Sustainable challenges on the moon

For a permanently manned outpost on the moon – a moon village – a first holistic concept of a sustainable material flow has been established. From this context three dedicated topics have been investigated to more depth: Additive manufacturing (AM) of Al from disused space crafts, AM of structural elements with local resources, and resource extraction from regolith via thermal processes.     

A high-order full-discretization method using Hermite interpolation for periodic time-delayed differential equations

A high-order full-discretization method(FDM)using Hermite interpolation(HFDM) is proposed and implemented for periodic systems with time delay. Both Lagrange interpolation and Hermite interpolation are used to approximate state values and delayed state values in each discretization step. The transition matrix over a single period is determined and used for stability analysis. The proposed method increases the approximation order of the semidiscretization method and the FDM without increasing the computational time. The convergence, precision, and efficiency of the proposed method are investigated using several Mathieu equations and a complex turning model as examples. Comparison shows that the proposed HFDM converges faster and uses less computational time than existing methods.     

A theory of finite tensile deformation of double-network hydrogels

A continuum damage model was developed to describe the finite tensile deformation of tough double-network (DN) hydrogels synthesized by polymerization of a water-soluble monomer inside a highly crosslinked rigid polyelectrolyte network. Damage evolution in DN hydrogels was characterized by performing loading-unloading tensile tests and oscillatory shear rheometry on DN hydrogels synthesized from 3-sulfopropyl acrylate potassium salt (SAPS) and acrylamide (AAm). The model can explain all the mechanical features of finite tensile deformation of DN hydrogels, including idealized Mullins effect and permanent set observed after unloading, qualitatively and quantitatively. The constitutive equation can describe the finite elasto-plastic tensile behavior of DN hydrogels without resorting to a yield function. It was showed that tensile mechanics of DN hydrogels in the model is controlled by two material parameters which are related to the elastic moduli of first and second networks. In effect, the ratio of these two parameters is a dimensionless number that controls the behavior of material. The model can capture the stable branch of material response during neck propagation where engineering stress becomes constant. Consistent with experimental data, by increasing the elastic modulus of the second network the finite tensile behavior of the DN hydrogel changes from necking to strain hardening.     

Regioselective Ring‐Opening Polymerization of a Polyhydroxycarboxylic Acid for the Synthesis of a Nanoscale Carrier Material with pH‐Dependent Stability and Sustained Drug Release

Synthetic polyesters are usually composed of monohydroxycarboxylic acids to avoid the problem of regioselectivity during ring‐opening polymerization. In contrast, the linear polyester BICpoly contains four secondary OH groups and is nevertheless esterified regioselectively at only one of these positions. Neither the synthesis of the tricyclic monomers nor the ring‐opening polymerization requires protecting groups, making BICpoly an attractive novel and biocompatible polymer. BICpoly nanoparticles can be loaded with low‐molecular weight drugs or coated onto surfaces as thin films. The release of loaded compounds makes BICpoly an attractive depot for drug release, as shown herein by loading BICpoly with dyes or the cytostatic drug doxorubicin. BICpoly is distinguishable from other polymers by its characteristic pH‐dependent degradation.     

Trapping Nanostructures on Surfaces through Weak Interactions

The assembly of imidazole‐functionalized phenanthroline‐strapped zinc porphyrins (ZnPorphen) with alkyl or polyethylene glycol (PEG) side chains was studied in solution and by AFM after casting on highly oriented pyrolytic graphite (HOPG) or mica. The nature of the solvent and its evaporation time influenced the morphology of the objects observed. On HOPG, short rods of about 100 nm were observed after fast evaporation of solutions of the alkyl derivatives in CHCl₃, THF, or pyridine, whereas islands of aligned rows of longer wires were obtained from methylcyclohexane (MCH). Slow evaporation of MCH led to a three‐dimensional assembly. The PEG porphyrin assembled into short wires on HOPG or fibers on mica after slow evaporation of solutions in THF. This study shows the role of surface–molecule interactions in the interfacial assembly of ZnPorphen derivatives and contributes to understanding the parameters that control their noncovalent assembly into molecular wires on a surface.     

