2021, Liu, Kejun, Li, Jiang, Qi, Haoyuan, Hambsch, Mike, Rawle, Jonathan, Vázquez, Adrián Romaní, Nia, Ali Shaygan, Pashkin, Alexej, Schneider, Harald, Polozij, Mirosllav, Heine, Thomas, Helm, Manfred, Mannsfeld, Stefan C.B., Kaiser, Ute, Dong, Renhao, Feng, Xinliang

Two-dimensional polymers (2DPs) are a class of atomically/molecularly thin crystalline organic 2D materials. They are intriguing candidates for the development of unprecedented organic–inorganic 2D van der Waals heterostructures (vdWHs) with exotic physicochemical properties. In this work, we demonstrate the on-water surface synthesis of large-area (cm2), monolayer 2D polyimide (2DPI) with 3.1-nm lattice. Such 2DPI comprises metal-free porphyrin and perylene units linked by imide bonds. We further achieve a scalable synthesis of 2DPI-graphene (2DPI-G) vdWHs via a face-to-face co-assembly of graphene and 2DPI on the water surface. Remarkably, femtosecond transient absorption spectroscopy reveals an ultra-fast interlayer charge transfer (ca. 60 fs) in the resultant 2DPI-G vdWH upon protonation by acid, which is equivalent to that of the fastest reports among inorganic 2D vdWHs. Such large interlayer electronic coupling is ascribed to the interlayer cation–π interaction between 2DP and graphene. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

2020, Hosseini, Kamran, Taubenberger, Anna, Werner, Carsten, Fischer-Friedrich, Elisabeth

To undergo mitosis successfully, most animal cells need to acquire a round shape to provide space for the mitotic spindle. This mitotic rounding relies on mechanical deformation of surrounding tissue and is driven by forces emanating from actomyosin contractility. Cancer cells are able to maintain successful mitosis in mechanically challenging environments such as the increasingly crowded environment of a growing tumor, thus, suggesting an enhanced ability of mitotic rounding in cancer. Here, it is shown that the epithelial–mesenchymal transition (EMT), a hallmark of cancer progression and metastasis, gives rise to cell-mechanical changes in breast epithelial cells. These changes are opposite in interphase and mitosis and correspond to an enhanced mitotic rounding strength. Furthermore, it is shown that cell-mechanical changes correlate with a strong EMT-induced change in the activity of Rho GTPases RhoA and Rac1. Accordingly, it is found that Rac1 inhibition rescues the EMT-induced cortex-mechanical phenotype. The findings hint at a new role of EMT in successful mitotic rounding and division in mechanically confined environments such as a growing tumor.

2021, Schirmer, Lucas, Atallah, Passant, Freudenberg, Uwe, Werner, Carsten

Excessive inflammation often impedes the healing of chronic wounds. Scavenging of chemokines by multiarmed poly(ethylene glycol)-glycosaminoglycan (starPEG-GAG) hydrogels has recently been shown to support regeneration in a diabetic mouse chronic skin wound model. Herein, a textile-starPEG-GAG composite wound contact layer (WCL) capable of selectively sequestering pro-inflammatory chemokines is reported. Systematic variation of the local and integral charge densities of the starPEG-GAG hydrogel component allows for tailoring its affinity profile for biomolecular signals of the wound milieu. The composite WCL is subsequently tested in a large animal (porcine) model of human wound healing disorders. Dampening excessive inflammatory signals without affecting the levels of pro-regenerative growth factors, the starPEG-GAG hydrogel-based WCL treatment induced healing with increased granulation tissue formation, angiogenesis, and deposition of connective tissue (collagen fibers). Thus, this biomaterials technology expands the scope of a new anti-inflammatory therapy toward clinical use.

2021, Ruland, André, Schenker, Saskia, Schirmer, Lucas, Friedrichs, Jens, Meinhardt, Andrea, Schwartz, Véronique B., Kaiser, Nadine, Konradi, Rupert, MacDonald, William, Helmecke, Tina, Sikosana, Melissa K.L.N., Valtin, Juliane, Hahn, Dominik, Renner, Lars D., Werner, Carsten, Freudenberg, Uwe

Precision surface engineering is key to advanced biomaterials. A new platform of PEGylated styrene-maleic acid copolymers for adsorptive surface biofunctionalization is reported. Balanced amphiphilicity renders the copolymers water-soluble but strongly affine for surfaces. Fine-tuning of their molecular architecture provides control over adsorptive anchorage onto specific materials-which is why they are referred to as "anchor polymers" (APs)-and over structural characteristics of the adsorbed layers. Conjugatable with an array of bioactives-including cytokine-complexing glycosaminoglycans, cell-adhesion-mediating peptides and antimicrobials-APs can be applied to customize materials for demanding biotechnologies in uniquely versatile, simple, and robust ways. Moreover, homo- and heterodisplacement of adsorbed APs provide unprecedented means of in situ alteration and renewal of the functionalized surfaces. The related options are exemplified with proof-of-concept experiments of controlled bacterial adhesion, human umbilical vein endothelial cell, and induced pluripotent cell growth on AP-functionalized surfaces.

