TY - JOUR A1 - Liu, Yue A1 - Razzaq, Muhammad Yasar A1 - Rudolph, Tobias A1 - Fang, Liang A1 - Kratz, Karl A1 - Lendlein, Andreas T1 - Two-Level Shape Changes of Polymeric Microcuboids Prepared from Crystallizable Copolymer Networks JF - Macromolecules : a publication of the American Chemical Society N2 - Polymeric microdevices bearing features like nonspherical shapes or spatially segregated surface properties are of increasing importance in biological and medical analysis, drug delivery, and bioimaging or microfluidic systems as well as in micromechanics, sensors, information storage, or data carrier devices. Here, a method to fabricate programmable microcuboids with shape-memory capability and the quantification of their recovery at different levels is reported. The method uses the soft lithographic technique to create microcuboids with well-defined sizes and surface properties. Microcuboids having an edge length of 25 mu m and a height of 10 mu m were prepared from cross-linked poly[ethylene-co-(vinyl acetate)] (cPEVA) with different vinyl acetate contents and were programmed by compression with various deformation degrees at elevated temperatures. The microlevel shape-recovery of the cuboidal geometry during heating was monitored by optical microscopy (OM) and atomic force microscopy (AFM) studying the related changes in the projected area (PA) or height, while the nanolevel changes of the nanosurface roughness were investigated by in situ AFM. The shape-memory effect at the microlevel was quantified by the recovery ratio of cuboids (R-r,R-micro), while at the. nanolevel, the recovery ratio of the nanoroughness (R-r,R-nano) was measured. The values of R-r,R-micro,,micro could be tailored in a range from 42 +/- 1% to 102 +/- 1% and Rr,nano from 89 +/- 6% to 136 +/- 21% depending on the applied compression ratio and the amount of vinyl acetate content in the cPEVA microcuboids. Y1 - 2017 U6 - https://doi.org/10.1021/acs.macromol.6b02237 SN - 0024-9297 SN - 1520-5835 VL - 50 SP - 2518 EP - 2527 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Farhan, Muhammad A1 - Rudolph, Tobias A1 - Kratz, Karl A1 - Lendlein, Andreas T1 - Torsional Fiber Actuators from Shape-memory Polymer JF - MRS Advances N2 - Humanoid robots, prosthetic limbs and exoskeletons require soft actuators to perform their primary function, which is controlled movement. In this wont we explored whether crosslinked poly[ethylene-co-(vinyl acetate)] (cPEVA) fibers, with different vinyl acetate (VA) content can serve as torsional fiber actuators. exhibiting temperature controlled reversible rotational changes. Broad melting transitions ranging from 50 to 90 degrees C for cPEVA18-165 or from 40 to 80 degrees C for cPEVA28-165 fibers in combination with complete crystallization at temperatures around 10 degrees C make them suitable actuating materials with adjustable actuation temperature ranges between 10 and 70 degrees C during repetitive cooling and heating. The obtained fibers exhibited a circular cross section with diameters around 0.4 +/- 0.1 mm, while a length of 4 cm was employed for the investigation of reversible rotational actuation after programming by twist insertion using 30 complete rotations at a temperature above melting transition. Repetitive heating and cooling between 10 to 60 degrees C or 70 degrees C of one-end-tethered programmed fibers revealed reversible rotations and torsional force. During cooling 3 +/- 1 complete rotations (Delta theta(r) = + 1080 +/- 360 degrees) in twisting direction were observed, while 4 +/- 1 turns in the opposite direction (Delta theta(r) = - 1440 +/- 1360 degrees) were found during heating. Such torsional fiber actuators, which are capable of approximately one rotation per cm fiber length, can serve as miniaturized rotary motors to provide rotational actuation in futuristic humanoid robots. Y1 - 2018 U6 - https://doi.org/10.1557/adv.2018.621 SN - 2059-8521 VL - 3 IS - 63 SP - 3861 EP - 3868 PB - Cambridge Univ. Press CY - New York ER - TY - JOUR A1 - Schöne, Anne-Christin A1 - Kratz, Karl A1 - Schulz, Burkhard A1 - Lendlein, Andreas T1 - The relevance of hydrophobic segments in multiblock copolyesterurethanes for their enzymatic degradation at the air-water interface JF - Polymer : the international journal for the science and technology of polymers N2 - The interplay of an enzyme with a multiblock copolymer PDLCL containing two segments of different hydrophilicity and degradability is explored in thin films at the air-water interface. The enzymatic degradation was studied in homogenous Langmuir monolayers, which are formed when containing more than 40 wt% oligo(epsilon-caprolactone) (OCL). Enzymatic