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Gas-Phase Fluorination on PLA Improves Cell Adhesion and Spreading
2020, Schroepfer, Michaela, Junghans, Frauke, Voigt, Diana, Meyer, Michael, Breier, Anette, Schulze-Tanzil, Gundula, Prade, Ina
For the regeneration or creation of functional tissues, biodegradable biomaterials including polylactic acid (PLA) are widely preferred. Modifications of the material surface are quite common to improve cell-material interactions and thereby support the biological outcome. Typical approaches include a wet chemical treatment with mostly hazardous substances or a functionalization with plasma. In the present study, gas-phase fluorination was applied to functionalize the PLA surfaces in a simple and one-step process. The biological response including biocompatibility, cell adhesion, cell spreading, and proliferation was analyzed in cell culture experiments with fibroblasts L929 and correlated with changes in the surface properties. Surface characterization methods including surface energy and isoelectric point measurements, X-ray photoelectron spectroscopy, and atomic force microscopy were applied to identify the effects of fluorination on PLA. Gas-phase fluorination causes the formation of C-F bonds in the PLA backbone, which induce a shift to a more hydrophilic and polar surface. The slightly negatively charged surface dramatically improves cell adhesion and spreading of cells on the PLA even with low fluorine content. The results indicate that this improved biological response is protein-but not integrin-dependent. Gas-phase fluorination is therefore an efficient technique to improve cellular response to biomaterial surfaces without losing cytocompatibility. Copyright © 2020 American Chemical Society.
Nanoscopic tip sensors fabricated by gas phase etching of optical glass fibers
2012, Bierlich, J., Kobelke, J., Brand, D., Kirsch, K., Dellith, J., Bartelt, H.
Silica-based fiber tips are used in a variety of spectroscopic, micro- or nano-scopic optical sensor applications and photonic micro-devices. The miniaturization of optical sensor systems and the technical implementation using optical fibers can provide new sensor designs with improved properties and functionality for new applications. The selective-etching of specifically doped silica fibers is a promising method in order to form complex photonic micro structures at the end or within fibers such as tips and cavities in various shapes useful for the all-fiber sensor and imaging applications. In the present study, we investigated the preparation of geometrically predefined, nanoscaled fiber tips by taking advantage of the dopant concentration profiles of highly doped step-index fibers. For this purpose, a gas phase etching process using hydrofluoric acid (HF) vapor was applied. The shaping of the fiber tips was based on very different etching rates as a result of the doping characteristics of specific optical fibers. Technological studies on the influence of the etching gas atmosphere on the temporal tip shaping and the final geometry were performed using undoped and doped silica fibers. The influence of the doping characteristics was investigated in phosphorus-, germanium-, fluorine- and boron-doped glass fibers. Narrow exposed as well as protected internal fiber tips in various shapes and tip radiuses down to less than 15 nm were achieved and characterized geometrically and topologically. For investigations into surface plasmon resonance effects, the fiber tips were coated with nanometer-sized silver layers by means of vapour deposition and finally subjected to an annealing treatment.
Tunable charge transfer properties in metal-phthalocyanine heterojunctions
2016, Siles, P.F., Hahn, T., Salvan, G., Knupfer, M., Zhu, F., Zahn, D.R.T., Schmidt, O.G.
Organic materials such as phthalocyanine-based systems present a great potential for organic device applications due to the possibility of integrating films of different organic materials to create organic heterostructures which combine the electrical capabilities of each material. This opens the possibility to precisely engineer and tune new electrical properties. In particular, similar transition metal phthalocyanines demonstrate hybridization and charge transfer properties which could lead to interesting physical phenomena. Although, when considering device dimensions, a better understanding and control of the tuning of the transport properties still remain in the focus of research. Here, by employing conductive atomic force microscopy techniques, we provide an insight about the nanoscale electrical properties and transport mechanisms of MnPc and fluorinated phthalocyanines such as F16CuPc and F16CoPc. We report a transition from typical diode-like transport mechanisms for pure MnPc thin films to space-charge-limited current transport regime (SCLC) for Pc-based heterostructures. The controlled addition of fluorinated phthalocyanine also provides highly uniform and symmetric-polarized transport characteristics with conductance enhancements up to two orders of magnitude depending on the polarization. We present a method to spatially map the mobility of the MnPc/F16CuPc structures with a nanoscale resolution and provide theoretical calculations to support our experimental findings. This well-controlled nanoscale tuning of the electrical properties for metal transition phthalocyanine junctions stands as key step for future phthalocyanine-based electronic devices, where the low dimension charge transfer, mediated by transition metal atoms could be intrinsically linked to a transfer of magnetic moment or spin.
Diffusion and interface effects during preparation of all-solid microstructured fibers
2014, Kobelke, J., Bierlich, J., Wondraczek, K., Aichele, C., Pan, Z., Unger, S., Schuster, K., Bartelt, H.
All-solid microstructured optical fibers (MOF) allow the realization of very flexible optical waveguide designs. They are prepared by stacking of doped silica rods or canes in complex arrangements. Typical dopants in silica matrices are germanium and phosphorus to increase the refractive index (RI), or boron and fluorine to decrease the RI. However, the direct interface contact of stacking elements often causes interrelated chemical reactions or evaporation during thermal processing. The obtained fiber structures after the final drawing step thus tend to deviate from the targeted structure risking degrading their favored optical functionality. Dopant profiles and design parameters(e.g., the RI homogeneity of the cladding) are controlled by the combination of diffusion and equilibrium conditions of evaporation reactions. We show simulation results of diffusion and thermal dissociation in germanium and fluorine doped silica rod arrangements according to the monitored geometrical disturbances in stretched canes or drawn fibers. The paper indicates geometrical limits of dopant structures in sub-μm-level depending on the dopant concentration and the thermal conditions during the drawing process. The presented results thus enable an optimized planning of the preform parameters avoiding unwanted alterations in dopant concentration profiles or in design parameters encountered during the drawing process.
2 MW peak power generation in fluorine co-doped Yb fiber prepared by powder-sinter technology
2020, Leich, Martin, Kalide, André, Eschrich, Tina, Lorenz, Adrian, Lorenz, Martin, Wondraczek, Katrin, Schönfeld, Dörte, Langner, Andreas, Schötz, Gerhard, Jäger, Matthias
We report on the first, to the best of our knowledge, implementation of a fluorine co-doped large-mode-area REPUSIL fiber for high peak power amplification in an ultrashort-pulse master oscillator power amplifier. The core material of the investigated step-index fiber with high Yb-doping level, 52 µm core and high core-to-clad ratio of 1:4.2 was fabricated by means of the REPUSIL powder-sinter technology. The core numerical aperture was adjusted by fluorine codoping to 0.088. For achieving high beam quality and for ensuring a monolithic seed path, the LMA fiber is locally tapered. We demonstrate an Yb fiber amplifier with near-diffraction-limited beam quality of M2 = 1.3, which remains constant up to a peak power of 2 MW. This is a record for a tapered single core fiber. © 2020 Optical Society of America
Maintenance of Ligament Homeostasis of Spheroid-Colonized Embroidered and Functionalized Scaffolds after 3D Stretch
2021, Gögele, Clemens, Konrad, Jens, Hahn, Judith, Breier, Annette, Schröpfer, Michaela, Meyer, Michael, Merkel, Rudolf, Hoffmann, Bernd, Schulze-Tanzil, Gundula
Anterior cruciate ligament (ACL) ruptures are usually treated with autograft implantation to prevent knee instability. Tissue engineered ACL reconstruction is becoming promising to circumvent autograft limitations. The aim was to evaluate the influence of cyclic stretch on lapine (L) ACL fibroblasts on embroidered scaffolds with respect to adhesion, DNA and sulphated glycosaminoglycan (sGAG) contents, gene expression of ligament-associated extracellular matrix genes, such as type I collagen, decorin, tenascin C, tenomodulin, gap junctional connexin 43 and the transcription factor Mohawk. Control scaffolds and those functionalized by gas phase fluorination and cross-linked collagen foam were either pre-cultured with a suspension or with spheroids of LACL cells before being subjected to cyclic stretch (4%, 0.11 Hz, 3 days). Stretch increased significantly the scaffold area colonized with cells but impaired sGAGs and decorin gene expression (functionalized scaffolds seeded with cell suspension). Stretching increased tenascin C, connexin 43 and Mohawk but decreased decorin gene expression (control scaffolds seeded with cell suspension). Pre-cultivation of functionalized scaffolds with spheroids might be the more suitable method for maintaining ligamentogenesis in 3D scaffolds compared to using a cell suspension due to a significantly higher sGAG content in response to stretching and type I collagen gene expression in functionalized scaffolds.
Enhanced growth of lapine anterior cruciate ligament-derived fibroblasts on scaffolds embroidered from poly(L-lactide-co-ε-caprolactone) and polylactic acid threads functionalized by fluorination and hexamethylene diisocyanate cross-linked collagen foams
2020, Gögele, Clemens, Hahn, Judith, Elschner, Cindy, Breier, Annette, Schröpfer, Michaela, Prade, Ina, Meyer, Michael, Schulze-Tanzil, Gundula
Reconstruction of ruptured anterior cruciate ligaments (ACLs) is limited by the availability and donor site morbidity of autografts. Hence, a tissue engineered graft could present an alternative in the future. This study was undertaken to determine the performance of lapine (L) ACL-derived fibroblasts on embroidered poly(l-lactide-co-e-caprolactone) (P(LA-CL)) and polylactic acid (PLA) scaffolds in regard to a tissue engineering approach for ACL reconstruction. Surface modifications of P(LA-CL)/PLA by gas-phase fluorination and cross-linking of a collagen foam using either ethylcarbodiimide (EDC) or hexamethylene diisocyanate (HMDI) were tested regarding their influence on cell adhesion, growth and gene expression. The experiments were performed using embroidered P(LA-CL)/PLA scaffolds that were seeded dynamically or statically with LACL-derived fibroblasts. Scaffold cytocompatibility, cell survival, numbers, metabolic activity, ultrastructure and sulfated glycosaminoglycan (sGAG) synthesis were evaluated. Quantitative real-time polymerase chain reaction (QPCR) revealed gene expression of collagen type I (COL1A1), decorin (DCN), tenascin C (TNC), Mohawk (MKX) and tenomodulin (TNMD). All tested scaffolds were highly cytocompatible. A significantly higher cellularity and larger scaffold surface areas colonized by cells were detected in HMDI cross-linked and fluorinated scaffolds compared to those cross-linked with EDC or without any functionalization. By contrast, sGAG synthesis was higher in controls. Despite the fact that the significance level was not reached, gene expressions of ligament extracellular matrix components and differentiation markers were generally higher in fluorinated scaffolds with cross-linked collagen foams. LACL-derived fibroblasts maintained their differentiated phenotype on fluorinated scaffolds supplemented with a HMDI cross-linked collagen foam, making them a promising tool for ACL tissue engineering. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.