TY - JOUR A1 - Zhang, Quanchao A1 - Rudolph, Tobias A1 - Benitez, Alejandro J. A1 - Gould, Oliver E. C. A1 - Behl, Marc A1 - Kratz, Karl A1 - Lendlein, Andreas T1 - Temperature-controlled reversible pore size change of electrospun fibrous shape-memory polymer actuator based meshes JF - Smart materials and structures N2 - Fibrous membranes capable of dynamically responding to external stimuli are highly desirable in textiles and biomedical materials, where adaptive behavior is required to accommodate complex environmental changes. For example, the creation of fabrics with temperature-dependent moisture permeability or self-regulating membranes for air filtration is dependent on the development of materials that exhibit a reversible stimuli-responsive pore size change. Here, by imbuing covalently crosslinked poly(ε-caprolactone) (cPCL) fibrous meshes with a reversible bidirectional shape-memory polymer actuation (rbSMPA) we create a material capable of temperature-controlled changes in porosity. Cyclic thermomechanical testing was used to characterize the mechanical properties of the meshes, which were composed of randomly arranged microfibers with diameters of 2.3 ± 0.6 μm giving an average pore size of approx. 10 μm. When subjected to programming strains of εm = 300% and 100% reversible strain changes of εʹrev = 22% ± 1% and 6% ± 1% were measured, with switching temperature ranges of 10 °C–30 °C and 45 °C–60 °C for heating and cooling, respectively. The rbSMPA of cPCL fibrous meshes generated a microscale reversible pore size change of 11% ± 3% (an average of 1.5 ± 0.6 μm), as measured by scanning electron microscopy. The incorporation of a two-way shape-memory actuation capability into fibrous meshes is anticipated to advance the development and application of smart membrane materials, creating commercially viable textiles and devices with enhanced performance and novel functionality. KW - reversible shape-memory effect KW - fiber meshes KW - electrospinning Y1 - 2019 U6 - https://doi.org/10.1088/1361-665X/ab10a1 SN - 0964-1726 SN - 1361-665X VL - 28 IS - 5 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Hommes-Schattmann, Paul J. A1 - Neffe, Axel T. A1 - Ahmad, Bilal A1 - Williams, Gareth R. A1 - Vanneaux, Valerie A1 - Menasche, Philippe A1 - Kalfa, David A1 - Lendlein, Andreas T1 - RGD constructs with physical anchor groups as polymer co-electrospinnable cell adhesives JF - Polymers for advanced technologies N2 - The tissue integration of synthetic polymers can be promoted by displaying RGD peptides at the biointerface with the objective of enhancing colonization of the material by endogenous cells. A firm but flexible attachment of the peptide to the polymer matrix, still allowing interaction with receptors, is therefore of interest. Here, the covalent coupling of flexible physical anchor groups, allowing for temporary immobilization on polymeric surfaces via hydrophobic or dipole-dipole interactions, to a RGD peptide was investigated. For this purpose, a stearate or an oligo(ethylene glycol) (OEG) was attached to GRGDS in 51-69% yield. The obtained RGD linker constructs were characterized by NMR, IR and MALDI-ToF mass spectrometry, revealing that the commercially available OEG and stearate linkers are in fact mixtures of similar compounds. The RGD linker constructs were co-electrospun with poly(p-dioxanone) (PPDO). After electrospinning, nitrogen could be detected on the surface of the PPDO fibers by X-ray photoelectron spectroscopy. The nitrogen content exceeded the calculated value for the homogeneous material mixture suggesting a pronounced presentation of the peptide on the fiber surface. Increasing amounts of RGD linker constructs in the electrospinning solution did not lead to a detection of an increased amount of peptide on the scaffold surface, suggesting inhomogeneous distribution of the peptide on the PPDO fiber surface. Human adipose-derived stem cells cultured on the patches showed similar viability as when cultured on PPDO containing pristine RGD. The fully characterized RGD linker constructs could serve as valuable tools for the further development of tissue-integrating polymeric scaffolds. Copyright (c) 2016 John Wiley & Sons, Ltd. KW - electrospinning KW - RGD peptides KW - cell adhesion KW - biofunctionalization Y1 - 2017 U6 - https://doi.org/10.1002/pat.3963 SN - 1042-7147 SN - 1099-1581 VL - 28 SP - 1312 EP - 1317 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Thielke, Michael W. A1 - Secker, Christian A1 - Schlaad, Helmut A1 - Theato, Patrick T1 - Electrospinning of Crystallizable Polypeptoid Fibers JF - Macromolecular rapid communications N2 - A unique fabrication process of low molar mass, crystalline polypeptoid fibers is described. Thermoresponsive fiber mats are prepared by electrospinning a homogeneous blend of semicrystalline poly(N-(n-propyl) glycine) (PPGly; 4.1 kDa) with high molar mass poly(ethylene oxide) (PEO). Annealing of these fibers at approximate to 100 degrees C selectively removes the PEO and produces stable crystalline fiber mats of pure PPGly, which are insoluble in aqueous solution but can be redissolved in methanol or ethanol. The formation of water-stable polypeptoid fiber mats is an important step toward their utilization in biomedical applications such as tissue engineering or wound dressing. KW - biomaterials KW - crystallization KW - electrospinning KW - polypeptoids KW - thermoresponsive Y1 - 2016 U6 - https://doi.org/10.1002/marc.201500502 SN - 1022-1336 SN - 1521-3927 VL - 37 SP - 100 EP - 104 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Sauter, Tilman A1 - Geiger, Brett A1 - Kratz, Karl A1 - Lendlein, Andreas T1 - Encasement of metallic cardiovascular stents with endothelial cell-selective copolyetheresterurethane microfibers JF - Polymers for advanced technologies N2 - Cardiovascular metallic stents established in clinical application are typically coated by a thin polymeric layer on the stent struts to improve hemocompatibility, whereby often a drug is added to the coating to inhibit neointimal hyperplasia. Besides such thin film coatings recently nano/microfiber coated stents are investigated, whereby the fibrous coating was applied circumferential on stents. Here, we explored whether a thin fibrous encasement of metallic stents with preferentially longitudinal aligned fibers and different local fiber densities can be achieved by electrospinning. An elastic degradable copolyetheresterurethane, which is reported to selectively enhance the adhesion of endothelial cells, while simultaneously rejecting smooth muscle cells, was utilized for stent coating. The fibrous stent encasements were microscopically assessed regarding their single fiber diameters, fiber covered area and fiber alignment at three characteristic stent regions before and after stent expansion. Stent coatings with thicknesses in the range from 30 to 50 mu m were achieved via electrospinning with 1,1,1,3,3,3-hexafluoro-2-propanol (HFP)-based polymer solution, while a mixture of HFP and formic acid as solvent resulted in encasements with a thickness below 5 mu m comprising submicron sized single fibers. All polymeric encasements were mechanically stable during expansion, whereby the fibers deposited on the struts remained their position. The observed changes in fiber density and diameter indicated diverse local deformation mechanisms of the microfibers at the different regions between the struts. Based on these results it can be anticipated that the presented fibrous encasement of stents might be a promising alternative to stents with polymeric strut coatings releasing anti-proliferative drugs. Copyright (c) 2015 John Wiley & Sons, Ltd. KW - multifunctional polymers KW - stent coatings KW - electrospinning KW - biomaterials KW - degradable polymers Y1 - 2015 U6 - https://doi.org/10.1002/pat.3583 SN - 1042-7147 SN - 1099-1581 VL - 26 IS - 10 SP - 1209 EP - 1216 PB - Wiley-Blackwell CY - Hoboken ER - TY - JOUR A1 - Schneider, Tobias A1 - Kohl, Benjamin A1 - Sauter, Tilman A1 - Kratz, Karl A1 - Lendlein, Andreas A1 - Ertel, Wolfgang A1 - Schulze-Tanzil, Gundula T1 - Influence of fiber orientation in electrospun polymer scaffolds on viability, adhesion and differentiation of articular chondrocytes JF - Clinical hemorheology and microcirculation : blood flow and vessels N2 - Degradable polymers with a tailorable degradation rate might be promising candidate materials for biomaterial-based cartilage repair. In view of the poor intrinsic healing capability of cartilage, implantation of autologous chondrocytes seeded on a biocompatible slow degrading polymer might be an encouraging approach to improve cartilage repair in the future. This study was undertaken to test if the fiber orientation (random versus aligned) of two different degradable polymers and a polymer intended for long term applications could influence primary articular chondrocytes growth and ultrastructure. A degradable copoly(ether) esterurethane (PDC) was synthesized via co-condensation of poly(p-dioxanone) diol and poly(epsilon-caprolactone) diol using an aliphatic diisocyanate as linker. Poly(p-dioxanone) (PPDO) was applied as commercially available degradable polymer, while polyetherimide (PEI) was chosen as biomaterial enabling surface functionalization. The fibrous scaffolds of PDC and PPDO were obtained by electrospinning using 1,1,1,3,3,3 hexafluoro-2-propanol (HFP), while for PEI dimethyl acetamide (DMAc) was applied as solvent. Primary porcine articular chondrocytes were seeded at different cell densities on the fibrous polymer scaffolds and analyzed for viability (fluorescein diacetate/ethidiumbromide staining), for type II collagen synthesis (immunolabelling), ultrastructure and orientation on the fibers (SEM: scanning electron microscopy). Vital chondrocytes adhered on all electrospun scaffolds irrespective of random and aligned topologies. In addition, the chondrocytes produced the cartilage-specific type II collagen on all tested polymer topologies suggesting their differentiated functions. SEM revealed an almost flattened chondrocytes shape on scaffolds with random fiber orientation: whereby chondrocytes growth remained mainly restricted to the scaffold surface. On aligned fibers the chondrocytes exhibited a more spindle-shaped morphology with rougher cell surfaces but only a minority of the cells aligned according to the fibers. As a next step the reduction of the fiber diameter of electrospun scaffolds should be addressed as an important parameter to mimic cartilage ECM structure. KW - Chondrocytes KW - electrospinning KW - scaffold KW - differentiation KW - multiblock copolymer Y1 - 2012 U6 - https://doi.org/10.3233/CH-2012-1608 SN - 1386-0291 VL - 52 IS - 2-4 SP - 325 EP - 336 PB - IOS Press CY - Amsterdam ER - TY - JOUR A1 - Rüder, Constantin A1 - Sauter, Tilman A1 - Kratz, Karl A1 - Haase, Tobias A1 - Peter, Jan A1 - Jung, Friedrich A1 - Lendlein, Andreas A1 - Zohlnhöfer, Dietlind T1 - Influence of fibre diameter and orientation of electrospun copolyetheresterurethanes on smooth muscle and endothelial cell behaviour JF - Clinical hemorheology and microcirculation : blood flow and vessels N2 - Polymers exhibiting cell-selective effects represent an extensive research field with high relevance for biomedical applications e.g. in the cardiovascular field supporting re-endothelialization while suppressing smooth muscle cell overgrowth. Such an endothelial cell-selective effect could be recently demonstrated for a copolyetheresterurethane (PDC) containing biodegradable poly(p-dioxanone) and poly(epsilon-caprolactone) segments, which selectively enhanced the adhesion of human umbilical vein endothelial cells (HUVEC) while suppressing the attachment of smooth muscle cells (SMC). In this study we investigated the influence of the fibre orientation (random and aligned) and fibre diameter (2 mu m and 500 nm) of electrospun PDC scaffolds on the adhesion, proliferation and apoptosis of HUVEC and SMC. Adhesion, viability and proliferation of HUVEC was diminished when the fibre diameter was reduced to a submicron scale, while the orientation of the microfibres did only slightly influence the cellular behaviour. In contrast, a submicron fibre diameter improved SMC viability. In conclusion, PDC scaffolds with micron-sized single fibres could be promising candidate materials for cell-selective stent coatings. KW - Endothelialization KW - drug eluting stent KW - degradable polymer KW - electrospinning KW - cell selectivity Y1 - 2013 U6 - https://doi.org/10.3233/CH-131787 SN - 1386-0291 SN - 1875-8622 VL - 55 IS - 4 SP - 513 EP - 522 PB - IOS Press CY - Amsterdam ER -