@article{ZhangLiuMachatscheketal.2022, author = {Zhang, Shanshan and Liu, Yue and Machatschek, Rainhard Gabriel and Lendlein, Andreas}, title = {Ultrathin collagen type I films formed at the air-water interface}, series = {MRS advances : a journal of the Materials Research Society (MRS)}, volume = {7}, journal = {MRS advances : a journal of the Materials Research Society (MRS)}, number = {4}, publisher = {Springer Nature Switzerland AG}, address = {Cham}, issn = {2059-8521}, doi = {10.1557/s43580-021-00160-8}, pages = {56 -- 62}, year = {2022}, abstract = {Collagen-based biomaterials with oriented fibrils have shown great application potential in medicine. However, it is still challenging to control the type I collagen fibrillogenesis in ultrathin films. Here, we report an approach to produce cohesive and well-organized type I collagen ultrathin films of about 10 nm thickness using the Langmuir-Blodgett technique. Ellipsometry, rheology, and Brewster angle microscopy are applied to investigate in situ how the molecules behave at the air-water interface, both at room temperature and 37 degrees C. The interfacial storage modulus observed at room temperature vanishes upon heating, indicating the existence and disappearance of the network structure in the protein nanosheet. The films were spanning over holes as large as 1 mm diameter when transferred at room temperature, proving the strong cohesive interactions. A highly aligned and fibrillar structure was observed by atomic force microscopy (AFM) and optical microscopy.}, language = {en} } @article{HoffmannMachatschekLendlein2022, author = {Hoffmann, Falk and Machatschek, Rainhard Gabriel and Lendlein, Andreas}, title = {Analytical model and Monte Carlo simulations of polymer degradation with improved chain cut statistics}, series = {Journal of materials research : JMR}, volume = {37}, journal = {Journal of materials research : JMR}, number = {5}, publisher = {Springer}, address = {Heidelberg}, issn = {0884-2914}, doi = {10.1557/s43578-022-00495-4}, pages = {1093 -- 1101}, year = {2022}, abstract = {The degradation of polymers is described by mathematical models based on bond cleavage statistics including the decreasing probability of chain cuts with decreasing average chain length. We derive equations for the degradation of chains under a random chain cut and a chain end cut mechanism, which are compared to existing models. The results are used to predict the influence of internal molecular parameters. It is shown that both chain cut mechanisms lead to a similar shape of the mass or molecular mass loss curve. A characteristic time is derived, which can be used to extract the maximum length of soluble fragments l of the polymer. We show that the complete description is needed to extract the degradation rate constant k from the molecular mass loss curve and that l can be used to design polymers that lose less mechanical stability before entering the mass loss phase.}, language = {en} } @article{TarazonaLizcanoMachatschekBalcuchoetal.2022, author = {Tarazona Lizcano, Natalia Andrea and Machatschek, Rainhard Gabriel and Balcucho, Jennifer and Castro-Mayorga, Jinneth Lorena and Saldarriaga, Juan Francisco and Lendlein, Andreas}, title = {Opportunities and challenges for integrating the development of sustainable polymer materials within an international circular (bio)economy concept}, series = {MRS energy \& sustainability : science \& technology \& socio-economics \& policy}, volume = {9}, journal = {MRS energy \& sustainability : science \& technology \& socio-economics \& policy}, number = {1}, publisher = {Springer Nature}, address = {London}, issn = {2329-2229}, doi = {10.1557/s43581-021-00015-7}, pages = {28 -- 34}, year = {2022}, abstract = {The production and consumption of commodity polymers have been an indispensable part of the development of our modern society. Owing to their adjustable properties and variety of functions, polymer-based materials will continue playing important roles in achieving the Sustainable Development Goals (SDG)s, defined by the United Nations, in key areas such as healthcare, transport, food preservation, construction, electronics, and water management. Considering the serious environmental crisis, generated by increasing consumption of plastics, leading-edge polymers need to incorporate two types of functions: Those that directly arise from the demands of the application (e.g. selective gas and liquid permeation, actuation or charge transport) and those that enable minimization of environmental harm, e.g., through prolongation of the functional lifetime, minimization of material usage, or through predictable disintegration into non-toxic fragments. Here, we give examples of how the incorporation of a thoughtful combination of properties/functions can enhance the sustainability of plastics ranging from material design to waste management. We focus on tools to measure and reduce the negative impacts of plastics on the environment throughout their life cycle, the use of renewable sources for their synthesis, the design of biodegradable and/or recyclable materials, and the use of biotechnological strategies for enzymatic recycling of plastics that fits into a circular bioeconomy. Finally, we discuss future applications for sustainable plastics with the aim to achieve the SDGs through international cooperation.
