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- ItemA Mechanistic Perspective on Plastically Flexible Coordination Polymers(Weinheim : Wiley-VCH, 2019) Bhattacharya, Biswajit; Michalchuk, Adam A.L.; Silbernagl, Dorothee; Rautenberg, Max; Schmid, Thomas; Feiler, Torvid; Reimann, Klaus; Ghalgaoui, Ahmed; Sturm, Heinz; Paulus, Beate; Emmerling, FranziskaMechanical flexibility in single crystals of covalently bound materials is a fascinating and poorly understood phenomenon. We present here the first example of a plastically flexible one-dimensional (1D) coordination polymer. The compound [Zn(μ-Cl)2(3,5-dichloropyridine)2]n is flexible over two crystallographic faces. Remarkably, the single crystal remains intact when bent to 180°. A combination of microscopy, diffraction, and spectroscopic studies have been used to probe the structural response of the crystal lattice to mechanical bending. Deformation of the covalent polymer chains does not appear to be responsible for the observed macroscopic bending. Instead, our results suggest that mechanical bending occurs by displacement of the coordination polymer chains. Based on experimental and theoretical evidence, we propose a new model for mechanical flexibility in 1D coordination polymers. Moreover, our calculations propose a cause of the different mechanical properties of this compound and a structurally similar elastic material. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemNonspherical Nanoparticle Shape Stability Is Affected by Complex Manufacturing Aspects: Its Implications for Drug Delivery and Targeting(Weinheim : Wiley-VCH, 2019) Haryadi, Bernard Manuel; Hafner, Daniel; Amin, Ihsan; Schubel, Rene; Jordan, Rainer; Winter, Gerhard; Engert, JuliaThe shape of nanoparticles is known recently as an important design parameter influencing considerably the fate of nanoparticles with and in biological systems. Several manufacturing techniques to generate nonspherical nanoparticles as well as studies on in vitro and in vivo effects thereof have been described. However, nonspherical nanoparticle shape stability in physiological-related conditions and the impact of formulation parameters on nonspherical nanoparticle resistance still need to be investigated. To address these issues, different nanoparticle fabrication methods using biodegradable polymers are explored to produce nonspherical nanoparticles via the prevailing film-stretching method. In addition, systematic comparisons to other nanoparticle systems prepared by different manufacturing techniques and less biodegradable materials (but still commonly utilized for drug delivery and targeting) are conducted. The study evinces that the strong interplay from multiple nanoparticle properties (i.e., internal structure, Young's modulus, surface roughness, liquefaction temperature [glass transition (Tg) or melting (Tm)], porosity, and surface hydrophobicity) is present. It is not possible to predict the nonsphericity longevity by merely one or two factor(s). The most influential features in preserving the nonsphericity of nanoparticles are existence of internal structure and low surface hydrophobicity (i.e., surface-free energy (SFE) > ≈55 mN m−1, material–water interfacial tension <6 mN m−1), especially if the nanoparticles are soft (<1 GPa), rough (Rrms > 10 nm), porous (>1 m2 g−1), and in possession of low bulk liquefaction temperature (<100 °C). Interestingly, low surface hydrophobicity of nanoparticles can be obtained indirectly by the significant presence of residual stabilizers. Therefore, it is strongly suggested that nonsphericity of particle systems is highly dependent on surface chemistry but cannot be appraised separately from other factors. These results and reviews allot valuable guidelines for the design and manufacturing of nonspherical nanoparticles having adequate shape stability, thereby appropriate with their usage purposes. Furthermore, they can assist in understanding and explaining the possible mechanisms of nonspherical nanoparticles effectivity loss and distinctive material behavior at the nanoscale. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
- ItemThe Biomedical Use of Silk: Past, Present, Future(Weinheim : Wiley-VCH, 2019) Holland, Chris; Numata, Keiji; Rnjak-Kovacina, Jelena; Seib, F. PhilippHumans have long appreciated silk for its lustrous appeal and remarkable physical properties, yet as the mysteries of silk are unraveled, it becomes clear that this outstanding biopolymer is more than a high-tech fiber. This progress report provides a critical but detailed insight into the biomedical use of silk. This journey begins with a historical perspective of silk and its uses, including the long-standing desire to reverse engineer silk. Selected silk structure–function relationships are then examined to appreciate past and current silk challenges. From this, biocompatibility and biodegradation are reviewed with a specific focus of silk performance in humans. The current clinical uses of silk (e.g., sutures, surgical meshes, and fabrics) are discussed, as well as clinical trials (e.g., wound healing, tissue engineering) and emerging biomedical applications of silk across selected formats, such as silk solution, films, scaffolds, electrospun materials, hydrogels, and particles. The journey finishes with a look at the roadmap of next-generation recombinant silks, especially the development pipeline of this new industry for clinical use. © 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
- ItemEnzyme Activity by Design: An Artificial Rhodium Hydroformylase for Linear Aldehydes(Weinheim : Wiley-VCH, 2017-9-13) Jarvis, Amanda G.; Obrecht, Lorenz; Deuss, Peter J.; Laan, Wouter; Gibson, Emma K.; Wells, Peter P.; Kamer, Paul C. J.Artificial metalloenzymes (ArMs) are hybrid catalysts that offer a unique opportunity to combine the superior performance of natural protein structures with the unnatural reactivity of transition-metal catalytic centers. Therefore, they provide the prospect of highly selective and active catalytic chemical conversions for which natural enzymes are unavailable. Herein, we show how by rationally combining robust site-specific phosphine bioconjugation methods and a lipid-binding protein (SCP-2L), an artificial rhodium hydroformylase was developed that displays remarkable activities and selectivities for the biphasic production of long-chain linear aldehydes under benign aqueous conditions. Overall, this study demonstrates that judiciously chosen protein-binding scaffolds can be adapted to obtain metalloenzymes that provide the reactivity of the introduced metal center combined with specifically intended product selectivity.
