A decision support method for designing vegetation layers with minimised irrigation need

Annals of Operations Research - Selecting a vegetation layer design goes along with determining its future irrigation need. Therefore, it is essential to take a design decision that is minimising...     

Consolidation of composite cathodes with NCM and sulfide solid-state electrolytes by hot pressing for all-solid-state Li metal batteries

Journal of Solid State Electrochemistry - In this study, hot pressing was evaluated as a method of cell fabrication to increase the energy density of next-generation all-solid-state batteries with...     

A Gleason–Kahane–Żelazko theorem for the Dirichlet space

We show that every linear functional on the Dirichlet space that is non-zero on nowhere-vanishing functions is necessarily a multiple of a point evaluation. Continuity of the functional is not assumed. As an application, we obtain a characterization of weighted composition operators on the Dirichlet space as being exactly those linear maps that send nowhere-vanishing functions to nowhere-vanishing functions.We also investigate possible extensions to weighted Dirichlet spaces with superharmonic weights. As part of our investigation, we are led to determine which of these spaces contain functions that map the unit disk onto the whole complex plane.     

Coordination mode of cyclohex-1-enylolonium cation and bridging pyridyl derivatives as gem-diol chelates to rhenium(I) and (VII)

Transition Metal Chemistry - Rhenium(I) and (VII) complexes with cyclohex-1-enylolonium cation and bridging pyridyl derivatives are reported. Additionally, the CO-bridged pyridyl and their related...     

Reactivity of urethanes at high temperature: Transurethanization and side reactions

The reactivity of urethanes based on 1,6‐hexamethylene diisocyanate (HDI) and 4,4′‐methylene diphenyl diisocyanate (MDI) was investigated at temperatures between 190 °C and 235 °C. Diurethane model compounds end‐capped with either 1‐dodecanol (D‐core‐D) or 1‐hexadecanol (H‐core‐H) were mixed and annealed at high temperature. The core was either MDI or HDI. The transurethanization reaction was followed based on the formation of the compounds (H‐core‐D). The amount of H‐core‐D and of side products, which had formed after variable annealing times, were identified with ¹H NMR, FTIR, SEC, and MALDI‐TOF. Transurethanization was considerably faster for MDI‐based urethanes than for HDI‐based urethanes. Only traces of side products were formed during annealing of MDI‐based urethanes, whereas a significant amount of allophanates was formed from HDI‐based urethanes under the same conditions. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 621–629     

Furanosyl Oxocarbenium Ion Conformational Energy Landscape Maps as a Tool to Study the Glycosylation Stereoselectivity of 2-Azidofuranoses, 2-Fluorofuranoses and Methyl Furanosyl Uronates

The 3D shape of glycosyl oxocarbenium ions determines their stability and reactivity and the stereochemical course of S_N1 reactions taking place on these reactive intermediates is dictated by the conformation of these species. The nature and configuration of functional groups on the carbohydrate ring affect the stability of glycosyl oxocarbenium ions and control the overall shape of the cations. We herein map the stereoelectronic substituent effects of the C2-azide, C2-fluoride and C4-carboxylic acid ester on the stability and reactivity of the complete suite of diastereoisomeric furanoses by using a combined computational and experimental approach. Surprisingly, all furanosyl donors studied react in a highly stereoselective manner to provide the 1,2-cis products, except for the reactions in the xylose series. The 1,2-cis selectivity for the ribo-, arabino- and lyxo-configured furanosides can be traced back to the lowest-energy ³E or E₃ conformers of the intermediate oxocarbenium ions. The lack of selectivity for the xylosyl donors is related to the occurrence of oxocarbenium ions adopting other conformations.     

