An Approach to Paracyclophane-Based Tetrathiafulvalenes: Synthesis and Characterization of a Pseudo-Geminal [2.2]Paracyclophane 1,3-Dithia-2-Thione

The synthesis of paracyclophane-based tetrathiafulvalene precursors is described in the context of the importance of these compounds in the field of material chemistry. Pseudo-geminal bis(1,3-dithia-2-thione) was synthesized via the corresponding 1,3-dithiol-2-ylium salt. The latter was obtained by a synthetic procedure that involves 4,15-bis(acetyl)[2.2]paracyclophane, a new compound of interest for many researchers.     

Variable cant angle winglets for improvement of aircraft flight performance

Meccanica - Traditional winglets are designed as fixed devices attached at the tips of the wings. The primary purpose of the winglets is to reduce the lift-induced drag, therefore improving...     

Fracture behavior and mechanical,thermal, and rheological properties of biodegradable films extruded by flat die and calender

The development of biodegradable materials for tailored applications, particularly in the field of polymeric films and sheets, is a challenging technological goal as well as a contribution to help protect the environment. Poly(lactic) acid (PLA) is a promising substitute for several oil-based polymers; however, to overcome its thermal and mechanical drawbacks, researchers have developed solutions such as blending PLA with polybutylene adipate terephthalate (PBAT), which is capable of increasing the ductility of the final material. In this study, PLA/PBAT binary blends, with minimum possible content of nonrenewable materials, were examined from processing, thermal, morphological, and rheological perspective. An optimized PLA/PBAT ratio was chosen as the polymeric basis to obtain a biodegradable formulation by adding a biobased plasticizer and appropriate fillers to produce a micrometer film with tailored flexibility and tear resistance. The processing technology involved flat-die extrusion, followed by calendering. The tearing resistance of the produced film was investigated, and the results were compared with literature data. A study on the essential work of fracture was implemented to explore the mode III out-of-plane fracture resistance starting from a trouser tear test.     

Applications of dynamic combinatorial chemistry for the determination of effective molarity

A new strategy for determining thermodynamic effective molarities (EM) for macrocylisation reactions using dynamic combinatorial chemistry under dilute conditions is presented. At low concentrations, below the critical value, Dynamic Libraries (DLs) of bifunctional building blocks contain only cyclic species, so it is not possible to quantify the equilibria between linear and cyclic species. However, addition of a monofunctional chain stopper can be used to promote the formation of linear oligomers allowing measurement of EM for all cyclic species present in the DL. The effectiveness of this approach was demonstrated for DLs generated from mixtures of 1,3-diimine calix[4]arenes, linear diaminoalkanes and monoaminoalkanes. For macrocycles deriving from one bifunctional calixarene and one diamine, there is an alternating pattern of EM values with the number of methylene units in the diamine: odd numbers give significantly higher EMs than even numbers. For odd numbers of methylene units, the alkyl chain can adopt an extended all anti conformation, whereas for even numbers of methylene units, gauche conformations are required for cyclisation, and the associated strain reduces EM. The value of EM for the five-carbon linker indicates that this macrocycle is a strainless ring.     

Interpreting technical evidence from spectral imaging of paintings by Édouard Manet in the Courtauld Gallery

The paintings by Édouard Manet in The Courtauld Gallery Déjeuner sur l'herbe (1863–68), Marguerite de Conflans en Toilette de Bal (1870–1880), Banks of the Seine at Argenteuil (1874), and A Bar at the Folies–Bergère (1882) were investigated for the first time using a range of non-invasive in situ analyses. The aims of the study were to investigate the painting techniques and materials used for this group of works and to critically evaluate the technical evidence derived from the integrated use of imaging techniques and portable spectroscopic methods in this context. The paintings were investigated by means of macro X-ray fluorescence (MA-XRF), reflection spectral imaging, portable UV–Vis–NIR spectroscopy, portable Raman spectroscopy, and reflection FTIR. MA-XRF and reflection spectral imaging allowed visualising elements in the compositions that were not visible using traditional methods of technical study. For example, MA-XRF analysis of Déjeuner sur l'herbe revealed elements of the development of the composition that provided new evidence to consider its relationship to other versions of the composition. The study also highlighted questions about the interpretation of elemental distribution maps and spectral images that did not correspond to the reworking visible in X-radiographs. For example, in A Bar at the Folies–Bergère Manet made numerous changes during painting, which were not clearly visualised with any of the techniques used. The research has wider implications for the study of Impressionist paintings, as the results will support technical studies of works by other artists of the period who used similar materials and painting methods.     

Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis

Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β^2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis.