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Combining Hydrophilic and Hydrophobic Materials in 3D Printing for Fabricating Microfluidic Devices with Spatial Wettability

2021, MƤnnel, Max J., Weigel, Niclas, Hauck, Nicolas, Heida, Thomas, Thiele, Julian

The fabrication of microfluidic flow cells via projection micro-stereolithography (PĪ¼SL) has excited researchers in recent years. However, due to the inherent process properties of most commercial PĪ¼SL, microfluidic devices are fabricated in a monolithic fashion with uniform material properties across a flow cell. Yet, the large surface-to-volume ratio in microfluidics demands to tailor microchannel surface propertiesā€”particularly in planar microchannel arrangementsā€”with spatial control and micron-scale resolution to form a desired flow profile, e.g., emulsion droplets. Here, the fabrication of planar microfluidic devices by PĪ¼SLbased 3D printing with spatial control over surface properties is presented. For that, homemade photopolymer formulations being either hydrophilic or hydrophobic are designed. Adding acrylic acid to a resin containing poly(ethylene glycol) diacrylate lowers the contact angle down to 0Ā° against water creating a superhydrophilic surface. By utilizing 1H,1H,2H,2H-perfluorodecyl acrylate, a photopolymer formulation allowing for 3D-printing a hydrophobic microchannel surface with a contact angle >120Ā° against water is obtained. Combining these two materials, microfluidic flow cells with spatially defined wettability are 3D-printed for emulsion formation. Finally, the resin vat of the commercial PĪ¼SL printer is switched during the printing process for fabricating multimaterial geometries, as exemplarily applied for realizing a hydrophobic-hydrophilic-hydrophobic device for forming O/W/O double emulsions.

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Mitigating Water Crossover by Crosslinked Coating of Cationā€Exchange Membranes for Brine Concentration

2021, Rommerskirchen, Alexandra, Roth, Hannah, Linnartz, Christian J., Egidi, Franziska, Kneppeck, Christian, Roghmans, Florian, Wessling, Matthias

Undesired water crossover through ion-exchange membranes is a significant limitation in electrically driven desalination processes. The effect of mitigating water crossover is twofold: 1) The desalination degree is less reduced due to the unwanted removal of water, and 2) the brine concentration is increased due to decreased dilution by an unwanted crossover of water molecules. Hence, water crossover limits the desalination and concentration efficiency of the processes, while the energy demand to achieve a certain level of desalination or concentration increases. This effect is especially pronounced when treating high salinity solutions, which goes hand in hand with the crossover of many ions through the ion-exchange membranes. A crosslinked coating for cation-exchange membranes (CEMs) is presented in this work, which can significantly mitigate such undesired water crossover. The efficacy is demonstrated using the flow-electrode capacitive deionization process applied for desalination and concentration of saline brines at feed concentrations of 60 and 120 g Lāˆ’1 NaCl. With just a single coated CEM, the water crossover was reduced by up to 54%.

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Microscopic Softening Mechanisms of an Ionic Liquid Additive in an Electrically Conductive Carbon-Silicone Composite

2022, Zhang, Long, Schmidt, Dominik S., GonzĆ”lezā€GarcĆ­a, Lola, Kraus, Tobias

The microstructural changes caused by the addition of the ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide to polydimethylsiloxane (PDMS) elastomer composites filled with carbon black (CB) are analyzed to explain the electrical, mechanical, rheological, and optical properties of IL-containing precursors and composites. Swelling experiments and optical analysis indicate a limited solubility of the IL in the PDMS matrix that reduces the cross-linking density of PDMS both globally and locally, which reduces the Young's moduli of the composites. A rheological analysis of the precursor mixture shows that the IL reduces the strength of carbonā€“carbon and carbonā€“PDMS interactions, thus lowering the fillerā€“matrix coupling and increasing the elongation at break. Electromechanical testing reveals a combination of reversible and irreversible piezoresistive responses that is consistent with the presence of IL at microscopic carbonā€“carbon interfaces, where it enables re-established electrical connections after stress release but reduces the absolute conductivity.

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A Photoreceptor-Based Hydrogel with Red Light-Responsive Reversible Sol-Gel Transition as Transient Cellular Matrix

2023, Hƶrner, Maximilian, Becker, Jan, Bohnert, Rebecca, BaƱos, Miguel, Jerezā€Longres, Carolina, MĆ¼hlhƤuser, Vanessa, HƤrrer, Daniel, Wong, Tin Wang, Meier, Matthias, Weber, Wilfried