Direct Imaging of Octahedral Distortion in a Complex Molybdenum Vanadium Mixed Oxide

Complex Mo,V‐based mixed oxides that crystallize in the orthorhombic M1‐type structure are promising candidates for the selective oxidation of small alkanes. The oxygen sublattice of such a complex oxide has been studied by annular bright field scanning transmission electron microscopy. The recorded micrographs directly display the local distortion in the metal oxygen octahedra. From the degree of distortion we are able to draw conclusions on the distribution of oxidation states in the cation columns at different sites. The results are supported by X‐ray diffraction and electron paramagnetic resonance measurements that provide integral details about the crystal structure and spin coupling, respectively.     

High-precision measurements of seawater Pb isotope compositions by double spike thermal ionization mass spectrometry

A new method for the determination of seawater Pb isotope compositions and concentrations was developed, which combines and optimizes previously published protocols for the separation and isotopic analysis of this element. For isotopic analysis, the procedure involves initial separation of Pb from 1 to 2 L of seawater by co-precipitation with Mg hydroxide and further purification by a two stage anion exchange procedure. The Pb isotope measurements are subsequently carried out by thermal ionization mass spectrometry using a ²⁰⁷Pb–²⁰⁴Pb double spike for correction of instrumental mass fractionation. These methods are associated with a total procedural Pb blank of 28 ± 21 pg (1sd) and typical Pb recoveries of 40–60%. The Pb concentrations are determined by isotope dilution (ID) on 50 mL of seawater, using a simplified version of above methods. Analyses of multiple aliquots of six seawater samples yield a reproducibility of about ±1 to ±10% (1sd) for Pb concentrations of between 7 and 50 pmol/kg, where precision was primarily limited by the uncertainty of the blank correction (12 ± 4 pg; 1sd). For the Pb isotope analyses, typical reproducibilities (±2sd) of 700–1500 ppm and 1000–2000 ppm were achieved for ²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb and ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, ²⁰⁸Pb/²⁰⁴Pb, respectively. These results are superior to literature data that were obtained using plasma source mass spectrometry and they are at least a factor of five more precise for ratios involving the minor ²⁰⁴Pb isotope. Both Pb concentration and isotope data, furthermore, show good agreement with published results for two seawater intercomparison samples of the GEOTRACES program. Finally, the new methods were applied to a seawater depth profile from the eastern South Atlantic. Both Pb contents and isotope compositions display a smooth evolution with depth, and no obvious outliers. Compared to previous Pb isotope data for seawater, the ²⁰⁶Pb/²⁰⁴Pb ratios are well correlated with ²⁰⁷Pb/²⁰⁶Pb, underlining the significant improvement achieved in the measurement of the minor ²⁰⁴Pb isotope.     

Acceleration of Long‐Range Photoinduced Electron Transfer through DNA by Hydroxyquinolines as Artificial Base Pairs

The C‐nucleoside based on the hydroxyquinoline ligand (Hq) is complementary to itself and forms stable Hq–Hq pairs in double‐stranded DNA. These artificial Hq–Hq pairs may serve as artificial electron carriers for long‐range photoinduced electron transfer in DNA, as elucidated by a combination of gel electrophoretic analysis of irradiated samples and time‐resolved transient absorption spectroscopy. For this study, the Hq–Hq pair was combined with a DNA‐based donor–acceptor system consisting of 6‐N,N‐dimethylaminopyrene conjugated to 2′‐deoxyuridine as photoinducible electron donor, and methyl viologen attached to the 2′‐position of uridine as electron acceptor. The Hq radical anion was identified in the time‐resolved measurements and strand cleavage products support its role as an intermediate charge carrier. Hence, the Hq–Hq pair significantly enhances the electron hopping capability of DNA compared to natural DNA bases over long distances while keeping the self‐assembly properties as the most attractive feature of DNA as a supramolecular architecture.