Synthesis of mono and Bis[60]fullerene-based dicationic peptoids

Increasing numbers of biological applications of fullerenyl amino acids and their derivatives encouraged us to synthesise [60]fullerenyldihydropyrrole peptides, prepared from the coupling of mono- and bis[60]fullerenyldihydropyrrolecarboxylic acids 4, 5 and 41 with presynthesised peptides 13, 16, 24, 28, 29 and 46. The resulting hydrophobic scaffolded di- and tetra-cationic derivatives were tested against Staphylococcus aureus NCTC 6571 and Escherichia coli NCTC 10418. The synthesis, characterisation and biological results are discussed in this paper

Spectrum of antibacterial activity and mode of action of a novel tris-stilbene bacteriostatic compound

The spectrum of activity and mode of action of a novel antibacterial agent, 135C, was investigated using a range of microbiological and genomic approaches. Compound 135C was active against Gram-positive bacteria with MICs for Staphylococcus aureus ranging from 0.12–0.5 μg/ml. It was largely inactive against Gram-negative bacteria. The compound showed bacteriostatic activity in time-kill studies and did not elicit bacterial cell leakage or cell lysis. Checkerboard assays showed no synergy or antagonism when 135C was combined with a range of other antibacterials. Multi-step serial passage of four S. aureus isolates with increasing concentrations of 135C showed that resistance developed rapidly and was stable after drug-free passages. Minor differences in the fitness of 135C-resistant strains and parent wildtypes were evident by growth curves, but 135C-resistant strains did not show cross-resistance to other antibacterial agents. Genomic comparison of resistant and wildtype parent strains showed changes in genes encoding cell wall teichoic acids. 135C shows promising activity against Gram-positive bacteria but is currently limited by the rapid resistance development. Further studies are required to investigate the effects on cell wall teichoic acids and to determine whether the issue of resistance development can be overcome

Strange form factors and Chiral Perturbation Theory

We review the contributions of Chiral Perturbation Theory to the theoretical understanding or not-quite-yet-understanding of the nucleon matrix elements of the strange vector current.Comment: 4 pages, 6 figures, presented at the International Workshop on Parity Violation and Hadronic Structure (PAVI04), Grenoble, France, 8-11 Jun 200

Binaphthyl-1,2,3-triazole peptidomimetics with activity against Clostridium difficile and other pathogenic bacteria

Clostridium difficile (C. difficile) is a problematic Gram positive bacterial pathogen causing moderate to severe gastrointestinal infections. Based on a lead binaphthyl-tripeptide dicationic antimicrobial, novel mono-, di- and tri-peptidomimetic analogues targeting C. difficile were designed and synthesized incorporating one, two or three d-configured cationic amino acid residues, with a common 1,2,3-triazole ester isostere at the C-terminus. Copper- and ruthenium-click chemistry facilitated the generation of a 46 compound library for in vitro bioactivity assays, with structure-activity trends over the largest compound subset revealing a clear advantage to triazole-substitution with a linear or branched hydrophobic group. The most active compounds were dicationic-dipeptides where the triazole was substituted with a 4- or 5-cyclohexylmethyl or 4,5-diphenyl moiety, providing MICs of 4 μg mL-1 against three human isolates of C. difficile. Further biological screening revealed significant antimicrobial activity for several compounds against other common bacterial pathogens, both Gram positive and negative, including S. aureus (MICs ≥2 μg mL-1), S. pneumoniae (MICs ≥1 μg mL-1), E. coli (MICs ≥4 μg mL-1), A. baumannii (MICs ≥4 μg mL-1) and vancomycin-resistant E. faecalis (MICs ≥4 μg mL-1)

Strange chiral nucleon form factors

We investigate the strange electric and magnetic form factors of the nucleon in the framework of heavy baryon chiral perturbation theory to third order in the chiral expansion. All counterterms can be fixed from data. In particular, the two unknown singlet couplings can be deduced from the parity-violating electron scattering experiments performed by the SAMPLE and the HAPPEX collaborations. Within the given uncertainties, our analysis leads to a small and positive electric strangeness radius, $= (0.05 \pm 0.09) fm^2$. We also deduce the consequences for the upcoming MAMI A4 experiment.Comment: 7 pp, REVTeX, uses epsf, minor correction

