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- ItemMicrofluidic-assisted silk nanoparticle tuning(Cambridge : Royal Society of Chemistry, 2019) Wongpinyochit, Thidarat; Totten, John D.; Johnston, Blair F.; Seib, F. PhilippSilk is now making inroads into advanced pharmaceutical and biomedical applications. Both bottom-up and top-down approaches can be applied to silk and the resulting aqueous silk solution can be processed into a range of material formats, including nanoparticles. Here, we demonstrate the potential of microfluidics for the continuous production of silk nanoparticles with tuned particle characteristics. Our microfluidic-based design ensured efficient mixing of different solvent phases at the nanoliter scale, in addition to controlling the solvent ratio and flow rates. The total flow rate and aqueous : solvent ratios were important parameters affecting yield (1 mL min−1 > 12 mL min−1). The ratios also affected size and stability; a solvent : aqueous total flow ratio of 5 : 1 efficiently generated spherical nanoparticles 110 and 215 nm in size that were stable in water and had a high beta-sheet content. These 110 and 215 nm silk nanoparticles were not cytotoxic (IC50 > 100 μg mL−1) but showed size-dependent cellular trafficking. Overall, microfluidic-assisted silk nanoparticle manufacture is a promising platform that allows control of the silk nanoparticle properties by manipulation of the processing variables.
- ItemSize Separation Techniques for the Characterisation of Cross-Linked Casein: A Review of Methods and Their Applications(Basel : MDPI, 2018) Raak, Norbert; Abbate, Raffaele Andrea; Lederer, Albena; Rohm, Harald; Jaros, DorisCasein is the major protein fraction in milk, and its cross-linking has been a topic of scientific interest for many years. Enzymatic cross-linking has huge potential to modify relevant techno-functional properties of casein, whereas non-enzymatic cross-linking occurs naturally during the storage and processing of milk and dairy products. Two size separation techniques were applied for characterisation of these reactions: gel electrophoresis and size exclusion chromatography. This review summarises their separation principles and discusses the outcome of studies on cross-linked casein from the last ~20 years. Both methods, however, show limitations concerning separation range and are applied mainly under denaturing and reducing conditions. In contrast, field flow fractionation has a broad separation range and can be easily applied under native conditions. Although this method has become a powerful tool in polymer and nanoparticle analysis and was used in few studies on casein micelles, it has not yet been applied to investigate cross-linked casein. Finally, the principles and requirements for absolute molar mass determination are reviewed, which will be of increased interest in the future since suitable calibration substances for casein polymers are scarce.
- 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.
- ItemRecent Progress and Perspectives in the Electrokinetic Characterization of Polyelectrolyte Films(Basel : MDPI, 2015) Zimmermann, Ralf; Werner, Carsten; Duval, Jérôme F LThe analysis of the charge, structure and molecular interactions of/within polymeric substrates defines an important analytical challenge in materials science. Accordingly, advanced electrokinetic methods and theories have been developed to investigate the charging mechanisms and structure of soft material coatings. In particular, there has been significant progress in the quantitative interpretation of streaming current and surface conductivity data of polymeric films from the application of recent theories developed for the electrohydrodynamics of diffuse soft planar interfaces. Here, we review the theory and experimental strategies to analyze the interrelations of the charge and structure of polyelectrolyte layers supported by planar carriers under electrokinetic conditions. To illustrate the options arising from these developments, we discuss experimental and simulation data for plasma-immobilized poly(acrylic acid) films and for a polyelectrolyte bilayer consisting of poly(ethylene imine) and poly(acrylic acid). Finally, we briefly outline potential future developments in the field of the electrokinetics of polyelectrolyte layers.
