2019, Quilis, Nestor Gisbert, van Dongen, Marcel, Venugopalan, Priyamvada, Kotlarek, Daria, Petri, Christian, Cencerrado, Alberto Moreno, Stanescu, Sorin, Herrera, Jose Luis Toca, Jonas, Ulrich, Möller, Martin, Mourran, Ahmed, Dostalek, Jakub

Collective (lattice) localized surface plasmons (cLSP) with actively tunable and extremely narrow spectral characteristics are reported. They are supported by periodic arrays of gold nanoparticles attached to a stimuli-responsive hydrogel membrane, which can on demand swell and collapse to reversibly modulate arrays period and surrounding refractive index. In addition, it features a refractive index-symmetrical geometry that promotes the generation of cLSPs and leads to strong suppression of radiative losses, narrowing the spectral width of the resonance, and increasing of the electromagnetic field intensity. Narrowing of the cLSP spectral band down to 13 nm and its reversible shifting by up to 151 nm is observed in the near infrared part of the spectrum by varying temperature and by solvent exchange for systems with a poly(N-isopropylacrylamide)-based hydrogel membrane that is allowed to reversibly swell and collapse in either one or in three dimensions. The reported structures with embedded periodic gold nanoparticle arrays are particularly attractive for biosensing applications as the open hydrogel structure can be efficiently post-modified with functional moieties, such as specific ligands, and since biomolecules can rapidly diffuse through swollen polymer networks. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2021, Jelken, Joachim, Jung, Se-Hyeong, Lomadze, Nino, Gordievskaya, Yulia D., Kramarenko, Elena Yu., Pich, Andrij, Santer, Svetlana

Temperature-responsive microgels find widespread applications as soft materials for designing actuators in microfluidic systems, as carriers for drug delivery or catalysts, as functional coatings, and as adaptable sensors. The key property is their volume phase transition temperature, which allows for thermally induced reversible swelling/deswelling. It is determined by the gel's chemical structure as well as network topology and cannot be varied easily within one system. Here a paradigm change of this notion by facilitating a light-triggered reversible switching of the microgel volume in the range between 32 and 82 °C is suggested. Photo-sensitivity is introduced by photosensitive azobenzene containing surfactant, which forms a complex with microgels consisting of poly(N-isopropylacrylamide-co-acrylic acid) (PNIPAM-AAc) chains when assuming a hydrophobic trans-state, and prefers to leave the gel matrix in its cis-state. Using a similar strategy, it is demonstrated that at a fixed temperature, for example, 37 °C, one can reversibly change the microgel radius by a factor of 3 (7–21 µm) by irradiating either with UV (collapsed state) or green light (swollen state). It is envisaged that the possibility to deploy a swift external means of adapting the swelling behavior of microgels may impact and redefine the latter's application across all fields. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH

2017, Omidinia-Anarkoli, Abdolrahman, Boesveld, Sarah, Tuvshindorj, Urandelger, Rose, Jonas C., Haraszti, Tamás, De Laporte, Laura

To regenerate soft aligned tissues in living organisms, low invasive biomaterials are required to create 3D microenvironments with a structural complexity to mimic the tissue's native architecture. Here, a tunable injectable hydrogel is reported, which allows precise engineering of the construct's anisotropy in situ. This material is defined as an Anisogel, representing a new type of tissue regenerative therapy. The Anisogel comprises a soft hydrogel, surrounding magneto-responsive, cell adhesive, short fibers, which orient in situ in the direction of a low external magnetic field, before complete gelation of the matrix. The magnetic field can be removed after gelation of the biocompatible gel precursor, which fixes the aligned fibers and preserves the anisotropic structure of the Anisogel. Fibroblasts and nerve cells grow and extend unidirectionally within the Anisogels, in comparison to hydrogels without fibers or with randomly oriented fibers. The neurons inside the Anisogel show spontaneous electrical activity with calcium signals propagating along the anisotropy axis of the material. The reported system is simple and elegant and the short magneto-responsive fibers can be produced with an effective high-throughput method, ideal for a minimal invasive route for aligned tissue therapy.

2021, Haehnle, Bastian, Schuster, Philipp A., Chen, Lisa, Kuehne, Alexander J. C.

