TY - JOUR A1 - Balk, Maria A1 - Behl, Marc A1 - Lendlein, Andreas T1 - Quadruple-shape hydrogels JF - Smart materials and structures N2 - The capability of directed movements by two subsequent shape changes could be implemented in shape-memory hydrogels by incorporation of two types of crystallizable side chains While in non-swollen polymer networks even more directed movements could be realized, the creation of multi-shape hydrogels is still a challenge. We hypothesize that a quadruple-shape effect in hydrogels can be realized, when a swelling capacity almost independent of temperature is generated, whereby directed movements could be enabled, which are not related to swelling. In this case, entropy elastic recovery could be realized by hydrophilic segments and the fixation of different macroscopic shapes by means of three semi-crystalline side chains generating temporary crosslinks. Monomethacrylated semi-crystalline oligomers were connected as side chains in a hydrophilic polymer network via radical copolymerization. Computer assisted modelling was utilized to design a demonstrator capable of complex shape shifts by creating a casting mold via 3D printing from polyvinyl alcohol. The demonstrator was obtained after copolymerization of polymer network forming components within the mold, which was subsequently dissolved in water. A thermally-induced quadruple-shape effect was realized after equilibrium swelling of the polymer network in water. Three directed movements were successfully obtained when the temperature was continuously increased from 5 degrees C to 90 degrees C with a recovery ratio of the original shape above 90%. Hence, a thermally-induced quadruple-shape effect as new record for hydrogels was realized. Here, the temperature range for the multi-shape effect was limited by water as swelling media (0 degrees C-100 degrees C), simultaneously distinctly separated thermal transitions were required, and the overall elasticity indispensable for successive deformations was reduced as result of partially chain segment orientation induced by swelling in water. Conclusively the challenges for penta- or hexa-shape gels are the design of systems enabling higher elastic deformability and covering a larger temperature range by switching to a different solvent. KW - shape-memory KW - hydrogels KW - semi-crystalline Y1 - 2019 U6 - https://doi.org/10.1088/1361-665X/ab0e91 SN - 0964-1726 SN - 1361-665X VL - 28 IS - 5 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Balk, Maria A1 - Behl, Marc A1 - Lendlein, Andreas T1 - Hydrolytic Degradation of Actuators Based on Copolymer Networks From Oligo(epsilon-caprolactone) Dimethacrylate and n-Butyl Acrylate JF - MRS advances N2 - Shape-memory polymer actuators often contain crystallizable polyester segments. Here, the influence of accelerated hydrolytic degradation on the actuation performance in copolymer networks based on oligo(epsilon-caprolactone) dimethacrylate (OCL) and n-butyl acrylate is studied The semi-crystalline OCL was utilized as crosslinker with molecular weights of 2.3 and 15.2 kg.mol(-1) (ratio: 1:1 wt%) and n-butyl acrylate (25 wt% relative to OCL content) acted as softening agent creating the polymer main chain segments within the network architecture. The copolymer networks were programmed by 50% elongation and were degraded by means of alkaline hydrolysis utilizing sodium hydroxide solution (pH = 13). Experiments were performed in the range of the broad melting range of the actuators at 40 degrees C. The degradation of test specimen was monitored by the sample mass, which was reduced by 25 wt% within 105 d .45 degradation products, fragments of OCL with molecular masses ranging from 400 to 50.000 g.mol(-1) could be detected by NMR spectroscopy and GPC measurements. The cleavage of ester groups included in OCL segments resulted in a decrease of the melting temperature (T-m) related to the actuator domains (amorphous at the temperature of degradation) and simultaneously, the T-m associated to the skeleton domain was increased (semi-crystalline at the temperature of degradation). The alkaline hydrolysis decreased the polymer chain orientation of OCL domains until a random alignment of crystalline domains was obtained. This result was