Linear and Cyclic Hybrids of Alternating Thiophene–Amino Acid Units: Synthesis and Effects of Chirality on Conformation and Molecular Packing

The dipeptide isostere 5‐aminothiophene carboxylic acid has been combined with L ‐phenylalanine moieties to provide linear and cyclic hybrid oligopeptides. A suitable protecting group strategy and appropriate coupling methods have been developed to guarantee a high degree of enantiopurity of the resulting amides. Cyclic tetraamides have been efficiently obtained by macrocyclization of the linear derivatives. In the case of racemized cyclization precursors, two diastereomeric macrocycles (S,S/R,R and meso) have been isolated. Their crystal structures show clear effects of the stereogenic centers on the ring conformations and molecular packing.     

Azimuthal Dipolar Rotor Arrays on Surfaces

A set of dipolar molecular rotor compounds was designed, synthesized and adsorbed as self-assembled 2D arrays on Ag(111) surfaces. The title molecules are constructed from three building blocks: (a) 4,8,12-trioxatriangulene (TOTA) platforms that are known to physisorb on metal surfaces such as Au(111) and Ag(111), (b) phenyl groups attached to the central carbon atom that function as pivot joints to reduce the barrier to rotation, (c) pyridine and pyridazine units as small dipolar units on top. Theoretical calculations and scanning tunneling microscopy (STM) investigations hint at the fact that the dipoles of neighboring rotors interact through space through pairs of energetically favorable head-to-tail arrangements.     

Development of Surface Nano-Crystallization in Alloys by Surface Mechanical Attrition Treatment (SMAT)

Nanometer-sized grain structures that exhibit a large number of grain boundaries on the surface of a bulk material demonstrate excellent properties relative to their coarse-grained (CG) equivalents. Surface modification using surface mechanical attrition treatment (SMAT) is an option that cab be used to tailor the corrosion, tribological, mechanical, and chemical reaction properties of a surface. SMAT is an effective route to create the nanostructured surface layer. The SMAT process has unique advantages compared with the other coating and deposition techniques for surface nanocrystallization. For example, SMAT does not alter the chemical composition of the nanocrystalline surface layer in the matrix. In addition, SMAT has been demonstrated to activate the material surface layer by surface modification and enhance the atomic diffusivity. This article presents a review of the advantages offered by the SMAT technique for the creation of high performance surface layers. The influence of the created nanocrystalline layer on mechanical, physical, and chemical properties is assessed. Developments and the current status of the surface nanolayer that are formed are evaluated from a physical approach. Finally, prospects for the future development of grain refinement on the surface of a material matrix and potential applications are presented.     

Enzymatic Conversion of Flavonoids using Bacterial Chalcone Isomerase and Enoate Reductase

Flavonoids are a large group of plant secondary metabolites with a variety of biological properties and are therefore of interest to many scientists, as they can lead to industrially interesting intermediates. The anaerobic gut bacterium Eubacterium ramulus can catabolize flavonoids, but until now, the pathway has not been experimentally confirmed. In the present work, a chalcone isomerase (CHI) and an enoate reductase (ERED) could be identified through whole genome sequencing and gene motif search. These two enzymes were successfully cloned and expressed in Escherichia coli in their active form, even under aerobic conditions. The catabolic pathway of E. ramulus was confirmed by biotransformations of flavanones into dihydrochalcones. The engineered E. coli strain that expresses both enzymes was used for the conversion of several flavanones, underlining the applicability of this biocatalytic cascade reaction.     

Rapid Autoxidation Forms Highly Oxidized RO2 Radicals in the Atmosphere

Gas‐phase oxidation routes of biogenic emissions, mainly isoprene and monoterpenes, in the atmosphere are still the subject of intensive research with special attention being paid to the formation of aerosol constituents. This laboratory study shows that the most abundant monoterpenes (limonene and α‐pinene) form highly oxidized RO₂ radicals with up to 12 O atoms, along with related closed‐shell products, within a few seconds after the initial attack of ozone or OH radicals. The overall process, an intramolecular ROO→QOOH reaction and subsequent O₂ addition generating a next R′OO radical, is similar to the well‐known autoxidation processes in the liquid phase (QOOH stands for a hydroperoxyalkyl radical). Field measurements show the relevance of this process to atmospheric chemistry. Thus, the well‐known reaction principle of autoxidation is also applicable to the atmospheric gas‐phase oxidation of hydrocarbons leading to extremely low‐volatility products which contribute to organic aerosol mass and hence influence the aerosol–cloud–climate system.     

Asymptotic Formulas for Two Continued Fractions in Ramanujan's Lost Notebook

On page 45 of his lost notebook, Ramanujan recorded two asymptoticformulas for two continued fractions involving the Riemann zeta-functionand Dirichlet L-functions. The paper proves a more general theoremand derives Ramanujan's claims as a corollary of the theorem.     

A -normal, not densely normal Tychonoff space

We give an example of a -normal space which is not densely normal.