Electrochemical Synthesis and Characterisation of Alternating Tripyridyl–Dipyrrole Molecular Strands with Multiple Nitrogen‐Based Donor–Acceptor Binding Sites

Synthesis of alternating pyridine–pyrrole molecular strands composed of two electron‐rich pyrrole units (donors) sandwiched between three pyridinic cores (acceptors) is described. The envisioned strategy was a smooth electrosynthesis process involving ring contraction of corresponding tripyridyl–dipyridazine precursors. 2,6‐Bis[6‐(pyridazin‐3‐yl)]pyridine ligands 2 a – c bearing pyridine residues at the terminal positions were prepared in suitable quantities by a Negishi metal cross‐coupling procedure. The yields of heterocyclic coupling between 2‐pyridyl zinc bromide reagents 12 a – c and 2,6‐bis(6‐trifluoromethanesulfonylpyridazin‐3‐yl)pyridine increased from 68 to 95 % following introduction of electron‐donating methyl groups on the metallated halogenopyridine units. Favorable conditions for preparative electrochemical reduction of tripyridyl–dipyridazines 2 b , c were established in THF/acetate buffer (pH 4.6)/acetonitrile to give the targeted 2,6‐bis[5‐(pyridin‐2‐yl)pyrrol‐2‐yl]pyridines 1 b and 1 c in good yields. The absorption behavior of the donor–acceptor tripyridyl–dipyrrole ligands was evaluated and compared to theoretical calculations. Highly fluorescent properties of these chromophores were found (ν_em≈2×10⁴ cm^?1 in MeOH and CH₂Cl₂), and both pyrrolic ligands exhibit a remarkable quantum yield in CH₂Cl₂ (?_f=0.10). Structural studies in the solid state established the preferred cis conformation of the dipyrrolic ligands, which adopting a planar arrangement with an embedded molecule of water having a complexation energy exceeding 10 kcal mol^?1. The ability of the tripyridyl–dipyrrole to complex two copper(II) ions in a pentacoordinate square was investigated.     

Layer‐by‐Layer Nano‐Encapsulation of Microbes: Controlled Cell Surface Modification and Investigation of Substrate Uptake in Bacteria

LbL nano self‐assembly coating of A. vinosum with different polyelectrolyte combinations is presented as an example to investigate substrate uptake in bacteria. The effects of surface charge and the formation of a physical barrier provides new insights in the contact mechanisms between the cell surface and insoluble elemental sulfur. Furthermore, uptake of sulfide by encapsulated cells was investigated. Growth experiments of coated cells showed that surface charge did neither affect sulfide uptake nor the contact formation between the cells and solid sulfur. However, increasing layers slowed or inhibited the uptake of sulfide and elemental sulfur. This work demonstrates how defining surface properties of bacteria has potential for microbiological and biotechnological applications.

     

Polygon exploration with time-discrete vision

With the advent of autonomous robots with two- and three-dimensional scanning capabilities, classical visibility-based exploration methods from computational geometry have gained in practical importance. However, real-life laser scanning of useful accuracy does not allow the robot to scan continuously while in motion; instead, it has to stop each time it surveys its environment. This requirement was studied by Fekete, Klein and Nüchter for the subproblem of looking around a corner, but until now has not been considered in an online setting for whole polygonal regions.We give the first algorithmic results for this important optimization problem that combines stationary art gallery-type aspects with watchman-type issues in an online scenario: We demonstrate that even for orthoconvex polygons, a competitive strategy can be achieved only for limited aspect ratio A (the ratio of the maximum and minimum edge length of the polygon), i.e., for a given lower bound on the size of an edge; we give a matching upper bound by providing an O(logA)-competitive strategy for simple rectilinear polygons, using the assumption that each edge of the polygon has to be fully visible from some scan point.     

The Quadratic Numerical Range of an Analytic Operator Function

We introduce a new concept of numerical range for analytic operator functions. This so-called quadratic numerical range is induced by a decomposition of the underlying Hilbert space. Like the classical numerical range of an operator function, it is not convex, it has the spectral inclusion property, and it provides resolvent estimates and estimates for the lengths of Jordan chains in boundary points having the exterior cone property. As the quadratic numerical range is contained in the numerical range, it yields tighter enclosures for the eigenvalues and the spectrum of analytic operator functions.     

On the role of (weak) compressibility for fluid-structure interaction solvers

In the present study, a weakly compressible formulation of the Navier-Stokes equations is developed and examined for the solution of fluid-structure interaction (FSI) problems. Newtonian viscous fluids under isothermal conditions are considered, and the Murnaghan-Tait equation of state is employed for the evaluation of mass density changes with pressure. A pressure-based approach is adopted to handle the low Mach number regime, ie, the pressure is chosen as primary variable, and the divergence-free condition of the velocity field for incompressible flows is replaced by the continuity equation for compressible flows. The approach is then embedded into a partitioned FSI solver based on a Dirichlet-Neumann coupling scheme. It is analytically demonstrated how this formulation alleviates the constraints of the instability condition of the artificial added mass effect, due to the reduction of the maximal eigenvalue of the so-called added mass operator. The numerical performance is examined on a selection of benchmark problems. In comparison to a fully incompressible solver, a significant reduction of the coupling iterations and the computational time and a notable increase in the relaxation parameter evaluated according to Aitken's Δ² method are observed.     

A planar rod model with flexible thin-walled cross-sections. Application to the folding of tape springs

This paper is focused on the modeling of rod-like elastic bodies that have an initially curved and thin-walled cross-section and that undergo important localized changes of the cross-section shape. The typical example is the folding of a carpenter’s tape measure for which the folds are caused by the flattening of the cross-section in some localized areas. In this context, we propose a planar rod model that accounts for large displacements and large rotations in dynamics. Starting from a classical shell model, the main additional assumption consists in introducing an elastica kinematics to describe the large changes of the cross-section shape with very few parameters. The expressions of the strain and kinetic energies are derived by performing an analytical integration over the section. The Hamilton principle is directly introduced in a suitable finite element software to solve the problem. The folding, coiling and deployment of a tape spring is studied to demonstrate the ability of the model to account for several phenomena: creation of a single fold and associated snap-through behavior, splitting of a fold into two, motion of a fold along the tape during a dynamic deployment, scenarios of coiling and uncoiling of a bistable tape spring. This 1D model may also be relevant for future applications in biomechanics, biophysics and nanomechanics.     

Improvement of the ESR detection of irradiated food containing cellulose employing a simple extraction method

Fruit may be irradiated at rather low doses, below 1 kGy in combination treatments or for quarantine purposes. To improve the ESR detection sensitivity of irradiated fruit de Jesus et al. (Int. J. Food Sci. Technol. 34 (1999) 173.) proposed extracting the fruit pulp with 80% ethanol and measuring the residue with ESR using low power (0.25 mW) for detection of ‘cellulosic’ radicals. An improvement in ESR sensitivity using the extraction procedure could be confirmed in this paper for strawberries and papayas. In most cases, a radiation dose of 0.5 kGy could be detected in both fruits even after 2–3 weeks storage. In addition, some herbs and spices were also tested, but only for a few of them the ESR detection of the ‘cellulosic’ signal was improved by previous alcoholic extraction.

As an alternative to ESR measurements, other detection methods like DNA Comet Assay and thermoluminescence were also tested.