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Author: Möller, Martin × End date: 2022 × Start date: 2020 × End date: 2019 × Start date: 2010 ×

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Now showing 1 - 10 of 21
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    Actively Tunable Collective Localized Surface Plasmons by Responsive Hydrogel Membrane
    (Weinheim : Wiley-VCH, 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
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    Quantifying ligand-cell interactions and determination of the surface concentrations of ligands on hydrogel films: The measurement challenge
    (Melville, NY : AIP Publishing, 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.
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    Polymer Brush-Functionalized Chitosan Hydrogels as Antifouling Implant Coatings
    (Columbus, Ohio : American Chemical Society, 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.
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    Thermodynamic Parameters of Temperature-Induced Phase Transition for Brushes onto Nanoparticles: Hydrophilic versus Hydrophobic End-Groups Functionalization
    (Weinheim : Wiley-VCH, 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.
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    Polymers Diffusivity Encoded by Stimuli-Induced Phase Transition: Theory and Application to Poly(N-Isopropylacrylamide) with Hydrophilic and Hydrophobic End Groups
    (Weinheim : Wiley-VCH, 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.
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    Approach to Obtain Electrospun Hydrophilic Fibers and Prevent Fiber Necking
    (New York, NY [u.a.] : Wiley InterScience, 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.
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    The Influence of Particle Size Distribution and Shell Imperfections on the Plasmon Resonance of Au and Ag Nanoshells
    (New York, NY [u.a.] : Springer, 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.
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    Synthesis, Characterization, and Antimicrobial Properties of Peptides Mimicking Copolymers of Maleic Anhydride and 4-Methyl-1-pentene
    (Basel : Molecular Diversity Preservation International (MDPI), 2018) Szkudlarek, Marian; Heine, Elisabeth; Keul, Helmut; Beginn, Uwe; Möller, Martin
    Synthetic amphiphilic copolymers with strong antimicrobial properties mimicking natural antimicrobial peptides were obtained via synthesis of an alternating copolymer of maleic anhydride and 4-methyl-1-pentene. The obtained copolymer was modified by grafting with 3-(dimethylamino)-1-propylamine (DMAPA) and imidized in a one-pot synthesis. The obtained copolymer was modified further to yield polycationic copolymers by means of quaternization with methyl iodide and dodecyl iodide, as well as by being sequentially quaternized with both of them. The antimicrobial properties of obtained copolymers were tested against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus epidermidis, and Staphylococcus aureus. Both tested quaternized copolymers were more active against the Gram-negative E. coli than against the Gram-positive S. aureus. The copolymer modified with both iodides was best when tested against E. coli and, comparing all three copolymers, also exhibited the best effect against S. aureus. Moreover, it shows (limited) selectivity to differentiate between mammalian cells and bacterial cell walls. Comparing the minimum inhibitory concentration (MIC) of Nisin against the Gram-positive bacteria on the molar basis instead on the weight basis, the difference between the effect of Nisin and the copolymer is significantly lower.
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    Novel Antibacterial Polyglycidols: Relationship between Structure and Properties
    (Basel : MDPI, 2018) Marquardt, Fabian; Stöcker, Cornelia; Gartzen, Rita; Heine, Elisabeth; Keul, Helmut; Möller, Martin
    Antimicrobial polymers are an attractive alternative to low molecular weight biocides, because they are non-volatile, chemically stable, and can be used as non-releasing additives. Polymers with pendant quaternary ammonium groups and hydrophobic chains exhibit antimicrobial properties due to the electrostatic interaction between polymer and cell wall, and the membrane disruptive capabilities of the hydrophobic moiety. Herein, the synthesis of cationic–hydrophobic polyglycidols with varying structures by post-polymerization modification is presented. The antimicrobial properties of the prepared polyglycidols against E. coli and S. aureus are examined. Polyglycidol with statistically distributed cationic and hydrophobic groups (cationic–hydrophobic balance of 1:1) is compared to (i) polyglycidol with a hydrophilic modification at the cationic functionality; (ii) polyglycidol with both—cationic and hydrophobic groups—at every repeating unit; and (iii) polyglycidol with a cationic–hydrophobic balance of 1:2. A relationship between structure and properties is presented.
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    SET-LRP in biphasic mixtures of fluorinated alcohols with water
    (Cambridge : RSC Publ., 2018) Moreno, Adrian; Liu, Tong; Ding, Liang; Buzzacchera, Irene; Galià, Marina; Möller, Martin; Wilson, Christopher J.; Lligadas, Gerard; Percec, Virgil
    Biphasic-binary mixtures of 2,2,2-trifluoroethanol (TFE) or 2,2,3,3-tetrafluoropropanol (TFP) with water were used as reaction media to synthesize well-defined poly(methyl acrylate) (PMA) with chain end functionality close to 100% by SET-LRP. Non-activated Cu(0) wire was used as a catalyst, taking advantage of the Cu(0)-activation property that these fluorinated alcohols possess. Biphasic-binary mixtures of water, containing a ligand and Cu(II)Br2 either generated by disproportionation of Cu(I)Br or externally added, and an organic solvent, containing a monomer and a polymer, were studied. Two N-ligands were investigated: the classic tris(2-dimethylaminoethyl)amine (Me6-TREN) and tris(2-aminoethyl)amine (TREN), as a more economically attractive alternative for technological purposes. The results reported here support the replacement of Me6-TREN by TREN, taking into account the fact that the latter requires small loadings of an externally added Cu(II)Br2 deactivator and a ligand in the water phase to mediate a living radical polymerization process. Both catalytic systems ensure efficient SET-LRP processes with first order kinetics to high conversion, linear dependence of experimental Mn on conversion, narrow molecular weight distribution, and near-quantitative chain end functionality.