- ItemViscoelastic Behavior of Embroidered Scaffolds for ACL Tissue Engineering Made of PLA and P(LA-CL) After In Vitro Degradation(Basel : Molecular Diversity Preservation International, 2019) Hahn, Judith; Schulze-Tanzil, Schulze-Tanzil; Schröpfer, Michaela; Meyer, Michael; Gögele, Clemens; Hoyer, Mariann; Spickenheuer, Axel; Heinrich, Gert; Breier, AnnetteA rupture of the anterior cruciate ligament (ACL) is the most common knee ligament injury. Current applied reconstruction methods have limitations in terms of graft availability and mechanical properties. A new approach could be the use of a tissue engineering construct that temporarily reflects the mechanical properties of native ligament tissues and acts as a carrier structure for cell seeding. In this study, embroidered scaffolds composed of polylactic acid (PLA) and poly(lactic-co-"-caprolactone) (P(LA-CL)) threads were tested mechanically for their viscoelastic behavior under in vitro degradation. The relaxation behavior of both scaffold types (moco: mono-component scaffold made of PLA threads, bico: bi-component scaffold made of PLA and P(LA-CL) threads) was comparable to native lapine ACL. Most of the lapine ACL cells survived 32 days of cell culture and grew along the fibers. Cell vitality was comparable for moco and bico scaffolds. Lapine ACL cells were able to adhere to the polymer surfaces and spread along the threads throughout the scaffold. The mechanical behavior of degrading matrices with and without cells showed no significant differences. These results demonstrate the potential of embroidered scaffolds as an ACL tissue engineering approach. © 2019 by the authors. Licensee MDPI, Basel, Switzerland.
- ItemNaphtalenediimide-based donor-acceptor copolymer prepared by chain-growth catalyst-transfer polycondensation: Evaluation of electron-transporting properties and application in printed polymer transistors(London [u.a.] : Royal Society of Chemistry, 2014) Schmidt, G.C.; Höft, D.; Haase, K.; Hübler, A.C.; Karpov, E.; Tkachov, R.; Stamm, M.; Kiriy, A.; Haidu, F.; Zahn, D.R.T.; Yan, H.; Facchetti, A.The semiconducting properties of a bithiophene-naphthalene diimide copolymer (PNDIT2) prepared by Ni-catalyzed chain-growth polycondensation (P1) and commercially available N2200 synthesized by Pd-catalyzed step-growth polycondensation were compared. Both polymers show similar electron mobility of ∼0.2 cm2 V-1 s-1, as measured in top-gate OFETs with Au source/drain electrodes. It is noteworthy that the new synthesis has several technological advantages compared to traditional Stille polycondensation, as it proceeds rapidly at room temperature and does not involve toxic tin-based monomers. Furthermore, a step forward to fully printed polymeric devices was achieved. To this end, transistors with PEDOT:PSS source/drain electrodes were fabricated on plastic foils by means of mass printing technologies in a roll-to-roll printing press. Surface treatment of the printed electrodes with PEIE, which reduces the work function of PEDOT:PSS, was essential to lower the threshold voltage and achieve high electron mobility. Fully polymeric P1 and N2200-based OFETs achieved average linear and saturation FET mobilities of >0.08 cm2 V-1 s-1. Hence, the performance of n-type, plastic OFET devices prepared in ambient laboratory conditions approaches those achieved by more sophisticated and expensive technologies, utilizing gold electrodes and time/energy consuming thermal annealing and lithographic steps.
- ItemDefect-free Naphthalene Diimide Bithiophene Copolymers with Controlled Molar Mass and High Performance via Direct Arylation Polycondensation(Washington, DC : ACS Publications, 2015) Matsidik, Rukiya; Komber, Hartmut; Luzio, Alessandro; Caironi, Mario; Sommer, MichaelA highly efficient, simple, and environmentally friendly protocol for the synthesis of an alternating naphthalene diimide bithiophene copolymer (PNDIT2) via direct arylation polycondensation (DAP) is presented. High molecular weight (MW) PNDIT2 can be obtained in quantitative yield using aromatic solvents. Most critical is the suppression of two major termination reactions of NDIBr end groups: nucleophilic substitution and solvent end-capping by aromatic solvents via C–H activation. In situ solvent end-capping can be used to control MW by varying monomer concentration, whereby end-capping is efficient and MW is low for low concentration and vice versa. Reducing C–H reactivity of the solvent at optimized conditions further increases MW. Chain perfection of PNDIT2 is demonstrated in detail by NMR spectroscopy, which reveals PNDIT2 chains to be fully linear and alternating. This is further confirmed by investigating the optical and thermal properties as a function of MW, which saturate at Mn ≈ 20 kDa, in agreement with controls made by Stille coupling. Field-effect transistor (FET) electron mobilities μsat up to 3 cm2/(V·s) are measured using off-center spin-coating, with FET devices made from DAP PNDIT2 exhibiting better reproducibility compared to Stille controls.
