Ink transport modelling in Dip-Pen Nanolithography and Polymer Pen Lithography

Dip-pen nanolithography (DPN) and Polymer pen lithography (PPL) are powerful lithography techniques being able to pattern a wide range of inks. Transport and surface spreading depend on the ink physicochemical properties, defining its diffusive and fluid character. Structure assembly on surface arises from a balance between the entanglement of the ink itself and the interaction with the substrate. According to the transport characteristics, different models have been proposed. In this article we review the common types of inks employed for patterning, the particular physicochemical characteristics that make them flow following different dynamics as well as the corresponding transport mechanisms and models that describe them

FluidFM-Based Fabrication of Nanopatterns: Promising Surfaces for Platelet Storage Application

Platelets are cell fragments from megakaryocytes devoid of the cell nucleus. They are highly sensitive and easily activated by nonphysiological surfaces. Activated platelets have an intrinsic mechanism to release various proteins that participate in multiple pathways, initiating the platelet activation cascade. Surface-induced platelet activation is a challenge encountered during platelet storage, which eventually leads to aggregation of platelets and can thereby result in the degradation of the platelet concentrates. We have previously reported that surface-induced platelet activation can be minimized by either modifying their contact surfaces with polymers or introducing nanogroove patterns underneath the platelets. Here, we investigated the response of platelets to various nanotopographical surfaces printed using fluidic force microscopy (FluidFM). We found that the hemispherical array (grid) and hexagonal tile (hive) structures caused a reduction of surface stiffness, which leads to an inhibition of platelet adhesion. Our results reveal that nanopatterns enable the inhibition of platelet activation on surfaces, thus implying that development in nanotexturing of storage bags can extend the lifetime of platelet concentrates

Computergestützte Zahnbogenformberechnungen zur Verbesserung der Ergebnisqualität in der Orthodontie

Die drei Zielsetzungen dieser Arbeit sind erstens ein umfassender Review internationaler Literatur zum Thema "Humane Zahnbogenformen", zweitens die Entwicklung einer Klassifikation der mathematischen Modelle zur computergestützten Berechnung von Zahnbogenformen mit einer Systematik als Entscheidungshilfe für die Auswahl mathematischer Formeln bei spezifischen klinischen und wissenschaftlichen Fragestellungen; als drittes umfasst diese Arbeit die Konzeption, einschließlich der Programmierung und Pilotierung des Computerprogramms "Dental Archform Manager (DAM)", welches dem klinisch tätigen Fachzahnarzt für Kieferorthopädie ein leistungsfähiges digitales Werkzeug zur Dokumentation und virtuellen Planung der in der Multibracketbehandlung therapeutisch relevanten Zahnbogenformen zur Verfügung stellt. Gleichzeitig wurden die Bogenformen führender Hersteller konfektionierter Behandlungsbögen im Hinblick auf die Verwendung innerhalb dieser Software analysiert und pragmatisch gruppiert

Surface structuring by bottom-up and top-down approaches

In dieser Arbeit wurden neue Strategien zur Strukturierung von Oberflächen mittels verschiedener „top-down“ und „bottom-up“ Methoden entwickelt. Die zentrale „bottom-up“ Methode war dabei die selbstorganisierte Musterbildung von Phospholipiden bei Langmuir-Blodgett Transfer. Der Einfluss von Substratbehandlungen und Feuchtigkeit auf die Musterbildung wurde untersucht, sowie die Interaktion der Muster mit vorgegebenen Strukturen auf dem Substrat. Nach Untersuchungen zur Auswirkung von Beimischungen wurden durch den Transfer eines DPPC/Initiator-Mischfilms strukturierte Polymerbürsten erzeugt. Die mechanischen Eigenschaften von Polymerbürsten unter AFM Lithographie sind denen von herkömmlichen Polymerfilmen überlegen und ermöglichen eine nachfolgende selektive Ablagerung von chemischen Stoffen. Im letzten Teil werden Molekulardynamiksimulationen dazu genutzt die molekularen Mechanismen hinter der selektiven Ablagerung organischer Moleküle auf DPPC-Templatstrukturen zu klären.New strategies for the structuring of surfaces utilizing different “top-down” and “bottom-up” methods were developed. The central “bottom-up” element was the self-organized pattern formation in monolayers of phospholipids during Langmuir-Blodgett transfer onto solid substrates. The influence of substrate treatment and humidity onto the pattern formation was explored as well as the interaction of the pattern with prestructures on the substrate. The influence of admixing other compounds was studied and structured polymer brushes were obtained by transfer of a mixed DPPC/initiator film. The mechanical properties of polymer brushes were found to be superior to spin-coated polymers under AFM lithography and subsequent selective deposition of dyes was demonstrated on the structured samples. In the last part molecular dynamics simulations were used to elucidate the molecular mechanisms behind the selective deposition of organic molecules onto templates fabricated by LB transfer of DPPC

How Does Chemistry Influence Liquid Wettability on Liquid-Infused Porous Surface?

Design of Nepenthes pitcher-inspired slippery liquid-infused porous surface (SLIPS) appeared as an important avenue for various potential and practically relevant applications. In general, hydrophobic base layers were infused with selected liquid lubricants for developing chemically inert SLIPS. Here, in this current study, an inherently hydrophilic (soaked beaded water droplet with ∼20° within a couple of minutes), porous and thick (above 200 μm) polymeric coating, loaded with readily chemically reactive acrylate moieties yielded a chemically reactive SLIPS, where residual acrylate groups in the synthesized hydrophilic and porous interface rendered stability to the infused lubricants. The chemically reactive SLIPS is capable of reacting with the solution of primary amine-containing nucleophiles in organic solvent through 1,4-conjugate addition reaction, both in the presence (referred as “in situ” modification) and absence (denoted as pre-modification) of lubricated phase in the porous polymeric coating. Such amine reactive SLIPS was further extended to (1) examining the impact of different chemical modifications on the performance of SLIPS and (2) developing a spatially selective and “in situ” postmodification with primary amine-containing nucleophiles through 1,4-conjugate addition reaction. Moreover, the chemically reactive SLIPS was capable of sustaining various physical abrasions and prolonged (minimum 10 days) exposure to complex and harsh aqueous phases, where infused lubricants protect the residual acrylate groups from harsh aqueous exposures. Such, principle will be certainly useful for spatially selective covalent immobilization of water-insoluble functional molecules/polymers directly from organic solvents, which would be of potential interest for various applied and fundamental contexts

Enhanced Stability of Lipid Structures by Dip-Pen Nanolithography on Block-Type MPC Copolymer

Biomimetic lipid membranes on solid supports have been used in a plethora of applications, including as biosensors, in research on membrane proteins or as interfaces in cell experiments. For many of these applications, structured lipid membranes, e.g., in the form of arrays with features of different functionality, are highly desired. The stability of these features on a given substrate during storage and in incubation steps is key, while at the same time the substrate ideally should also exhibit antifouling properties. Here, we describe the highly beneficial properties of a 2-methacryloyloxyethyl phosphorylcholine (MPC) copolymer for the stability of supported lipid membrane structures generated by dip-pen nanolithography with phospholipids (L-DPN). The MPC copolymer substrates allow for more stable and higher membrane stack structures in comparison to other hydrophilic substrates, like glass or silicon oxide surfaces. The structures remain highly stable under immersion in liquid and subsequent incubation and washing steps. This allows multiplexed functionalization of lipid arrays with antibodies via microchannel cantilever spotting (µCS), without the need of orthogonal binding tags for each antibody type. The combined properties of the MPC copolymer substrate demonstrate a great potential for lipid-based biomedical sensing and diagnostic platforms

A supramolecular cucurbit[8]uril-based rotaxane chemosensor for the optical tryptophan detection in human serum and urine

Sensing small biomolecules in biofluids remains challenging for many optical chemosensors based on supramolecular host-guest interactions due to adverse interplays with salts, proteins, and other biofluid components. Instead of following the established strategy of developing alternative synthetic binders with improved affinities and selectivity, we report a molecular engineering approach that addresses this biofluid challenge. Here we introduce a cucurbit[8]uril-based rotaxane chemosensor feasible for sensing the health-relevant biomarker tryptophan at physiologically relevant concentrations, even in protein- and lipid-containing human blood serum and urine. Moreover, this chemosensor enables emission-based high-throughput screening in a microwell plate format and can be used for label-free enzymatic reaction monitoring and chirality sensing. Printed sensor chips with surface-immobilized rotaxane-microarrays are used for fluorescence microscopy imaging of tryptophan. Our system overcomes the limitations of current supramolecular host-guest chemosensors and will foster future applications of supramolecular sensors for molecular diagnostics

Cucurbit[n]uril-Immobilized Sensor Arrays for Indicator-Displacement Assays of Small Bioactive Metabolites

The patterned immobilization of chemosensors into nano/microarrays has often boosted utilization in diagnostics and environmental sensing applications. While this is a standard approach for biosensors, e.g., with antibodies, other proteins, and DNA, arraying is not yet adopted widely for supramolecular chemosensors which are still predominantly used in solution systems. Here we introduce the patterned immobilization of cucurbit[n]urils (CBn) into multiplexed microarrays and elucidate their prospects for the advancement of surface-bound indicator-displacement assays to detect small molecule analytes. The microarrays were generated by microchannel cantilever spotting of functionalized CBn and subsequent self-assembly of the corresponding indicator dyes from solution. Enhanced sensitivity of surface-bound microarrays was established in demonstrations with small bioactive metabolites (spermine, amantadine, and cadaverine) compared to bulk assays. Furthermore, the integration of the CBn/indicator microarrays into microfluidic channels provides an efficient route for real-time monitoring of the sensing process, allows easier handling, and reduces need for analyte volume. The concept was further extended to differential sensing of analytes on diplex or multiplex CBn/indicator microarrays, opening up a route for multicomponent sensing of small molecule analytes in complex liquids

Integration of Biofunctional Molecules into 3D-Printed Polymeric Micro-/Nanostructures

Three-dimensional printing at the micro-/nanoscale represents a new challenge in research and development to achieve direct printing down to nanometre-sized objects. Here, FluidFM, a combination of microfluidics with atomic force microscopy, offers attractive options to fabricate hierarchical polymer structures at different scales. However, little is known about the effect of the substrate on the printed structures and the integration of (bio)functional groups into the polymer inks. In this study, we printed micro-/nanostructures on surfaces with different wetting properties, and integrated molecules with different functional groups (rhodamine as a fluorescent label and biotin as a binding tag for proteins) into the base polymer ink. The substrate wetting properties strongly affected the printing results, in that the lateral feature sizes increased with increasing substrate hydrophilicity. Overall, ink modification only caused minor changes in the stiffness of the printed structures. This shows the generality of the approach, as significant changes in the mechanical properties on chemical functionalization could be confounders in bioapplications. The retained functionality of the obtained structures after UV curing was demonstrated by selective binding of streptavidin to the printed structures. The ability to incorporate binding tags to achieve specific interactions between relevant proteins and the fabricated micro-/nanostructures, without compromising the mechanical properties, paves a way for numerous bio and sensing applications. Additional flexibility is obtained by tuning the substrate properties for feature size control, and the option to obtain functionalized printed structures without post-processing procedures will contribute to the development of 3D printing for biological applications, using FluidFM and similar dispensing techniques