Large‐Scale Synthesis of Helicene‐Like Molecules for the Design of Enantiopure Thin Films with Strong Chiroptical Activity

Helicenes are fascinating molecules owing to their unusual properties and applications in many fields from catalysis to organic electronics. Herein, we report a straightforward pathway for the synthesis of helicene‐like molecules on a gram scale in an enantiopure form. Thin‐film materials with good propagating optical properties and very high chiroptical responses have been grown by using pulsed laser ablation without altering the structure or the enantiopurity of the molecules. Moreover, electronic and vibrational circular dichroism spectroscopies coupled with theoretical calculations enabled some dependences of the chiroptical properties with the structure to be highlighted, for example, effects of rigidification, aromatization, or the state of matter (liquid versus solid).     

Probing Multiconfigurational States by Spectroscopy: The Cerium XAS L3-edge Puzzle

The Ce L₃ edge XAS spectra of CeO₂ and cerocene [Ce(C₈H₈)₂] were calculated with relativistic ab-initio multireference wavefunction approaches capable of reproducing the observed spectra accurately. The study aims to resolve the decades-long puzzle regarding the relationship between the number and relative intensities of the XAS peaks and the 4f electron occupation in the ground state (GS) versus the core-excited states (ESs). CeO₂ and cerocene exemplify the different roles of covalent bonding and wavefunction configurational composition in the observed intensity patterns. Good agreement is found between the calculated GS 4f-shell occupations and the value derived from XAS measurements using peak areas (n_f). The identity of the two-peaked Ce L₃ edge is fully rationalized from the perspective of the relaxed wavefunctions for the GS and core ESs. The states underlying the different peaks differ from each other in a surprisingly simple way that can be associated with 4f¹ vs. 4f⁰ sub-configurations. Furthermore, part of one of the cerocene spectral peaks is associated with 4f² sub-configurations. The pattern therefore reveals excited states that can be interpreted in terms of Ce IV and III oxidation numbers, as long assumed, with Ce II states additionally appearing in the cerocene spectrum. While this work demonstrates the rough accuracy of the conventional approach to determining n_f from Ce L₃-edge XAS, limitations are highlighted in terms of the ultimate accuracy of this approach and the potential of observing new types of excited states. The need to determine the sources of n_f by calculations, is stressed.     

The need for new isotope reference materials

Isotope reference materials are needed to calibrate and validate analytical procedures used for the determination of isotope amount ratios, procedurally defined isotope ratios or so-called δ values. In contrast to the huge analytical progress in isotope ratio analytics, the production of isotope reference materials has not kept pace with the increasing needs of isotope analysts. Three representative isotope systems are used to explain the technical and non-technical difficulties and drawbacks, on one hand, and to demonstrate what can be achieved at its best, on the other hand. A clear statement is given that new isotope reference materials are needed to obtain traceable and thus comparable data, which is essential for all kinds of isotope research. The range of available isotope reference materials and δ reference materials should be increased and matrix reference materials certified for isotope compositions or δ values, which do not exist yet, should be provided.     

An efficient and convenient synthesis of unsymmetrical disulfides from thioacetates

We have developed convenient methods for the synthesis of functionalized unsymmetrical dialkyl disulfides under mild conditions in very good yields. The designed method is based on the reaction of (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)-disulfanyl derivatives 1 with functionalized alkyl thiolate anions, generated in situ from thioacetates 2 and sodium methoxide or butylamine. The developed method allows the preparation of unsymmetrical disulfides bearing additional hydroxy, carboxy, amino, azido, biotin, or maleimide functionalities.     

Influence of Charge Density of Anionic Polyelectrolytes on Structure Formation in Liquid Crystalline Systems

The influence of different amounts of anionic copolymers of N-Methyl N-vinyl acetamide (NMVA) and acrylic acid with various charge densities on the formation of the lamellar liquid crystal formed by sodium dodecyl sulfate (SDS)/decanol/water was investigated by means of polarization microscopy, small angle x-ray scattering (SAXS), transmission electron microscopy and rheology. On the contrary to the incorporation of poly(acrylic acid)     

Cycloaddition mit ungesättigten Zuckern,VI Die Synthese Diastereomerer 4H-Pyrano [3, 4-d] Isoxazol-4-One

Abstract

By 1, 3-dipolar cycloaddition of benzonitrile oxide to 4, 6-di-O-acetyl-2, 3-dideoxy-D-erythro-hex-2-enono-1, 5-lactone (1), [3aR- (3aα, 6β,7α, 7aα)] - (2) and [3aS-(3aβ, 6β, 7α, 7aα)] -7- (acetyloxy) -6- (acetyloxymethyl) -3a, 6, 7, 7a-tetrahydro-3-phenyl-4H-pyrano [3, 4-d] isoxazole-4-one (3) were prepared in 58 and 7% yield respectively. From 2, [1′ R, 3aR-(3aα, 6β, 6aα)] -6-(1′, 2′-dihydroxymethyl)-6, 6a - dihydro-3-phenyl-furano [3, 4-d] isoxazole-4 (3aH) -one (5) was prepared by deacetylation. The structure of 3 was determined by X-ray analysis.