Hydrogels with adjustable mechanical properties have been engineered as matrices for mammalian cells and allow the dynamic, mechano-responsive manipulation of cell fate and function. Recent research yields hydrogels, where biological photoreceptors translated optical signals into a reversible and adjustable change in hydrogel mechanics. While their initial application provides important insights into mechanobiology, broader implementation is limited by a small dynamic range of addressable stiffness. Herein, this limitation is overcome by developing a photoreceptor-based hydrogel with reversibly adjustable stiffness from ā‰ˆ800 Pa to the sol state. The hydrogel is based on star-shaped polyethylene glycol, functionalized with the red/far-red light photoreceptor phytochrome B (PhyB), or phytochrome-interacting factor 6 (PIF6). Upon illumination with red light, PhyB heterodimerizes with PIF6, thus crosslinking the polymers and resulting in gelation. However, upon illumination with far-red light, the proteins dissociate and trigger a complete gel-to-sol transition. The hydrogel's light-responsive mechanical properties are comprehensively characterized and it is applied as a reversible extracellular matrix for the spatiotemporally controlled deposition of mammalian cells within a microfluidic chip. It is anticipated that this technology will open new avenues for the site- and time-specific positioning of cells and will contribute to overcome spatial restrictions.

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Porous PEDOT:PSS Particles and their Application as Tunable Cell Culture Substrate

2021, Rauer, Sebastian Bernhard, Bell, Daniel Josef, Jain, Puja, Rahimi, Khosrow, Felder, Daniel, Linkhorst, John, Wessling, Matthias

Due to its biocompatibility, electrical conductivity, and tissue-like elasticity, poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) constitutes a highly promising material regarding the fabrication of smart cell culture substrates. However, until now, high-throughput synthesis of pure PEDOT:PSS geometries was restricted to flat sheets and fibers. In this publication, the first microfluidic process for the synthesis of spherical, highly porous, pure PEDOT:PSS particles of adjustable material properties is presented. The particles are synthesized by the generation of PEDOT:PSS emulsion droplets within a 1-octanol continuous phase and their subsequent coagulation and partial crystallization in an isopropanol (IPA)/sulfuric acid (SA) bath. The process allows to tailor central particle characteristics such as crystallinity, particle diameter, pore size as well as electrochemical and mechanical properties by simply adjusting the IPA:SA ratio during droplet coagulation. To demonstrate the applicability of PEDOT:PSS particles as potential cell culture substrate, cultivations of L929 mouse fibroblast cells and MRC-5 human fibroblast cells are conducted. Both cell lines present exponential growth on PEDOT:PSS particles and reach confluency with cell viabilities above 95 vol.% on culture day 9. Single cell analysis could moreover reveal that mechanotransduction and cell infiltration can be controlled by the adjustment of particle crystallinity.

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A Novel Large-Scale, Multilayer, and Facilely Aligned Micropatterning Technique Based on Flexible and Reusable SU-8 Shadow Masks

2019, Moradi, Somayeh, Bandari, Nooshin, Bandari, Vineeth Kumar, Zhu, Feng, Schmidt, Oliver G.

A simple method to fabricate flexible, mechanically robust, and reusable SU-8 shadow masks is demonstrated. This shadow mask technology has high pattern flexibility as various shapes with different dimensions can be created. The fabricated shadow masks are characterized in terms of the resolution, reusability, and capability of multilayer surface micropatterning. Fabrication of a new plastic photomask for the exposure process simplifies the shadow mask fabrication process and results in higher resolution in the shadow mask structures compared to the commercial chromium photomasks. For the multilayer surface micropatterning technology, a simple and fast alignment technique based on SU-8 pillars and without usage of any microscopic tools is reported. This unique method leads to a less complicated alignment process with the alignment accuracy of ā‰ˆ2 Āµm. The proposed shadow mask technology can be easily employed for wafer-scale micropatterning process. The capability of fabricated SU-8 shadow masks in micropatterning on polymer thin films is evaluated by fabricating metallic contacts on poly(3,4-ethylenedioxythiophene) samples and electrical characterization. Ā© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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Porous PVDF Monoliths with Templated Geometry

2021, Djeljadini, Suzana, Bongartz, Patrick, Alders, Michael, Hartmann, Nils, Oing, Alexander, Cornelissen, Christian, Hesselmann, Felix, Arens, Jutta, Steinseifer, Ulrich, Linkhorst, John, Wessling, Matthias

Additive manufacturing of complex porous polymer geometries is a new field of advanced materials processing. Such new geometries can be used to fabricate porous polymer monoliths serving as a support for other material functions. Here, a novel fabrication technology to manufacture tailored 3D porous monoliths via additive manufacturing and templating is presented. The method is based on replicating a 3D-printed mold with a polymer solution of polyvinylidenfluorid-triethyl phosphate (PVDF-TEP) and induce phase separation of the polymer solution subsequently. In a second step, the mold is removed without affecting the porous PVDF phase. As a result, porous monoliths with a templated 3D architecture are successfully fabricated. The manufacturing process is successfully applied to complex structures and can be applied to any conceivable geometry. Coating the porous 3D monoliths with another PVDF solution allows applying a skin layer yielding an asymmetric membrane monolith. As a showcase, a polydimethylsiloxane coating even leads to a smooth and dense layer of micrometer size. The methodology enables a new generation of complex porous polymer monoliths with tailored surface coatings. For the combination of poly(dimethylsiloxane) on a porous support, gas/liquid mass transfer is used in blood oxygenation with reduced diffusion limitation is within reach.

