Reductive cleavage of axially disymmetric tertiary amines and quaternary ammonium salts by lithium aluminium hydride. Synthesis of new 1,1′-binaphthyl substituted amines

Axially disymmetric tertiary amines or quaternary ammonium salts $\text{A}$ are synthesized by double alkylation of primary or secondary amines with racemic or optically pure 2,2′-bis (bromomethyl)-1,1′-binaphthyl. Their reductive cleavage by lithium aluminium hydride in refluxing THF leads to chiral secondary or tertiary amines $\text{B}$, substituted by a binaphthyl unit, with high yields and absence of racemization.     

4-Amino-1-oxyl-2,2,6,6-tetramethylpiperidine-3-carboxylic acid (β-TOAC), the first spin-labelled, cyclic, chiral β-amino acid resolved in an enantiomerically pure state

Amination of 3-carboxymethyl-1-oxyl-2,2,6,6-tetramethyl-4-piperidone with (R)-α-methylbenzylamine, NaBH₃CN reduction of the resulting enamine and removal of the chiral auxiliary from the separated diastereoisomers, led to enantiomerically pure (3S,4S) and (3R,4R) methyl 4-amino-1-oxyl-2,2,6,6-tetramethylpiperidine-3-carboxylates.     

The Williamson Reaction: A New and Efficient Method for the Alternate Resolution of 2,2'-Bis(bromomethyl)-1,1'-binaphthyl and 1,1'-Binaphthalene-2,2'-diol

Treatment of 2,2'-bis(bromomethyl)-1,1'-binaphthyl [(R,S)-2] with 1,1'-binaphthalene-2,2'-diol (+)-(R)-1 and cesium or potassium carbonate in refluxing acetone, gave the diastereoisomeric dioxacyclophanes (-)-(R,S)-3a and (+)-(R,R)-3b, both obtained in high yield, and the cyclic tetraether (+)-(R,R,R,S)-4 as isolated side product. Boron tribomide-promoted ether cleavage of 3a and 3b gave optically pure (-)-(S)-2 and (+)-(R)-2, respectively, and the recovered diol (+)-(R)-1. Alternatively, the same reaction sequence furnished the resolved diols (-)-(S)-1 and (+)-(R)-1 from (R,S)-1 and (+)-(R)-2, as well as optically pure 2,2'-bis(chloromethyl)-1,1'-binaphthyl (+)-(R)-5 from the racemic dibromide (R,S)-2 by using boron trichloride for ether cleavage.     

First access to the spin-labelled β-amino acid POAC in an enantiopure state by resolution through its binaphthyl esters

Resolution of trans 3-(9-fluorenylmethyloxycarbonylamino)-1-oxyl-2,2,5,5-tetramethylpyrrolidine-4-carboxylic acid (Fmoc-POAC-OH) was quickly achieved upon esterification with (aR)-1,1′-binaphthyl-2,2′-diol, chromatographic separation of the obtained diastereomers, and facile saponification of the aryl ester function with removal of the chiral auxiliary.     

Copper-assisted oxidation of catechols into quinone derivatives

Catechols are ubiquitous substances often acting as antioxidants, thus of importance in a variety of biological processes. The Fenton and Haber–Weiss processes are thought to transform these molecules into aggressive reactive oxygen species (ROS), a source of oxidative stress and possibly inducing degenerative diseases. Here, using model conditions (ultrahigh vacuum and single crystals), we unveil another process capable of converting catechols into ROSs, namely an intramolecular redox reaction catalysed by a Cu surface. We focus on a tri-catechol, the hexahydroxytriphenylene molecule, and show that this antioxidant is thereby transformed into a semiquinone, as an intermediate product, and then into an even stronger oxidant, a quinone, as final product. We argue that the transformations occur via two intramolecular redox reactions: since the Cu surface cannot oxidise the molecules, the starting catechol and the semiquinone forms each are, at the same time, self-oxidised and self-reduced. Thanks to these reactions, the quinone and semiquinone are able to interact with the substrate by readily accepting electrons donated by the substrate. Our combined experimental surface science and ab initio analysis highlights the key role played by metal nanoparticles in the development of degenerative diseases.

An antioxidant catechol transforms following intramolecular redox reactions into highly reactive oxygen species, a semiquinone and a quinone, on copper.     

A novel method determining longitudinally induced magnetic anisotropy in amorphous and nanocrystalline soft materials

In ferromagnetic amorphous and nanocrystalline soft magnetic alloys the induced magnetic anisotropy plays a fundamental role in the hysteresis behavior but, due to the elongated shape, it can be measured only if K_U is perpendicular to the sample long axis. In order to measure the longitudinal induced anisotropy, an original method derived from known thin layers measurement techniques was used. Hysteresis loops shifted by perpendicular bias field were recorded for this purpose. Direct measurement of the longitudinal induced anisotropy in amorphous and nanocrystalline ribbons or wire without needing sample preparation is reported for the first time. Evidence of self-induced anisotropy is brought in a Fe–Co-based nanocrystalline alloy.     

High-temperature soft magnetic properties of Co-doped nanocrystalline alloys

In situ hysteresis measurements were used to follow the evolution of soft magnetic properties of various Co containing Finemet- and Hitperm-type nanocrystalline materials. This work is aimed at obtaining the proper chemical composition of nanocrystalline alloys, which can be applied for highest temperatures and is less affected by the inevitable decoupling phenomena, which is common to all two-phase nanocrystalline systems. Experimental results pointed out that in the Co-added Finemet-type alloys the decoupling temperature can be increased by about 50–70 K as compared to Co-free Finemet alloy. Hitperm alloys, close to equiatomic Fe/Co ratio, have much higher decoupling temperature, but their coercivity is an order of magnitude larger at low temperatures compared to the Co-free alloys so their advantage is evident above 400 °C only.     

Observation and modelling of magnetic vortex core structure in Permalloy nanoparticles

We use an approximate micromagnetic model, based on geometrical simplifications of the problem, to describe the vortex core structure observed in spherical Permalloy nanoparticles using off-axis electron holography. The magnetisation distribution inside the vortex core is directly calculated by minimising the micromagnetic energy functional and is compared with the experimental results. The symmetry constraints underlying the model are discussed envisaging possible generalisation to the case of vortex cores with structure strongly dependent on the coordinate directed along the axis of the vortex. Moreover the many-body effect associated with the presence of two small satellite particles is described by rescaling the size of the particle.     

Internal stress influence on the coercivity of FeCuNbSiB thin films

Thin films of Finemet-type alloy with thickness varying from 50 to 1000 nm have been deposited by RF sputtering and annealed at temperature ranging from 150 to 450 °C. Their magnetic and structural properties have been characterized using alternating gradient field magnetometry and X-ray diffraction. In addition, the stress in the films has been measured as a function of temperature from the curvature of the wafers using a laser scanning technique.The coercive field of the films first decreases with annealing temperature due to stress relaxation, and then increases again when crystallisation begins. The optimal annealing conditions comprises between the glass transition and the crystallisation temperature.Its is observed that the coercivity of the as-deposited material is continuously decreasing as the thickness increases, following an inverse square root dependence, in relation with the stress-induced magneto-elastic contribution to the total anisotropy. By opposition, it has been found that the coercive field of devitrified and totally relaxed films is inversely proportional to film thickness. In order to explain this evolution, a model is proposed, based on random anisotropy considerations applied to thin films in which the anisotropy was considered localised in the dimension of thickness.