2021, Steiner, Anja Maria, Lissel, Franziska, Fery, Andreas, Lauth, Jannika, Scheele, Marcus

We review the field of organic–inorganic nanocomposites with a focus on materials that exhibit a significant degree of electronic coupling across the hybrid interface. These nanocomposites undergo a variety of charge and energy transfer processes, enabling optoelectronic applications in devices which exploit singlet fission, triplet energy harvesting, photon upconversion or hot charge carrier transfer. We discuss the physical chemistry of the most common organic and inorganic components. Based on those we derive synthesis and assembly strategies and design criteria on material and device level with a focus on photovoltaics, spin memories or optical upconverters. We conclude that future research in the field should be directed towards an improved understanding of the binding motif and molecular orientation at the hybrid interface. © 2020 The Authors. Published by Wiley-VCH GmbH

2023, Aftenieva, Olha, Sudzius, Markas, Prudnikau, Anatol, Adnan, Mohammad, Sarkar, Swagato, Lesnyak, Vladimir, Leo, Karl, Fery, Andreas, König, Tobias A.F.

Miniaturized laser sources with low threshold power are required for integrated photonic devices. Photostable core/shell nanocrystals are well suited as gain material and their laser properties can be exploited by direct patterning as distributed feedback (DFB) lasers. Here, the 2nd-order DFB resonators tuned to the photoluminescence wavelength of the QDs are used. Soft lithography based on template-assisted colloidal self-assembly enables pattern resolution in the subwavelength range. Combined with the directional Langmuir–Blodgett arrangement, control of the waveguide layer thickness is further achieved. It is shown that a lasing threshold of 5.5 mJ cm−2 is reached by a direct printing method, which can be further reduced by a factor of ten (0.6 mJ cm−2) at an optimal waveguide thickness. Moreover, it is discussed how one can adjust the DFB geometries to any working wavelength. This colloidal approach offers prospects for applications in bioimaging, biomedical sensing, anti-counterfeiting, or displays.

2021, Hahn, Dominik, Sonntag, Jannick M., Lück, Steffen, Maitz, Manfred F., Freudenberg, Uwe, Jordan, Rainer, Werner, Carsten

Poly(ethylene glycol) (PEG)-glycosaminoglycan (GAG) hydrogel networks are established as very versatile biomaterials. Herein, the synthetic gel component of the biohybrid materials is systematically varied by combining different poly(2-alkyl-2-oxazolines) (POx) with heparin applying a Michael-type addition crosslinking scheme: POx of gradated hydrophilicity and temperature-responsiveness provides polymer networks of distinctly different stiffness and swelling. Adjusting the mechanical properties and the GAG concentration of the gels to similar values allows for modulating the release of GAG-binding growth factors (VEGF165 and PDGF-BB) by the choice of the POx and its temperature-dependent conformation. Adsorption of fibronectin, growth of fibroblasts, and bacterial adhesion scale with the hydrophobicity of the gel-incorporated POx. In vitro hemocompatibility tests with freshly drawn human whole blood show advantages of POx-based gels compared to the PEG-based reference materials. Biohybrid POx hydrogels can therefore enable biomedical technologies requiring GAG-based materials with customized and switchable physicochemical characteristics. © 2021 The Authors. Advanced Healthcare Materials published by Wiley-VCH GmbH.

2020, Zessin, Johanna, Schnepf, Max, Oertel, Ulrich, Beryozkina, Tetyana, König, Tobias A.F., Fery, Andreas, Mertig, Michael, Kiriy, Anton

A novel mechanism for well-pronounced mechanochromism in blends of a π-conjugated polymer based on reversible conformational transitions of a chromophore rather than caused by its aggregation state, is exemplified. Particularly, a strong stretching-induced bathochromic shift of the light absorption, or hypsochromic shift of the emission, is found in blends of the water-soluble poly(3-tri(ethylene glycol)) (P3TEOT) embedded into the matrix of thermoplastic polyvinyl alcohol. This counterintuitive phenomenon is explained in terms of the concentration dependency of the P3TEOT's aggregation state, which in turn results in different molecular conformations and optical properties. A molecular flexibility, provided by low glass transition temperature of P3TEOT, and the fact that P3TEOT adopts an intermediate, moderately planar conformation in the solid state, are responsible for the unusual complex mechanochromic behavior. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2021, Rossner, Christian, König, Tobias A.F., Fery, Andreas

The assembly of metal nanoparticles into supracolloidal structures unlocks optical features, which can go beyond synergistic combinations of the properties of their primary building units. This is due to inter-particle plasmonic coupling effects, which give rise to emergent properties. The motivation for this progress report is twofold: First, it is described how simulation approaches can be used to predict and understand the optical properties of supracolloidal metal clusters. These simulations may form the basis for the rational design of plasmonic assembly architectures, based on the desired functional cluster properties, and they may also spark novel material designs. Second, selected scalable state-of-the-art preparative strategies based on synthetic polymers to guide the supracolloidal assembly are discussed. These routes also allow for equipping the assembly structures with adaptive properties, which in turn enables (inter-)active control over the cluster optical properties. © 2021 The Authors. Advanced Optical Materials published by Wiley-VCH GmbH

2021, Ye, Jingjing, Aftenieva, Olha, Bayrak, Türkan, Jain, Archa, König, Tobias A.F., Erbe, Artur, Seidel, Ralf

Advances in DNA nanotechnology allow the design and fabrication of highly complex DNA structures, uisng specific programmable interactions between smaller nucleic acid building blocks. To convey this concept to the fabrication of metallic nanoparticles, an assembly platform is developed based on a few basic DNA structures that can serve as molds. Programming specific interactions between these elements allows the assembly of mold superstructures with a range of different geometries. Subsequent seeded growth of gold within the mold cavities enables the synthesis of complex metal structures including tightly DNA-caged particles, rolling-pin- and dumbbell-shaped particles, as well as T-shaped and loop particles with high continuity. The method further supports the formation of higher-order assemblies of the obtained metal geometries. Based on electrical and optical characterizations, it is expected that the developed platform is a valuable tool for a self-assembly-based fabrication of nanoelectronic and nanooptic devices. © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH