Filtern
Volltext vorhanden
- nein (29)
Erscheinungsjahr
- 2021 (29) (entfernen)
Dokumenttyp
Sprache
- Englisch (29)
Gehört zur Bibliographie
- ja (29) (entfernen)
Schlagworte
- Polymer (5)
- Actuation (2)
- Biomimetic (2)
- Membrane (2)
- Nanostructure (2)
- Shape memory (2)
- Thin film (2)
- biomaterial (2)
- degradation (2)
- endothelial cells (2)
Institut
- Institut für Chemie (29)
Copolyesterurethanes (PDLCLs) based on oligo(epsilon-caprolactone) (OCL) and oligo(omega-pentadecalactone) (OPDL) segments are biodegradable thermoplastic temperature-memory polymers. The temperature-memory capability in these polymers with crystallizable control units is implemented by a thermomechanical programming process causing alterations in the crystallite arrangement and chain organization. These morphological changes can potentially affect degradation. Initial observations on the macroscopic level inspire the hypothesis that switching of the controlling units causes an accelerated degradation of the material, resulting in programmable degradation by sequential coupling of functions. Hence, detailed degradation studies on Langmuir films of a PDLCL with 40 wt% OPDL content are carried out under enzymatic catalysis. The temperature-memory creation procedure is mimicked by compression at different temperatures. The evolution of the chain organization and mechanical properties during the degradation process is investigated by means of polarization-modulated infrared reflection absorption spectroscopy, interfacial rheology and to some extend by X-ray reflectivity. The experiments on PDLCL Langmuir films imply that degradability is not enhanced by thermal switching, as the former depends on the temperature during cold programming. Nevertheless, the thin film experiments show that the leaching of OCL segments does not induce further crystallization of the OPDL segments, which is beneficial for a controlled and predictable degradation.
The Venus flytrap is a fascinating plant with a finely tuned mechanical bi-stable system, which can switch between mono- and bi-stability. Here, we combine geometrical design of compliant mechanics and the function of shape-memory polymers to enable switching between bi- and mono-stable states. Digital design and modelling using the Chained Beam Constraint Model forecasted two geometries, which were experimentally realized as structured films of cross-linked poly[ethylene-co-(vinyl acetate)] supported by digital manufacturing. Mechanical evaluation confirmed our predicted features. We demonstrated that a shape-memory effect could switch between bi- and mono-stability for the same construct, effectively imitating the Venus flytrap.
Complexes from catalysts and initiator can be used to insert a specific number of additional chemical functional groups in (co)polymers prepared by ring-opening polymerization (ROP) of lactones. We report on the synthesis of cooligomers from sec-butyl-morpholine-2,5-dione (SBMD) and para-dioxanone (PDX) by ROP with varied feed ratios in the bulk using the catalyst complex SnOct(2)/2-hydroxyethyl sulfide. M-n of the cooligomers (determined by GPC) decreased with decreasing SBMD feed ratio from 4200 +/- 420 to 800 +/- 80 g mol(-1). When the feed ratio was reduced from 80 to 50 mol% the molar ratio of SBMD of the cooligomers (determined by H-1-NMR) remained nearly unchanged between 81 and 86 mol% and was attributed to a higher reactivity of SBMD. This assumption was confirmed by fractionation of GPC, in which an increase of SBMD with increasing molecular weight was observed. The catalyst/initiator system provides a high potential to create orthogonal building blocks by cleavage of the sulfide bond.
Crystallization and degradation behaviour of multiblock copolyester blends in Langmuir monolayers
(2021)
Supporting the wound healing of soft tissues requires fixation devices becoming more elastic while degrading. To address this unmet need, we designed a blend of degradable multiblock copolymers, which is cross-linked by PLA stereocomplexation combining two soft segments differing substantially in their hydrolytic degradation rate. The degradation path and concomitant structural changes are predicted by Langmuir monolayer technique. The fast hydrolysis of one soft segment leads to a decrease of the total polymer mass at constant physical cross-linking density. The corresponding increase of the average spacing between the network nodes suggests the targeted increase of the blend's flexibility.
