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.     

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.

     

Resonant photoemission study ofK-derived valence-band states in K X C60

The electronic structure of K-doped C₆₀ was investigated by photoemission (PE) and X-ray absorption near-edge structure (XANES) studies at the C-1s and K-2p thresholds. In addition, information on the local K-derived partial density of states in superconducting K₃C₆₀ was obtained by resonant PE at the K-2p _1/2 threshold. The experimental observations support a complete charge transfer from K to C₆₀ and we clearly observe a finite density of states atE _F . From resonant PE, occupied states with K-p, d character could be identified in the binding-energy region from 1.5 to 8 eV below, but not directly at the Fermi level. This partial-density-of-states structure agrees well with the results of our band-structure calculations based on the local-density approximation.     

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.     

Terminal Ligand and Packing Effects on Slow Relaxation in an Isostructural Set of [Dy(H2dapp)X2]+ Single Molecule Magnets**

We report three structurally related single ion Dy compounds using the pentadentate ligand 2,6-bis((E)-1-(2-(pyridin-2-yl)-hydrazineylidene)ethyl)pyridine (H₂dapp) [Dy(H₂dapp)(NO₃)₂]NO₃ ( 1 ), [Dy(H₂dapp)(OAc)₂]Cl ( 2 ) and [Dy(H₂dapp)(NO₃)₂]Cl_0.92(NO₃)_0.08 ( 3 ). The (H₂dapp) occupies a helical twisted pentagonal equatorial arrangement with two anionic ligands in the axial positions. Further influence on the electronic and magnetic structure is provided by a closely associated counterion interacting with the central N−H group of the (H₂dapp). The slow relaxation of the magnetisation shows that the anionic acetates give the greatest slowing down of the magnetisation reversal. Further influence on the relaxation properties of compounds 1 and 2 is the presence of short nitrate-nitrate intermolecular ligand contact opening further lattice relaxation pathways.     

Untersuchungen über die Konzentration von D2O in natürlichem Eis. II

Ohne Zusammenfassung