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- ItemHalloysite Nanotubes Noncovalently Functionalised with SDS Anionic Surfactant and PS-b-P4VP Block Copolymer for Their Effective Dispersion in Polystyrene as UV-Blocking Nanocomposite Films(New York, NY : Hindawi Publ., 2017) Tzounis, Lazaros; Herlekar, Shreya; Tzounis, Antonios; Charisiou, Nikolaos D.; Goula, Maria; Stamm, ManfredAsimple and versatilemethod is reported for the noncovalent functionalisation of natural and "green" halloysite nanotubes (HNTs) allowing their effective dispersion in a polystyrene (PS) thermoplastic matrix via solvent mixing. Initially, HNTs (pristine HNTs) were modified with physically adsorbed surfactant molecules of sodium dodecyl sulphate (SDS) and PS-b-P4VP [P4VP: poly(4-vinylpyridine)] block copolymer (BCP). Hereafter, SDS and BCP modified HNTs will be indicated as SDS-m-HNT and BCP-m-HNT.Nanocomposite films with 1, 2, and 5 wt.%HNTloadingswere prepared, abbreviated as PS-SDS-m-HNT1, PS-SDS-m-HNT2, and PS-SDS-m-HNT5 and PS-BCP-m-HNT1, PS-BCP-m-HNT2, and PS-BCP-m-HNT5 (where 1, 2, and 5 correspond to the wt.% of HNTs). All nanocomposites depicted improved thermal degradation compared to the neat PS as revealed by thermogravimetric analysis (TGA). Transmission electron microscopy (TEM) confirmed the good dispersion state of HNTs and the importance of modification by SDS and BCP. X-ray diffraction (XRD) studies showed the characteristic interlayer spacing between the two silicate layers of pristine and modified HNTs. The PS/HNT nanocomposite films exhibited excellent ultraviolent-visible (UV-vis) absorbance properties and their potential application as UV-filters could be envisaged.
- ItemPolysulfide driven degradation in lithium–sulfur batteries during cycling – quantitative and high time-resolution operando X-ray absorption study for dissolved polysulfides probed at both electrode sides(London [u.a.] : RSC, 2021) Zech, Claudia; Hönicke, Philipp; Kayser, Yves; Risse, Sebastian; Grätz, Olga; Stamm, Manfred; Beckhoff, BurkhardThe development of operando characterization techniques on realistic batteries is essential for an advanced mechanistic understanding in battery chemistry and, therefore, contributes to their further performance improvement. This manuscript presents operando Near-Edge X-ray Absorption Spectroscopy (NEXAFS) traceable to the SI units (SI is the abbreviation for the International System of Units) during multiple charge–discharge cycles on both electrodes of lithium–sulfur (Li/S) coin cells which enables an absolute quantification of dissolved polysulfides with no need for calibration samples or reference material. We could reveal that during the charging process, polysulfide (PS) movement from the negative to the positive electrode is inhibited. This leads to a steady increase of dissolved polysulfides at the anode side and, therefore, is one of the key points for capacity fading. We quantitatively track the polysulfides dissolved in the electrolyte and correlate for the first time their evolution with the capacity fading of the cell. We analyze the appearance of PS during cell operation at the cathode and anode side to characterize the transport mechanisms of the polysulfide shuttle phenomena and to reveal quantitative information about their evolution at different states of charge and states of health. Our cell design suppresses the contribution of cathodic sulfur, which is mandatory for reference-sample-free quantification in X-ray spectrometry and allows us to use only slightly modified standard coin cell batteries.
- ItemCopolymerization of zinc-activated isoindigo- and naphthalene-diimide based monomers: an efficient route to low bandgap π-conjugated random copolymers with tunable properties(Cambridge : RSC Publ., 2016) Karpov, Yevhen; Maiti, Jatindranath; Tkachov, Roman; Beryozkina, Tetyana; Bakulev, Vasiliy; Liu, Wei; Komber, Hartmut; Lappan, Uwe; Al-Hussein, Mahmoud; Stamm, Manfred; Voit, Brigitte; Kiriy, AntonThe present work aims at the extension of the scope of a recently discovered polycondensation of AB-type anion-radical monomers. To this end, we investigate the polymerization of isoindigo-based monomer and its copolymerization with the naphthalenediimide-based monomer. Although polycondensations of parent naphthalenediimide- and perylenediimide-based monomers involve chain-growth mechanism, we found that the corresponding isoindigo-based monomer polymerizes in a step-growth manner under the same reaction conditions. In contrast to Stille, Suzuki and direct arylation polycondensations which require prolonged stirring at high temperatures, the polymerization approach we employed in this study proceeds fast at room temperature. It was found that near statistical copolymerization of isoindigo-based anion-radical monomers with corresponding naphtalenediimide-based monomers proceeds smoothly resulting in a library of copolymers with varying composition and properties depending on the ratio of the monomers.
- ItemIn Situ Monitoring of Linear RGD-Peptide Bioconjugation with Nanoscale Polymer Brushes(Washington, DC : ACS Publications, 2017) Psarra, Evmorfia; König, Ulla; Müller, Martin; Bittrich, Eva; Eichhorn, Klaus-Jochen; Welzel, Petra B.; Stamm, Manfred; Uhlmann, PetraBioinspired materials mimicking the native extracellular matrix environment are promising for biotechnological applications. Particularly, modular biosurface engineering based on the functionalization of stimuli-responsive polymer brushes with peptide sequences can be used for the development of smart surfaces with biomimetic cues. The key aspect of this study is the in situ monitoring and analytical verification of the biofunctionalization process on the basis of three complementary analytical techniques. In situ spectroscopic ellipsometry was used to quantify the amount of chemisorbed GRGDS at both the homopolymer poly(acrylic acid) (PAA) brush and the binary poly(N-isopropylacrylamide) (PNIPAAm)-PAA brushes, which was finally confirmed by an acidic hydrolysis combined with a subsequent reverse-phase high-performance liquid chromatography analysis. In situ attenuated total reflection-Fourier transform infrared spectroscopy provided a step-by-step detection of the biofunctionalization process so that an optimized protocol for the bioconjugation of GRGDS could be identified. The optimized protocol was used to create a temperature-responsive binary brush with a high amount of chemisorbed GRGDS, which is a promising candidate for the temperature-sensitive control of GRGDS presentation in further cell-instructive studies.
