2023, Toshchevikov, Vladimir, Saphiannikova, Marina

Azobenzene-containing polymers (azo-polymers) have been a subject of extensive investigations during the last two and half decades, due to their remarkable ability to undergo pronounced alignment and deformation under irradiation with light. The molecular ordering and deformation in azo-polymers of various structures under irradiation with linearly polarized light was described in a series of theoretical works, based on the effect of the reorientation of azobenzene moieties due to the anisotropic character of the photoisomerization processes. In the present study, we generalize the previous orientation approach to describe the photo-alignment and deformation of azo-polymer networks under irradiation with elliptically polarized light. We demonstrate that, in general, the light-induced ordering and deformation have a biaxial symmetry defined by the polarization ellipse. Azobenzene chromophores have a tendency to align along the direction of light propagation, the orientation in the other two directions being dependent of the aspect ratio of the polarization ellipse. This causes deformation of azo-polymer networks along the direction of light propagation, the sign of which (expansion/contraction) is defined by a chemical structure of network strands. Theoretical results are in agreement with experiments and have a practical importance to predict the photo-mechanical response of azo-polymers depending on their structure and on the polarization of light.

2020, Schulze-Tanzil, Gundula, Arnold, Philipp, Gögele, Clemens, Hahn, Judith, Breier, Annette, Meyer, Michael, Kohl, Benjamin, Schröpfer, Michaela, Schwarz, Silke

Cultured human primary cells have a limited lifespan undergoing dedifferentiation or senescence. Anterior cruciate ligaments (ACL) are hypocellular but tissue engineering (TE) requires high cell numbers. Simian virus (SV) 40 tumor (T) antigen expression could extend the lifespan of cells. This study aimed to identify cellular changes induced by SV40 expression in human ACL ligamentocytes by comparing them with non-transfected ligamentocytes and tissue of the same donor to assess their applicability as TE model. Human ACL ligamentocytes (40-year-old female donor after ACL rupture) were either transfected with a SV40 plasmid or remained non-transfected (control) before monitored for SV40 expression, survival, and DNA content. Protein expression of cultured ligamentocytes was compared with the donor tissue. Ligamentocyte spheroids were seeded on scaffolds embroidered either from polylactic acid (PLA) threads solely or combined PLA and poly (L-lactide-co-e-caprolactone) (P(LA-CL)) threads. These scaffolds were further functionalized with fluorination and fibrillated collagen foam. Cell distribution and survival were monitored for up to five weeks. The transfected cells expressed the SV40 antigen throughout the entire observation time, but often exhibited random and incomplete cell divisions with significantly more dying cells, significantly more DNA and more numerous nucleoli than controls. The expression profile of non-transfected and SV40-positive ligamentocytes was similar. In contrast to controls, SV40-positive cells formed larger spheroids, produced less vimentin and focal adhesions and died on the scaffolds after 21 d. Functionalized scaffolds supported human ligamentocyte growth. SV40 antigen expressing ligamentocytes share many properties with their non-transfected counterparts suggesting them as a model, however, applicability for TE is limited. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.

2021, Moreno, Silvia, Boye, Susanne, Ajeilat, Hane George Al, Michen, Susanne, Tietze, Stefanie, Voit, Brigitte, Lederer, Albena, Temme, Achim, Appelhans, Dietmar

Synthetic platforms for mimicking artificial organelles or for designing multivalent protein therapeutics for targeting cell surface, extracellular matrix, and tissues are in the focus of this study. Furthermore, the availability of a multi-functionalized and stimuli-responsive carrier system is required that can be used for sequential in situ and/or post loading of different proteins combined with post-functionalization steps. Until now, polymersomes exhibit excellent key characteristics to fulfill those requirements, which allow specific transport of proteins and the integration of proteins in different locations of polymeric vesicles. Herein, different approaches to fabricate multivalent protein-loaded, pH-responsive, and pH-stable polymersomes are shown, where a combination of therapeutic action and targeting can be achieved, by first choosing two model proteins such as human serum albumin and avidin. Validation of the molecular parameters of the multivalent biohybrids is performed by dynamic light scattering, cryo-TEM, fluorescence spectroscopy, and asymmetrical flow-field flow fractionation combined with light scattering techniques. To demonstrate targeting functions of protein-loaded polymersomes, avidin post-functionalized polymersomes are used for the molecular recognition of biotinylated cell surface receptors. These versatile protein-loaded polymersomes present new opportunities for designing sophisticated biomolecular nanoobjects in the field of (extracellular matrix) protein therapeutics.