- ItemHydrogenation of Polyesters to Polyether Polyols(Weinheim : Wiley-VCH, 2019) Stadler, Bernhard M.; Hinze, Sandra; Tin, Sergey; de Vries, Johannes G.The amount of plastic waste is continuously increasing. Besides conventional recycling, one solution to deal with this problem could be to use this waste as a resource for novel materials. In this study, polyesters are hydrogenated to give polyether polyols by using in situ-generated Ru-Triphos catalysts in combination with Lewis acids. The choice of Lewis acid and its concentration relative to the ruthenium catalyst are found to determine the selectivity of the reaction. Monitoring of the molecular weight during the reaction confirms a sequential mechanism in which the diols that are formed by hydrogenation are etherified to the polyethers. To probe the applicability of this tandem hydrogenation etherification approach, a range of polyester substrates is investigated. The oligoether products that form in these reactions have the chain lengths that are appropriate for application in the adhesives and coatings industries. This strategy makes polyether polyols accessible that are otherwise difficult to obtain from conventional fossil-based feedstocks. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemProperties of Novel Polyesters Made from Renewable 1,4-Pentanediol(Weinheim : Wiley-VCH, 2019) Stadler, Bernhard M.; Brandt, Adrian; Kux, Alexander; Beck, Horst; de Vries, Johannes G.Novel polyester polyols were prepared in high yields from biobased 1,4-pentanediol catalyzed by non-toxic phosphoric acid without using a solvent. These oligomers are terminated with hydroxyl groups and have low residual acid content, making them suitable for use in adhesives by polyurethane formation. The thermal behavior of the polyols was studied by differential scanning calorimetry, and tensile testing was performed on the derived polyurethanes. The results were compared with those of polyurethanes obtained with fossil-based 1,4-butanediol polyester polyols. Surprisingly, it was found that a crystalline polyester was obtained when aliphatic long-chain diacids (>C12) were used as the diacid building block. The low melting point of the C12 diacid-based material allows the development of biobased shape-memory polymers with very low switching temperatures (<0 °C), an effect that has not yet been reported for a material based on a simple binary polyester. This might find application as thermosensitive adhesives in the packaging of temperature-sensitive goods such as pharmaceuticals. Furthermore, these results indicate that, although 1,4-pentanediol cannot be regarded as a direct substitute for 1,4-butanediol, its novel structure expands the toolbox of the adhesives, coatings, or sealants formulators. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemHigh Blocking Temperature of Magnetization and Giant Coercivity in the Azafullerene Tb 2 @C 79 N with a Single-Electron Terbium–Terbium Bond(Weinheim : Wiley-VCH, 2019) Velkos, Georgios; Krylov, Denis S.; Kirkpatrick, Kyle; Spree, Lukas; Dubrovin, Vasilii; Büchner, Bernd; Avdoshenko, Stanislav M.; Bezmelnitsyn, Valeriy; Davis, Sean; Faust, Paul; Duchamp, James; Dorn, Harry C.; Popov, Alexey A.The azafullerene Tb 2 @C 79 N is found to be a single-molecule magnet with a high 100-s blocking temperature of magnetization of 24 K and large coercivity. Tb magnetic moments with an easy-axis single-ion magnetic anisotropy are strongly coupled by the unpaired spin of the single-electron Tb−Tb bond. Relaxation of magnetization in Tb 2 @C 79 N below 15 K proceeds via quantum tunneling of magnetization with the characteristic time τ QTM =16 462±1230 s. At higher temperature, relaxation follows the Orbach mechanism with a barrier of 757±4 K, corresponding to the excited states, in which one of the Tb spins is flipped. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemOn Silylated Oxonium and Sulfonium Ions and Their Interaction with Weakly Coordinating Borate Anions(Weinheim : Wiley-VCH, 2019) Bläsing, Kevin; Labbow, Rene; Michalik, Dirk; Reiß, Fabian; Schul, Axel; Villinger, Alexander; Walker, SvenjaAttempts have been made to prepare salts with the labile tris(trimethylsilyl)chalconium ions, [(Me3Si)3E]+ (E=O, S), by reacting [Me3Si-H-SiMe3][B(C6F5)4] and Me3Si[CB] (CB−=carborate=[CHB11H5Cl6]−, [CHB11Cl11]−) with Me3Si-E-SiMe3. In the reaction of Me3Si-O-SiMe3 with [Me3Si-H-SiMe3][B(C6F5)4], a ligand exchange was observed in the [Me3Si-H-SiMe3]+ cation leading to the surprising formation of the persilylated [(Me3Si)2(Me2(H)Si)O]+ oxonium ion in a formal [Me2(H)Si]+ instead of the desired [Me3Si]+ transfer reaction. In contrast, the expected homoleptic persilylated [(Me3Si)3S]+ ion was formed and isolated as [B(C6F5)4]− and [CB]− salt, when Me3Si-S-SiMe3 was treated with either [Me3Si-H-SiMe3][B(C6F5)4] or Me3Si[CB]. However, the addition of Me3Si[CB] to Me3Si-O-SiMe3 unexpectedly led to the release of Me4Si with simultaneous formation of a cyclic dioxonium dication of the type [Me3Si-μO-SiMe2]2[CB]2 in an anion-mediated reaction. DFT studies on structure, bonding and thermodynamics of the [(Me3Si)3E]+ and [(Me3Si)2(Me2(H)Si)E]+ ion formation are presented as well as mechanistic investigations on the template-driven transformation of the [(Me3Si)3E]+ ion into a cyclic dichalconium dication [Me3Si-μE-SiMe2]22+. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemSurface modification of the laser sintering standard powder polyamide 12 by plasma treatments(Weinheim : Wiley-VCH, 2018-6-7) Almansoori, Alaa; Masters, Robert; Abrams, Kerry; Schäfer, Jan; Gerling, Torsten; Majewski, Candice; Rodenburg, CorneliaPolyamide 12 (PA12) powder was exposed for up to 3 h to low pressure air plasma treatment (LP-PT) and several minutes by two different atmospheric pressure plasma jets (APPJ) i.e., kINPen (K-APPJ) and Hairline (H-APPJ). The chemical and physical changes resulting from LP-PT were observed by a combination of Scanning Electron Microscopy (SEM), Hot Stage Microscopy (HSM) and Fourier transform infrared spectroscopy (FTIR), which demonstrated significant changes between the plasma treated and untreated PA12 powders. PA12 exposed to LP-PT showed an increase in wettability, was relatively porous, and possessed a higher density, which resulted from the surface functionalization and materials removal during the plasma exposure. However, it showed poor melt behavior under heating conditions typical for Laser Sintering. In contrast, brief PJ treatments demonstrated similar changes in porosity, but crucially, retained the favorable melt characteristics of PA12 powder.
- ItemMagnetic Nanoparticle Chains in Gelatin Ferrogels: Bioinspiration from Magnetotactic Bacteria(Weinheim : Wiley-VCH, 2019) Sturm, Sebastian; Siglreitmeier, Maria; Wolf, Daniel; Vogel, Karin; Gratz, Micha; Faivre, Damien; Lubk, Axel; Büchner, Bernd; Sturm, Elena V.; Cölfen, HelmutInspired by chains of ferrimagnetic nanocrystals (NCs) in magnetotactic bacteria (MTB), the synthesis and detailed characterization of ferrimagnetic magnetite NC chain-like assemblies is reported. An easy green synthesis route in a thermoreversible gelatin hydrogel matrix is used. The structure of these magnetite chains prepared with and without gelatin is characterized by means of transmission electron microscopy, including electron tomography (ET). These structures indeed bear resemblance to the magnetite assemblies found in MTB, known for their mechanical flexibility and outstanding magnetic properties and known to crystallographically align their magnetite NCs along the strongest <111> magnetization easy axis. Using electron holography (EH) and angular dependent magnetic measurements, the magnetic interaction between the NCs and the generation of a magnetically anisotropic material can be shown. The electro- and magnetostatic modeling demonstrates that in order to precisely determine the magnetization (by means of EH) inside chain-like NCs assemblies, their exact shape, arrangement and stray-fields have to be considered (ideally obtained using ET). © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim