Simulation of the gelation process of hydrogel droplets in 3D bioprinting

The aim of this work is to numerically simulate the gelation of a crosslinking polymer, which is a very complex process involving chemical reactions and phase transitions from a viscous fluid to a viscoelastic solid. A phenomenological model is proposed to simulate the gelation process of agarose droplets, considering the thermal boundary conditions. The numerical model is implemented using the finite element package FlexPDE. The temperature- and time-dependent degree of gelation and the deformation of the droplets during the gelation process are investigated. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

An Approach to Feed-Forward Controller Design for Underactuated Multibody Systems in the Presence of Uncertainty

The performance of a model-based tracking controller depends on the quality of the underlying model. Especially for flexible multibody systems, the derivation of a suitable model and the subsequent controller design are challenging tasks. In the paper, it is shown how in a straightforward approach a feed-forward controller for a flexible multibody system is designed based on a simplified model which approximates an elastic beam by a combination of rigid beams and force elements. Furthermore, the modelling error due to this harsh simplification is included as uncertainty in the simplified model and considered in the model-based feed-forward controller design using fuzzy arithmetic. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of a Bicyclic Diamine Derived from Kemp's Acid

A bicyclic diamine with defined and stable conformation in solution was prepared from Kemp's triacid. The efficient four-step synthesis of the Boc-protected diamine requires only a single purification by column chromatography. X-ray analysis and NMR spectroscopy confirm the structure of the diamine in the solid state and in solution.     

Scope and Applicability of an Expedient Synthesis Leading to Polysubstituted 3‐(Carboxyphenyl)pyrroles

A convenient three‐step route toward a functionalized pyrrole building block for novel anti‐inflammatory agents is reported. In contrast to previous strategies, the present approach focuses on inexpensive starting materials and application on a multigram scale. A high degree of functional diversity is demonstrated in various derivatives, and the scope and limitations of this route are discussed. Complementary to the described tetrasubstituted pyrroles, a novel ring‐closure protocol based on the Feist–Benary condensation affords trisubstituted analogues.     

Giant Fullerene Polyelectrolytes Composed of C60 Building Blocks with an Octahedral Addition Pattern and Discovery of a New Cyclopropanation Reaction Involving Dibromomalonates

We report here on the facile synthetic access of a new family of bis‐, tetra‐, hexa‐, and heptafullerenes (prototypes I–IV), which can be easily converted into very water soluble polyelectrolytes with up to 60 charges located on their periphery. Their very regioselective formation is based on the use of C_2v‐symmetrical pentakisadducts 3 and hexakisadducts 2 as key intermediates. All fullerene moieties incorporated in these macromolecular structures involve a complete or partial octahedral addition pattern. Tripod‐shaped tetrafullerenes 9 a , b (type II), which can accumulate up to thirty positive or negative charges, are very soluble in acidic or basic water, respectively. Hexafullerenes 13 a , b (type III) were synthesized via isoxazolinofullerenes 10 followed by photolytic cleavage of the isoxazoline group. The giant heptafullerene 1 b (type IV) representing the anionic counterpart of the previously synthesized polyelectrolyte 1 a can store up to 60 negative charges on its periphery within a defined three‐dimensional structure. We also discovered a new cyclopropanation reaction of C₆₀ involving dibromomalonates and 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU). This reaction allows even for the highly regioselective formation of hexakisadducts with an octahedral addition pattern without requiring activation with reversibly binding addends such as 9,10‐dimethylanthracene (DMA).     

Structure and Biosynthesis of Xenoamicins from Entomopathogenic Xenorhabdus

During the search for novel natural products from entomopathogenic Xenorhabdus doucetiae DSM17909 and X. mauleonii DSM17908 novel peptides named xenoamicins were identified in addition to the already known antibiotics xenocoumacin and xenorhabdin. Xenoamicins are acylated tridecadepsipeptides consisting of mainly hydrophobic amino acids. The main derivative xenoamicin A ( 1 ) was isolated from X. mauleonii DSM17908, and its structure elucidated by detailed 1 D and 2 D NMR experiments. Detailed MS experiments, also in combination with labeling experiments, confirmed the determined structure and allowed structure elucidation of additional derivatives. Moreover, the xenoamicin biosynthesis gene cluster was identified and analyzed in X. doucetiae DSM17909, and its participation in xenoamicin biosynthesis was confirmed by mutagenesis. Advanced Marfey’s analysis of 1 showed that the absolute configuration of the amino acids is in agreement with the predicted stereochemistry deduced from the nonribosomal peptide synthetase XabABCD. Biological testing revealed activity of 1 against Plasmodium falciparum and other neglected tropical diseases but no antibacterial activity.     

A Minty variational principle for set optimization

Extremal problems are studied involving an objective function with values in (order) complete lattices of sets generated by so-called set relations. Contrary to the popular paradigm in vector optimization, the solution concept for such problems, introduced by F. Heyde and A. Löhne, comprises the attainment of the infimum as well as a minimality property. The main result is a Minty type variational inequality for set optimization problems which provides a sufficient optimality condition under lower semicontinuity assumptions and a necessary condition under appropriate generalized convexity assumptions. The variational inequality is based on a new Dini directional derivative for set-valued functions which is defined in terms of a “lattice difference quotient.” A residual operation in a lattice of sets replaces the inverse addition in linear spaces. Relationships to families of scalar problems are pointed out and used for proofs. The appearance of improper scalarizations poses a major difficulty which is dealt with by extending known scalar results such as Diewert's theorem to improper functions.