2023, Sharapov, Ainur D., Fatykhov, Ramil F., Khalymbadzha, Igor A., Zyryanov, Grigory V., Chupakhin, Oleg N., Tsurkan, Mikhail V.

This review summarizes and systematizes the literature on the anti-HIV activity of plant coumarins with emphasis on isolation and the mechanism of their antiviral action. This review summarizes the information on the anti-HIV properties of simple coumarins as well as annulated furano- and pyranocoumarins and shows that coumarins of plant origin can act by several mechanisms: inhibition of HIV reverse transcriptase and integrase, inhibition of cellular factors that regulate HIV-1 replication, and transmission of viral particles from infected macrophages to healthy ones. It is important to note that some pyranocoumarins are able to act through several mechanisms or bind to several sites, which ensures the resistance of these compounds to HIV mutations. Here we review the last two decades of research on the anti-HIV activity of naturally occurring coumarins.

2020, Gögele, Clemens, Hahn, Judith, Elschner, Cindy, Breier, Annette, Schröpfer, Michaela, Prade, Ina, Meyer, Michael, Schulze-Tanzil, Gundula

Reconstruction of ruptured anterior cruciate ligaments (ACLs) is limited by the availability and donor site morbidity of autografts. Hence, a tissue engineered graft could present an alternative in the future. This study was undertaken to determine the performance of lapine (L) ACL-derived fibroblasts on embroidered poly(l-lactide-co-e-caprolactone) (P(LA-CL)) and polylactic acid (PLA) scaffolds in regard to a tissue engineering approach for ACL reconstruction. Surface modifications of P(LA-CL)/PLA by gas-phase fluorination and cross-linking of a collagen foam using either ethylcarbodiimide (EDC) or hexamethylene diisocyanate (HMDI) were tested regarding their influence on cell adhesion, growth and gene expression. The experiments were performed using embroidered P(LA-CL)/PLA scaffolds that were seeded dynamically or statically with LACL-derived fibroblasts. Scaffold cytocompatibility, cell survival, numbers, metabolic activity, ultrastructure and sulfated glycosaminoglycan (sGAG) synthesis were evaluated. Quantitative real-time polymerase chain reaction (QPCR) revealed gene expression of collagen type I (COL1A1), decorin (DCN), tenascin C (TNC), Mohawk (MKX) and tenomodulin (TNMD). All tested scaffolds were highly cytocompatible. A significantly higher cellularity and larger scaffold surface areas colonized by cells were detected in HMDI cross-linked and fluorinated scaffolds compared to those cross-linked with EDC or without any functionalization. By contrast, sGAG synthesis was higher in controls. Despite the fact that the significance level was not reached, gene expressions of ligament extracellular matrix components and differentiation markers were generally higher in fluorinated scaffolds with cross-linked collagen foams. LACL-derived fibroblasts maintained their differentiated phenotype on fluorinated scaffolds supplemented with a HMDI cross-linked collagen foam, making them a promising tool for ACL tissue engineering. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.

2022-2-26, Anju, Yadav, Raghvendra Singh, Pötschke, Petra, Pionteck, Jürgen, Krause, Beate, Kuřitka, Ivo, Vilčáková, Jarmila, Škoda, David, Urbánek, Pavel, Machovský, Michal, Masař, Milan, Urbánek, Michal

CuxCo1-x Fe2O4 (x = 0.33,0.67,1)-reduced graphene oxide (rGO)-thermoplastic polyurethane (TPU) nanocomposites exhibiting highly efficient electromagnetic interference (EMI) shielding were prepared by a melt-mixing approach using a microcompounder. Spinel ferrite Cu0.33Co0.67Fe2O4 (Cu-CoF1), Cu0.67Co0.33Fe2O4 (CuCoF2) and CuFe2O4 (CuF3) nanoparticles were synthesized using the sonochemical method. The CuCoF1 and CuCoF2 exhibited typical ferromagnetic features, whereas CuF3 displayed superparamagnetic characteristics. The maximum value of EMI total shielding effectiveness (SEt) was noticed to be 42.9 dB, 46.2 dB, and 58.8 dB for CuCoF1-rGO-TPU, CuCoF2-rGO-TPU, and CuF3-rGO-TPU nanocomposites, respectively, at a thickness of 1 mm. The highly efficient EMI shielding performance was attributed to the good impedance matching, conductive, dielectric, and magnetic loss. The demonstrated nanocomposites are promising candidates for a lightweight, flexible, and highly efficient EMI shielding material.

