A quadruply-bonded [Cr2(guanidinate)4]4- tetraanion

The reaction of chromocene, Cp(2)Cr, with dilithiated 2,3-diphenylguanidine [(PhNH)(2)C=NH = L(2)H(3)] gives the novel, quadruply-bonded tetraanion [Cr(2)(L(2)H)(4)](4-).     

Transition metal catalysed ammonia-borane dehydrogenation in ionic liquids

Significant advantages result from combining the disparate hydrogen release pathways for ammonia-borane (AB) dehydrogenation using ionic liquids (ILs) and transition metal catalysts. With the RuCl(2)(PMe(3))(4) catalyst precursor, AB dehydrogenation selectivity and extent are maximized in an IL with a moderately coordinating ethylsulfate anion.     

The role of CN and CO ligands in the vibrational relaxation dynamics of model compounds of the [FeFe]-hydrogenase enzyme

The vibrational dynamics of (μ-propanedithiolate)Fe(2)(CO)(4)(CN)(2)(2-), a model compound of the active site of the [FeFe]-hydrogenase enzyme, have been examined via ultrafast 2D-IR spectroscopy. The results indicate that the vibrational coupling between the stretching modes of the CO and CN ligands is small and restricted to certain modes but the slow growth of off-diagonal peaks is assigned to population transfer processes occurring between these modes on timescales of 30-40 ps. Analysis of the dynamics in concert with anharmonic density functional theory simulations shows that the presence of CN ligands alters the vibrational relaxation dynamics of the CO modes in comparison to all-carbonyl model systems and suggests that the presence of these ligands in the enzyme may be an important feature in terms of directing the vibrational relaxation mechanism.     

Gas-phase ion-molecule reactions using regioselectively generated radical cations to model oxidative damage and probe radical sites in peptides

Collision induced dissociation (CID) of sodiated peptide derivatives containing a nitrate ester functionality was used to regiospecifically generate three isomeric radicals of the model peptide Bz-Ala-Gly-OMe corresponding to radicals formed at: C(α) of the alanine residue [4+Na](+); C(α) of the glycine residue [5+Na](+); and the side chain of alanine [6+Na](+). The ion-molecule reactions of these peptide radicals were examined to model oxidative damage to peptides and to probe whether the radical sites maintain their integrity or whether they isomerise via intramolecular hydrogen atom transfer (HAT). Only [6+Na](+) is reactive towards O(2), forming the peroxyl radical [7+Na](+), which loses O(2), HO˙ and HO(2)˙ under CID. The radical ion [7 + Na](+) abstracts a hydrogen atom from 4-fluorothiophenol to form the hydroperoxide [8+Na](+), which upon CID fragments via the combined loss of HO˙ and CH(2)O. In contrast, all three of the isomeric sodiated radicals react with NO˙ and NO(2)˙ to form adducts. CID of the NO adducts only regenerates the radicals via NO˙ loss, thus providing no structural information. In contrast, CID of the NO(2) adducts gives rise to a range of product ions and the spectra are different for each of the three adducts, suggesting that the isomeric radicals [4+Na](+), [5+Na](+) and [6+Na](+) are produced as discrete species. Finally, CID of the NO(2) adducts was used to probe the rearrangement of the radicals [4+Na](+), [5+Na](+) and [6+Na](+) prior to their reaction with NO(2)˙: [6 + Na](+) rearranges to a mixture of [4+Na](+) and [5+Na](+) while [5+Na](+) rearranges to [4+Na](+).     

Highly substituted oxabicyclic derivatives from furan: synthesis of (±)-platensimycin

A stereocontrolled approach to a key platensimycin intermediate was achieved from a commercially available furylcarboxylate. Key to our approach is the highly efficient formal [4 + 3] cyclocondensation of a substituted furan with tetrabromocyclopropene along with an intramolecular γ-alkylation to construct the final ring of the caged intermediate.     