Strange nucleon form factors in the perturbative chiral quark model

We apply the perturbative chiral quark model at one loop to calculate the strange form factors of the nucleon. A detailed numerical analysis of the strange magnetic moments and radii of the nucleon, and also the momentum dependence of the form factors is presented.Comment: 18 pages, 6 figure

First-principles extrapolation method for accurate CO adsorption energies on metal surfaces

We show that a simple first-principles correction based on the difference between the singlet-triplet CO excitation energy values obtained by DFT and high-level quantum chemistry methods yields accurate CO adsorption properties on a variety of metal surfaces. We demonstrate a linear relationship between the CO adsorption energy and the CO singlet-triplet splitting, similar to the linear dependence of CO adsorption energy on the energy of the CO 2$\pi$* orbital found recently {[Kresse {\em et al.}, Physical Review B {\bf 68}, 073401 (2003)]}. Converged DFT calculations underestimate the CO singlet-triplet excitation energy $\Delta E_{\rm S-T}$, whereas coupled-cluster and CI calculations reproduce the experimental $\Delta E_{\rm S-T}$. The dependence of $E_{\rm chem}$ on $\Delta E_{\rm S-T}$ is used to extrapolate $E_{\rm chem}$ for the top, bridge and hollow sites for the (100) and (111) surfaces of Pt, Rh, Pd and Cu to the values that correspond to the coupled-cluster and CI $\Delta E_{\rm S-T}$ value. The correction reproduces experimental adsorption site preference for all cases and obtains $E_{\rm chem}$ in excellent agreement with experimental results.Comment: Table sent as table1.eps. 3 figure

The local structure of OH species on the V2O3(0 0 0 1) surface: a scanned-energy mode photoelectron diffraction study

Scanned-energy mode photoelectron diffraction (PhD), using O 1s photoemission, together with multiple-scattering simulations, have been used to investigate the structure of the hydroxyl species, OH, adsorbed on a V2O3(0 0 0 1) surface. Surface OH species were obtained by two alternative methods; reaction with molecular water and exposure to atomic H resulted in closely similar PhD spectra. Both qualitative assessment and the results of multiple-scattering calculations are consistent with a model in which only the O atoms of outermost layer of the oxide surface are hydroxylated. These results specifically exclude significant coverage of OH species atop the outermost V atoms, i.e. in vanadyl O atom sites. Ab initio density-functional theory cluster calculations provide partial rationalisation of this result, which is discussed the context of the general understanding of this system

Strange form factors in the context of SAMPLE, HAPPEX, and A4 experiments

The strange properties of the nucleon are investigated within the framework of the SU(3) chiral quark-soliton model assuming isospin symmetry and applying the symmetry conserving SU(3) quantization. We present the form factors $G^0_{E,M}(Q^2)$, $G^Z_M(Q^2)$ and the electric and magnetic strange form factors $G^s_{E,M}(Q^2)$ incorporating pion and kaon asymptotics. The results show a fairly good agreement with the recent experimental data from the SAMPLE and HAPPEX collaborations. We also present predictions for future measurements including the A4 experiment at MAMI (Mainz).Comment: 10 pages with four figures. RevTeX4 is used. Few lines are changed. Accepted for publication in Phys.Rev.

Electroweak Radiative Corrections to Parity-Violating Electroexcitation of the Δ\Delta

We analyze the degree to which parity-violating (PV) electroexcitation of the $\Delta(1232)$ resonance may be used to extract the weak neutral axial vector transition form factors. We find that the axial vector electroweak radiative corrections are large and theoretically uncertain, thereby modifying the nominal interpretation of the PV asymmetry in terms of the weak neutral form factors. We also show that, in contrast to the situation for elastic electron scattering, the axial $N\to\Delta$ PV asymmetry does not vanish at the photon point as a consequence of a new term entering the radiative corrections. We argue that an experimental determination of these radiative corrections would be of interest for hadron structure theory, possibly shedding light on the violation of Hara's theorem in weak, radiative hyperon decays.Comment: RevTex, 76 page