Covalent Attachment of Fibronectin onto Emulsion‐Templated Porous Polymer Scaffolds Enhances Human Endometrial Stromal Cell Adhesion,Infiltration, and Function

A novel strategy for the surface functionalization of emulsion‐templated highly porous (polyHIPE) materials as well as its application to in vitro 3D cell culture is presented. A heterobifunctional linker that consists of an amine‐reactive N‐hydroxysuccinimide ester and a photoactivatable nitrophenyl azide, N‐sulfosuccinimidyl‐6‐(4′‐azido‐2′‐nitrophenylamino)hexanoate (sulfo‐SANPAH), is utilized to functionalize polyHIPE surfaces. The ability to conjugate a range of compounds (6‐aminofluorescein, heptafluorobutylamine, poly(ethylene glycol) bis‐amine, and fibronectin) to the polyHIPE surface is demonstrated using fluorescence imaging, FTIR spectroscopy, and X‐ray photoelectron spectroscopy. Compared to other existing surface functionalization methods for polyHIPE materials, this approach is facile, efficient, versatile, and benign. It can also be used to attach biomolecules to polyHIPE surfaces including cell adhesion‐promoting extracellular matrix proteins. Cell culture experiments demonstrated that the fibronectin‐conjugated polyHIPE scaffolds improve the adhesion and function of primary human endometrial stromal cells. It is believed that this approach can be employed to produce the next generation of polyHIPE scaffolds with tailored surface functionality, enhancing their application in 3D cell culture and tissue engineering whilst broadening the scope of applications to a wider range of cell types.     

Quantifying Guest–Host Dynamics in Supramolecular Assemblies to Analyze Their Robustness

The most basic function of synthetic microenvironments for tissue engineering is to act as a physical substrate for cell attachment, migration, and proliferation, similar to the natural cell environment. Functionalization of supramolecular materials with guest compounds that display the same recognition moieties is a common strategy to introduce biofunctionality. However, besides a robust interaction with the material, a certain level of dynamics needs to be conserved for an adaptive interface toward the living environment. A balance between robust material functionalization and dynamic cell interaction needs to be met. The detailed analysis hereof using a ureido‐pyrimidinone (UPy) poly(ethylene glycol) system in dilute and transient network regime is demonstrated. Monovalent and bivalent UPy‐functionalized guest molecules are designed and their interaction with UPy‐host fibers is evaluated. Analysis of guest interaction in the dilute state by microfluidics, and in the gel state, by fluorescence recovery after photobleaching and fluorescence resonance energy transfer is proven to be suitable to quantify the local and ensemble guest mobility. The results demonstrate that the interaction of bioactive moieties through supramolecular host–guest chemistry yields a dynamic system, which is stronger for divalent guests but risks unintended leakage in the case of functional monomeric units.     

Nucleophilic Aromatic Substitution at Benzene with Powerful Strontium Hydride and Alkyl Complexes

Key to the isolation of the first alkyl strontium complex was the synthesis of a strontium hydride complex that is stable towards ligand exchange reactions. This goal was achieved by using the super bulky β‐diketiminate ligand ^DIPePBDI (CH[C(Me)N‐DIPeP]₂, DIPeP=2,6‐diisopentylphenyl). Reaction of ^DIPePBDI‐H with Sr[N(SiMe₃)₂]₂ gave (^DIPePBDI)SrN(SiMe₃)₂, which was converted with PhSiH₃ into [(^DIPePBDI)SrH]₂. Dissolved in C₆D₆, the strontium hydride complex is stable up to 70 °C. At 60 °C, H–D isotope exchange gave full conversion into [(^DIPePBDI)SrD]₂ and C₆D₅H. Since H–D exchange with D₂ is facile, the strontium hydride complex served as a catalyst for the deuteration of C₆H₆ by D₂. Reaction of [(^DIPePBDI)SrH]₂ with ethylene gave [(^DIPePBDI)SrEt]₂. The high reactivity of this alkyl strontium complex is demonstrated by facile ethylene polymerization and nucleophilic aromatic substitution with C₆D₆, giving alkylated aromatic products and [(^DIPePBDI)SrD]₂.