Leading-edge polymer-based materials for consumer and advanced applications are necessary to achieve sustainable development at a global scale. It is essential to understand how sustainability can be incorporated in these materials via green chemistry, the integration of bio-based building blocks from biorefineries, circular bioeconomy strategies, and combined smart and functional capabilities.}, language = {en} } @article{IzraylitLiuTarazonaetal.2021, author = {Izraylit, Victor and Liu, Yue and Tarazona, Natalia A. and Machatschek, Rainhard Gabriel and Lendlein, Andreas}, title = {Crystallization and degradation behaviour of multiblock copolyester blends in Langmuir monolayers}, series = {MRS communications / a publication of the Materials Research Society}, volume = {11}, journal = {MRS communications / a publication of the Materials Research Society}, number = {6}, publisher = {Springer}, address = {Berlin}, issn = {2159-6859}, doi = {10.1557/s43579-021-00107-y}, pages = {850 -- 855}, year = {2021}, abstract = {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.}, language = {en} } @article{MachatschekHeuchelLendlein2021, author = {Machatschek, Rainhard Gabriel and Heuchel, Matthias and Lendlein, Andreas}, title = {Thin-layer studies on surface functionalization of polyetherimide}, series = {Journal of materials research : JMR / Materials Research Society}, volume = {37}, journal = {Journal of materials research : JMR / Materials Research Society}, number = {1}, publisher = {Springer}, address = {Berlin}, issn = {0884-2914}, doi = {10.1557/s43578-021-00339-7}, pages = {67 -- 76}, year = {2021}, abstract = {Among the high-performance and engineering polymers, polyimides and the closely related polyetherimide (PEI) stand out by their capability to react with nucleophiles under relatively mild conditions. By targeting the phthalimide groups in the chain backbone, post-functionalization offers a pathway to adjust surface properties such as hydrophilicity, solvent resistance, and porosity. Here, we use ultrathin PEI films on a Langmuir trough as a model system to investigate the surface functionalization with ethylene diamine and tetrakis(4-aminophenyl)porphyrin as multivalent nucleophiles. By means of AFM, Raman spectroscopy, and interfacial rheology, we show that hydrolysis enhances the chemical and mechanical stability of ultrathin films and allows for the formation of EDC/NHS-activated esters. Direct amidation of PEI was achieved in the presence of a Lewis acid catalyst, resulting in free amine groups rather than cross-linking. When comparing amidation with hydrolysis, we find a greater influence of the latter on material properties.}, language = {en} } @article{MachatschekHeuchelLendlein2021, author = {Machatschek, Rainhard Gabriel and Heuchel, Matthias and Lendlein, Andreas}, title = {Hydrolytic stability of polyetherimide investigated in ultrathin films}, series = {Journal of materials research : JMR / Materials Research Society}, volume = {36}, journal = {Journal of materials research : JMR / Materials Research Society}, number = {14}, publisher = {Springer}, address = {Berlin}, issn = {0884-2914}, doi = {10.1557/s43578-021-00267-6}, pages = {2987 -- 2994}, year = {2021}, abstract = {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.}, language = {en} } @article{MachatschekSaretiaLendlein2021, author = {Machatschek, Rainhard Gabriel and Saretia, Shivam and Lendlein, Andreas}, title = {Assessing the influence of temperature-memory creation on the degradation of copolyesterurethanes in ultrathin films}, series = {Advanced materials interfaces}, volume = {8}, journal = {Advanced materials interfaces}, number = {6}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {2196-7350}, doi = {10.1002/admi.202001926}, pages = {8}, year = {2021}, abstract = {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.