The formal combination of three singlet biradicaloid entities to a singlet hexaradicaloid metalloid Ge14[Si(SiMe3)3]5[Li(THF)2]3 cluster

The reaction of GeBr with LiSi(SiMe(3))(3) leads to the metalloid cluster compound [(THF)(2)Li](3)Ge(14)[Si(SiMe(3))(3)](5) (1). After the introduction of a first cluster of this type, in which 14 germanium atoms form an empty polyhedron, [(THF)(2)Li](3)Ge(14)[Ge(SiMe(3))(3)](5) (2), we present here further investigations on 1 to obtain preliminary insight into its chemical and bonding properties. The molecular structure of 1 is determined via X-ray crystal structure solution using synchrotron radiation. The electronic structure of the Ge(14) polyhedron is further examined by quantum chemical calculations, which indicate that three singlet biradicaloid entities formally combine to yield the singlet hexaradicaloid character of 1. Moreover, the initial reactions of 1 after elimination of the [Li(THF)(2)](+) groups by chelating ligands (e.g., TMEDA or 12-crown-4) are presented. Collision induced dissociation experiments in the gas phase, employing FT-ICR mass spectrometry, lead to the elimination of the singlet biradicaloid Ge(5)H(2)[Si(SiMe(3))(3)](2) cluster. The unique multiradicaloid bonding character of the metalloid cluster 1 might be used as a model for reactions and properties in the field of surface science and nanotechnology.     

In Situ Synchrotron Radiation X‐Ray Microspectroscopy of Polymer Microcontainers

Direct, real‐time analytical techniques that provide high‐resolution information on the chemical composition and submicrometer structure of various polymer micro‐ and nanoparticles are in high demand in a range of life science disciplines. Synchrotron‐based scanning transmission X‐ray microspectroscopy (STXM) combines both local‐spot chemical information (assessed via near‐edge X‐ray absorption fine structure spectroscopy) and imaging with resolution of several tens of nanometers, and thus can yield new insights into the nanoscale properties of these materials. Furthermore, this method allows in situ examination of soft‐matter samples in aqueous/gaseous environments and under external stimuli, such as temperature, pressure, ultrasound, and light irradiation. This Minireview highlights some recent progress in the application of the STXM technique to study the temperature‐dependent behavior of polymer core–shell microcapsules and to characterize the physicochemical properties of the supporting shells of gas‐filled microbubbles in their natural hydrated state.     

Paracyclophanes as model compounds for strongly interacting π-systems. Part 2: mono-hydroxy[2.2]paracyclophane

The structure of the electronic ground- and first excited state of mono-hydroxy [2.2]paracyclophane (MHPC) and the S(1)← S(0) electronic transition have been investigated by resonance-enhanced multiphoton ionisation (REMPI) and by quantum chemical spin-component-scaled-approximate coupled cluster second order (SCS-CC2) computations. The origin of the S(1)← S(0) transition was located at 30,772 cm(-1) (3.815 eV) in the REMPI spectrum. The value has to be compared with a computed excitation energy of 3.79 eV. The vibrational structure of the spectrum confirms a significant geometry change upon excitation along the coordinates corresponding to twist- and shift-motions in the molecule. It gives rise to an experimentally observed progression with a fundamental of +30 cm(-1) and an inverse anharmonicity. From the experimental data a shallow potential along the twist coordinate was derived for the S(1) state. For the shift vibration a wavenumber of +91 cm(-1) was observed, while +85 cm(-1) was computed. The ionisation energy of MHPC was determined to be 7.63 ± 0.05 eV using synchrotron radiation. When compared to earlier results on the parent compound [2.2]paracyclophane and pseudo-ortho-dihydroxy[2.2]paracyclophane it can be seen that already small variations in the substitution pattern have a significant impact on the shapes of the involved potential energy surfaces leading to strong variations in ground and excited state geometries and opto-electronic properties governing the exciton transfer processes.     