degradation rates were significantly reduced with increasing content of hydrophobic oligo(omega-pentadecalactone) (OPDL). The apparent deceleration of the enzymatic process is caused by smaller portion of water-soluble degradation fragments formed from degradable OCL fragments. Beside the film degradation, a second competing process occurs after adding lipase from Pseudomonas cepacia into the subphase, namely the enrichment of the lipase molecules in the polymeric monolayer. The incorporation of the lipase into the Langmuir film is experimentally revealed by concurrent surface area enlargement and by Brewster angle microscopy (BAM). Aside from the ability to provide information about the degradation behavior of polymers, the Langmuir monolayer degradation (LMD) approach enables to investigate polymer-enzyme interactions for non-degradable polymers. (C) 2016 Elsevier Ltd. All rights reserved. KW - Multiblock copolymer KW - Enzymatic polymer degradation KW - Oligo(omega-pentadecalactone) KW - Oligo(epsilon-caprolactone) KW - Langmuir monolayer degradation technique Y1 - 2016 U6 - https://doi.org/10.1016/j.polymer.2016.09.001 SN - 0032-3861 SN - 1873-2291 VL - 102 SP - 92 EP - 98 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Wang, Weiwei A1 - Kratz, Karl A1 - Behl, Marc A1 - Yan, Wan A1 - Liu, Yue A1 - Xu, Xun A1 - Baudis, Stefan A1 - Li, Zhengdong A1 - Kurtz, Andreas A1 - Lendlein, Andreas A1 - Ma, Nan T1 - The interaction of adipose-derived human mesenchymal stem cells and polyether ether ketone JF - Clinical hemorheology and microcirculation : blood flow and vessels N2 - Polyether ether ketone (PEEK) as a high-performance, thermoplastic implant material entered the field of medical applications due to its structural function and commercial availability. In bone tissue engineering, the combination of mesenchymal stem cells (MSCs) with PEEK implants may accelerate the bone formation and promote the osseointegration between the implant and the adjacent bone tissue. In this concept the question how PEEK influences the behaviour and functions of MSCs is of great interest. Here the cellular response of human adipose-derived MSCs to PEEK was evaluated and compared to tissue culture plate (TCP) as the reference material. Viability and morphology of cells were not altered when cultured on the PEEK film. The cells on PEEK presented a high proliferation activity in spite of a relatively lower initial cell adhesion rate. There was no significant difference on cell apoptosis and senescence between the cells on PEEK and TCP. The inflammatory cytokines and VEGF secreted by the cells on these two surfaces were at similar levels. The cells on PEEK showed up-regulated BMP2 and down-regulated BMP4 and BMP6 gene expression, whereas no conspicuous differences were observed in the committed osteoblast markers (BGLAP, COL1A1 and Runx2). With osteoinduction the cells on PEEK and TCP exhibited a similar osteogenic differentiation potential. Our results demonstrate the biofunctionality of PEEK for human MSC cultivation and differentiation. Its clinical benefits in bone tissue engineering may be achieved by combining MSCs with PEEK implants. These data may also provide useful information for further modification of PEEK with chemical or physical methods to regulate the cellular processes of MSCs and to consequently improve the efficacy of MSC-PEEK based therapies. KW - Polyether ether ketone KW - mesenchymal stem cells KW - biocompatibility KW - cell-material interaction KW - osteogenic differentiation Y1 - 2015 U6 - https://doi.org/10.3233/CH-152001 SN - 1386-0291 SN - 1875-8622 VL - 61 IS - 2 SP - 301 EP - 321 PB - IOS Press CY - Amsterdam ER - TY - JOUR A1 - Yan, Wan A1 - Fang, Liang A1 - Weigel, Thomas A1 - Behl, Marc A1 - Kratz, Karl A1 - Lendlein, Andreas T1 - The influence of thermal treatment on the morphology in differently prepared films of a oligodepsipeptide based multiblock copolymer JF - Polymers for advanced technologies N2 - Degradable multiblock copolymers prepared from equal weight amounts of poly(epsilon-caprolactone)-diol (PCL-diol) and poly[oligo(3S-iso-butylmorpholine-2,5-dione)]-diol (PIBMD-diol), named PCL-PIBMD, provide a phase-segregated morphology. It exhibits a low melting temperature from PCL domains (T-m,T-PCL) of 382 degrees C and a high T-m,T-PIBMD of 170 +/- 2 degrees C with a glass transition temperature (T-g,T-PIBMD) at 42 +/- 2 degrees C from PIBMD domains. In this study, we explored the influence of applying different thermal treatments on the resulting morphologies of solution-cast and spin-coated PCL-PIBMD thin films, which showed different initial surface