confirmed by cyclic thermomechanical actuation tests. The performance of directed movements decreased almost linearly as function of degradation time resulting in the loss of functionality when the orientation of polymer chains disappeared. Here, actuators were able to provide reversible movements until 91 d when the accelerated bulk degradation procedure using alkaline hydrolysis (pH = 13) was applied. Accordingly, a lifetime of more than one year can be guaranteed under physiological conditions (pH = 7.4) when, e.g., artificial muscles for biomimetic robots as potential application for these kind of shape-memory polymer actuators will be addressed. Y1 - 2019 U6 - https://doi.org/10.1557/adv.2019.202 SN - 2059-8521 VL - 4 IS - 21 SP - 1193 EP - 1205 PB - Cambridge Univ. Press CY - New York ER - TY - JOUR A1 - Balk, Maria A1 - Behl, Marc A1 - Lendlein, Andreas T1 - Actuators based on oligo[(epsilon-caprolactone)-co-glycolide] with accelerated hydrolytic degradation JF - MRS advances : a journal of the Materials Research Society (MRS) N2 - Polyester-based shape-memory polymer actuators are multifunctional materials providing reversible macroscopic shape shifts as well as hydrolytic degradability. Here, the function-function interdependencies (between shape shifts and degradation behaviour) will determine actuation performance and its life time. In this work, glycolide units were incorporated in poly(epsilon-caprolactone) based actuator materials in order to achieve an accelerated hydrolytic degradation and to explore the function-function relationship. Three different oligo[(epsilon-caprolactone)-co-glycolide] copolymers (OCGs) with similar molecular weights (10.5 +/- 0.5 kg center dot mol(-1)) including a glycolide content of 8, 16, and 26 mol% (ratio 1:1:1 wt%) terminated with methacrylated moieties were crosslinked. The obtained actuators provided a broad melting transition in the range from 27 to 44 degrees C. The hydrolytic degradation of programmed OCG actuators (200% of elongation) resulted in a reduction of sample mass to 51 wt% within 21 days at pH = 7.4 and 40 degrees C. Degradation results in a decrease of T-m associated to the actuating units and increasing T-m associated to the skeleton forming units. The actuation capability decreased almost linear as function of time. After 11 days of hydrolytic degradation the shape-memory functionality was lost. Accordingly, a fast degradation behaviour as required, e.g., for actuator materials intended as implant material can be realized. KW - actuation KW - shape memory KW - polymer KW - crystalline Y1 - 2020 U6 - https://doi.org/10.1557/adv.2019.447 SN - 2059-8521 VL - 5 IS - 12-13 SP - 655 EP - 666 PB - Cambridge University Press CY - New York, NY ER - TY - JOUR A1 - Balk, Maria A1 - Behl, Marc A1 - Nöchel, Ulrich A1 - Lendlein, Andreas T1 - Enzymatically triggered Jack-in-the-box-like hydrogels JF - ACS applied materials & interfaces / American Chemical Society N2 - Enzymes can support the synthesis or degradation of biomacromolecules in natural processes. Here, we demonstrate that enzymes can induce a macroscopic-directed movement of microstructured hydrogels following a mechanism that we call a "Jack-in-the-box" effect. The material's design is based on the formation of internal stresses induced by a deformation load on an architectured microscale, which are kinetically frozen by the generation of polyester locking domains, similar to a Jack-in-thebox toy (i.e., a compressed spring stabilized by a closed box lid). To induce the controlled macroscopic movement, the locking domains are equipped with enzyme-specific cleavable bonds (i.e., a box with a lock and key system). As a result of enzymatic reaction, a transformed shape is achieved by the release of internal stresses. There is an increase in entropy in combination with a swelling-supported stretching of polymer chains within the microarchitectured hydrogel (i.e., the encased clown pops-up with a pre-stressed movement when the box is unlocked). This utilization of an enzyme as a physiological stimulus may offer new approaches to create interactive and enzyme-specific materials for different applications such as an optical indicator of the enzyme's presence or actuators and sensors in