Future applications of conjugated polymer particles (CPP) in medicine, organic photonics, and optoelectronics greatly depend on high performance and precisely adjustable optical properties of the particles. To meet these criteria, current particle systems often combine conjugated polymers with inorganic particles in core-shell geometries, extending the possible optical characteristics of CPP. However, current conjugated polymer particles are restricted to a single polymer phase composed of a distinct polymer or a polymer blend. Here, a synthetic toolbox is presented that enables the synthesis of monodisperse core-shell and core-shell-shell particles, which consist entirely of conjugated polymers but of different types in the core and the shells. Seeded and fed-batch dispersion polymerizations based on Suzuki-Miyaura-type cross-coupling are investigated. The different approaches allow accurate control over the created interface between the conjugated polymer phases and thus also over the energy transfer phenomena between them. This approach opens up completely new synthetic freedom for fine tuning of the optical properties of CPP, enabling, for example, the synthesis of individual white light-emitting particles.

2020, Haehnle, Bastian, Lamla, Markus, Sparrer, Konstantin M.J., Gather, Malte C., Kuehne, Alexander J.C.

Conjugated polymer particles are brightly fluorescing and stable materials for live cell imaging. Combination of conjugated polymers with a whispering gallery mode (WGM) resonator allows laser emission from microscale particles. Once internalized by cells, the mode pattern of the laser emission can be used for tagging and tracking, as each laser spectrum represents a bar code to identify individual cells. However, currently these particle systems are limited by their large size, which might interfere with cellular functions. Here, stimulated resonance Raman scattering (SRRS) in small conjugated polymer microparticles is presented as a new method for generating narrow emission as an alternative to WGM-based laser emission. This opens up spectral range for multiplexing optical readout and multicolor imaging of live cells. The synthesis of monodisperse micrometer-sized poly(fluorene-co-divinylbenzene) particles is discussed and their WGM and SRRS emission are characterized. Finally, how these particles and their emission can be employed in live cell imaging and tagging is showcased. © 2020 The Authors. Advanced Optical Materials published by Wiley-VCH GmbH

2020, Al Enezy-Ulbrich, Miriam Aischa, Malyaran, Hanna, de Lange, Robert Dirk, Labude, Norina, Plum, René, Rütten, Stephan, Terefenko, Nicole, Wein, Svenja, Neuss, Sabine, Pich, Andrij

Mechanical properties of hydrogels can be modified by the variation of structure and concentration of reactive building blocks. One promising biological source for the synthesis of biocompatible hydrogels is fibrinogen. Fibrinogen is a glycoprotein in blood, which can be transformed enzymatically to fibrin playing an important role in wound healing and clot formation. In the present work, it is demonstrated that hybrid hydrogels with their improved mechanical properties, tunable internal structure, and enhanced resistance to degradation can be synthesized by a combination of fibrinogen and reactive amphiphilic copolymers. Water-soluble amphiphilic copolymers with tunable molecular weight and controlled amounts of reactive epoxy side groups are used as reactive crosslinkers to reinforce fibrin hydrogels. In the present work, copolymers that can influence the mechanical properties of fibrin-based hydrogels are used. The reactive copolymers increase the storage modulus of the hydrogels from 600 Pa to 30 kPa. The thickness of fibrin fibers is regulated by the copolymer concentration. It could be demonstrated that the fibrin-based hydrogels are biocompatible and support cell proliferation. Their degradation rate is considerably slower than that of native fibrin gels. In conclusion, fibrin-based hydrogels with tunable elasticity and fiber thickness useful to direct cell responses like proliferation and differentiation are produced. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2019, Zhang, Hang, Koens, Lyndon, Lauga, Eric, Mourran, Ahmed, Möller, Martin

The current understanding of motility through body shape deformation of micro-organisms and the knowledge of fluid flows at the microscale provides ample examples for mimicry and design of soft microrobots. In this work, a 2D spiral is presented that is capable of rotating by non-reciprocal curling deformations. The body of the microswimmer is a ribbon consisting of a thermoresponsive hydrogel bilayer with embedded plasmonic gold nanorods. Such a system allows fast local photothermal heating and nonreciprocal bending deformation of the hydrogel bilayer under nonequilibrium conditions. It is shown that the spiral acts as a spring capable of large deformations thanks to its low stiffness, which is tunable by the swelling degree of the hydrogel and the temperature. Tethering the ribbon to a freely rotating microsphere enables rotational motion of the spiral by stroboscopic irradiation. The efficiency of the rotor is estimated using resistive force theory for Stokes flow. This research demonstrates microscopic locomotion by the shape change of a spiral and may find applications in the field of microfluidics, or soft microrobotics.

