A 59Co NMR study to observe the effects of ball milling on small ferromagnetic cobalt particles

To demonstrate the potential of nuclear magnetic resonance (NMR) spectroscopy for investigating detailed structural properties in ferromagnetic materials, three different particle sized cobalt (Co) powders have been ball milled for 24 h are accurately characterised by internal-field ⁵⁹Co NMR. The ⁵⁹Co NMR spectra show distinct resonance bands corresponding to the different Co sites, face-centred-cubic (fcc), hexagonal-close-packed (hcp) and stacking faults (sfs), in Co metal powders. The hcp+fcc→hcp phase transition encouraged by ball-milling was observed and quantitative values for each Co environment were obtained.     

A new plasmid display technology for the in vitro selection of functional phenotype-genotype linked proteins

BACKGROUND: Display technologies which allow peptides or proteins to be physically associated with the encoding DNA are central to procedures which involve screening of protein libraries in vitro for new or altered function. Here we describe a new system designed specifically for the display of libraries of diverse, functional proteins which utilises the DNA binding protein nuclear factor kappa B (NF-kappa B) p50 to establish a phenotype-genotype link between the displayed protein and the encoding gene. RESULTS: A range of model fusion proteins to either the amino- or carboxy-terminus of NF-kappa B p50 have been constructed and shown to retain the picomolar affinity and DNA specificity of wild-type NF-kappa B p50. Through use of an optimal combination of binding buffer and DNA target sequence, the half-life of p50-DNA complexes could be increased to over 47 h, enabling the competitive selection of a variety of protein-plasmid complexes with enrichment factors of up to 6000-fold per round. The p50-based plasmid display system was used to enrich a maltose binding protein complex to homogeneity in only three rounds from a binary mixture with a starting ratio of 1:10(8) and to enrich to near homogeneity a single functional protein from a phenotype-genotype linked Escherichia coli genomic library using in vitro functional selections. CONCLUSIONS: A new display technology is described which addresses the challenge of functional protein display. The results demonstrate that plasmid display is sufficiently sensitive to select a functional protein from large libraries and that it therefore represents a useful addition to the repertoire of display technologies.     

Disappearing Polymorphs in Metal–Organic Framework Chemistry: Unexpected Stabilization of a Layered Polymorph over an Interpenetrated Three-Dimensional Structure in Mercury Imidazolate

The “disappearing polymorph” phenomenon is well established in organic solids, and has had a profound effect in pharmaceutical materials science. The first example of this effect in metal-containing systems in general, and in coordination-network solids in particular, is here reported. Specifically, attempts to mechanochemically synthesize a known interpenetrated diamondoid (dia) mercury(II) imidazolate metal–organic framework (MOF) yielded a novel, more stable polymorph based on square-grid (sql) layers. Simultaneously, the dia-form was found to be highly elusive, observed only as a short-lived intermediate in monitoring solvent-free synthesis and not at all from solution. The destabilization of a dense dia-framework relative to a lower dimensionality one is in contrast to the behavior of other imidazolate MOFs, with periodic density functional theory (DFT) calculations showing that it arises from weak interactions, including structure-stabilizing agostic C−H⋅⋅⋅Hg contacts. While providing a new link between MOFs and crystal engineering of organic solids, these findings highlight a possible role for agostic interactions in directing topology and stability of MOF polymorphs.     

Magnetic bubble refraction and quasibreathers in inhomogeneous antiferromagnets

We study the dynamics of magnetic bubble solitons in a two-dimensional isotropic antiferromagnetic spin lattice in the case where the exchange integral J(x, y) is position dependent. In the near-continuum regime, this system is described by the relativistic O(3) sigma model on a space-time with a spatially inhomogeneous metric determined by J. We use the geodesic approximation to describe the low-energy soliton dynamics in this system: the n-soliton motion is approximated by geodesic motion in the moduli space M _n of static n-solitons equipped with the L ² metric γ. We obtain explicit formulas for γ for various natural choices of J(x, y). Based on these, we show that single soliton trajectories are refracted with J⁻¹ being analogous to the refractive index and that this refraction effect allows constructing simple bubble lenses and bubble guides. We consider the case where J has a disk inhomogeneity (with the value J ₊ outside a disk and J ₋ < J ₊ inside) in detail. We argue that for sufficiently large J ₊/J ₋, this type of antiferromagnet supports approximate quasibreathers: two or more coincident bubbles confined within the disk spin internally while their shape oscillates with a generically incommensurate period. __________ Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 152, No. 1, pp. 191–208, July, 2007.     

Synthesis of 2,6-disubstituted dihydropyrans via an efficient BiBr3-initiated three component, one-pot cascade

The rapid synthesis of cis-2,6-disubstituted dihydropyrans is achieved in a three-component, one-pot cascade reaction. BiBr₃-mediated addition of ketene silyl acetals or silyl enol ethers to β,γ-unsaturated cis-4-trimethylsilyl-3-butenal provides a Mukaiyama aldol adduct containing a vinylsilane moiety tethered to a silyl ether. Addition of a second aldehyde initiates a domino sequence involving intermolecular addition followed by an intramolecular silyl-modified Sakurai (ISMS) reaction. Isolated yields of this one-pot reaction vary from 44 to 80% and all compounds were isolated as the cis-diastereomers (10 examples).     

Identification of broad specificity P450CAM variants by primary screening against indole as substrate

High-throughput screening of cytochrome P450CAM libraries, for their ability to oxidise indole to indigo and indirubin, has resulted in the identification of variants with activity towards the structurally unrelated substrate diphenylmethane.     

Application of Spectroscopic Techniques to the Structural Analysis of Coal

Abstract

Coal is defined as an organic rock that is composed of macerals and minerals (Given, 1988). The macerals are believed to be derived from plant tissue that has been altered by microbial, thermal, and nonbiological processes in locales that are often referred to as “peat swamps.” One of the issues that often requires debate is the extent to which thermal processes have played in coal formation, and the extent of temperature increase during the metamorphosis of plant material to coal.     

Porosity,Differentiability and Pansu’s Theorem

We use porosity to study differentiability of Lipschitz maps on Carnot groups. Our first result states that directional derivatives of a Lipschitz function act linearly outside a \(\sigma \)-porous set. The second result states that irregular points of a Lipschitz function form a \(\sigma \)-porous set. We use these observations to give a new proof of Pansu’s theorem for Lipschitz maps from a general Carnot group to a Euclidean space.