}, language = {en} } @article{SaretiaMachatschekLendlein2021, author = {Saretia, Shivam and Machatschek, Rainhard Gabriel and Lendlein, Andreas}, title = {Degradation kinetics of oligo(ε-caprolactone) ultrathin films}, series = {MRS advances : a journal of the Materials Research Society (MRS)}, volume = {6}, journal = {MRS advances : a journal of the Materials Research Society (MRS)}, number = {33}, publisher = {Springer Nature Switzerland AG}, address = {Cham}, issn = {2059-8521}, doi = {10.1557/s43580-021-00067-4}, pages = {790 -- 795}, year = {2021}, abstract = {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.}, language = {en} } @article{TarazonaMachatschekLendlein2020, author = {Tarazona, Natalia A. and Machatschek, Rainhard Gabriel and Lendlein, Andreas}, title = {Influence of depolymerases and lipases on the degradation of polyhydroxyalkanoates determined in Langmuir degradation studies}, series = {Advanced materials interfaces}, volume = {7}, journal = {Advanced materials interfaces}, number = {17}, publisher = {Wiley}, address = {Hoboken}, issn = {2196-7350}, doi = {10.1002/admi.202000872}, pages = {9}, year = {2020}, abstract = {Microbially produced polyhydroxyalkanoates (PHAs) are polyesters that are degradable by naturally occurring enzymes. Albeit PHAs degrade slowly when implanted in animal models, their disintegration is faster compared to abiotic hydrolysis under simulated physiological environments. Ultrathin Langmuir-Blodgett (LB) films are used as models for fast in vitro degradation testing, to predict enzymatically catalyzed hydrolysis of PHAs in vivo. The activity of mammalian enzymes secreted by pancreas and liver, potentially involved in biomaterials degradation, along with microbial hydrolases is tested toward LB-films of two model PHAs, poly(3-R-hydroxybutyrate) (PHB) and poly[(3-R-hydroxyoctanoate)-co-(3-R-hydroxyhexanoate)] (PHOHHx). A specific PHA depolymerase fromStreptomyces exfoliatus, used as a positive control, is shown to hydrolyze LB-films of both polymers regardless of their side-chain-length and phase morphology. From amorphous PHB and PHOHHx, approximate to 80\% is eroded in few hours, while mass loss for semicrystalline PHB is 25\%. Surface potential and interfacial rheology measurements show that material dissolution is consistent with a random-chain-scission mechanism. Degradation-induced crystallization of semicrystalline PHB LB-films is also observed. Meanwhile, the surface and the mechanical properties of both LB-films remain intact throughout the experiments with lipases and other microbial hydrolases, suggesting that non-enzymatic hydrolysis could be the predominant factor for acceleration of PHAs degradation in vivo.}, language = {en} } @article{HoffmannMachatschekLendlein2020, author = {Hoffmann, Falk and Machatschek, Rainhard Gabriel and Lendlein, Andreas}, title = {Understanding the impact of crystal lamellae organization on small molecule diffusion using a Monte Carlo approach}, series = {MRS advances : a journal of the Materials Research Society (MRS)}, volume = {5}, journal = {MRS advances : a journal of the Materials Research Society (MRS)}, number = {52-53}, publisher = {Cambridge University Press}, address = {Cambridge}, issn = {2059-8521}, doi = {10.1557/adv.2020.386}, pages = {2737 -- 2749}, year = {2020}, abstract = {Many physicochemical processes depend on the diffusion of small molecules through solid materials. While crystallinity in polymers is advantageous with respect to structure performance, diffusion in such materials is difficult to predict. Here, we investigate the impact of crystal morphology and organization on the diffusion of small molecules using a lattice Monte Carlo approach. Interestingly, diffusion determined with this model does not depend on the internal morphology of the semi-crystalline regions. The obtained insight is highly valuable for developing predictive models for all processes in semi-crystalline polymers involving mass transport, like polymer degradation or drug release, and provide design criteria for the time-dependent functional behavior of multifunctional polymer systems.}, language = {en} } @article{SaretiaMachatschekSchulzetal.2019, author = {Saretia, Shivam and Machatschek, Rainhard Gabriel and Schulz, Burkhard and Lendlein, Andreas}, title = {Reversible 2D networks of oligo(epsilon-caprolactone) at the air-water interface}, series = {Biomedical Materials}, volume = {14}, journal = {Biomedical Materials}, number = {3}, publisher = {IOP Publ. Ltd.