The potential of using crystallinity as morphological parameter to control polyester degradation in acidic environments is explored in ultrathin films by Langmuir technique. Films of hydroxy or methacrylate end-capped oligo(epsilon-caprolactone) (OCL) are prepared at the air-water interface as a function of mean molecular area (MMA). The obtained amorphous, partially crystalline or highly crystalline ultrathin films of OCL are hydrolytically degraded at pH similar to 1.2 on water surface or on silicon surface as-transferred films. A high crystallinity reduces the hydrolytic degradation rate of the films on both water and solid surfaces. Different acceleration rates of hydrolytic degradation of semi-crystalline films are achieved either by crystals complete melting, partially melting, or by heating them below their melting temperatures. Semi-crystalline OCL films transferred via water onto a solid surface retain their crystalline morphology, degrade in a controlled manner, and are of interest as thermoswitchable coatings for cell substrates and medical devices.
Insufficient endothelialization of cardiovascular grafts is a major hurdle in vascular surgery and regenerative medicine, bearing a risk for early graft thrombosis. Neither of the numerous strategies pursued to solve these problems were conclusive. Endothelialization is regulated by the endothelial basement membrane (EBM), a highly specialized part of the vascular extracellular matrix. Thus, a detailed understanding of the structure-function interrelations of the EBM components is fundamental for designing biomimetic materials aiming to mimic EBM functions. In this review, a detailed description of the structure and functions of the EBM are provided, including the luminal and abluminal interactions with adjacent cell types, such as vascular smooth muscle cells. Moreover, in vivo as well as in vitro strategies to build or renew EBM are summarized and critically discussed. The spectrum of methods includes vessel decellularization and implant biofunctionalization strategies as well as tissue engineering-based approaches and bioprinting. Finally, the limitations of these methods are highlighted, and future directions are suggested to help improve future design strategies for EBM-inspired materials in the cardiovascular field.
Oligodepsipeptides (ODPs) attract increasing attention as degradable materials in controlled drug delivery or as building blocks for nano-carriers. Their strong intermolecular interactions provide high stability. Tailoring the side groups of the amino acid repeating units to achieve a strong affinity to particular drugs allows a high drug-loading capacity. Here we describe synthesis and characterization of dihydroxy terminated teroligodepsipeptides (ter-ODPs) by ring-opening copolymerization (ROP) of three different morpholine-2,5-diones (MDs) in bulk in order to provide a set of teroligomers with structural variation for drug release or transfection. Ter-ODPs with equivalent co-monomer feed ratios were prepared as well as ter-ODPs, in which the co-monomer feed ratio was varied between 9 mol% and 78 mol%. Ter-ODPs were synthesized by ROP using 1,1,10,10-tetra-n-butyl-1,10-distanna-2,9,11,18-tetraoxa-5,6,14,15-tetrasulfur-cyclodecane (tin(IV) alkoxide) that was obtained by the reaction of dibutyl tin(II) oxide with 2-hydroxyethyl disulfide. The number average molecular weight (M-n) of ter-ODPs, determined by H-1 NMR and gel permeation chromatography (GPC), ranged between 4000 g center dot mol(-1) and 8600 g center dot mol(-1). Co-monomer compositions in ter-ODPs could be controlled by changing the feed ratio of co-monomers as observed by H-1 NMR spectroscopy and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). The amount of remaining monomers as determined by H-1 NMR could be kept below 1 wt%. Macrocycles as main sources of byproducts as determined from MALDI-TOF-MS measurements were significantly lower as compared to polymerization by Sn(Oct)(2). Glass-transition temperature (T-g) of ter-ODPs ranged between 59 degrees C and 70 degrees C.