2020, Ye, Jingjing, Weichelt, Richard, Kemper, Ulrich, Gupta, Vaibhav, König, Tobias A.F., Eychmüller, Alexander, Seidel, Ralf

DNA nanostructures provide a powerful platform for the programmable assembly of nanomaterials. Here this approach is extended to synthesize rod-like gold nanoparticles in a full DNA controlled manner. The approach is based on DNA molds containing elongated cavities. Gold is deposited inside the molds using a seeded-growth procedure. By carefully exploring the growth parameters it is shown that gold nanostructures with aspect ratios of up to 7 can be grown from single seeds. The highly anisotropic growth is in this case controlled only by the rather soft and porous DNA walls. The optimized seeded growth procedure provides a robust and simple routine to achieve continuous gold nanostructures using DNA templating.

2020, Moreno, Silvia, Sharan, Priyanka, Engelke, Johanna, Gumz, Hannes, Boye, Susanne, Oertel, Ulrich, Wang, Peng, Banerjee, Susanta, Klajn, Rafal, Voit, Brigitte, Lederer, Albena, Appelhans, Dietmar

Temporal activation of biological processes by visible light and subsequent return to an inactive state in the absence of light is an essential characteristic of photoreceptor cells. Inspired by these phenomena, light-responsive materials are very attractive due to the high spatiotemporal control of light irradiation, with light being able to precisely orchestrate processes repeatedly over many cycles. Herein, it is reported that light-driven proton transfer triggered by a merocyanine-based photoacid can be used to modulate the permeability of pH-responsive polymersomes through cyclic, temporally controlled protonation and deprotonation of the polymersome membrane. The membranes can undergo repeated light-driven swelling-contraction cycles without losing functional effectiveness. When applied to enzyme loaded-nanoreactors, this membrane responsiveness is used for the reversible control of enzymatic reactions. This combination of the merocyanine-based photoacid and pH-switchable nanoreactors results in rapidly responding and versatile supramolecular systems successfully used to switch enzymatic reactions ON and OFF on demand.

2021, Wong, Felix, Wilson, Sean, Helbig, Ralf, Hegde, Smitha, Aftenieva, Olha, Zheng, Hai, Liu, Chenli, Pilizota, Teuta, Garner, Ethan C., Amir, Ariel, Renner, Lars D.

Mechanical rupture, or lysis, of the cytoplasmic membrane is a common cell death pathway in bacteria occurring in response to β-lactam antibiotics. A better understanding of the cellular design principles governing the susceptibility and response of individual cells to lysis could indicate methods of potentiating β-lactam antibiotics and clarify relevant aspects of cellular physiology. Here, we take a single-cell approach to bacterial cell lysis to examine three cellular features-turgor pressure, mechanosensitive channels, and cell shape changes-that are expected to modulate lysis. We develop a mechanical model of bacterial cell lysis and experimentally analyze the dynamics of lysis in hundreds of single Escherichia coli cells. We find that turgor pressure is the only factor, of these three cellular features, which robustly modulates lysis. We show that mechanosensitive channels do not modulate lysis due to insufficiently fast solute outflow, and that cell shape changes result in more severe cellular lesions but do not influence the dynamics of lysis. These results inform a single-cell view of bacterial cell lysis and underscore approaches of combatting antibiotic tolerance to β-lactams aimed at targeting cellular turgor.

2021, Horn, Christoph, Ihmann, Stephanie, Müller, Felix, Pospiech, Doris, Borchert, Konstantin B. L., Hommel, Rolf, Qin, Kaite, Licha, Kai, Allertz, Peter J., Drache, Marco

Advanced oxidation processes are the main way to remove persistent organic trace compounds from water. For these processes, heterogeneous Fenton catalysts with low iron leaching and high catalytic activity are required. Here, the preparation of such catalysts consisting of silica-supported iron oxide (Fe2O3/SiOx) embedded in thermoplastic polymers is presented. The iron oxide catalysts are prepared by a facile sol–gel procedure followed by thermal annealing (calcination). These materials are mixed in a melt compounding process with modified polypropylenes to stabilize the Fe2O3 catalytic centers and to further reduce the iron leaching. The catalytic activity of the composites is analyzed by means of the Reactive Black 5 (RB5) assay, as well as by the conversion of phenol which is used as an example of an organic trace compound. It is demonstrated that embedding of silica-supported iron oxide in modified polypropylene turns the reaction order from pseudo-first order (found for Fe2O3/SiOx catalysts), which represents a mainly homogeneous Fenton reaction, to pseudo-zeroth order in the polymer composites, indicating a mainly heterogeneous, surface-diffusion-controlled process.