A Multiphasic Model Describing the CO2 Injection Problem

According to the annual data, the portion of ejected carbon dioxide (CO₂) into the atmosphere is much higher in comparison to other greenhouse gases. Therefore, the development of various scenarios in order to reduce the CO₂ concentration in the atmosphere is nowadays a challenge and a relevant subject in research. The current investigation is dedicated to the modelling of a CO₂ injection into a water-saturated aquifer as the most capable reservoir, where its upward migration is blocked by a dense cap-rock layer. The major part of the study is focused on two specific processes taking place in the stored reservoir: the phase transfer phenomenon of the supercritical CO₂ which occurs under changeable surrounding conditions and the sequestration-driven deformation of the solid skeleton acting under the pressure of the pumped CO₂. For the numerical simulations within a continuum-mechanical framework, a multiphasic model based on the Theory of Porous Media is introduced. Moreover, the main principles of developing a constitutive equation for the mass production term for the mass balance equation are discussed here. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Particle simulation of granular media and homogenisation towards continuum quantities

From a microscopic point of view, various natural and engineering materials consist of individual grains, whose motion strongly influence the macroscopic material behaviour. Exemplarily, one may look at the development of shear zones in natural granular materials, such as sand, occurring as a result of local grain dislocations and the transition of the granulate from a denser to a looser packing. The intuitive modelling approach for granular assemblies is consequently the consideration of each grain as a rigid particle. In a numerical framework, this leads to the Discrete Element Method (DEM), wherein the motion of each particle can be obtained solving Newton's equations for each particle. The present contribution discusses the basic fundaments of modelling granular material on the microscopic scale by use of the DEM. Special interest is taken to the constitutive choice of the governing particle-to-particle contact forces, as they have to account for plastic material behaviour as well as for assumptions concerning particle shape, size and distribution. As engineering problems are regularly described on the macroscale by means of continuum mechanics, a homogenisation strategy transfers the information from the microscale towards continuum quantities via volume averaging. Therefore, characteristic Representative Elementary Volumes (REV) are constructed by an ensemble of particles, where each particle can be chosen as the centre of a REV. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Selective Carbanion–Pyridine Coordination of a Reactive P,N Ligand to RhI

Ligands with reactive carbon sites in the periphery of a metal center have emerged as a powerful approach for metal–ligand bond activation. These reactive carbon sites are commonly generated by deprotonation strategies. Carbon–silicon bond cleavage is a potential alternative to access such constructs. Herein, the monodesilylation of bis-silyl-substituted P,N scaffold PN^Si2 in the coordination sphere of [Rh^I(Cl)(CO)( PN^Si2 )] ( 1 ) with sodium azide is disclosed. This affords a unique dinucleating anionic κ²-C,N-κ¹-P ligand with a carbanionic methine carbon atom directly bound to rhodium as part of a four-membered Rh-N-C-C rhodacycle. This dimer undergoes meta-pyridine C−H activation facilitated by weak bases, which leads to a desymmetrization of the system and provides a σ,π-bridging 3-pyridyl fragment bound to Rh^I. The facile Si−C cleavage strategy may pave the way to studying the reactivity and functionalization of a variety of κ²-C,N-coordinated pyridine scaffolds for selective transformations.     

Correction to: Quantitative analysis of PET microplastics in environmental model samples using quantitative 1H-NMR spectroscopy: validation of an optimized and consistent sample clean-up method

Analytical and Bioanalytical Chemistry - The original version of this article contained a mistake.     

Chemoselective Suzuki-Miyaura reactions of 4-bromo-3-O-triflyl-estrone. Synthesis and atropisomerism of arylated estrones

4-Bromo-3-O-triflyl-estrone has been synthesized in 2 steps from estrone and was successfully employed in chemoselective palladium catalysed Suzuki-Miyaura reactions. Mono- and bis-arylations were carried out selectively by variation of ligands and solvents. Overall 19 derivatives of mono- and bis-arylated estrones were synthesized under optimized conditions in high yields. Various products showed atropisomerism which was studied in detail by NMR spectroscopy.     

Alkane hydroxylation by peroxy acids: a comparison with the cytochrome P450 hydroxylation

Alkane hydroxylation by peroxy acids proceeds by a synchronous nonconcerted peroxy oxygen insertion into the C-H bond according to density functional theory. A comparable reaction sequence, initiated by homolytic peroxy bond cleavage, can be formulated for the alkane hydroxylation by the cytochrome P450 hydroperoxo-heme Compound 0. This hydroxylation reaction proceeds by a two-step process because the formed reactive intermediate, Compound II, is significantly stabilized.     

Use of an Octapeptide–Guanidiniocarbonylpyrrole Conjugate for the Formation of a Supramolecular β‐Helix that Self‐Assembles into pH‐Responsive Fibers

Peptides that adopt β‐helix structures are predominantly found in transmembrane protein domains or in the lipid bilayer of vesicles. Constructing a β‐helix structure in pure water has been considered difficult without the addition of membrane mimics. Herein, we report such an example; peptide 1 self‐assembles into a supramolecular β‐helix in pure water based on charge interactions between the individual peptides. Peptide 1 further showed intriguing transitions from small particles to helical fibers in a time‐dependent process. The fibers can be switched to vesicles by changing the pH value.