Column generation for vehicle routing problems with multiple synchronization constraints

Synchronization of workers and vehicles plays a major role in many industries such as logistics, healthcare or airport ground handling. In this paper, we focus on operational ground handling planning and model it as an archetype of vehicle routing problems with multiple synchronization constraints, coined as “abstract vehicle routing problem with worker and vehicle synchronization” (AVRPWVS). The AVRPWVS deals with routing workers to ground handling jobs such as unloading baggage or refuelling an aircraft, while meeting each job’s time window. Moreover, each job can be performed by a variable number of workers. As airports span vast distances and due to security regulations, workers use vehicles to travel between locations. Furthermore, each vehicle, moved by a driver, can carry several workers. We propose two mathematical multi-commodity flow formulations based on time-space networks to efficiently model five synchronization types including movement and load synchronization. Moreover, we develop a branch-and-price heuristic that employs both conventional variable branching and a novel variable fixing strategy. We demonstrate that the procedure achieves results close to the optimal solution in short time when compared to the two integer models.     

Left Ventricular Geometry,Tissue Composition,and Residual Stress in High Fat Diet Dahl-Salt Sensitive Rats

Background

Hypertension drives myocardial remodeling, leading to changes in structure, composition and mechanical behavior, including residual stress, which are linked to heart disease progression in a gender-specific manner. Emerging therapies are also targeting constituent-specific pathological features. All previous studies, however, have characterized remodeling in the intact tissue, rather than isolated tissue constituents, and did not include sex as a biological variable.

Objective

In this study we first identified the contribution of collagen fiber network and myocytes to the myocardial residual stress/strain in Dahl-Salt sensitive rats fed with high fat diet. Then, we quantified the effect of hypertension on the remodeling of the left ventricle (LV), as well as the existence of sex-specific remodeling features.

Methods

We performed mechanical tests (opening angle, ring-test) and histological analysis on isolated constituents and intact tissue of the LV. Based on the measurements from the tests, we performed a stress analysis to evaluate the residual stress distribution. Statistical analysis was performed to identify the effects of constituent isolation, elevated blood pressure, and sex of the animal on the experimental measurements and modeling results.

Results

Hypertension leads to reduced residual stress/strain in the intact tissue, isolated collagen fibers, and isolated myocytes in male and female rats. Collagen remains the largest contributor to myocardial residual stress in both normotensive and hypertensive animals. We identified sex-differences in both hypertensive and normotensive animals.

Conclusions

We observed both constituent- and sex-specific remodeling features in the LV of an animal model of hypertension.

     

Zur Thermochemie und Struktur von Berylliumchlorid

Thermochemistry and Structure of Beryllium Chloride BeCl₂ is dimorphous, with a transition point at 405°C. The transition enthalpy and transition entropy have been determined by solution calorimetry: Δ_UH° = 2.9 kJmol^?1 and Δ_US° = 9.7 JK^?1mol^?1. The previously known SiS₂-type structure of BeCl₂ is that of the high temperature phase. The structure of the phase stable at room temperature has been determined from single crystal data. a = 1 062.4(6) pm, c = 1 804(2) pm, I4₁/acd, Z = 32, R = 0.038 (Mg(NH₂)₂-type). The structure consists of P₄O₁₀-like [Be₄Cl₆Cl_4/2]-units, connected by their terminal anions.     

Precipitation of dissolved alkali salts and fullerenes on surfaces of doped porous matter

Standard porcelain samples burnt at different temperatures were doped with LiCl, organo-Li solutions, or with fullerene solution and then dried. The depth profiles of both Li and fullerene were determined. The distributions of the incorporated dopants strongly depend on the samples' porosity. Additional ultrasonic treatment during the diffusion process has a fatal influence on the porcelain structure, resulting in enhanced dopant uptake of the remaining sample. The surface-near shape of the depth profiles is interpreted by solvation, i.e., by precipitation of the dissolved salts or fullerenes in the surface-near zone during the drying process. It is shown that the solvation effect is important only in the case of media with high porosity.     

Conductivity of aged non-overlapping and overlapping tracks in ion irradiated polyimide

Non-overlapping as well as overlapping tracks of energetic ions have been introduced into polyimide foils. After aging their conductivity was measured. This — to our knowledge — first systematic study shows that conductivity does not only result from multiple track overlapping, but can be found already in single ion tracks. This conductivity is shown to be primarily a consequence of electronic energy transfer. The conductivity of single ion tracks is higher than that of typical insulators, but still orders of magnitude lower than that of typical semiconductors. The conductivity is independent of the applied electric field strength until at excessive voltages the electric current increases nonlinearly up to complete breakthrough. The total conductivity of an irradiated polyimide foil increases proportionally with ion fluence for large ion track spacings, and approaches saturation when the electronically active track regimes begin to overlap. Above some thousand times track overlapping however, new chemical and structural changes in the irradiated material lead to another strong increase in conductivity.