}, address = {Bristol}, issn = {1748-6041}, doi = {10.1088/1748-605X/ab0cef}, pages = {10}, year = {2019}, abstract = {Hydroxyl terminated oligo(epsilon-caprolactone) (OCL) monolayers were reversibly cross-linked forming two dimensional networks (2D) at the air-water interface. The equilibrium reaction with glyoxal as the cross-linker is pH-sensitive. Pronounced contraction in the area of the prepared 2DOCL films in dependence of surface pressure and time revealed the process of the reaction. Cross-linking inhibited crystallization and retarded enzymatic degradation of the OCLfilm. Altering the subphase pH led to a cleavage of the covalent acetal cross-links. The reversibility of the covalent acetal cross-links was proved by observing an identical isotherm as non-cross-linked sample. Besides as model systems, these customizable reversible OCL2D networks are intended for use as pHresponsive drug delivery systems or functionalized cell culture substrates.}, language = {en} } @article{BhuvaneshMachatschekLysyakovaetal.2019, author = {Bhuvanesh, Thanga and Machatschek, Rainhard Gabriel and Lysyakova, Liudmila and Kratz, Karl and Schulz, Burkhard and Ma, Nan and Lendlein, Andreas}, title = {Collagen type-IV Langmuir and Langmuir-Schafer layers as model biointerfaces to direct stem cell adhesion}, series = {Biomedical materials : materials for tissue engineering and regenerative medicine}, volume = {14}, journal = {Biomedical materials : materials for tissue engineering and regenerative medicine}, number = {2}, publisher = {Inst. of Physics Publ.}, address = {Bristol}, issn = {1748-6041}, doi = {10.1088/1748-605X/aaf464}, pages = {17}, year = {2019}, abstract = {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.}, language = {en} } @article{TarazonaMachatschekSchulzetal.2019, author = {Tarazona, Natalia A. and Machatschek, Rainhard Gabriel and Schulz, Burkhard and Auxiliadora Prieto Jim{\´e}nez, M. and Lendlein, Andreas}, title = {Molecular Insights into the Physical Adsorption of Amphiphilic Protein PhaF onto Copolyester Surfaces}, series = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, volume = {20}, journal = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, number = {9}, publisher = {American Chemical Society}, address = {Washington}, issn = {1525-7797}, doi = {10.1021/acs.biomac.9b00069}, pages = {3242 -- 3252}, year = {2019}, abstract = {Phasins are amphiphilic proteins located at the polymer-cytoplasm interface of bacterial polyhydroxyalkanoates (PHA). The immobilization of phasins on biomaterial surfaces is a promising way to enhance the hydrophilicity and supply cell- directing elements in bioinstructing processes. Optimizing the physical adsorption of phasins requires deep insights into molecular processes during polymer-protein interactions to preserve their structural conformation while optimizing surface coverage. Here, the assembly, organization, and stability of phasin PhaF from Pseudomonas putida at interfaces is disclosed. The Langmuir technique, combined with in situ microscopy and spectroscopic methods, revealed that PhaF forms stable and robust monolayers at different temperatures, with an almost flat orientation of its alpha-helix at the air-water interface. PhaF adsorption onto preformed monolayers of poly[(3-R-hydroxyoctanoate)-co-(3-R-hydroxyhexanoate)] (PHOHHx), yields stable mixed layers below pi = similar to 15.7 mN/m. Further insertion induces a molecular reorganization. PHOHHx with strong surface hydrophobicity is a more adequate substrate for PhaF adsorption than the less hydrophobic poly[(rac-lactide)-co-glycolide] (PLGA). The observed orientation of the main axis of the protein in relation to copolyester interfaces ensures the best exposure of the hydrophobic residues, providing a suitable coating strategy for polymer functionalization.}, language = {en} } @article{MachatschekLendlein2019, author = {Machatschek, Rainhard Gabriel and Lendlein, Andreas}, title = {Fundamental insights in PLGA degradation from thin film studies}, series = {Journal of controlled release : official journal of the Controlled Release Society and of the Japanese Society of Drug Delivery Systems}, volume = {319}, journal = {Journal of controlled release : official journal of the Controlled Release Society and of the Japanese Society of Drug Delivery Systems}, publisher = {Elsevier}, address = {New York}, issn = {0168-3659}, doi = {10.1016/j.jconrel.2019.12.044}, pages = {276 -- 284}, year = {2019}, abstract = {Poly(lactide-co-glycolide)s are commercially available degradable implant materials, which are typically selected based on specifications given by the manufacturer, one of which is their molecular weight. Here, we address the question whether variations in the chain length and their distribution affect the degradation behavior of Poly[(rac-lactide)-co-glycolide]s (PDLLGA). The hydrolysis was studied in ultrathin films at the air-water interface in order to rule out any morphological effects. We found that both for purely hydrolytic degradation as well as under enzymatic catalysis, the molecular weight has very little effect on the overall degradation kinetics of PDLLGAs. The quantitative