2015, Hess, Samuel C., Kohll, A. Xavier, Raso, Renzo, Schumacher, Christoph M., Grass, Robert N., Stark, Wendelin J.

A novel solvent-evaporation-based process that exploits template-particle stabilized bicontinuous emulsions for the formation of previously unreached membrane morphologies is reported in this article. Porous membranes have a wide range of applications spanning from water filtration, pharmaceutical purification, and battery separators to scaffolds for tissue engineering. Different situations require different membrane morphologies including various pore sizes and pore gradients. However, most of the previously reported membrane preparation procedures are restricted to specific morphologies and morphology alterations require an extensive optimization process. The tertiary system presented in this article, which consists of a poly(ether sulfone)/dimethylacetamide (PES/DMAc) solution, glycerol, and ZnO-nanoparticles, allows simple and exact tuning of pore diameters ranging from sub-20 nm, up to 100 nm. At the same time, the pore size gradient is controlled from 0 up to 840%/μm yielding extreme asymmetry. In addition to structural analysis, water flux rates of over 5600 L m–2 h–1 are measured for membranes retaining 45 nm silica beads.

2014, Schneider, Elia M., Raso, Renzo, Hofer, Corinne J., Zeltner, Martin, Stettler, Robert D., Hess, Samuel C., Grass, Robert N., Stark, Wendelin J.

Workup in organic synthesis can be very time-consuming, particularly when using reagents with both a solubility similar to that of the desired products and a tendency not to crystallize. In this respect, reactions involving organic bases would strongly benefit from a tremendously simplified separation process. Therefore, we synthesized a derivative of the superbasic proton sponge 1,8-bis(dimethylamino)naphthalene (DMAN) and covalently linked it to the strongest currently available nanomagnets based on carbon-coated cobalt metal nanoparticles. The immobilized magnetic superbase reagent was tested in Knoevenagel- and Claisen-Schmidt-type condensations and showed conversions of up to 99%. High yields of up to 97% isolated product could be obtained by simple recrystallization without using column chromatography. Recycling the catalyst was simple and fast with an insignificant decrease in catalytic activity.

2014, Raso, Renzo, Stoessel, P. R., Stark, W. J.

Removal of volatile organic compounds (VOC) and indoor air quality regulation through adsorbers required exchange or maintenance of active materials. In this work, we combine well known VOC adsorbers with oxidation catalysts as intimate particulate mixtures. We demonstrate how typical VOC can subsequently adsorb on such mixed material fixed beds (usually days to weeks; the common state of the system, adsorption phase) using small organic compounds (diethyl ether, triethylamine), monoterpenes such as linalool and limonene, and hexanoic acid. Occasional regeneration runs through heat up of the fixed bed results in simultaneous desorption and oxidation of the accumulated VOC, thus regenerating full adsorption capacity for a next adsorption phase. We investigated both small pore zeolites (H-ZSM-5) and larger pore zeolites (13X) and found a distinct interplay between the pore size and the type of VOC. Thermogravimetry coupled with mass spectroscopy was used to quantitatively study the effects of mixing composition and temperature on adsorber performance and regeneration. The here investigated bi-functional systems combine very low maintenance costs and materials requirement with low air flow and exchange costs, thus suggesting mixed (two-functional) bed adsorbers with catalytic function as sustainable alternatives to currently used single use systems based on granulated zeolites or activated carbon. In this work we show the ability of zeolite/cerium oxide physical mixtures to adsorb and capture different classes of VOC at room temperature and release them for oxidation at higher temperatures in a regenerative and sustainable process.

2013, Zeltner, Martin, Toedtli, Laura M., Hild, Nora, Fuhrer, Roland, Rossier, Michaël, Gerber, Lukas C., Raso, Renzo, Grass, Robert N., Stark, Wendelin J.

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 (preselection, washing, and magnetic separation of fibers). Preseparation of printed from nonprinted scraps of paper is feasible and reduces the paper mass which has to be fed into a deinking process. A consecutive 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 nonmagnetic 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.

2015, Mora, Carlos A., Herzog, Antoine F., Raso, Renzo, Stark, Wendelin J.

The increasing molecular understanding of many diseases today permits the development of new diagnostic methods. However, few easy-to-handle and inexpensive tools exist for common diseases such as food disorders. Here we present a living material based analytical sensor (LiMBAS) containing genetically modified bacteria (Escherichia coli) immobilized and protected in a thin layer between a nanoporous and support polymer membrane for a facile quantification of disease-relevant oligosaccharides. The bacteria were engineered to fluoresce in response to the analyte to reveal its diffusion behavior when using a blue-light source and optical filter. We demonstrated that the diffusion zone diameter was related semi-logarithmically to the analyte concentration. LiMBAS could accurately quantify lactose or galactose in undiluted food samples and was able to measure food intolerance relevant concentrations in the range of 1-1000 mM requiring a sample volume of 1-10 μL. LiMBAS was storable for at least seven days without losing functionality at 4 °C. A wide range of genetic tools for E. coli are readily available thus allowing the reprogramming of the material to serve as biosensor for other molecules. In combination with smartphones, an automated diagnostic analysis becomes feasible which would also allow untrained people to use LiMBAS.

