Hydroxy- and aminomethylation reactions in the formation of oligomers from l-tyrosine and formaldehyde in basic medium

The study of the reaction of l-tyrosine or its tetrabutylammonium salt with formaldehyde was performed. The results established that this reaction does not lead to macrocyclic amino acid-type compounds, and in all cases, mixtures of linear oligomers of two or more l-tyrosine units bound by methylene groups were obtained. The formation of ion pair-type linear aggregates in the tetrabutylammonium salt hinders the oligomerization reaction, allowing the isolation of an l-tyrosine dimer, unlike the l-tyrosine reaction, in which a trimer could be isolated.     

N-Benzylazacyclophane synthesis via aromatic Mannich reaction

A new method for synthesizing phenolic N-benzylazacyclophanes starting from tyramine is presented here. Computational calculations showed that macrocyclization is favored by the formation of hydrogen bond-based templates; these templates are not affected by including benzyl groups in the nitrogen atom of the tyramine moiety. The results showed that N-benzyl groups with electron-donating substituents have more nucleophilic nitrogen atoms, thereby favoring macrocyclization, while electron-withdrawing groups favor polymerization.     

Formation of lithium,sodium and potassium complexes with 1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol (taci)

Single crystals of (1,3‐diamino‐5‐azaniumyl‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)(1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)lithium(I) diiodide dihydrate, [Li(C₆H₁₆N₃O₃)(C₆H₁₅N₃O₃)]I₂·2H₂O or [Li(Htaci)(taci)]I₂·2H₂O (taci is 1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol), (I), bis(1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)sodium(I) iodide, [Na(C₆H₁₅N₃O₃)₂]I or [Na(taci)₂]I, (II), and bis(1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)potassium(I) iodide, [K(C₆H₁₅N₃O₃)₂]I or [K(taci)₂]I, (III), were grown by diffusion of MeOH into aqueous solutions of the complexes. The structures of the Na and K complexes are isotypic. In all three complexes, the taci ligands adopt a chair conformation with axial hydroxy groups, and the metal cations exhibit exclusive O‐atom coordination. The six O atoms of the resulting MO₆ unit define a centrosymmetric trigonal antiprism with approximate D_3d symmetry. The interligand O...O distances increase significantly in the order Li < Na < K. The structure of (I) exhibits a complex three‐dimensional network of R—NH₂—H...NH₂—R, R—O—H...NH₂—R and R—O—H...O(H)—H...NH₂—R hydrogen bonds. The structures of the Na and K complexes consist of a stack of layers, in which each taci ligand is bonded to three neighbours via pairwise O—H...NH₂ interactions between vicinal HO—CH—CH—NH₂ groups.     

The fiber reorientation problem revisited in the context of Eshelbian micromechanics: theory and computations

A multiscale micromechanical model for soft tissue is presented. This model accounts for the progressive stiffening of the mechanical response due to load-induced microstructural rearrangements of the fibers within the microstructure. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Phase-Field Modeling of Hydraulic Fracture

Hydraulically driven fracture has gained more and more research activity in the last few years, especially due to the growing interest of the petroleum industry. Key challenge for a powerful simulation of this scenario is an effective modeling and numerical implementation of the behavior of the solid skeleton and the fluid phase, the mechanical coupling between the two phases as well as the incorporation of the fracture process. Existing models for hydraulic fracturing can be found for example in [1], where the crack path is predetermined, or in [2] who use a phase field fracture model in an elastic framework, however without incorporating the fluid flow. In this work we propose a new compact model structure for the Biot-type fluid transport in porous media at finite strains based on only two constitutive functions, that is the free energy function ψ and a dissipation potential ϕ that includes the incorporation of an additional Poiseuille-type fluid flow in cracks. This formulation is coupled to a phase field approach for fracture and is fully variational in nature, as shown in [3]. In contrast to formulations with a sharp-crack discontinuity, the proposed regularized approach has the main advantage of a straight-forward modeling of complex crack patterns including branching. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Control of Nonlinearly Coupled Oscillators Using a Method of Averaging

Container cranes belong to the class of underactuated systems for which the design of control laws is a challenging task. We study the stabilization of certain modes of a crane system using a method of averaging. Based on the local approximation to the system dynamics by a second order Taylor series expansion, the effects of nonlinear couplings are exploited to steer degrees of freedom, for which no linear actuation is available. Rotations of the load about the vertical axis are analyzed and a control method is derived and tested experimentally. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)