analysis suggested a random scission mechanism. The monolayer experiments showed that an acidic micro-pH does not accelerate the degradation of PDLLGAs, in contrast to alkaline conditions. The degradation experiments were combined with interfacial rheology measurements, which showed a drastic decrease of the viscosity at little mass loss. The extrapolated molecular weight behaved similar to the viscosity, dropping to a value near to the solubility limit of PDLLGA oligomers before mass loss set in. This observation suggests a solubility controlled degradation of PDLLGA. Conclusively, the molecular weight affects the degradation of PDLLGA devices mostly in indirect ways, e.g. by determining their morphology and porosity during fabrication. Our study demonstrates the relevance of the presented Langmuir degradation method for the design of controlled release systems.}, language = {en} } @article{TarazonaMachatschekLendlein2019, author = {Tarazona, Natalia A. and Machatschek, Rainhard Gabriel and Lendlein, Andreas}, title = {Unraveling the interplay between abiotic hydrolytic degradation and crystallization of bacterial polyesters comprising short and medium side-chain-length Polyhydroxyalkanoates}, series = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, volume = {21}, journal = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, number = {2}, publisher = {American Chemical Society}, address = {Washington}, issn = {1525-7797}, doi = {10.1021/acs.biomac.9b01458}, pages = {761 -- 771}, year = {2019}, abstract = {Polyhydroxyalkanoates (PHAs) have attracted attention as degradable (co)polyesters which can be produced by microorganisms with variations in the side chain. This structural variation influences not only the thermomechanical properties of the material but also its degradation behavior. Here, we used Langmuir monolayers at the air-water (A-W) interface as suitable models for evaluating the abiotic degradation of two PHAs with different side-chain lengths and crystallinity. By controlling the polymer state (semi crystalline, amorphous), the packing density, the pH, and the degradation mechanism, we could draw several significant conclusions. (i) The maximum degree of crystallinity for a PHA film to be efficiently degraded up to pH = 12.3 is 40\%. (ii) PHA made of repeating units with shorter side-chain length are more easily hydrolyzed under alkaline conditions. The efficiency of alkaline hydrolysis decreased by about 65\% when the polymer was 40\% crystalline. (iii) In PHA films with a relatively high initial crystallinity, abiotic degradation initiated a chemicrystallization phenomenon, detected as an increase in the storage modulus (E'). This could translate into an increase in brittleness and reduction in the material degradability. Finally, we demonstrate the stability of the measurement system for long-term experiments, which allows degradation conditions for polymers that could closely simulate real-time degradation.}, language = {en} } @article{MachatschekSchoeneRaschdorfetal.2019, author = {Machatschek, Rainhard Gabriel and Sch{\"o}ne, Anne-Christin and Raschdorf, Elisa and Ihlenburg, Ramona and Schulz, Burkhard and Lendlein, Andreas}, title = {Interfacial properties of morpholine-2,5-dione-based oligodepsipeptides and multiblock copolymers}, series = {MRS Communications}, volume = {9}, journal = {MRS Communications}, number = {1}, publisher = {Cambridge Univ. Press}, address = {New York}, issn = {2159-6859}, doi = {10.1557/mrc.2019.21}, pages = {170 -- 180}, year = {2019}, abstract = {Oligodepsipeptides (ODPs) with alternating amide and ester bonds prepared by ring-opening polymerization of morpholine-2,5-dione derivatives are promising matrices for drug delivery systems and building blocks for multifunctional biomaterials. Here, we elucidate the behavior of three telechelic ODPs and one multiblock copolymer containing ODP blocks at the air-water interface. Surprisingly, whereas the oligomers and multiblock copolymers crystallize in bulk, no crystallization is observed at the air-water interface. Furthermore, polarization modulation infrared reflection absorption spectroscopy is used to elucidate hydrogen bonding and secondary structures in ODP monolayers. The results will direct the development of the next ODP-based biomaterial generation with tailored properties for highly sophisticated applications.