biotechnology and in fermentation processes. KW - enzyme KW - hydrogels KW - stimuli-sensitive materials KW - shape change KW - poly(e-caprolactone) KW - switch KW - microporous Y1 - 2021 U6 - https://doi.org/10.1021/acsami.1c00466 SN - 1944-8244 SN - 1944-8252 VL - 13 IS - 7 SP - 8095 EP - 8101 PB - American Chemical Society CY - Washington, DC ER - TY - JOUR A1 - Behl, Marc A1 - Balk, Maria A1 - Lützow, Karola A1 - Lendlein, Andreas T1 - Impact of block sequence on the phase morphology of multiblock copolymers obtained by high-throughput robotic synthesis JF - European polymer journal : EPJ N2 - The chemical nature, the number length of integrated building blocks, as well as their sequence structure impact the phase morphology of multiblock copolymers (MBC) consisting of two non-miscible block types. We hypothesized that a strictly alternating sequence should favour phase segregation and in this way the elastic properties. A library of well-defined MBCs composed of two different hydrophobic, semi-crystalline blocks providing domains with well-separated melting temperatures (T(m)s) were synthesized from the same type of precursor building blocks as strictly alternating (MBCsalt) or random (MBCsran) MBCs and compared. Three different series of MBCsalt or MBCsran were synthesized by high-throughput synthesis by coupling oligo(e-caprolactone) (OCL) of different molecular weights (2, 4, and 8 kDa) with oligotetrahydrofuran (OTHF, 2.9 kDa) via Steglich esterification in which the molar ratio of the reaction partners was slightly adjusted. Maximum of weight average molecular weight (M-w) were 65,000 g center dot mol(-1), 165,000 g center dot mol(-1), and 168,000 g center dot mol(-1) for MBCsalt and 80,500 g center dot mol(-1), 100,000 g center dot mol(-1), and 147,600 g center dot mol(-1) for MBCsran. When Mw increased, a decrease of both Tms associated to the melting of the OCL and OTHF domains was observed for all MBCs. T-m (OTHF) of MBCsran was always higher than Tm (OTHF) of MBCsalt, which was attributed to a better phase segregation. In addition, the elongation at break of MBCsalt was almost half as high when compared to MBCsran. In this way this study elucidates role of the block length and sequence structure in MBCs and enables a quantitative discussion of the structure-function relationship when two semi-crystalline block segments are utilized for the design of block copolymers. KW - Multiblock copolymers KW - Sequence structure KW - Phase morphology KW - Polymer KW - library KW - Robotic synthesis KW - High-throughput Y1 - 2021 U6 - https://doi.org/10.1016/j.eurpolymj.2020.110207 SN - 0014-3057 SN - 1873-1945 VL - 143 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Behl, Marc A1 - Balk, Maria A1 - Mansfeld, Ulrich A1 - Lendlein, Andreas T1 - Phase morphology of multiblock copolymers differing in sequence of blocks JF - Macromolecular materials and engineering N2 - The chemical nature, the number length of integrated building blocks, as well as their sequence structure impact the phase morphology of multiblock copolymers (MBC) consisting of two non-miscible block types. It is hypothesized that a strictly alternating sequence should impact phase segregation. A library of well-defined MBC obtained by coupling oligo(epsilon-caprolactone) (OCL) of different molecular weights (2, 4, and 8 kDa) with oligotetrahydrofuran (OTHF, 2.9 kDa) via Steglich esterification results in strictly alternating (MBCalt) or random (MBCran) MBC. The three different series has a weight average molecular weight (M-w) of 65 000, 165 000, and 168 000 g mol(-1) for MBCalt and 80 500, 100 000, and 147 600 g mol(-1) for MBCran. When the chain length of OCL building blocks is increased, the tendency for phase segregation is facilitated, which is attributed to the decrease in chain mobility within the MBC. Furthermore, it is found that the phase segregation disturbs the crystallization by causing heterogeneities in the semi-crystalline alignment, which is attributed to an increase of the disorder of the OCL semi-crystalline alignment. KW - electron microscopy KW - multiblock copolymers KW - phase morphology KW - polymer KW - libraries KW - sequence structures KW - wide angle x‐ ray scattering Y1 - 2021 U6 - https://doi.org/10.1002/mame.202000672 