Steric and electronic tuning of chiral bis(oxazoline) ligands with 3,3'-bithiophene backbone

[structure: see text] The role played by the electronic properties and the steric features of bis(oxazoline) ligands in the Cu(I)-catalyzed cyclopropanation of styrene effected with ethyl diazoacetate was investigated. Two pairs of new bis(oxazolines) displaying flexible and atropisomeric 3,3'-bithiophene backbones were synthesized and structurally and electronically characterized. For the first time, the electrochemical oxidative potential was used as a reliable index of the electronic density on the nitrogen atom of the chelating groups of new and, for comparative purposes, of already known bis(oxazolines). The Cu(I) complexes of the new ligands were prepared, and their enantioselection ability and catalytic efficiency were tested. This investigation suggests that steric factors and catalyst geometrical features are clearly more important than any consideration of the electronic properties of the chiral ligands.     

Structural and Mechanistic Insights into s‐Block Bimetallic Catalysis: Sodium Magnesiate‐Catalyzed Guanylation of Amines

To advance the catalytic applications of s‐block mixed‐metal complexes, sodium magnesiate [NaMg(CH₂SiMe₃)₃] ( 1 ) is reported as an efficient precatalyst for the guanylation of a variety of anilines and secondary amines with carbodiimides. First examples of hydrophosphination of carbodiimides by using a Mg catalyst are also described. The catalytic ability of the mixed‐metal system is much greater than that of its homometallic components [NaCH₂SiMe₃] and [Mg(CH₂SiMe₃)₂]. Stoichiometric studies suggest that magnesiate amido and guanidinate complexes are intermediates in these catalytic routes. Reactivity and kinetic studies imply that these guanylation reactions occur via (tris)amide intermediates that react with carbodiiimides in insertion steps. The rate law for the guanylation of N,N′‐diisopropylcarbodiimide with 4‐tert‐butylaniline catalyzed by 1 is first order with respect to [amine], [carbodiimide], and [catalyst], and the reaction shows a large kinetic isotopic effect, which is consistent with an amine‐assisted rate‐determining carbodiimide insertion transition state. Studies to assess the effect of sodium in these transformations denote a secondary role with little involvement in the catalytic cycle.     

Synthesis of new optically active acridino-18-crown-6 ligands and studies of their potentiometric selectivity toward the enantiomers of protonated 1-phenylethylamine and metal ions

Starting from commercially available and relatively inexpensive chemicals, new enantiopure diisobutyl- and dioctyl-substituted acridino-18-crown-6 ether-type ligands [(R,R)-3] and [(R,R)-4], respectively were prepared. The two lipophilic isobutyl [(R,R)-3] and octyl [(R,R)-4] groups on the stereogenic centers of these macrocycles made it possible to use them as potentiometric sensor molecules when incorporated into plasticized PVC membrane electrodes. Ligand (R,R)-3 showed appreciable enantioselectivity toward the enantiomers of 1-phenylethylammonium chloride while macrocycle (R,R)-4 exhibited a high selectivity toward the silver ion.     

Oxidant aggregate-induced porosity in vapour-deposited polymer films and correlated impact on electrochemical properties

ABSTRACT

Persistently doped conjugated polymers are integral for energy storage, flexible electronics, and biosensors due to their unique ability to interact with both ionic and electronic currents. To maximise the performance of devices across these fields, research has focused on controlling material properties to optimise conductivities of both types of charge carriers. The challenge lies in improving ionic transport, which is typically the rate-limiting step in redox processes, without sacrificing electronic conductivity or desirable mechanical properties. Here we report on control of nanostructure in vapour deposited conducting polymer films and correlate changes in film structure with resulting electrochemical properties. Structural control is enabled by exploiting the growth of oxidant nanoaggregates during the reactive vapour deposition process. Relative to dense films, porous films exhibit faster response times in electrochemical testing. Scan rate analysis confirms a transition away from diffusion-limited charging kinetics and demonstrates the important role that porosity can play in ion transport through electroactive polymers. Advantageously, continuous polymer networks remain evident in nanostructured films, ensuring that high electronic conductivities are maintained along with high porosity. We find that such enhanced properties are retained even as polymer thickness increases ten-fold. The films reported herein may serve as robust electrodes in flexible electrochemical devices.     

In–CuInS2 nanocomposite film prepared by pulsed laser deposition using a single source precursor

An In–CuInS₂ nanocomposite film has been prepared by Pulsed Laser Deposition applying a single source precursor. X-ray powder diffraction, Raman spectroscopy and transmission electron microscopy observations evidence that the film consists of nanocrystals of elemental In and chalcopyrite type CuInS₂ with sizes of 36 and 17 nm respectively. A detailed analysis of the electrical performance of the film suggests that the nanoparticles are in Ohmic contact and that the resistivity is mainly caused by the CuInS₂ nanocrystals which are less conducting than the pure In metal. Irradiation of the film with light shows a photoconductive effect mainly with wavelengths larger than 515 nm and smaller than 850 nm.     

Estimating the domain of attraction of a stable equilibrium state for certain delayed differential systems of order two

Summary We discuss the influence exerted on the stability of an equilibrium state of a second order differential-difference system by the delays existing in the coupling terms of the two system equations. On certain hypotheses an asymptotic stability condition is determined which is independent of the magnitude of delays but dependent on the magnitude of coupling. A simple method for constructing regions belonging to the domain of attraction of the considered equilibrium state is developed. Several alternative constructions and applications are discussed in detail.

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Sommario Viene discussa l'influenza che sulla stabilità ai uno stato di equilibrio di un sistema differenziale alle differenze di secondo ordine banno i ritardi incorporati nei termini di accoppiamento fra le due equazioni del sistema. Si mostra come sotto opportune ipotesi si possa determinare una condizione di stabilità asintotica che non dipende dall'entità dei ritardi, mentre dipende da quella degli accoppiamenti, e si propone un metodo semplice e flessibile per costruire regioni contenute nel dominio di attrazione dello stato di equilibrio considerato. Si discutono in dettaglio numerose costruzioni alternative ed applicazioni.

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On leave of absence from CYFRONET, Institute of Nuclear Research, Swierk k/Otwocha, Poland.     

A condition number theorem in convex programming

Mathematical Programming - A finite-dimensional mathematical programming problem with convex data and inequality constraints is considered. A suitable definition of condition number is obtained via...