Resolution of discordant HIV-1 protease resistance rankings using molecular dynamics simulations

The emergence of drug resistance is a major challenge for the effective treatment of HIV. In this article, we explore the application of atomistic molecular dynamics simulations to quantify the level of resistance of a patient-derived HIV-1 protease sequence to the inhibitor lopinavir. A comparative drug ranking methodology was developed to compare drug resistance rankings produced by the Stanford HIVdb, ANRS, and RegaDB clinical decision support systems. The methodology was used to identify a patient sequence for which the three rival online tools produced differing resistance rankings. Mutations at only three positions ( L10I , A71IV, and L90M ) influenced the resistance level assigned to the sequence. We use ensemble molecular dynamics simulations to elucidate the origin of these discrepancies and the mechanism of resistance. By simulating not only the full patient sequences but also systems containing the constituent mutations, we gain insight into why resistance estimates vary and the interactions between the various mutations. In the same way, we also gain valuable knowledge of the mechanistic causes of resistance. In particular, we identify changes in the relative conformation of the two beta sheets that form the protease dimer interface which suggest an explanation of the relative frequency of different amino acids observed in patients at residue 71.     

Positively charged nanofiltration membranes: review of current fabrication methods and introduction of a novel approach

A review of the fabrication processes currently available to produce positively charged nanofiltration membranes has been conducted. The review highlights that there are few membranes and studies currently available. The preparation of a novel positively charged nanofiltration membrane is also described. This membrane was fabricated by surface modification of a prepared base membrane using polyethyleneimine followed by cross linking with butanedioldiglycidylether. The fabrication process uses standard organic solvents and avoids the need for hazardous materials, such as concentrated sulphuric acid, which significantly benefits the scale up potential of any future commercial manufacturing process. The new membrane was characterised using a number of state-of-the-art techniques, including a novel use of atomic force microscopy to determine pore size. Streaming potential measurements confirmed that this new membrane is indeed positively charged in the pH range below pH 9, which covers the majority of normal operating conditions. The performance characteristics for the new membrane were very favourable, with a pure water flux determined to be 20 LMH bar(-1) and a rejection of MgCl of 96%. Thus, this new membrane both adds to and complements the existing short supply of positively charged NF membranes and is suitable for applications such as the recovery of valuable cationic macromolecules in the bioprocess and pharmaceutical industries or removal of multi-valent cations such as dyes and heavy metals in the paper and pulp, textiles, nuclear, and automotive industries.     

Compact anti-self-dual orbifolds with torus actions

We give a classification of toric anti-self-dual conformal structures on compact 4-orbifolds with positive Euler characteristic. Our proof is twistor theoretic: the interaction between the complex torus orbits in the twistor space and the twistor lines induces meromorphic data, which we use to recover the conformal structure. A compact anti-self-dual orbifold can also be constructed by adding a point at infinity to an asymptotically locally Euclidean (ALE) scalar-flat K?hler orbifold. We use this observation to classify ALE scalar-flat K?hler 4-orbifolds whose isometry group contain a 2-torus.     

Scalar-flat K?hler orbifolds via quaternionic-complex reduction

We prove that any asymptotically locally Euclidean scalar-flat K?hler 4-orbifold whose isometry group contains a 2-torus is isometric, up to an orbifold covering, to a quaternionic-complex quotient of a k-dimensional quaternionic vector space by a (k−1)-torus. In order to do so, we first prove that any compact anti-self-dual 4-orbifold with positive Euler characteristic whose isometry group contains a 2-torus is conformally equivalent, up to an orbifold covering, to a quaternionic quotient of k-dimensional quaternionic projective space by a (k − 1)-torus.     

Zeeman-driven phase transition within the superconducting state of κ-(BEDT-TTF)2Cu(NCS)2

(13)C nuclear magnetic resonance measurements were performed on κ-(BEDT-TTF)(2)Cu(NCS)(2), with the external field placed parallel to the quasi-2D conducting layers. The absorption spectrum is used to determine the electronic spin polarization M(s) as a function of external field H at a temperature T=0.35 K. A discontinuity in the derivative dM(s)/dH at an applied field of H(s)=213±3 kOe is taken as evidence for a Zeeman-driven transition within the superconducting state and stabilization of inhomogeneous superconductivity.