagnets with graphene-like shells. Altogether, tuning the properties of carbon supports might lead to catalysts tailored not only in matters of reactivity (electron shuttle), but also to down-to-earth problems such as purification (magnetic separation and recycling). This critical review will highlight how far such concepts have already been implemented in the design of “heterogenized” catalysts and is meant to widen the perspectives where certain concepts have yet to be realized.
    ACS Catalysis 05/2012; 2(6):1267–1284. · 5.27 Impact Factor
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    ABSTRACT: A chemical approach to modify the electronic transport of graphene is investigated by detailed transport and Raman spectroscopy measurements on Hall bar shaped samples. The functionalization of graphene with nitrobenzene diazonium ions results in a strong p-doping of the graphene samples and only slightly lower mobilities. Comparing Raman and transport data taken after each functionalization step allowed the conclusion that two preferential reactions take place on the graphene surface. In the beginning a few nitrobenzene molecules are directly attached to the graphene atoms creating defects. Afterwards these act as seeds for a polymer like growth not directly connected to the graphene atoms. The effects of solvents were excluded by thorough control measurements.
    Nanoscale 05/2012; 4(12):3781-5. · 6.23 Impact Factor
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    ABSTRACT: More than 100 million tonnes of municipal solid waste are incinerated worldwide every year. However, little is known about the fate of nanomaterials during incineration, even though the presence of engineered nanoparticles in waste is expected to grow. Here, we show that cerium oxide nanoparticles introduced into a full-scale waste incineration plant bind loosely to solid residues from the combustion process and can be efficiently removed from flue gas using current filter technology. The nanoparticles were introduced either directly onto the waste before incineration or into the gas stream exiting the furnace of an incinerator that processes 200,000 tonnes of waste per year. Nanoparticles that attached to the surface of the solid residues did not become a fixed part of the residues and did not demonstrate any physical or chemical changes. Our observations show that although it is possible to incinerate waste without releasing nanoparticles into the atmosphere, the residues to which they bind eventually end up in landfills or recovered raw materials, confirming that there is a clear environmental need to develop degradable nanoparticles.
    Nature Nanotechnology 05/2012; 7(8):520-4. · 31.17 Impact Factor

Publication Stats

3k Citations
696.35 Total Impact Points

Institutions

  • 2011–2013
    • University of Zurich
      • Institut für Anästhesiologie
      Zürich, Zurich, Switzerland
  • 2008–2013
    • Universität Regensburg
      • Institute of Organic Chemistry
      Regensburg, Bavaria, Germany
  • 2012
    • Kansai University
      • Department of Chemistry and Materials Engineering
      Suita, Osaka-fu, Japan
  • 2002–2012
    • ETH Zurich
      • • Institute for Chemical and Bioengineering
      • • Institute of Process Engineering
      Zürich, ZH, Switzerland
    • Eawag: Das Wasserforschungs-Institut des ETH-Bereichs
      Duebendorf, Zurich, Switzerland
  • 2009–2010
    • Universität Bern
      • Institut für Anatomie
      Bern, BE, Switzerland
  • 2008–2010
    • Imperial College London
      • Department of Materials
      London, ENG, United Kingdom