2020, Michel, Ann-Katrin U., Meyer, Sebastian, Essing, Nicolas, Lassaline, Nolan, Lightner, Carin R., Bisig, Samuel, Norris, David J., Chigrin, Dmitry N.

Metasurfaces allow for the spatiotemporal variation of amplitude, phase, and polarization of optical wavefronts. Implementation of active tunability of metasurfaces promises compact flat optics capable of reconfigurable wavefront shaping. Phase-change materials (PCMs) are a prominent material class enabling reconfigurable metasurfaces due to their large refractive index change upon structural transition. However, commonly employed laser-induced switching of PCMs limits the achievable feature sizes and restricts device miniaturization. Thermal scanning-probe-induced local switching of the PCM germanium telluride is proposed to realize near-infrared metasurfaces with feature sizes far below what is achievable with diffraction-limited optical switching. The design is based on a planar multilayer and does not require fabrication of protruding resonators as commonly applied in the literature. Instead, it is numerically demonstrated that a broad-band tuning of perfect absorption can be realized by the localized tip-induced crystallization of the PCM. The spectral response of the metasurface is explained using resonance mode analysis and numerical simulations. To facilitate experimental realization, a theoretical description of the tip-induced crystallization employing multiphysics simulations is provided to demonstrate the great potential for fabricating compact reconfigurable metasurfaces. The concept can be applied not only for plasmonic sensing and spatial frequency filtering, but also be transferred to all-dielectric metasurfaces. © 2020 Wiley-VCH GmbH

2020, Willis-Fox, Niamh, Rognin, Etienne, Baumann, Christoph, Aljohani, Talal A., Göstl, Robert, Daly, Ronan

Mechanical forces can drive chemical transformations in polymers, directing reactions along otherwise inaccessible pathways, providing exciting possibilities for developing smart, responsive materials. The state-of-the-art test for solution-based polymer mechanochemistry development is ultrasonication. However, this does not accurately model the forces that will be applied during device fabrication using processes such as 3D printing or spray coating. Here, a step is taken toward predictably translating mechanochemistry from molecular design to manufacturing by demonstrating a highly controlled nozzle flow setup in which the shear forces being delivered are precisely tuned. The results show that solvent viscosity, fluid strain rate, and the nature of the breaking bond can be individually studied. Importantly, it is shown that the influence of each is different to that suggested by ultrasonication (altered quantity of chain breakage and critical polymer chain length). Significant development is presented in the understanding of polymer bond breakage during manufacturing flows to help guide design of active components that trigger on demand. Using an anthracene-based mechanophore, the triggering of a fluorescence turn-on is demonstrated through careful selection of the flow parameters. This work opens the avenue for programmed chemical transformations during inline manufacturing processes leading to tunable, heterogeneous final products from a single source material. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2023, Hosseinnejad, Aisa, Ludwig, Nadine, Mersmann, Sina, Winnerbach, Patrick, Bleilevens, Christian, Rossaint, Rolf, Rossaint, Jan, Singh, Smriti

Nitric oxide (NO) plays a significant role in controlling the physiology and pathophysiology of the body, including the endothelial antiplatelet function and therefore, antithrombogenic property of the blood vessels. This property of NO can be exploited to prevent thrombus formation on artificial surfaces like extracorporeal membrane oxygenators, which when come into contact with blood lead to protein adsorption and thereby platelet activation causing thrombus formation. However, NO is extremely reactive and has a very short biological half-life in blood, so only endogenous generation of NO from the blood contacting material can result into a stable and kinetically controllable local delivery of NO. In this regards, highly hydrophilic bioactive nanogels are presented which can endogenously generate NO in blood plasma from endogenous NO-donors thereby maintaining a physiological NO flux. It is shown that NO releasing nanogels could initiate cGMP-dependent protein kinase signaling followed by phosphorylation of vasodilator-stimulated phosphoprotein in platelets. This prevents platelet activation and aggregation even in presence of highly potent platelet activators like thrombin, adenosine 5′-diphosphate, and U46619 (thromboxane A2 mimetic).