Is the McLafferty rearrangement of ketones concerted or stepwise? The application of kinetic isotope effects

Intramolecular ¹³C and ²H isotope effects have been measured for unimolecular losses of ethene (the McLafferty rearrangement) from metastable molecular ions of 2-ethyl-1-phenylbutanl-1-one, 3-ethylpentan-2-one and heptan-4-one. Primary and secondary deuterium isotope effects are observed at the γ-(terminal) and β-positions, respectively. Large primary ¹³C isotope effects occur at β-positions and for the y positions of γ-ethylpentan-2-one and heptan-4-one. The carbon isotope effects in the cases of the doubly isotopically labelled CH₃COCH(C₂H₅)(¹³CH₂CH₃) and CD₃COCD(C₂D₅)(¹³CD₂CD₃) are 1.17 (±0.01) and 1.04 (±0.01), respectively. All of these isotope effects are consistent with a stepwise mechanism in which more than one step is rate determining.     

Random aggregation and random-walking center of mass

Two random aggregation models are used in demonstrating the properties of the random displacementsr _i of the center of mass of aggregating particles. It is found that r _i is a randomly decreasing sequence that scales with the cluster size (steps)s and _i ^=1/s r _i s ^1/D , whereD is the fractal dimension. The center-of-mass random walk is a consistent representation of the dynamics of aggregation.     

Improvements in carbon fibre reinforced composites by inkjet printing of thermoplastic polymer patterns

A thermoplastic polymer solution was inkjet printed in a pre‐defined hexagonal pattern onto carbon fibre reinforced epoxy resin (CFRP), leading to a significant increase in strength, stiffness and toughness of the final aerospace grade compo‐site system. The approach consisted of depositing low‐viscosity polymer microdroplets having chemically and me‐chanically comparable properties to epoxy polymer, onto CFRP before curing and solidification. The microdroplets remained arrested between composite plies without direct contact with the neighbouring microdroplets ensuring preservation of the structural integrity of the new composite system after curing. The key to achieving this synergistic effect was in appropriately selected additive materials; however, the novel aspects also included the method itself, which enabled an accurate crack arrest mechanism.

     

Extraordinarily robust polyproline type I peptoid helices generated via the incorporation of α-chiral aromatic N-1-naphthylethyl side chains

Peptoids, or oligomers of N-substituted glycines, are a class of foldamers that have shown extraordinary functional potential since their inception nearly two decades ago. However, the generation of well-defined peptoid secondary structures remains a difficult task. This challenge is due, in part, to the lack of a thorough understanding of peptoid sequence-structure relationships and, consequently, an incomplete understanding of the peptoid folding process. We seek to delineate sequence-structure relationships through the systematic study of noncovalent interactions in peptoids and the design of novel amide side chains capable of such interactions. Herein, we report the synthesis and detailed structural analysis of a series of (S)-N-(1-naphthylethyl)glycine (Ns1npe) peptoid homo-oligomers by X-ray crystallography, NMR spectroscopy, and circular dichroism (CD) spectroscopy. Four of these peptoids were found to adopt well-defined structures in the solid state, with dihedral angles similar to those observed in polyproline type I (PPI) peptide helices and in peptoids with α-chiral side chains. The X-ray crystal structure of a representative Ns1npe tetramer revealed an all cis-amide helix, with approximately three residues per turn, and a helical pitch of approximately 6.0 ?. 2D-NMR analysis of the length-dependent Ns1npe series showed that these peptoids have very high overall backbone amide K(cis/trans) values in acetonitrile, indicative of conformationally homogeneous structures in solution. Additionally, CD spectroscopy studies of the Ns1npe homo-oligomers in acetonitrile and methanol revealed a striking length-dependent increase in ellipticity per amide. These Ns1npe helices represent the most robust peptoid helices to be reported, and the incorporation of (S)-N-(1-naphthylethyl)glycines provides a new approach for the generation of stable helical structure in this important class of foldamers.     

An asymmetric synthesis of (+)-kjellmanianone

Racemic and asymmetric syntheses of kjellmanianone, a novel cyclopentenoid antibiotic, are described.     

Bilayer-by-bilayer antiferroelectric ordering in freely suspended films of an achiral polymer-monomer liquid crystal mixture

Thin freely suspended films of a mixture of an achiral side-chain liquid crystal polymer and its monomer have been studied with depolarized reflected light microscopy. We observe that regions with an odd number of bilayers exhibit a net spontaneous polarization in the tilt plane of the molecules, while regions with an even number of bilayers have no net polarization. These odd-even effects are direct evidence that the tilted smectic bilayers are anticlinic at the polymer backbone and synclinic at bilayer interface and confirm that the phase is bilayer-by-bilayer antiferroelectric.