@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} } @misc{SchoeneRochSchulzetal.2017, author = {Sch{\"o}ne, Anne-Christin and Roch, Toralf and Schulz, Burkhard and Lendlein, Andreas}, title = {Evaluating polymeric biomaterial-environment interfaces by Langmuir monolayer techniques}, series = {Interface : journal of the Royal Society}, volume = {14}, journal = {Interface : journal of the Royal Society}, publisher = {Royal Society}, address = {London}, issn = {1742-5689}, doi = {10.1098/rsif.2016.1028}, pages = {18}, year = {2017}, abstract = {Polymeric biomaterials are of specific relevance in medical and pharmaceutical applications due to their wide range of tailorable properties and functionalities. The knowledge about interactions of biomaterials with their biological environment is of crucial importance for developing highly sophisticated medical devices. To achieve optimal in vivo performance, a description at the molecular level is required to gain better understanding about the surface of synthetic materials for tailoring their properties. This is still challenging and requires the comprehensive characterization of morphological structures, polymer chain arrangements and degradation behaviour. The review discusses selected aspects for evaluating polymeric biomaterial-environment interfaces by Langmuir monolayer methods as powerful techniques for studying interfacial properties, such as morphological and degradation processes. The combination of spectroscopic, microscopic and scattering methods with the Langmuir techniques adapted to polymers can substantially improve the understanding of their in vivo behaviour.}, language = {en} } @article{RottkeSchulzRichauetal.2016, author = {Rottke, Falko O. and Schulz, Burkhard and Richau, Klaus and Kratz, Karl and Lendlein, Andreas}, title = {An ellipsometric approach towards the description of inhomogeneous polymer-based Langmuir layers}, series = {Beilstein journal of nanotechnology}, volume = {7}, journal = {Beilstein journal of nanotechnology}, publisher = {Beilstein-Institut zur F{\~A}\Prderung der Chemischen Wissenschaften}, address = {Frankfurt, Main}, issn = {2190-4286}, doi = {10.3762/bjnano.7.107}, pages = {1156 -- 1165}, year = {2016}, abstract = {The applicability of nulling-based ellipsometric mapping as a complementary method next to Brewster angle microscopy (BAM) and imaging ellipsometry (IE) is presented for the characterization of ultrathin films at the air-water interface. First, the methodology is demonstrated for a vertically nonmoving Langmuir layer of star-shaped, 4-arm poly(omega-pentadecalactone) (PPDL-D4). Using nulling-based ellipsometric mapping, PPDL-D4-based inhomogeneously structured morphologies with a vertical dimension in the lower nm range could be mapped. In addition to the identification of these structures, the differentiation between a monolayer and bare water was possible. Second, the potential and limitations of this method were verified by applying it to more versatile Langmuir layers of telechelic poly[(rac-lactide)-co-glycolide]-diol (PLGA). All ellipsometric maps were converted into thickness maps by introduction of the refractive index that was derived from independent ellipsometric experiments, and the result was additionally evaluated in terms of the root mean square roughness, R-q. Thereby, a three-dimensional view into the layers was enabled and morphological inhomogeneity could be quantified.}, language = {en} } @article{SchoeneRichauKratzetal.2015, author = {Sch{\"o}ne, Anne-Christin and Richau, Klaus and Kratz, Karl and Schulz, Burkhard and Lendlein, Andreas}, title = {Influence of Diurethane Linkers on the Langmuir Layer Behavior of Oligo[(rac-lactide)-co-glycolide]-based Polyesterurethanes}, series = {Macromolecular rapid communications}, volume = {36}, journal = {Macromolecular rapid communications}, number = {21}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1336}, doi = {10.1002/marc.201500316}, pages = {1910 -- 1915}, year = {2015}, abstract = {Three oligo[(rac-lactide)-co-glycolide] based polyesterurethanes (OLGA-PUs) containing different diurethane linkers are investigated by the Langmuir monolayer technique and compared to poly[(rac-lactide)-co-glycolide] (PLGA) to elucidate the influence of the diurethane junction units on hydrophilicity and packing motifs of these polymers at the air-water interface. The presence of diurethane linkers does not manifest itself in the Langmuir layer behavior both in compression and expansion experiments when monomolecular films of OLGA-PUs are spread on the water surface. However, the linker retard the evolution of morphological structures at intermediate compression level under isobaric conditions (with a surface pressure greater than 11 mN m(-1)) compared to the PLGA, independent on the chemical structure of the diurethane moiety. The layer thicknesses of both OLGA-PU and PLGA films decrease in the high compression state with decreasing surface pressure, as deduced from ellipsometric data. All films must be described with the effective medium approximation as water swollen layers.}, language = {en} } @phdthesis{Heinig2003, author = {Heinig, Peter}, title = {The geometry of interacting liquid domains in Langmuir monolayers}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-0000814}, school = {Universit{\"a}t Potsdam}, year = {2003}, abstract = {Es werden die Strukturbildung und Benetzung zweidimensionaler (2D) Phasen von Langmuir-Monolagen im lokalen thermodynamischen Gleichgewicht untersucht. Eine Langmuir-Monolage ist ein isoliertes 2D System von Surfaktanten an der Wasser/Luft-Grenzfl{\"a}che, in dem kristalline, fl{\"u}ssigkristalline, fl{\"u}ssige oder gasf{\"o}rmige Phasen auftreten, die sich in Positionsordnung und/oder Orientierungsordnung unterscheiden. Permanente elektrische Dipolmomente der Surfaktanten f{\"u}hren zu einer langreichweitigen repulsiven Selbstwechselwirkung der Monolage und zur Bildung mesoskopischer Strukturen. Es wird ein Wechselwirkungsmodell verwendet, das die Strukturbildung als Wechselspiel kurzreichweitiger Anziehung (nackte Linienspannung) und langreichweitiger Abstoßung (Oberfl{\"a}chenpotential) auf einer Skala Delta beschreibt. Physikalisch trennt Delta die beiden L{\"a}ngenskalen der lang- und kurzreichweitigen Wechselwirkung. In dieser Arbeit werden die thermodynamischen Stabilit{\"a}tsbedingungen f{\"u}r die Form einer Phasengrenzlinie (Young-Laplace-Gleichung) und Dreiphasenkontaktpunkt (Young-Bedingung) hergeleitet und zur Beschreibung experimenteller Daten genutzt: Die Linienspannung benetzender 2D Tropfen wird mit Hilfe h{\"a}ngender-Tropfen-Tensiometrie gemessen. Die Blasenform und -gr{\"o}ße von 2D Sch{\"a}umen wird theoretisch modelliert und mit experimentellen 2D Sch{\"a}umen verglichen. Kontaktwinkel werden durch die Anpassung von experimentellen Tropfen mit numerischen L{\"o}sungen der Young-Laplace-Gleichung auf Mikrometerskalen gemessen. Das Skalenverhalten des Kontaktwinkels erm{\"o}glicht die Bestimmung einer unteren Schranke von Delta. Weiterhin wird diskutiert, inwieweit das Schalten von 2D Benetzungsmodi in biologischen Membranen zur Steuerung der Reaktionskinetik ein Rolle spielen k{\"o}nnte. Hierzu werden Experimente aus unserer Gruppe, die in einer Langmuir-Monolage durchgef{\"u}hrt wurden, herangezogen. Abschließend wird die scheinbare Verletzung der Gibbs\′schen Phasenregel in Langmuir-Monolagen (nicht-horizontales Plateau der Oberfl{\"a}chendruck-Fl{\"a}che Isotherme, ausgedehntes Dreiphasengebiet in Einkomponentensystemen) quantitativ untersucht. Eine Verschmutzung der verwendeten Substanzen ist demnach die wahscheinlichste Erkl{\"a}rung, w{\"a}hrend Finite-Size-Effekte oder der Einfluss der langreichweitigen Elektrostatik die Gr{\"o}ßenordnung des Effektes nicht beschreiben k{\"o}nnen.}, language = {en} }