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Elastomeric Optical Waveguides by Extrusion Printing

2022, Feng, Jun, Zheng, Yijun, Jiang, Qiyang, Włodarczykā€Biegun, Małgorzata K., Pearson, Samuel, del Campo, ArĆ”nzazu

Advances in optogenetics and the increasing use of implantable devices for therapies and health monitoring are driving demand for compliant, biocompatible optical waveguides and scalable methods for their manufacture. Molding, thermal drawing, and dip-coating are the most prevalent approaches in recent literature. Here the authors demonstrate that extrusion printing at room temperature can be used for continuous fabrication of compliant optical waveguides with polydimethylsiloxane (PDMS) core and crosslinked Pluronic F127-diacrylate (Pluronic-DA) cladding. The optical fibers are printed from fluid precursor inks and stabilized by physical interactions and photoinitiated crosslinking in the Pluronic-DA. The printed fibers show optical loss values of 0.13ā€“0.34 dB cmā€“1 in air and tissue within the wavelength range of 405ā€“520 nm. The fibers have a Young's Modulus (Pluronic cladding) of 150 kPa and can be stretched to more than 5 times their length. The optical loss of the fibers shows little variation with extension. This work demonstrates how printing can simplify the fabrication of compliant and stretchable devices from materials approved for clinical use. These can be of interest for optogenetic or photopharmacology applications in extensible tissues, like muscles or heart.

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3Dā€Printed Bioreactor with Integrated Impedance Spectroscopy for Cell Barrier Monitoring

2021, Linz, Georg, Rauer, Sebastian Bernhard, Kuhn, Yasmin, Wennemaring, Simon, Siedler, Laura, Singh, Smriti, Wessling, Matthias

Cell culture experiments often suffer from limited commercial availability of laboratory-scale bioreactors, which allow experiments to be conducted under flow conditions and additional online monitoring techniques. A novel 3D-printed bioreactor with a homogeneously distributed flow field enabling epithelial cell culture experiments and online barrier monitoring by integrated electrodes through electrical impedance spectroscopy (EIS) is presented. Transparent and conductive indium tin oxide glass as current-injecting electrodes allows direct visualization of the cells, while measuring EIS simultaneously. The bioreactor's design considers the importance of a homogeneous electric field by placing the voltage pick-up electrodes in the electrical field. The device's functionality is demonstrated by the cultivation of the epithelial cell line Caco-2 under continuous flow and monitoring of the cell layer by online EIS. The collected EIS data were fitted by an equivalent electric circuit, resulting in the cell layer's resistance and capacitance. This data is used to monitor the cell layer's reaction to ethylene glycol-bis-(2-aminoethyl ether)-N,N,Nā€²,Nā€²-tetraacetic acid and forskolin. These two model substances show the power of impedance spectroscopy as a non-invasive way to characterize cell barriers. In addition, the bioreactor design is available as a print-ready file in the Appendix, enabling its use for other scientific institutions.

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Silicon-Based Integrated Label-Free Optofluidic Biosensors: Latest Advances and Roadmap

2020, Wang, Jiawei, Medina Sanchez, Mariana, Yin, Yin, Herzer, Raffael, Ma, Libo, Schmidt, Oliver G.

By virtue of the well-developed micro- and nanofabrication technologies and rapidly progressing surface functionalization strategies, silicon-based devices have been widely recognized as a highly promising platform for the next-generation lab-on-a-chip bioanalytical systems with a great potential for point-of-care medical diagnostics. Herein, an overview of the latest advances in silicon-based integrated optofluidic label-free biosensing technologies relying on the efficient interactions between the evanescent light field at the functionalized surface and specifically bound analytes is presented. State-of-the-art technologies demonstrating label-free evanescent wave-based biomarker detection mainly encompass three device configurations, including on-chip waveguide-based interferometers, microring resonators, and photonic-crystal-based cavities. Moreover, up-to-date strategies for elevating the sensitivities and also simplifying the sensing processes are discussed. Emerging laboratory prototypes with advanced integration and packaging schemes incorporating automatic microfluidic components or on-chip optoelectronic devices lead to one significant step forward in real applications of decentralized diagnostics. Besides, particular attention is paid to currently commercialized label-free optical bioanalytical models on the market. Finally, the prospects are elaborated with several research routes toward chip-scale, low-cost, highly sensitive, multi-functional, and user-friendly bioanalytical systems benefiting to global healthcare. Ā© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim