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- ItemTowards New Robust Zn(II) Complexes for the Ring-Opening Polymerization of Lactide Under Industrially Relevant Conditions(Weinheim : Wiley-VCH, 2019) Schäfer, Pascal M.; Dankhoff, Katja; Rothemund, Matthias; Ksiazkiewicz, Agnieszka N.; Pich, Andrij; Schobert, Rainer; Weber, Birgit; Herres-Pawlis, SonjaThe synthesis of bio-based and biodegradable plastics is a hot topic in research due to growing environmental problems caused by omnipresent plastics. As a result, polylactide, which has been known for years, has seen a tremendous increase in industrial production. Nevertheless, the manufacturing process using the toxic catalyst Sn(Oct)2 is very critical. As an alternative, five zinc acetate complexes have been synthesized with Schiff base-like ligands that exhibit high activity in the ring-opening polymerization of non-purified lactide. The systems bear different side arms in the ligand scaffold. The influence of these substituents has been analyzed. For a detailed description of the catalytic activities, the rate constants kapp and kp were determined using in-situ Raman spectroscopy at a temperature of 150 °C. The polymers produced have molar masses of up to 71 000 g mol−1 and are therefore suitable for a variety of applications. Toxicity measurements carried out for these complexes proved the nontoxicity of the systems. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemEnabling the measurement of particle sizes in stirred colloidal suspensions by embedding dynamic light scattering into an automated probe head(Amsterdam [u.a.] : Elsevier Science, 2016) de Kanter, Martinus; Meyer-Kirschner, Julian; Viell, Jörn; Mitsos, Alexander; Kather, Michael; Pich, Andrij; Janzen, ChristophA novel probe head design is introduced, which enables in-line monitoring of particle sizes in undiluted stirred fluids using dynamic light scattering. The novel probe head separates a small sample volume of 0.65 ml from the bulk liquid by means of an impeller. In this sample volume, particle sizing is performed using a commercially available fiber-optical backscatter probe. While conventional light scattering measurements in stirred media fail due to the superposition of Brownian’ motion and forced convection, undistorted measurements are possible with the proposed probe head. One measurement takes approximately 30 s used for liquid exchange by rotation of the impeller and for collection of scattered light. The probe head is applied for in-line monitoring of the particle growth during microgel synthesis by precipitation polymerization in a one liter laboratory reactor. The in-line measurements are compared to off-line measurements and show a good agreement.
- ItemBiadhesive Peptides for Assembling Stainless Steel and Compound Loaded Micro-Containers(Weinheim : Wiley-VCH, 2019) Apitius, Lina; Buschmann, Sven; Bergs, Christian; Schönauer, David; Jakob, Felix; Pich, Andrij; Schwaneberg, UlrichBiadhesive peptides (peptesives) are an attractive tool for assembling two chemically different materials—for example, stainless steel and polycaprolactone (PCL). Stainless steel is used in medical stents and PCL is used as a biodegradable polymer for fabrication of tissue growth scaffolds and drug delivering micro-containers. Biadhesive peptides are composed of two domains (e.g., dermaseptin S1 and LCI) with different material-binding properties that are separated through a stiff peptide-spacer. The peptesive dermaseptin S1-domain Z-LCI immobilizes antibiotic-loaded PCL micro-containers on stainless steel surfaces. Immobilization is visualized by microscopy and field emission scanning electron microscopy analysis and released antibiotic from the micro-containers is confirmed through growth inhibition of Escherichia coli cells.
- ItemOne‐Pot Two‐Step Chemoenzymatic Cascade for the Synthesis of a Bis‐benzofuran Derivative(Weinheim : Wiley-VCH Verl., 2019) Mertens, M.A. Stephanie; Thomas, Fabian; Nöth, Maximilian; Moegling, Julian; El‐Awaad, Islam; Sauer, Daniel F.; Dhoke, Gaurao V.; Xu, Wenjing; Pich, Andrij; Herres‐Pawlis, Sonja; Schwaneberg, UlrichChemoenzymatic cascades enable reactions with the high productivity of chemocatalysts and high selectivity of enzymes. Nevertheless, the combination of these different fields of catalysis is prone to mutual deactivation of metal- and biocatalysts. In this study, a one-pot sequential two-step catalytic cascade reaction was successfully implemented for the synthesis of a methylene-bridged bis(2-substituted benzofuran). In the first step, a palladium-free Sonogashira reaction is used for the synthesis of a benzofuran derivative. In the subsequent step, the formed 2-substituted benzofuran is hydroxylated by the monooxygenase P450 BM3 variant (A74S-F87V-L188Q) and undergoes further elimination reactions. The study proofs that combination of Cu scorpionate catalyzed Sonogashira cross-coupling and P450 mediated oxidation is possible and results in up to 84 % yield of the final product. The oxidation reaction is boosted by capturing inhibiting reaction components.
- ItemHeterolepic β‐Ketoiminate Zinc Phenoxide Complexes as Efficient Catalysts for the Ring Opening Polymerization of Lactide(Weinheim : Wiley-VCH, 2019) Ghosh, Swarup; Schäfer, Pascal M.; Dittrich, Dennis; Scheiper, Christoph; Steiniger, Phillip; Fink, Gerhard; Ksiazkiewicz, Agnieszka N.; Tjaberings, Alexander; Wölper, Christoph; Gröschel, André H.; Pich, Andrij; Herres‐Pawlis, Sonja; Schulz, StephanZinc phenoxide complexes L1ZnOAr 1–4 (L1=Me2NC2H4NC(Me)CHC(Me)O) and L2ZnOAr 5–8 (L2=Me2NC3H6NC(Me)CHC(Me)O) with donor-functionalized β-ketoiminate ligands (L1/2) and OAr substituents (Ar=Ph 1, 5; 2,6-Me2-C6H3 2, 6; 3,5-Me2-C6H3 3, 7; 4-Bu-C6H4 4, 8) with tuneable electronic and steric properties were synthesized and characterized. 1–8 adopt binuclear structures in the solid state except for 5, while they are monomeric in CDCl3 solution. 1–8 are active catalysts for the ring opening polymerization (ROP) of lactide (LA) in CH2Cl2 at ambient temperature and the catalytic activity is controlled by the electronic and steric properties of the OAr substituent, yielding polymers with high average molecular weight (Mn) and moderately controlled molecular weight distribution (MWDs). 1 and 5 showed a living polymerization character and kinetic studies on the ROP of L–LA with 1 and 5 proved first order dependencies on the monomer concentration. Homonuclear decoupled 1H-NMR analyses of polylactic acid (PLA) formed with rac-LA proved isotactic enrichment of the PLA microstructure. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemSynthesis of Poly(N-vinylcaprolactam)-Based Microgels by Precipitation Polymerization: Pseudo-Bulk Model for Particle Growth and Size Distribution(Washington, DC : ACS Publications, 2019) Janssen, Franca A.L.; Kather, Michael; Ksiazkiewicz, Agnieszka; Pich, Andrij; Mitsos, AlexanderParticle size distribution and in particular the mean particle size are key properties of microgels, which are determined by synthesis conditions. To describe particle growth and particle size distribution over the progress of synthesis of poly(N-vinylcaprolactam)-based microgels, a pseudo-bulk model for precipitation copolymerization with cross-linking is formulated. The model is fitted and compared to experimental data from reaction calorimetry and dynamic light scattering, showing good agreement with polymerization progress, final particle size, and narrow particle size distribution. Predictions of particle growth and reaction progress for different experimental setups are compared to the corresponding experimental data, demonstrating the predictive capability and limitations of the model. The comparison to reaction calorimetry measurements shows the strength in the prediction of the overall polymerization progress. The results for the prediction of the particle radii reveal significant deviations and highlight the demand for further investigation, including additional data. Copyright © 2019 American Chemical Society.
- ItemSynthesis of acylglycerol derivatives by mechanochemistry(Frankfurt, M. : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2019) Ardila-Fierro, Karen J.; Pich, Andrij; Spehr, Marc; Hernández, José G.; Bolm, CarstenIn recent times, many biologically relevant building blocks such as amino acids, peptides, saccharides, nucleotides and nucleosides, etc. have been prepared by mechanochemical synthesis. However, mechanosynthesis of lipids by ball milling techniques has remained essentially unexplored. In this work, a multistep synthetic route to access mono- and diacylglycerol derivatives by mechanochemistry has been realized, including the synthesis of diacylglycerol-coumarin conjugates.
- ItemBiofunctionalized zinc peroxide (ZnO2) nanoparticles as active oxygen sources and antibacterial agents(London : RSC Publishing, 2017) Bergs, Christian; Brück, Lisa; Rosencrantz, Ruben R.; Conrads, Georg; Elling, Lothar; Pich, AndrijOxygen is one of the most important substances for physiological reactions and metabolisms in biological systems. Through the tailored design of oxygen-releasing materials it might be possible to control different biological processes. In this work we synthesized for the first time zinc peroxide nanoparticles with controlled sizes and biofunctionalized surfaces using a one-step reaction procedure. The zinc peroxide nanoparticles were obtained with tunable sizes (between 4.0 ± 1.2 nm and 9.4 ± 5.2 nm) and were decorated with glucose 1-phosphate (Glc-1P). The specific interaction of the phosphate function of Glc-1P with the nanoparticle surface was monitored by solid state 31P-NMR and zeta-potential measurements. Furthermore, using fluorescence measurements we demonstrated that anchored glucose molecules on the nanoparticle surface are accessible for specific interactions with lectins. It could be shown that these interactions strongly depend on the amount of Glc-1P attached to the nanoparticle surface. Additionally it was demonstrated that the oxygen release from biofunctionalized zinc peroxide nanoparticles could be tuned according to the chemical composition of the nanoparticles and the pH of the aqueous solution. The antibacterial efficiency of the synthesized nanoparticles against Enterococcus faecalis, Aggregatibacter actinomycetemcomitans, Porphyromonas gingivalis and Prevotella intermedia was evaluated by determination of minimal bactericidal concentration (MIC).
- ItemDiffusive Motion of Linear Microgel Assemblies in Solution(Basel : MDPI, 2016) Schürings, Marco-Philipp; Nevskyi, Oleksii; Eliasch, Kamill; Michel, Ann-Katrin; Liu, Bing; Pich, Andrij; Böker, Alexander; Von Plessen, Gero; Wöll, DominikDue to the ability of microgels to rapidly contract and expand in response to external stimuli, assemblies of interconnected microgels are promising for actuation applications, e.g., as contracting fibers for artificial muscles. Among the properties determining the suitability of microgel assemblies for actuation are mechanical parameters such as bending stiffness and mobility. Here, we study the properties of linear, one-dimensional chains of poly(N-vinylcaprolactam) microgels dispersed in water. They were fabricated by utilizing wrinkled surfaces as templates and UV-cross-linking the microgels. We image the shapes of the chains on surfaces and in solution using atomic force microscopy (AFM) and fluorescence microscopy, respectively. In solution, the chains are observed to execute translational and rotational diffusive motions. Evaluation of the motions yields translational and rotational diffusion coefficients and, from the translational diffusion coefficient, the chain mobility. The microgel chains show no perceptible bending, which yields a lower limit on their bending stiffness
- ItemNoninvasive Assessment of Elimination and Retention using CT-FMT and Kinetic Whole-body Modeling(Wyoming, NSW : Ivyspring, 2017) Al Rawashdeh, Wa'el; Zuo, Simin; Melle, Andrea; Appold, Lia; Koletnik, Susanne; Tsvetkova, Yoanna; Beztsinna, Nataliia; Pich, Andrij; Lammers, Twan; Kiessling, Fabian; Gremse, FelixFluorescence-mediated tomography (FMT) is a quantitative three-dimensional imaging technique for preclinical research applications. The combination with micro-computed tomography (μCT) enables improved reconstruction and analysis. The aim of this study is to assess the potential of μCT-FMT and kinetic modeling to determine elimination and retention of typical model drugs and drug delivery systems. We selected four fluorescent probes with different but well-known biodistribution and elimination routes: Indocyanine green (ICG), hydroxyapatite-binding OsteoSense (OS), biodegradable nanogels (NG) and microbubbles (MB). μCT-FMT scans were performed in twenty BALB/c nude mice (5 per group) at 0.25, 2, 4, 8, 24, 48 and 72 h after intravenous injection. Longitudinal organ curves were determined using interactive organ segmentation software and a pharmacokinetic whole-body model was implemented and applied to compute physiological parameters describing elimination and retention. ICG demonstrated high initial hepatic uptake which decreased rapidly while intestinal accumulation appeared for around 8 hours which is in line with the known direct uptake by hepatocytes followed by hepatobiliary elimination. Complete clearance from the body was observed at 48 h. NG showed similar but slower hepatobiliary elimination because these nanoparticles require degradation before elimination can take place. OS was strongly located in the bones in addition to high signal in the bladder at 0.25 h indicating fast renal excretion. MB showed longest retention in liver and spleen and low signal in the kidneys likely caused by renal elimination or retention of fragments. Furthermore, probe retention was found in liver (MB, NG and OS), spleen (MB) and kidneys (MB and NG) at 72 h which was confirmed by ex vivo data. The kinetic model enabled robust extraction of physiological parameters from the organ curves. In summary, μCT-FMT and kinetic modeling enable differentiation of hepatobiliary and renal elimination routes and allow for the noninvasive assessment of retention sites in relevant organs including liver, kidney, bone and spleen. © Ivyspring International Publisher.