SN - 1439-2054 VL - 306 IS - 3 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Behl, Marc A1 - Razzaq, Muhammad Yasar A1 - Mazurek-Budzynska, Magdalena A1 - Lendlein, Andreas T1 - Polyetheresterurethane based porous scaffolds with tailorable architectures by supercritical CO2 foaming JF - MRS advances N2 - Porous three-dimensional (3D) scaffolds are promising treatment options in regenerative medicine. Supercritical and dense-phase fluid technologies provide an attractive alternative to solvent-based scaffold fabrication methods. In this work, we report on the fabrication of poly-etheresterurethane (PPDO-PCL) based porous scaffolds with tailorable pore size, porosity, and pore interconnectivity by using supercritical CO2(scCO(2)) fluid-foaming. The influence of the processing parameters such as soaking time, soaking temperature and depressurization on porosity, pore size, and interconnectivity of the foams were investigated. The average pore diameter could be varied between 100-800 mu m along with a porosity in the range from (19 +/- 3 to 61 +/- 6)% and interconnectivity of up to 82%. To demonstrate their applicability as scaffold materials, selected foams were sterilized via ethylene oxide sterilization. They showed negligible cytotoxicity in tests according to DIN EN ISO 10993-5 and 10993-12 using L929 cells. The study demonstrated that the pore size, porosity and the interconnectivity of this multi-phase semicrystalline polymer could be tailored by careful control of the processing parameters during the scCO(2)foaming process. In this way, PPDO-PCL scaffolds with high porosity and interconnectivity are potential candidate materials for regenerative treatment options. Y1 - 2020 U6 - https://doi.org/10.1557/adv.2020.345 SN - 2059-8521 VL - 5 IS - 45 SP - 2317 EP - 2330 PB - Cambridge University Press CY - New York, NY ER - TY - JOUR A1 - Behl, Marc A1 - Zhao, Qian A1 - Lendlein, Andreas T1 - Glucose-responsive shape-memory cryogels JF - Journal of materials research : JMR N2 - Boronic ester bonds can be reversibly formed between phenylboronic acid (PBA) and triol moieties. Here, we aim at a glucose-induced shape-memory effect by implementing such bonds as temporary netpoints, which are cleavable by glucose and by minimizing the volume change upon stimulation by a porous cryogel structure. The polymer system consisted of a semi-interpenetrating network (semi-IPN) architecture, in which the triol moieties were part of the permanent network and the PBA moieties were located in the linear polymer diffused into the semi-IPN. In an alkaline medium (pH = 10), the swelling ratio was approximately 35, independent of C-glu varied between 0 and 300 mg/dL. In bending experiments, shape fixity R-f approximate to 80% and shape recovery R-r approximate to 100% from five programming/recovery cycles could be determined. R-r was a function of C-glu in the range from 0 to 300 mg/dL, which accords with the fluctuation range of C-glu in human blood. In this way, the shape-memory hydrogels could play a role in future diabetes treatment options. KW - shape memory KW - polymer KW - porosity Y1 - 2020 U6 - https://doi.org/10.1557/jmr.2020.204 SN - 0884-2914 SN - 2044-5326 VL - 35 IS - 18 SP - 2396 EP - 2404 PB - Springer CY - Berlin ER - TY - JOUR A1 - Bhaskar, Thanga Bhuvanesh Vijaya A1 - Ma, Nan A1 - Lendlein, Andreas A1 - Roch, Toralf T1 - The interaction of human macrophage subsets with silicone as a biomaterial JF - Clinical hemorheology and microcirculation : blood flow and vessels N2 - Silicones are widely used as biomaterials for medical devices such as extracorporeal equipments. However, there is often conflicting evidence about their supposed cell-and histocompatibility. Macrophages could mediate silicone-induced adverse responses such as foreign body reaction and fibrous encapsulation. The polarization behaviour of macrophages could determine the clinical outcome after implantation of biomaterials. Induction of classically activated macrophages (CAM) may induce and support uncontrolled inflammatory responses and undesired material degradation. In contrast, polarization into alternatively activated macrophages (AAM) is assumed to support healing processes and implant integration. This study compared the interaction of non-polarized macrophages (M0), CAM, and AAM with commercially available tissue culture polystyrene (TCP) and a medical grade silicone-based biomaterial, regarding the secretion of inflammatory mediators such as cytokines and chemokines. Firstly, by using the Limulus amoebocyte lysate (LAL) test the silicone films were shown to be free of soluble endotoxins, which is the prerequisite to investigate their interaction with primary immune cells. Primary human monocyte-derived macrophages (M0) were polarized into CAM and AAM by addition of suitable differentiation factors. These macrophage subsets were incubated on the materials for 24 hours and their viability and cytokine secretion was assessed. In comparison to TCP, cell adhesion was lower on silicone after 24 hours for all three macrophage subsets. However, compared to TCP, silicone induced higher levels of certain inflammatory and chemotactic cytokines in M0, CAM, and AAM macrophage subsets. Conclusively, it was shown that silicone has the ability to induce a pro-inflammatory state to different magnitudes dependent on the macrophage subsets. This priming of the macrophage phenotype by silicone could explain the incidence of severe foreign body complications observed in vivo. KW - Biomaterials KW - silicone KW - macrophage subsets KW - cytokines/chemokines Y1 - 2015 U6 - https://doi.org/10.3233/CH-151991 SN - 1386-0291 SN - 1875-8622 VL - 61 IS - 2 SP - 119 EP - 133 PB - IOS Press CY - Amsterdam ER - TY - JOUR A1 - Bhuvanesh, Thanga A1 - Machatschek, Rainhard Gabriel A1 - Lysyakova, Liudmila A1 - Kratz, Karl A1 - Schulz, Burkhard A1 - Ma, Nan A1 - Lendlein, Andreas T1 - Collagen type-IV Langmuir and Langmuir-Schafer layers as model biointerfaces to direct stem cell adhesion JF - Biomedical materials : materials for tissue engineering and regenerative medicine N2 - In biomaterial development, the design of material surfaces that mimic the extra-cellular matrix (ECM) in order to achieve favorable cellular instruction is rather challenging. Collagen-type IV (Col-IV), the major scaffolding component of Basement Membranes (BM), a specialized ECM with multiple biological functions, has the propensity to form networks by self-assembly and supports adhesion of cells such as endothelial cells or stem cells. The preparation of biomimetic Col-IV network-like layers to direct cell responses is difficult. We hypothesize that the morphology of the layer, and especially the density of the available adhesion sites, regulates the cellular adhesion to the layer. The Langmuir monolayer technique allows for preparation of thin layers with precisely controlled packing density at the air-water (A-W) interface. Transferring these layers onto cell culture substrates using the Langmuir-Schafer (LS) technique should therefore provide a pathway for preparation of BM mimicking layers with controlled cell adherence properties. In situ characterization using ellipsometry and polarization modulation-infrared reflection absorption spectroscopy of Col-IV layer during compression at the A-W interface reveal that there is linear increase of surface molecule concentration with negligible orientational changes up to a surface pressure of 25 mN m(-1). Smooth and homogeneous Col-IV network-like layers are successfully transferred by LS method at 15 mN m(-1) onto poly(ethylene terephthalate) (PET), which is a common substrate for cell culture. In contrast, the organization of Col-IV on PET prepared by the traditionally employed solution deposition method results in rather inhomogeneous layers with the appearance of aggregates and multilayers. Progressive increase in the number of early adherent mesenchymal stem cells (MSCs) after 24 h by controlling the areal Col-IV density by LS transfer at 10, 15 and 20 mN m(-1) on PET is shown. The LS method offers the possibility to control protein characteristics on biomaterial surfaces such as molecular density and thereby, modulate cell responses. KW - collagen-IV KW - basement membrane KW - Langmuir-Schafer films KW - stem cell adhesion KW - protein KW - ellipsometry Y1 - 2019 U6 - https://doi.org/10.1088/1748-605X/aaf464 SN - 1748-6041 SN - 1748-605X VL - 14 IS - 2 PB - Inst. of Physics Publ. CY - Bristol ER -