- ItemDetermination of Pressure Dependence of Polymer Phase Transitions by pVT Analysis(Basel : MDPI, 2018) Pionteck, JürgenGlass transitions, melting, crystallization, and the isotropization of polymers are connected with changes in the density, respectively the specific volume (Vsp), which can be analyzed by dilatometric methods. Here, the pressure dependence of such transitions is determined by pressure volume temperature (pVT) analysis for different thermoplastic polymers in the pressure range of 10 to 200 MPa, and the temperature range from room temperature to 350 °C. The values for ambient pressure are extrapolated. It is shown that polymer transitions always increase with pressure, and that the melting temperature and glass transition temperature are nearly linearly dependent on pressure. This information, as well as the observed density changes with pressure and temperature, is very important for the processing of thermoplastics, including their simulation, as well as for the thermodynamic interpretations of the transition’s nature.
- ItemStacks of Azobenzene Stars: Self-Assembly Scenario and Stabilising Forces Quantified in Computer Modelling(Basel : MDPI, 2019) Savchenko, Vladyslav; Koch, Markus; Pavlov, Aleksander S.; Saphiannikova, Marina; Guskova, OlgaIn this paper, the columnar supramolecular aggregates of photosensitive star-shaped azobenzenes with benzene-1,3,5-tricarboxamide core and azobenzene arms are analyzed theoretically by applying a combination of computer simulation techniques. Without a light stimulus, the azobenzene arms adopt the trans-state and build one-dimensional columns of stacked molecules during the first stage of the noncovalent association. These columnar aggregates represent the structural elements of more complex experimentally observed morphologies-fibers, spheres, gels, and others. Here, we determine the most favorable mutual orientations of the trans-stars in the stack in terms of (i) the p - p distance between the cores lengthwise the aggregate, (ii) the lateral displacements due to slippage and (iii) the rotation promoting the helical twist and chirality of the aggregate. To this end, we calculate the binding energy diagrams using density functional theory. The model predictions are further compared with available experimental data. The intermolecular forces responsible for the stability of the stacks in crystals are quantified using Hirshfeld surface analysis. Finally, to characterize the self-assembly mechanism of the stars in solution, we calculate the hydrogen bond lengths, the normalized dipole moments and the binding energies as functions of the columnar length. For this, molecular dynamics trajectories are analyzed. Finally, we conclude about the cooperative nature of the self-assembly of star-shaped azobenzenes with benzene-1,3,5-tricarboxamide core in aqueous solution.
- ItemOrganic Light-Emitting Diodes Based on Conjugation-Induced Thermally Activated Delayed Fluorescence Polymers: Interplay Between Intra- and Intermolecular Charge Transfer States(Lausanne : Frontiers Media, 2019) Li, Yungui; Wei, Qiang; Cao, Liang; Fries, Felix; Cucchi, Matteo; Wu, Zhongbin; Scholz, Reinhard; Lenk, Simone; Voit, Brigitte; Ge, Ziyi; Reineke, SebastianIn this work, interactions between different host materials and a blue TADF polymer named P1 are systematically investigated. In photoluminescence, the host can have substantial impact on the photoluminescence quantum yield (PLQY) and the intensity of delayed fluorescence (ΦDF), where more than three orders of magnitude difference of ΦDF in various hosts is observed, resulting from a polarity effect of the host material and energy transfer. Additionally, an intermolecular charge-transfer (CT) emission with pronounced TADF characteristics is observed between P1 and 2,4,6-tris[3-(diphenylphosphinyl)phenyl]-1,3,5-triazine (PO-T2T), with a singlet-triplet splitting of 7 meV. It is noted that the contribution of harvested triplets in monochrome organic light-emitting diodes (OLEDs) correlates with ΦDF. For devices based on intermolecular CT-emission, the harvested triplets contribute ~90% to the internal quantum efficiency. The results demonstrate the vital importance of host materials on improving the PLQY and sensitizing ΦDF of TADF polymers for efficient devices. Solution-processed polychrome OLEDs with a color close to a white emission are presented, with the emission of intramolecular (P1) and intermolecular TADF (PO-T2T:P1). © Copyright © 2019 Li, Wei, Cao, Fries, Cucchi, Wu, Scholz, Lenk, Voit, Ge and Reineke.