Bengazoles C-G from the Sponge Jaspis sp. Synthesis of the Side Chain and Determination of Absolute Configuration

Five new antifungal bengazoles (C-G) were isolated and fully characterized from a marine sponge of the genus Jaspis sp. Bengazoles C-G, together with the known bengazoles A and B, comprise a homologous series of n, iso, and anteiso fatty acid esters (C(13)-C(16)) of the same heterocyclic bis(oxazolyl)methanol parent. The complete relative and absolute configurations of the bengazoles were determined by application of the modified Mosher method and interpretation of exciton coupling in the CD spectra of the tetra-p-bromobenzoate derivatives of bengazole A and that of a model tetrol synthesized in seven steps from L-fucose.     

Structures and anion-binding properties of M4L6 tetrahedral cage complexes with large central cavities

Reaction of the bis-bidentate bridging ligand L(3), in which two bidentate chelating 3(2-pyridyl)pyrazole units are separated by a 3,3'-biphenyl spacer, with Co(II) salts affords tetranuclear cage complexes of composition [Co(4)(L(3))(6)]X(8)(X =[BF(4)](-), [ClO(4)](-), [PF(6)](-) or I(-)) in which four 6-coordinate Co(II) ions in an approximately tetrahedral array are connected by six bis-bidentate bridging ligands, one spanning each of the six edges of the Co(4) tetrahedron. In every case, X-ray crystallography reveals that the 'apical' Co(II) ion has a fac tris-chelate geometry, whereas the other three Co(II) ions have mer tris-chelate geometries, resulting in (non-crystallographic)C(3) symmetry for the cages; that this structure is retained in solution is confirmed by (1)H NMR spectroscopy of the paramagnetic cages. In every case one of the anions is located inside the central cavity of the cage, with the remaining seven outside. We found no clear evidence for an anion-based templating effect. The cage superstructure is sufficiently large to leave gaps in the centres of the faces through which the internal and external anions can exchange. Variable-temperature (19)F NMR spectroscopy was used to investigate the dynamic behaviour of the cages with X =[BF(4)](-) and [PF(6)](-) in MeCN solution: in both cases two separate signals, corresponding to external and internal anions, are clear at 233 K which have coalesced to a single signal at room temperature. Analysis of the linewidth of the minor signal (for the internal anion) at various temperatures below coalescence gave an activation energy for anion exchange of ca. 50 kJ mol(-1) in each case, a figure which suggests that anion exchange can occur via a conformational rearrangement of the cage superstructure in solution rather than opening of the cavity by cleavage of metal-ligand bonds.     

Microcionamides A and B, bioactive peptides from the philippine sponge Clathria (Thalysias) abietina

Microcionamides A (1) and B (2) have been isolated from the Philippine marine sponge Clathria (Thalysias) abietina. These new linear peptides are cyclized via a cystine moiety and have their C-terminus blocked by a 2-phenylethylenamine group. Their total structures, including absolute stereochemistry, were determined by a combination of spectral and chemical methods. Compound 1 was shown to slowly isomerize about the C-36/C-37 double bond when stored in DMSO. Microcionamides A (1) and B (2) exhibited significant cytotoxicity against the human breast tumor cells lines MCF-7 and SKBR-3 and displayed inhibitory activity against Mycobacterium tuberculosis H(37)Ra.     

Young modules and filtration multiplicities for Brauer algebras

We define permutation modules and Young modules for the Brauer algebra B _k (r,δ), and show that if the characteristic of the field k is neither 2 nor 3 then every permutation module is a sum of Young modules, respecting an ordering condition similar to that for symmetric groups. Moreover, we determine precisely in which cases cell module filtration multiplicities are well-defined, as done by Hemmer and Nakano for symmetric groups. Supported by the European Community through Marie Curie fellowship MCFI 2002-01325 Supported by EPSRC grant GR/S18151/01     

Simple on-line sample preconcentration technique for peptides based on dynamic pH junction in capillary electrophoresis-mass spectrometry

We report an on-line sample preconcentration technique based on dynamic pH junction in capillary electrophoresis-mass spectrometry (CE-MS). For peptide analysis, the samples were dissolved in a solution with higher pH than the background solution (BGS), and were injected into the capillary as a long plug. The pH difference between the sample matrix and BGS caused changes in analytes' mobilities during electrophoresis, resulting in narrowing of their bands at the boundary. Around 550-1000-fold sensitivity enhancement could be achieved in terms of peak intensity without degrading peak shape and resolution. This technique is easy to perform and will be useful for peptide mass fingerprinting in protein analysis.     

Metabolome analysis by capillary electrophoresis-mass spectrometry

Capillary electrophoresis (CE)-mass spectrometry (MS), as an analytical platform, has made significant contributions in advancing metabolomics research, if still limited up to this time. This review, covering reports published between 1998 and 2006, describes how CE-MS has been used thus far in this field, with the majority of the works dealing with targeted metabolite analyses and only a small fraction using it in the comprehensive context. It also discusses how some of the key features of CE-MS were exploited in selected metabolomic applications.     

(Semi-)Riemannian geometry of (para-)octonionic projective planes

We use reduced homogeneous coordinates to construct and study the (semi-)Riemannian geometry of the octonionic (or Cayley) projective plane , the octonionic projective plane of indefinite signature , the para-octonionic (or split octonionic) projective plane and the hyperbolic dual of the octonionic projective plane . We also show that our manifolds are isometric to the (para-)octonionic projective planes defined classically by quotients of Lie groups.