- ItemIn-situ-investigation of enzyme immobilization on polymer brushes(Lausanne : Frontiers Media, 2019) Koenig, Meike; König, Ulla; Eichhorn, Klaus-Jochen; Müller, Martin; Stamm, Manfred; Uhlmann, PetraHerein, we report on the use of a combined setup of quartz-crystal microbalance, with dissipation monitoring and spectroscopic ellipsometry, to comprehensively investigate the covalent immobilization of an enzyme to a polymer layer. All steps of the covalent reaction of the model enzyme glucose oxidase with the poly(acrylic acid) brush by carbodiimide chemistry, were monitored in-situ. Data were analyzed using optical and viscoelastic modeling. A nearly complete collapse of the polymer chains was found upon activation of the carboxylic acid groups with N-(3-Dimethylaminopropyl)-N'-ethylcarbodiimide and N-Hydroxysuccinimide. The reaction with the amine groups of the enzyme occurs simultaneously with re-hydration of the polymer layer. Significantly more enzyme was immobilized on the surface compared to physical adsorption at similar conditions, at the same pH. It was found that the pH responsive swelling behavior was almost not affected by the presence of the enzyme. © 2019 Koenig, König, Eichhorn, Müller, Stamm and Uhlmann.
- ItemFree polyethylenimine enhances substrate-mediated gene delivery on titanium substrates modified with RGD-functionalized poly(acrylic acid) brushes(Lausanne : Frontiers Media, 2019) Mantz, Amy; Rosenthal, Alice; Farris, Eric; Kozisek, Tyler; Bittrich, Eva; Nazari, Saghar; Schubert, Eva; Schubert, Mathias; Stamm, Manfred; Uhlmann, Petra; Pannier, Angela K.Substrate mediated gene delivery (SMD) is a method of immobilizing DNA complexes to a substrate via covalent attachment or nonspecific adsorption, which allows for increased transgene expression with less DNA compared to traditional bolus delivery. It may also increase cells receptivity to transfection via cell-material interactions. Substrate modifications with poly(acrylic) acid (PAA) brushes may improve SMD by enhancing substrate interactions with DNA complexes via tailored surface chemistry and increasing cellular adhesion via moieties covalently bound to the brushes. Previously, we described a simple method to graft PAA brushes to Ti and further demonstrated conjugation of cell adhesion peptides (i.e., RGD) to the PAA brushes to improve biocompatibility. The objective of this work was to investigate the ability of Ti substrates modified with PAA-RGD brushes (PAA-RGD) to immobilize complexes composed of branched polyethyleneimine and DNA plasmids (bPEI-DNA) and support SMD in NIH/3T3 fibroblasts. Transfection in NIH/3T3 cells cultured on bPEI-DNA complexes immobilized onto PAA-RGD substrates was measured and compared to transfection in cells cultured on control surfaces with immobilized complexes including Flat Ti, PAA brushes modified with a control peptide (RGE), and unmodified PAA. Transfection was two-fold higher in cells cultured on PAA-RGD compared to those cultured on all control substrates. While DNA immobilization measured with radiolabeled DNA indicated that all substrates (PAA-RGD, unmodified PAA, Flat Ti) contained nearly equivalent amounts of loaded DNA, ellipsometric measurements showed that more total mass (i.e., DNA and bPEI, both complexed and free) was immobilized to PAA and PAA-RGD compared to Flat Ti. The increase in adsorbed mass may be attributed to free bPEI, which has been shown to improve transfection. Further transfection investigations showed that removing free bPEI from the immobilized complexes decreased SMD transfection and negated any differences in transfection success between cells cultured on PAA-RGD and on control substrates, suggesting that free bPEI may be beneficial for SMD in cells cultured on bPEI-DNA complexes immobilized on PAA-RGD grafted to Ti. This work demonstrates that substrate modification with PAA-RGD is a feasible method to enhance SMD outcomes on Ti and may be used for future applications such as tissue engineering, gene therapy, and diagnostics. © 2019 Mantz, Rosenthal, Farris, Kozisek, Bittrich, Nazari, Schubert, Schubert, Stamm, Uhlmann and Pannier.
- ItemCharakterisierung und Optimierung von Nano-Templaten aus Polymeren : bmb+f-Förderschwerpunkt Kondensierte Materie, Großgeräte der physikalischen Grundlagenforschung ; Schlussbericht(Hannover : Technische Informationsbibliothek (TIB), 2004) Stamm, Manfred; Sydorenko, A.; Minko, S.; Tokarev, I.; Křenek, R.[no abstract available]
- ItemFraktale Beschreibung der Zugänglichkeit funktioneller Oberflächengruppen, Teilprojekt 2: Röntgenstreuung zur in-situ Strukturanalyse von Polymeren : Schlussbericht zum BMBF-Projekt(Hannover : Technische Informationsbibliothek (TIB), 2003) Jehnichen, Dieter; Pohlers, Andreas; Kummer, Sven; Weidisch, Roland; Stamm, Manfred[no abstract available]