}, language = {en} } @misc{MachatschekSchoeneRaschdorfetal.2019, author = {Machatschek, Rainhard Gabriel and Sch{\"o}ne, Anne-Christin and Raschdorf, Elisa and Ihlenburg, Ramona and Schulz, Burkhard and Lendlein, Andreas}, title = {Interfacial properties of morpholine-2,5-dione-based oligodepsipeptides and multiblock copolymers}, series = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe}, journal = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe}, number = {1106}, issn = {1866-8372}, doi = {10.25932/publishup-46975}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-469755}, pages = {170 -- 180}, year = {2019}, abstract = {Oligodepsipeptides (ODPs) with alternating amide and ester bonds prepared by ring-opening polymerization of morpholine-2,5-dione derivatives are promising matrices for drug delivery systems and building blocks for multifunctional biomaterials. Here, we elucidate the behavior of three telechelic ODPs and one multiblock copolymer containing ODP blocks at the air-water interface. Surprisingly, whereas the oligomers and multiblock copolymers crystallize in bulk, no crystallization is observed at the air-water interface. Furthermore, polarization modulation infrared reflection absorption spectroscopy is used to elucidate hydrogen bonding and secondary structures in ODP monolayers. The results will direct the development of the next ODP-based biomaterial generation with tailored properties for highly sophisticated applications.}, language = {en} } @article{MachatschekSchulzLendlein2018, author = {Machatschek, Rainhard Gabriel and Schulz, Burkhard and Lendlein, Andreas}, title = {The influence of pH on the molecular degradation mechanism of PLGA}, series = {MRS Advances}, volume = {3}, journal = {MRS Advances}, number = {63}, publisher = {Cambridge Univ. Press}, address = {New York}, issn = {2059-8521}, doi = {10.1557/adv.2018.602}, pages = {3883 -- 3889}, year = {2018}, abstract = {Poly[(rac-lactide)-co-glycolide] (PLGA) is used in medicine to provide mechanical support for healing tissue or as matrix for controlled drug release. The properties of this copolymer depend on the evolution of the molecular weight of the material during degradation. which is determined by the kinetics of the cleavage of hydrolysable bonds. The generally accepted description of the degradation of PLGA is a random fragmentation that is autocatalyzed by the accumulation of acidic fragments inside the bulk material. Since mechanistic studies with lactide oligomers have concluded a chain-end scission mechanism and monolayer degradation experiments with polylactide found no accelerated degradation at lower pH, we hypothesize that the impact of acidic fragments on the molecular degradation kinetics of PLGA is overestimated By means of the Langmuir monolayer degradation technique. the molecular degradation kinetics of PLGA at different pH could be determined. Protons did not catalyze the degradation of PLGA. The molecular mechanism at neutral pH and low pH is a combination of random and chainend-cut events, while the degradation under strongly alkaline conditions is determined by rapid chainend cuts. We suggest that the degradation of bulk PLGA is not catalyzed by the acidic degradation products. Instead. increased concentration of small fragments leads to accelerated mass loss via fast chain-end cut events. In the future, we aim to substantiate the proposed molecular degradation mechanism of PLGA with interfacial rheology.}, language = {en} } @misc{MachatschekSchulzLendlein2018, author = {Machatschek, Rainhard Gabriel and Schulz, Burkhard and Lendlein, Andreas}, title = {Langmuir Monolayers as Tools to Study Biodegradable Polymer Implant Materials}, series = {Macromolecular rapid communications}, volume = {40}, journal = {Macromolecular rapid communications}, number = {1}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1336}, doi = {10.1002/marc.201800611}, pages = {11}, year = {2018}, abstract = {Langmuir monolayers provide a fast and elegant route to analyze the degradation behavior of biodegradable polymer materials. In contrast to bulk materials, diffusive transport of reactants and reaction products in the (partially degraded) material can be neglected at the air-water interface, allowing for the study of molecular degradation kinetics in experiments taking less than a day and in some cases just a few minutes, in contrast to experiments with bulk materials that can take years. Several aspects of the biodegradation behavior of polymer materials, such as the interaction with biomolecules and degradation products, are directly observable. Expanding the technique with surface-sensitive instrumental techniques enables evaluating the evolution of the morphology, chemical composition, and the mechanical properties of the degrading material in situ. The potential of the Langmuir monolayer degradation technique as a predictive tool for implant degradation when combined with computational methods is outlined, and related open questions and strategies to overcome these challenges are pointed out.}, language = {en} }