Conversion of Aldoximes into Nitriles with Raney Nickel in Refluxing 2-Propanol

Aldoximes are readily dehydrated to nitriles with Raney nickel in refluxing 2-propanol.     

Mechanistic study of asymmetric Michael addition of malonates to enones catalyzed by a primary amino acid lithium salt

A mechanistic study was carried out for the asymmetric Michael addition reaction of malonates to enones catalyzed by a primary amino acid lithium salt to elucidate the origin of the asymmetric induction. A primary β-amino acid salt catalyst, O-TBDPS β-homoserine lithium salt, exhibited much higher enantioselectivity than that achieved with the corresponding catalysts derived from α- and γ-amino acids for this reaction. Detailed studies of the transition states with DFT calculations revealed that the lithium cation and carboxylate group of the β-amino acid salt catalyst have important roles in achieving high enantioselectivity in the Michael addition reaction of malonates to enones.     

A new high: Cannabis as a budding source of carbon-based materials for electrochemical power sources

Cannabis sativa L., a low-cost, fast-growing herbaceous plant, is seeing a resurgence in widespread cultivation as a result of new policies and product drive. Its biodegradable and environmentally benign nature coupled with its high specific surface area and three-dimensional hierarchal structure makes it an excellent candidate for use as a biomass-derived carbon material for electrochemical power sources. It is proposed that this ‘wonder crop’ could have an important role in the energy transition by providing high-functioning carbon-based materials for electrochemistry. In this article, all instances of C. sativa usage in batteries, fuel cells and supercapacitors are discussed with a focus on highlighting the high capacity, rate capability, capacitance, current density and half-wave potential that can be achieved with its utilisation in the field.     

Generalized Widder Theorem via fractional moments

We provide a necessary and sufficient condition for the representability of a function as the classical multidimensional Laplace transform, when the support of the representing measure is contained in some generalized semi-algebraic set. This is done by employing a method of Putinar and Vasilescu [M. Putinar, F.-H. Vasilescu, Solving moment problems by dimensional extension, Ann. of Math. (2) 149 (3) (1999) 1087-1107] for the corresponding multidimensional moment problem.     

The role of guaiacyl moiety in free radical scavenging by 3,5-dihydroxy-4-methoxybenzyl alcohol: thermodynamics of 3H+/3e− mechanisms

ABSTRACT

Participation of guaiacyl moiety of 3,5-dihydroxy-4-methoxybenzyl alcohol (DHMBA) in inactivation of free radicals was investigated using the DFT method. The thermodynamics of triple (3H⁺/3e^?) free radical scavenging mechanisms was investigated. The Gibbs free energies of reactions of inactivation of selected 10 free radicals indicate DHMBA as a potent scavenger. Obtained results allow us to suggest that the contribution of guaiacyl moiety to antioxidant activity of phenolic compounds should be taken into account, what has been scarcely considered until now.     

Thermal properties of defect melting

Using mean field theory and high temperature expansions the transition temperature, entropy jump and heat capacity are calculated in the recent microscopic model of defect melting proposed by Kleinert. The results are compared with the experimental data for almost isotropic substances.     

Riffs on the infinite ping-pong ball conundrum

This article presents a novel re-conceptualisation to a well-known problem – The Ping-Pong Ball Conundrum. We introduce a variant of this super-task by considering it through the lens of ‘measuring infinity’ – a conceptualisation of infinity that extrapolates measuring properties of numbers, rather than cardinal properties. This approach is consistent with a nonstandard analysis approach to infinite numbers, and gives credence to the intuitive (but otherwise normatively incorrect) resolution. We explore the mathematical motivation and consequences of this variant, as well as offer further ‘riffs’ on the infinite ball problem for consideration.     

X-ray Crystallographic Observation of Chiral Transformations within a Metal–Peptide Pore

Porous metal complexes enable single-crystal X-ray crystallographic observation of included guests or reaction intermediates through simple soaking with the guests/substrates. Previous studies on this technique have often encountered difficulties in the observation of chiral structures because the host frameworks had no chirality. We synthesized a new metal–peptide porous complex through a folding-and-assembly strategy and utilized the chiral pore for trapping chiral guests. Chiral alcohols and ketones were successfully included within the pore. Crystallographic analyses clearly revealed not only their chemical structures but also chiral transformation events within the pore such as fixed conformations or an unstable hemiacetal formation.     

Segmented conjugated macromolecules containing silicon and boron: ADMET synthesis and luminescent properties

Boron‐ and silicon‐containing conjugated homo‐ and copolymers could be synthesized using acyclic diene metathesis (ADMET) condensation of bis‐styryl monomers. Both, tri‐and tetra‐coordinated boron monomers were successfully polymerized forming homopolymers, or random copolymers (if polymerized together with a silicon containing co‐monomer). Polymer molecular weights M_n were measured at ～6000 to 15,000 g/mol (NMR end group analysis) with molecular weight distributions M_w/M_n ～1.8 to 2.2. The polymers absorbed at λ_max ～317 to 406 nm and emitted at λ_max ～370 to 494 nm with fluorescent quantum efficiencies ～24 to 48%. The copolymer with tri‐coordinate boron showed highly efficient fluorescence quenching in the presence of fluoride ions at ratios boron/fluoride ～5/1, demonstrating its potential as anion sensor. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1707–1718