2014, Raso, Renzo, Stepuk, A., Mohn, D., Paunescu, D., Koehler, F.M., Stark, W.J.

Indoor odor management currently relies on energy-intensive high air exchange rates, or, more sustainable, on single use volatile organic compounds (VOC) adsorbers or ozonisation. This study investigates a more sustainable, multi-cycle use of an odor adsorber system that combines concepts from catalytic oxidation and air cleaning. Both pure and sodium doped, nanostructured CeO2 were tested as adsorber material for high volume removal of odorous compounds from air. As a representative compound for unpleasant odors, hexanoic acid (HA) was used. After air cleaning on fixed beds of CeO2 or Na/CeO2, both hexanoic acid loaded adsorber materials were heated under air and displayed considerable oxidation activity at 191 °C and 263 °C, respectively. Mass spectroscopy was used to confirm that no hexanoic acid desorbed during combustion. Cerium oxide showed an adsorber efficiency of ≥96.5% over a period of 60 h (Cin = 0.044 mg/L, gas hourly space velocity, GHSV = 440 h−1) and sodium doped cerium oxide adsorbed ≥97% for over 90 h (Cin = 0.056 mg/L, GHSV = 1100 h−1). CeO2 was regenerated at 220 °C in air and could be successfully re-used as adsorber without noticeable loss in performance. The study demonstrates that CeO2 has most promising properties for application as re-usable air cleaner due to its very good ability for adsorption even at highly dilute conditions (ppm-level) using a representative acidic test compound with rancid and sweaty odor. Sodium as a basic dopant further improved the adsorption of hexanoic acid but requires a higher regeneration temperature.

2013-05-13, Koehler, F. M., Raso, Renzo, Grass, R. N., Stark, W. J.

Immunoassays are used for detecting protein targets for various applications. Here, a modification of immunoassays to allow a purely electrical detection of the target protein concentration is shown. The modification comprises a β-D-glucosidase as reporter enzyme and a cyanogenic glycoside as substrate. The enzymatic reaction produces cyanide in small quantities. For electrical detection of the cyanide, a novel sensor is developed, based on a gold micro wire. The cyanide dissolves the gold wire and changes the electrical resistance of the wire. Monitoring the resistance change allows a quantitative measurement of the target human C-reactive protein (an inflammatory marker) in blood plasma in the physiological relevant concentration range.

2014, Stoessel, Philipp R., Raso, Renzo, Kaufmann, Tim, Grass, Robert N., Stark, Wendelin J.

AbstractGelatin is an exceptional and versatile biopolymer with applications in various industries. As the most abundant structural protein in vertebrates it is available in megaton quantities. On these grounds, it would be a plausible substitute for synthetic polymers. Gelatin processing into fibers seems promising as continuous protein filaments do not have the limitation of natural fibers, i.e., small staple fiber length. Instead of spinning an aqueous gelatin solution, a protein precipitate from a phase‐separated system is used. Robust wet spinning with subsequent fiber drawing allows production of a gelatin filament with similar mechanical properties as sheep wool. Different degrees of fiber drawing and addition of plasticizers enable to tailor the mechanical and thermal fiber properties and demonstrate the versatility of the proposed spinning process.

2014, Raso, Renzo, Zeltner, Martin, Stark, Wendelin J.

In this study, we demonstrate a two-step process where activated carbon based air purifier systems can be regenerated in situ and eliminate volatile organic compounds (VOCs) from indoor air in an energy efficient way. A carbon based adsorber was combined in series with a CeO2/TiO2 oxidative catalyst for total oxidation of the previously adsorbed and periodically released volatile organic compounds during regeneration runs. We investigated the adsorption and desorption behavior of five different VOCs (diethyl ether, limonene, linalool, hexanoic acid, triethylamine and n-decane) with thermogravimetric measurements, mass spectrometry and elemental analysis. Cyclic loading and regeneration experiments were carried out with selected VOCs (limonene, linalool and n-decane) for testing regeneration at elevated temperature. We showed that in situ thermal regeneration and subsequent oxidation of released VOC is a sustainable and easy applicable technology for indoor air purification. This two-step approach allows energy saving as the VOCs are eliminated discontinuously (enriching VOCs; periodic catalytic combustion), and is of high environmental and economic interest, as much less maintenance services are required.

2013-03, Bühler, Theodor, Zurbriggen, Roger, Pieles, Uwe, Huwiler, L., Raso, Renzo

A freshly applied mortar layer is exposed to the environment and forms a skin in the following minutes. Skinning changes significantly the surface properties and therefore limits application procedures. In the case of a tile adhesive, the skin that is formed before the tile is embedded can reduce resulting adhesion properties. Reflected light microscopy reveals that surface “lakes” disappear between 5 and 10 min after mortar application and DRIFTS (diffuse reflectance infrared Fourier transformed spectroscopy) indicates that films of organics and carbonates form simultaneously at the surface.