Systematic Hydrogen‐Bond Manipulations To Establish Polysaccharide Structure–Property Correlations

A dense hydrogen‐bond network is responsible for the mechanical and structural properties of polysaccharides. Random derivatization alters the properties of the bulk material by disrupting the hydrogen bonds, but obstructs detailed structure–function correlations. We have prepared well‐defined unnatural oligosaccharides including methylated, deoxygenated, deoxyfluorinated, as well as carboxymethylated cellulose and chitin analogues with full control over the degree and pattern of substitution. Molecular dynamics simulations and crystallographic analysis show how distinct hydrogen‐bond modifications drastically affect the solubility, aggregation behavior, and crystallinity of carbohydrate materials. This systematic approach to establishing detailed structure–property correlations will guide the synthesis of novel, tailor‐made carbohydrate materials.     

Corrosion resistance in chloride solution of the AlSi10Mg alloy obtained by means of LPBF

The paper deals with the corrosion resistance in chloride solutions of an AlSi10Mg alloy obtained by laser powder bed fusion (LPBF) process. The potentiodynamic tests were carried out in solutions having different chloride contents. The results emphasize the role of chloride concentration on localized corrosion. The increase of concentration reduces pitting potential. In addition, the influence of the post-processing heat treatment temperature was recognized. Penetrating attacks occurred either on after low temperatures stress relieving or specimens without any treatment, promoted by selective dissolution of the α-Al phase stimulated by galvanic coupling with noble silicon precipitates at the border of the melt pool. Such penetrating morphology was not observed after heat treatments at high temperature.     

Organic Stereochemistry. Part 1. Symmetry Elements and Operations,Classification of Stereoisomers

This review initiates a general presentation of the principles of stereochemistry with special reference to medicinal compounds. The format is essentially identical with that of a previous Series of seven reviews on the Metabolism of Drugs and Other Xenobiotics published between October 2006 and October 2009 by B. T. and Stefanie Krämer in Chemistry & Biodiversity. Here, there will be eight reviews published in Helvetica Chimica Acta, to be grouped and published in book form together with some additional material. Part 1 introduces this new series by presenting and illustrating basic concepts on which the edifice of stereochemistry is built. At the most basic level of such foundations, we find symmetry as presented here in terms of its elements, operations, and point groups. This is followed by a classification of isomeric molecular structures, as well as a classification of steric relationships between molecular fragments.     

Inherently Chiral Spider‐Like Oligothiophenes

The racemate of an inherently chiral “spider‐like” octathiophene monomer T8₃ , in which chirality is generated by torsion in its backbone, was synthesized. The racemate was resolved into configurationally stable antipodes by HPLC on a chiral stationary phase. Electrooxidation of the enantiomers resulted in materials displaying high enantiorecognition ability towards the antipodes of some chiral probes. Moreover, the T8₃ racemate demonstrated great aptitude to stimulate formation of 3D rigid architectures if used as a cross‐linking monomer for molecular imprinting. This feature was exploited to devise a molecularly imprinted polymer‐based chemosensor selective for a thymine–adenine oligonucleotide.     

Reproducibility of Biomolecular Corona Experiments: A Primer for Reliable Results

The biomolecular corona is a key component controlling the identity of nanomaterials in physiological environments. Studies aimed at identifying factors shaping the biomolecular corona have proliferated in the last decade but have been performed by research groups with different backgrounds. Efforts made within the scientific community to guarantee the reproducibility of experimental data have identified protocol standardization as an indispensable step for advancing knowledge in this arena. To contribute to fulfill this gap, here the relevance of interoperator variability in biomolecular corona studies and the benefits arising from automated systems usage are explored. Moreover, the role of molecular crowding during nanoparticle-biofluid incubation and the effect of washing the pellet during corona isolation are thoroughly investigated. It is believed that the findings will help researchers enhance the accuracy of experimental design and reporting.     

Topological entropy of quadratic polynomials and dimension of sections of the Mandelbrot set

A fundamental theme in holomorphic dynamics is that the local geometry of parameter space (e.g. the Mandelbrot set) near a parameter reflects the geometry of the Julia set, hence ultimately the dynamical properties, of the corresponding dynamical system. We establish a new instance of this phenomenon in terms of entropy.