morphologies. Differential scanning calorimetry results and atomic force microscopy images after different thermal treatments indicated that PCL and PIBMD domains showed similar crystallization behaviors in 270 +/- 30 mu m thick solution-cast films as well as in 30 +/- 2 and 8 +/- 1nm thick spin-coated PCL-PIBMD films. Existing PIBMD crystalline domains highly restricted the generation of PCL crystalline domains during cooling when the sample was annealed at 180 degrees C. By annealing the sample above 120 degrees C, the PIBMD domains crystallized sufficiently and covered the free surface, which restricted the crystallization of PCL domains during cooling. The PCL domains can crystallize by hindering the crystallization of PIBMD domains via the fast vitrification of PIBMD domains when the sample was cooled/quenched in liquid nitrogen after annealing at 180 degrees C. These findings contribute to a better fundamental understanding of the crystallization mechanism of multi-block copolymers containing two crystallizable domains whereby the T-g of the higher melting domain type is in the same temperature range as the T-m of the lower melting domain type. Copyright (c) 2016 John Wiley & Sons, Ltd. KW - multiblock copolymer KW - oligodepsipeptides KW - phase morphology KW - thermal treatments KW - crystallization behavior Y1 - 2017 U6 - https://doi.org/10.1002/pat.3953 SN - 1042-7147 SN - 1099-1581 VL - 28 SP - 1339 EP - 1345 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Jiang, Yi A1 - Mansfeld, Ulrich A1 - Fang, Liang A1 - Kratz, Karl A1 - Lendlein, Andreas T1 - Temperature-induced evolution of microstructures on poly[ethylene-co-(vinyl acetate)] substrates switches their underwater wettability JF - Materials & design N2 - Material surfaces with tailored aerophobicity are crucial for applications where gas bubble wettability has to be controlled, e.g., gas storage and transport, electrodes, bioreactors or medical devices. Here, we present switchable underwater aerophobicity of hydrophobic polymeric substrates, which respond to heat with multilevel micro-and nanotopographical changes. The cross-linked poly[ethylene-co-(vinyl acetate)] substrates possess arrays of microcylinders with a nanorough top surface. It is hypothesized that the specific micro-/nanotopography of the surface allows trapping of a water film at the micro interspace and in this way generates the aerophobic behavior. The structured substrates were programmed to a temporarily stable, nanoscale flat substrate showing aerophilic behavior. Upon heating, the topographical changes caused a switch in contact angle from aerophilic to aerophobic for approaching air bubbles. In this way, the initial adhesion of air bubbles to the programmed flat substrate could be turned into repellence for the recovered substrate surface. The temperature at which the repellence of air bubbles starts can be adjusted from 58 +/- 3 degrees C to 73 +/- 3 degrees C by varying the deformation temperature applied during the temperature-memory programming procedure. The presented actively switching polymeric substrates are attractive candidates for applications, where an on-demand gas bubble repellence is advantageous. (c) 2018 Helmholtz-Zentrum Geesthacht, Zentrum fur Material- und Kustenforschung. Published by Elsevier Ltd. KW - Aerophobicity KW - Temperature-memory effect KW - Switchable wettability KW - Air bubble repellence KW - Thermo-responsive polymer Y1 - 2018 U6 - https://doi.org/10.1016/j.matdes.2018.12.002 SN - 0264-1275 SN - 1873-4197 VL - 163 PB - Elsevier CY - Oxford ER - TY - GEN A1 - Jiang, Yi A1 - Mansfeld, Ulrich A1 - Fang, Liang A1 - Kratz, Karl A1 - Lendlein, Andreas T1 - Temperature-induced evolution of microstructures on poly[ethylene-co-(vinyl acetate)] substrates switches their underwater wettability T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - Material surfaces with tailored aerophobicity are crucial for applications where gas bubble wettability has to be controlled, e.g., gas storage and transport, electrodes, bioreactors or medical devices. Here, we present switchable underwater aerophobicity of hydrophobic polymeric substrates, which respond to heat with multilevel micro- and nanotopographical changes. The cross-linked poly[ethylene-co-(vinyl acetate)] substrates possess arrays of microcylinders with a nanorough top surface. It is hypothesized that the specific micro-/nanotopography of the surface allows trapping of a water film at the micro interspace and in this way generates the aerophobic behavior. The structured substrates were programmed to a temporarily stable, nanoscale flat substrate showing aerophilic behavior. Upon heating, the topographical changes caused a switch in contact angle from aerophilic to aerophobic for approaching air bubbles. In this way, the initial adhesion of air bubbles to the programmed flat substrate could be turned into repellence for the recovered substrate surface. The temperature at which the repellence of air bubbles starts can be adjusted from 58 ± 3 °C to 73 ± 3 °C by varying the deformation temperature applied during the temperature-memory programming procedure. The presented actively switching polymeric substrates are attractive candidates for applications, where an on-demand gas bubble repellence is advantageous. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 639 KW - aerophobicity KW - temperature-memory effect KW - switchable wettability KW - air bubble repellence KW - thermo-responsive polymer Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-424601 SN - 1866-8372 IS - 639 ER - 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 - Ghobadi, Ehsan A1 - Heuchel, Matthias A1 - Kratz, Karl A1 - Lendlein, Andreas T1 - Simulation of volumetric swelling of degradable poly[(rac-lactide)-co-glycolide] based polyesterurethanes containing different urethane-linkers JF - Journal of applied biomaterials & functional materials N2 - Aim: The hydrolytic degradation behavior of degradable aliphatic polyester-based polymers is strongly influenced by the uptake or transport of water into the polymer matrix and also the hydrolysis rate of ester bonds. Methods: We examined the volumetric swelling behavior of poly[(rac-lactide)-co-glycolide] (PLGA) and PLGA-based polyurethanes (PLGA-PU) with water contents of 0 wt%, 2 wt% and 7 wt% water at 310 K using a molecular modeling approach. Polymer systems with a number average molecular weight of M-n = 10,126 g.mol(-1) were constructed from PLGA with a lactide content of 67 mol%, whereby PLGA-PU systems were composed of five PLGA segments with M-n = 2052 g.mol(-1), which were connected via urethane linkers originated from 2,2,4-trimethyl hexamethylene-1,6-diisocyanate (TMDI), hexamethyl-1,6-diisocyanate (HDI), or L-lysine-1,6-diisocyanate (LDI). Results: The calculated densities of the dry PLGA-PU systems were found to be lower than for pure PLGA. The obtained volumetric swelling of the PLGA-PU was depending on the type of urethane linker, whereby all swollen PLGA-PUs contained larger free volume distribution compared to pure PLGA. The mean square displacement curves for dry PLGA and PLGA-PUs showed that urethane linker units reduce the mobility of the polymer chains, while an increase in backbone atoms mobility was found, when water was added to these systems. Consequently, an increased water uptake of PLGA-PU matrices combined with a higher mobility of the chain segments should result in an accelerated hydrolytic chain scission rate in comparison to PLGA. Conclusions: It can be anticipated that the incorporation of urethane linkers might be a helpful tool to adjust the degradation behavior of polyesters. KW - Hydrolytic degradation KW - Molecular dynamics simulation KW - Polyesterurethane Y1 - 2012 U6 - https://doi.org/10.5301/JABFM.2012.10432 SN - 2280-8000 VL - 10 IS - 3 SP - 293 EP - 301 PB - Wichtig CY - Milano ER - TY - JOUR A1 - Ghobadi, Ehsan A1 - Heuchel, Matthias A1 - Kratz, Karl A1 - Lendlein, Andreas T1 - Simulating the shape-Memory behavior of amorphous switching domains of Poly(L-lactide) by molecular dynamics JF - Macromolecular chemistry and physics N2 - The thermally induced shape-memory effect of polymers is typically characterized by cyclic uniaxial thermomechanical tests. Here, a molecular-dynamics (MD) simulation approach of such a cyclic uniaxial thermomechanical test is presented for amorphous switching domains of poly(L-lactide) (PLLA). Uniaxial deformation of the constructed PLLA models is simulated with a Parinello-Rahman scheme, as well as a pragmatic geometrical approach. We are able to describe two subsequent test cycles using the presented simulation approach. The obtained simulated shape-memory properties in both test cycles are similar and independent of the applied deformation protocols. The simulated PLLA shows high shape fixity ratios (Rf 94%), but only a moderate shape recovery ratio is obtained (Rr 30%). Finally, the structural changes during the simulated test are characterized by analysis of the changes in the dihedral angle distributions. KW - molecular modeling KW - polyesters KW - shape-memory properties KW - stimuli-sensitive polymers KW - thermomechanical properties Y1 - 2013 U6 - https://doi.org/10.1002/macp.201200450 SN - 1022-1352 VL - 214 IS - 11 SP - 1273 EP - 1283 PB - Wiley-VCH CY - Weinheim ER -