Effect of endothelial culture medium composition on platelet responses to polymeric biomaterials
(2021)
Near-physiological in vitro thrombogenicity test systems for the evaluation of blood-contacting endothelialized biomaterials requires co-cultivation with platelets (PLT). However, the addition of PLT has led to unphysiological endothelial cell (EC) detachment in such in vitro systems. A possible cause for this phenomenon may be PLT activation triggered by the applied endothelial cell medium, which typically consists of basal medium (BM) and nine different supplements. To verify this hypothesis, the influence of BM and its supplements was systematically analyzed regarding PLT responses. For this, human platelet rich plasma (PRP) was mixed with BM, BM containing one of nine supplements, or with BM containing all supplements together. PLT adherence analysis was carried out in six-channel slides with plasma-treated cyclic olefin copolymer (COC) and poly(tetrafluoro ethylene) (PTFE, as a positive control) substrates as part of the six-channel slides in the absence of EC and under static conditions. PLT activation and aggregation were analyzed using light transmission aggregometry and flow cytometry (CD62P). Medium supplements had no effect on PLT activation and aggregation. In contrast, supplements differentially affected PLT adherence, however, in a polymer- and donor-dependent manner. Thus, the use of standard endothelial growth medium (BM + all supplements) maintains functionality of PLT under EC compatible conditions without masking the differences of PLT adherence on different polymeric substrates. These findings are important prerequisites for the establishment of a near-physiological in vitro thrombogenicity test system assessing polymer-based cardiovascular implant materials in contact with EC and PLT.
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.
Ethylene oxide sterilization of electrospun poly(L-lactide)/poly(D-lactide) core/shell nanofibers
(2021)
The application of polymers in medicine requires sterilization while retaining material structure and properties. This demands detailed analysis, which we show exemplarily for the sterilization of PLLA/PDLA core-shell nanofibers with ethylene oxide (EtO). The electrospun patch was exposed to EtO gas (6 vol% in CO2, 1.7 bar) for 3 h at 45 degrees C and 75% rel. humidity, followed by degassing under pressure/vacuum cycles for 12 h. GC-MS analysis showed that no residual EtO was retained. Fiber diameters (similar to 520 +/- 130 nm) of the patches remained constant as observed by electron microscopy. Young's modulus slightly increased and the elongation at break slightly decreased, determined at 37 degrees C. No changes were detected in H-1-NMR spectra, in molar mass distribution (GPC) or in crystallinity measured for annealed samples with comparable thermal history (Wide Angle X-Ray Scattering). Altogether, EtO emerged as suitable sterilization method for polylactide nanofibers with core-shell morphology.
Fibrous shape-memory polymer (SMP) scaffolds were investigated considering the fiber as basic microstructural feature. By reduction of the fiber diameter in randomly oriented electrospun polyetherurethane (PEU) meshes from the micro-to the nano-scale, we observed changes in the molecular orientation within the fibers and its impact on the structural and shape-memory performance. It was assumed that a spatial restriction by reduction of the fiber diameter increases molecular orientation along the orientation of the fiber. The stress-strain relation of random PEU scaffolds is initially determined by the 3D arrangement of the fibers and thus is independent of the molecular orientation. Increasing the molecular orientation with decreasing single fiber diameter in scaffolds composed of randomly arranged fibers did not alter the initial stiffness and peak stress but strongly influenced the elongation at break and the stress increase above the Yield point. Reduction of the single fiber diameter also distinctly improved the shape-memory performance of the scaffolds. Fibers with nanoscale diameters (< 100 nm) possessed an almost complete shape recovery, high recovery stresses and fast relaxation kinetics, while the shape fixity was found to decrease with decreasing fiber diameter. Hence, the fiber diameter is a relevant design parameter for SMP.
Functionalization of gelatin with glycidylmethacrylate (GMA-gelatin) enables network formation employing the double bond, so that the reaction is orthogonal to the inherent functional groups in the biomacromolecule. Here, network formation by crosslinking of GMA-gelatin with hexane 1,6-dithiol or nonane 1,9-dithiol to tailor properties and enable a shape-memory effect is shown by H-1 NMR and FT-IR spectroscopy. Hydrogel swelling (460-1900 vol%) and mechanical properties (Young's modulus E = 59-512 kPa, elongation at break epsilon(b) = 44-127%) depended on the molecular composition of the networks and temperature. Increased crosslinker length, thiol:methacrylate molar ratio, and precursor concentrations led to denser networks. Change of properties with temperature suggested adoption of triple helices by gelatin chains, forming physical netpoints at lower temperatures (< 20 degrees C). However, the limited freedom of the gelatin chains to move allowed only a minimal extent of triple helices formation, as it became apparent from the related signal in wide-angle X-ray scattering and the thermal transition associated to triple helices in some networks by DSC. The presented strategy is likely transferable to other biomacromolecules, and the results suggest that too short crosslinkers may result in a significant amount of grafting rather than network formation.
Increasing the surface hydrophilicity of polyetherimide (PEI) through partial hydrolysis of the imide groups while maintaining the length of the main-chain was explored for adjusting its function in biomedical and membrane applications. The outcome of the polymer analogous reaction, i.e., the degree of ring opening and chain cleavage, is difficult to address in bulk and microstructured systems, as these changes only occur at the interface. Here, the reaction was studied at the air-water interface using the Langmuir technique, assisted by atomic force microscopy and vibrational spectroscopy. Slow PEI hydrolysis sets in at pH > 12. At pH = 14, the ring opening is nearly instantaneous. Reduction of the layer viscosity with time at pH = 14 suggested moderate chain cleavage. No hydrolysis was observed at pH = 1. Hydrolyzed PEI films had a much more cohesive structure, suggesting that the nanoporous morphology of PEI can be tuned via hydrolysis.
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.
The need for multifunctional materials is driven by emerging technologies and innovations, such as in the field of soft robotics and tactile or haptic systems, where minimizing the number of operational components is not only desirable, but can also be essential for realizing such devices. This study report on designing a multifunctional soft polymer material that can address a number of operating requirements such as solvent resistance, reshaping ability, self-healing capability, fluorescence stimuli-responsivity, and anisotropic structural functions. The numerous functional abilities are associated to rhodium(I)-phosphine coordination bonds, which in a polymer network act with their dynamic and non-covalently bonded nature as multifunctional crosslinks. Reversible aggregation of coordination bonds leads to changes in fluorescence emission intensity that responds to chemical or mechanical stimuli. The fast dynamics and diffusion of rhodium-phosphine ions across and through contacting areas of the material provide for reshaping and self-healing abilities that can be further exploited for assembly of multiple pieces into complex forms, all without any loss to material-sensing capabilities.
The hierarchical design approach provides various opportunities to adjust the structural performance of polymer materials. Electrospinning processing techniques give access to molecular orientation as a design parameter, which we consider here in view of the shape-memory actuation performance. The aim of this work is to investigate how the reversible strain epsilon'(rev) can be affected by a morphology change from a bulk material to an electrospun mesh. epsilon'(rev) could be increased from 5.5 +/- 0.5% to 15 +/- 1.8% for a blend from a multiblock copolymer with poly(epsilon-caprolactone) (PCL) and poly(L-lactide) (PLLA) segments with oligo(D-lactide) (ODLA). This study demonstrates an effective design approach for enhancing soft actuator performance, which can be broadly applied in soft robotics and medicine.
Active fibers can serve as artificial muscles in robotics or components of smart textiles. Here, we present an origami hand robot, where single fibers control the reversible movement of the fingers. A recovery/contracting force of 0.2 N with a work capacity of 0.175 kJ kg(-1) was observed in crosslinked poly[ethylene-co-(vinyl acetate)] (cPEVA) fibers, which could enable the bending movement of the fingers by contraction upon heating. The reversible opening of the fingers was attributed to a combination of elastic recovery force of the origami structure and crystallization-induced elongation of the fibers upon cooling.
Toll-like receptor (TLR) can trigger an immune response against virus including SARS-CoV-2. TLR expression/distribution is varying in mesenchymal stromal cells (MSCs) depending on their culture environments. Here, to explore the effect of periodic thermomechanical cues on TLRs, thermally controlled shape-memory polymer sheets with programmable actuation capacity were created. The proportion of MSCs expressing SARS-CoV-2-associated TLRs was increased upon stimulation. The TLR4/7 colocalization was promoted and retained in the endoplasmic reticula. The TLR redistribution was driven by myosin-mediated F-actin assembly. These results highlight the potential of boosting the immunity for combating COVID-19 via thermomechanical preconditioning of MSCs.
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.