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Actively Tunable Collective Localized Surface Plasmons by Responsive Hydrogel Membrane
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
Polymer Brush-Functionalized Chitosan Hydrogels as Antifouling Implant Coatings
2017, Buzzacchera, Irene, Vorobii, Mariia, Kostina, Nina Yu, de Los Santos Pereira, Andres, Riedel, Tomáš, Bruns, Michael, Ogieglo, Wojciech, Möller, Martin, Wilson, Christopher J., Rodriguez-Emmenegger, Cesar
Implantable sensor devices require coatings that efficiently interface with the tissue environment to mediate biochemical analysis. In this regard, bioinspired polymer hydrogels offer an attractive and abundant source of coating materials. However, upon implantation these materials generally elicit inflammation and the foreign body reaction as a consequence of protein fouling on their surface and concomitant poor hemocompatibility. In this report we investigate a strategy to endow chitosan hydrogel coatings with antifouling properties by the grafting of polymer brushes in a "grafting-from" approach. Chitosan coatings were functionalized with polymer brushes of oligo(ethylene glycol) methyl ether methacrylate and 2-hydroxyethyl methacrylate using photoinduced single electron transfer living radical polymerization and the surfaces were thoroughly characterized by XPS, AFM, water contact angle goniometry, and in situ ellipsometry. The antifouling properties of these new bioinspired hydrogel-brush coatings were investigated by surface plasmon resonance. The influence of the modifications to the chitosan on hemocompatibility was assessed by contacting the surfaces with platelets and leukocytes. The coatings were hydrophilic and reached a thickness of up to 180 nm within 30 min of polymerization. The functionalization of the surface with polymer brushes significantly reduced the protein fouling and eliminated platelet activation and leukocyte adhesion. This methodology offers a facile route to functionalizing implantable sensor systems with antifouling coatings that improve hemocompatibility and pave the way for enhanced device integration in tissue.
Polymers Diffusivity Encoded by Stimuli-Induced Phase Transition: Theory and Application to Poly(N-Isopropylacrylamide) with Hydrophilic and Hydrophobic End Groups
2018, Schweizerhof, Sjören, Demco, Dan Eugen, Mourran, Ahmed, Fechete, Radu, Möller, Martin
The self-diffusion of various nano-objects investigated by high-resolution nuclear magnetic resonance diffusometry proves to be an efficient method for the characterization of dynamics, aggregation kinetic, and matrix morphology. This study investigates how the two-state model and Boltzmann function approach can be used for the evaluation of the thermodynamic parameters of temperature-induced phase transition encoded in polymer diffusivity. The characteristics of the phase transition given by the transition temperature, change of entropy, and width of transition are obtained for poly(N-isopropylacrylamide) (PNIPAm) linear polymers with hydrophilic and hydrophobic end-group functionalization. The effect of end groups upon the polymer diffusivity is investigated as a function of molecular weight (M n), from which fractal dimensions and hydrodynamic drag coefficients are obtained. The PNIPAm diffusivity is affected strongly by the end groups, and it is reflected in the hydrodynamic radius dependence upon molecular weight that obeys different power-law relations. In this study, the synthesis of α-ω-heterotelechelic PNIPAm of different molecular weights with a thiol end group and a hydrophilic NIPAm-like as well as a hydrophobic benzyl end group are described by reversible addition–fragmentation chain-transfer polymerization.
Formaldehyde-free curing of cotton cellulose fabrics in anhydrous media
2020, Mommer, Stefan, Kurniadi, Juliana, Keul, Helmut, Möller, Martin
The effect of formaldehyde-free curing on standard cotton cellulose fabrics in anhydrous media is studied. Different crosslinkers are applied via (1) a pad-cure-dry process (solid/liquid) and (2) in a vapor chamber (solid/gas). The performance of each crosslinker and set of conditions is assessed by measuring dry crease recovery angles, DCRAs. We find that in control samples (treatment without crosslinker) the DCRAs are altered depending on the solvent. Using DMF, carbonyldiimidazole shows the best DCRA (160.1°, 15° higher than the non-treated fabrics). In ethyl acetate, triglycidyl isocyanurate shows the highest DCRA (22° higher than the control). The most promising crosslinkers are applied with selected catalysts known from literature. Here, trigycidyl isocyanurate in combination with the superbase P4-t-Bu gives the best DCRA (35° higher than the control). Using the vapor-chemical finishing, divinylsulfone as crosslinker increases the DCRA to 162.7° (18° higher than non-treated fabrics). Hence, cotton cellulose fabrics can be successfully finished in anhydrous conditions. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48371. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc.
In-Gel Direct Laser Writing for 3D-Designed Hydrogel Composites That Undergo Complex Self-Shaping
2017, Nishiguchi, Akihiro, Mourran, Ahmed, Zhang, Hang, Möller, Martin
Self-shaping and actuating materials inspired by biological system have enormous potential for biosensor, microrobotics, and optics. However, the control of 3D-complex microactuation is still challenging due to the difficulty in design of nonuniform internal stress of micro/nanostructures. Here, we develop in-gel direct laser writing (in-gel DLW) procedure offering a high resolution inscription whereby the two materials, resin and hydrogel, are interpenetrated on a scale smaller than the wavelength of the light. The 3D position and mechanical properties of the inscribed structures could be tailored to a resolution better than 100 nm over a wide density range. These provide an unparalleled means of inscribing a freely suspended microstructures of a second material like a skeleton into the hydrogel body and also to direct isotropic volume changes to bending and distortion motions. In the combination with a thermosensitive hydrogel rather small temperature variations could actuate large amplitude motions. This generates complex modes of motion through the rational engineering of the stresses present in the multicomponent material. More sophisticated folding design would realize a multiple, programmable actuation of soft materials. This method inspired by biological system may offer the possibility for functional soft materials capable of biomimetic actuation and photonic crystal application.
Reconstruction of Ultra-thin Alveolar-capillary Basement Membrane Mimics
2021, Jain, Puja, Nishiguchi, Akihiro, Linz, Georg, Wessling, Matthias, Ludwig, Andreas, Rossaint, Rolf, Möller, Martin, Singh, Smriti
Alveolar-capillary basement membrane (BM) is ultra-thin (<2 µm) extracellular matrix that maintains integral epithelial-endothelial cell layers. In vitro reconstructions of alveolar-capillary barrier supported on synthetic scaffolds closely resembling the fibrous and ultra-thin natural BM are essential in mimicking the lung pathophysiology. Although BM topology and dimensions are well known to significantly influence cellular behavior, conventionally used BM mimics fail to recreate this natural niche. To overcome this, electrospun ultra-thin 2 µm poly(caprolactone) (PCL) nanofibrous mesh is used to establish an alveolar-capillary barrier model of lung endothelial/epithelial cells. Transepithelial electrical resistance (TEER) and permeability studies reveal integral tight junctions and improved mass transport through the highly porous PCL meshes compared to conventional dense membranes with etched pores. The chemotaxis of neutrophils is shown across the barrier in presence of inflammatory response that is naturally impeded in confined regions. Conventional requirement of 3 µm or larger pore size can lead to barrier disruption due to epithelial/endothelial cell invasion. Despite high porosity, the interconnected BM mimic prevents barrier disruption and allows neutrophil transmigration, thereby demonstrating the physiological relevance of the thin nanofibrous meshes. It is envisioned that these bipolar cultured barriers would contribute to an organ-level in vitro model for pathological disease, environmental pollutants, and nanotoxicology. © 2021 The Authors. Advanced Biology published by Wiley-VCH GmbH
Approach to Obtain Electrospun Hydrophilic Fibers and Prevent Fiber Necking
2019, Fischer, Thorsten, Möller, Martin, Singh, Smriti
Solution electrospinning of a blend containing a hydrophobic polymer with a hydrophilic functional polymer as an additive is a simple and straight-forward route to obtain functional and hydrophilic fibers accompanied by the mechanical properties of the hydrophobic polymer. However, this process of thermodynamically unfavored surface segregation of the hydrophilic additive is not well understood. To understand the process the dependencies of the surface hydrophilization on type of hydrophilic polymers, the solvent, and the process, using poly(caprolactone) (PCL) as the matrix polymer is explored. The results show that hydrophilic fibers can be obtained using different additive hydrophilic polymers. The combination of polymer blends which show this effect can be predicted using the Flory–Huggins interaction parameter. In addition mechanical and micromechanical properties of PCL fibers blended with NCO-terminated star-shaped poly(ethylene glycol) (sPEG-NCO) as additive are investigated. In this context blending with sPEG-NCO turns out to be a powerful tool to prevent fiber necking rendering this method an interesting candidate for tissue engineering application, where it is mandatory to retain the surface properties under mechanical stress.
Quantifying ligand-cell interactions and determination of the surface concentrations of ligands on hydrogel films: The measurement challenge
2015, Beer, Meike V., Hahn, Kathrin, Diederichs, Sylvia, Fabry, Marlies, Singh, Smriti, Spencer, Steve J., Salber, Jochen, Möller, Martin, Shard, Alexander G., Groll, Jürgen
Hydrogels are extensively studied for biomaterials application as they provide water swollen noninteracting matrices in which specific binding motifs and enzyme-sensitive degradation sites can be incorporated to tailor cell adhesion, proliferation, and migration. Hydrogels also serve as excellent basis for surface modification of biomaterials where interfacial characteristics are decisive for implant success or failure. However, the three-dimensional nature of hydrogels makes it hard to distinguish between the bioactive ligand density at the hydrogel-cell interface that is able to interact with cells and the ligands that are immobilized inside the hydrogel and not accessible for cells. Here, the authors compare x-ray photoelectron spectrometry (XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), enzyme linked immunosorbent assay (ELISA), and the correlation with quantitative cell adhesion using primary human dermal fibroblasts (HDF) to gain insight into ligand distribution. The authors show that although XPS provides the most useful quantitative analysis, it lacks the sensitivity to measure biologically meaningful concentrations of ligands. However, ToF-SIMS is able to access this range provided that there are clearly distinguishable secondary ions and a calibration method is found. Detection by ELISA appears to be sensitive to the ligand density on the surface that is necessary to mediate cell adhesion, but the upper limit of detection coincides closely with the minimal ligand spacing required to support cell proliferation. Radioactive measurements and ELISAs were performed on amine reactive well plates as true 2D surfaces to estimate the ligand density necessary to allow cell adhesion onto hydrogel films. Optimal ligand spacing for HDF adhesion and proliferation on ultrathin hydrogel films was determined as 6.5 ± 1.5 nm.
Thermodynamic Parameters of Temperature-Induced Phase Transition for Brushes onto Nanoparticles: Hydrophilic versus Hydrophobic End-Groups Functionalization
2017, Schweizerhof, Sjören, Demco, Dan Eugen, Mourran, Ahmed, Keul, Helmut, Fechete, Radu, Möller, Martin
Quantification of the stimuli-responsive phase transition in polymers is topical and important for the understanding and development of novel stimuli-responsive materials. The temperature-induced phase transition of poly(N-isopropylacrylamide) (PNIPAm) with one thiol end group depends on the confinement—free polymer or polymer brush—on the molecular weight and on the nature of the second end. This paper describes the synthesis of heterotelechelic PNIPAm of different molecular weights with a thiol end group—that specifically binds to gold nanorods and a hydrophilic NIPAm end group by reversible addition-fragmentation chain-transfer polymerization. Proton high-resolution magic angle sample spinning NMR spectra are used as an indicator of the polymer chain conformations. The characteristics of phase transition given by the transition temperature, entropy, and width of transition are obtained by a two-state model. The dependence of thermodynamic parameters on molecular weight is compared for hydrophilic and hydrophobic end functional-free polymers and brushes.
The Influence of Particle Size Distribution and Shell Imperfections on the Plasmon Resonance of Au and Ag Nanoshells
2017, Mann, Daniel, Nascimento-Duplat, Daniel, Keul, Helmut, Möller, Martin, Verheijen, Marcel, Xu, Man, Urbach, H. Paul, Adam, Aurèle J. L., Buskens, Pascal
Au and Ag nanoshells are of interest for a wide range of applications. The plasmon resonance of such nanoshells is the property of interest and can be tuned in a broad spectral regime, ranging from the ultraviolet to the mid-infrared. To date, a large number of manuscripts have been published on the optics of such nanoshells. Few of these, however, address the effect of particle size distribution and metal shell imperfections on the plasmon resonance. Both are inherent to the chemical synthesis of metal nanoshells and therefore to a large extent unavoidable. It is of vital importance to understand their effect on the plasmon resonance, since this determines the scope and limitations of the technology and may have a direct impact on the application of such particles. Here, we elucidate the effect of particle size distribution and imperfections in the metal shell on the plasmon resonance of Au and Ag nanoshells. The size of the polystyrene core and the thickness of the Au and Ag shells are systematically varied to study their influence on the plasmon resonance, and the results are compared to values obtained through optical simulations using extended Mie theory and finite element method. Discrepancies between theory and practice are studied in detail and discussed extensively. Quantitative information on the minimum thickness of the metal shell, which is required to realize a satisfactory plasmon resonance of a metal nanoshell, is provided for Au and Ag.