Gambieroxide,a novel epoxy polyether compound from the dinoflagellate Gambierdiscus toxicus GTP2 strain

A novel epoxy polyether compound named gambieroxide was isolated from the benthic dinoflagellate Gambierdiscus toxicus (GTP2 strain) collected at Papeete, Tahiti, French Polynesia and its structure comprising of a ladder-frame polyether with twelve contiguous trans-fused ether rings (6/7/6/6/6/7/6/8/6/6/6/6), a sulfate ester group, an epoxide, and two olefines in side chains was elucidated by detailed NMR and MS analysis. It is interesting that the structure strikingly resembles yessotoxin, one of lipophilic toxins in shellfish originating from the dinoflagellate Protoceratium reticulatum.     

Removal of aqueous As(III) and As(V) by hydrous titanium dioxide

Dissolved arsenic in drinking water is a global concern as it causes serious health problems. The purpose of this research was to study the applicability of an industrial intermediate product, a mixture of titanium hydroxide and titanium dioxide for removing aqueous arsenic. The material is common, inexpensive, and non-toxic, making it an attractive choice for drinking water purification. The kinetics and equilibrium of removing both primary inorganic arsenic forms, As(III) and As(V), were studied by separate batch experiments. The tested material functioned well in removing both of these arsenic forms. The apparent values for Langmuir monolayer sorption capacities were 31.8 mg/g for As(III) and 33.4 mg/g for As(V) at pH 4. The studied TiO(2) performed the best in acidic conditions, but also reasonably well in other pH conditions.     

A new route towards redox bistability through the inspection of manganese-porphyrin complexes

The redox and spin versatilities of manganese–porphyrin complexes [Mn^IIP] are examined to construct a redox‐switchable device. The electronic structure of [Mn^IIIP]⁺ was analyzed by using wavefunction‐based calculations (complete active spaces plus single excitations on top of the active spaces, that is, CAS+singles). A non‐negligible σ‐type electron‐transfer configuration is present in the [Mn^IIIP]⁺ S=2 ground state. By contrast, the [Mn^IIP^.]⁺ valence tautomer is a purely π‐type intramolecular charge transfer, thus reflecting an S=3 spin state as a result of the strong ferromagnetic interaction (J=30 meV) between the S=5/2 Mn^II ion and the S=1/2 porphyrin radical cation P^.+. The change of the redox‐sensitive site in the valence tautomer leads to a ‘triangular scheme’ that involves a critical step in which a simultaneous electron transfer and spin change are expected to induce bistability. From the wavefunction inspection, a meso‐substituted porphyrin candidate was designed to support this scenario. The complete active‐space second‐order perturbation theory (CASPT2) adiabatic energy difference between the S=2 and the S=3 spin states was reduced down to 0.15 eV, thereby giving rise to a metastable S=3 state characterized by a 0.10 Å extension of the porphyrin cavity radius. These results not only confirm the rather versatile nature of these inorganic systems but also demonstrate that redox and spin changes are intermingled in this class of compounds and can be used for applied devices.     

Morphological lattice complexes

Binary and pseudobinary compounds AB like NaCl and CaCO₃, with the center of charge at carbon position, are characterized by self‐coordination numbers of nearest, second and third neighbors T ₁ T ₂ T ₃ of A and B positions. The maximum Madelung factor of compounds with identical T _i values of A and B atoms is obtained for a maximum of B positions at the border of the A–A Dirichlet domain. The A and B positions form a packing with different T _i values, if all B positions are on the border of the Dirichlet domain. This packing like the primitive cubic packing of Na and Cl atoms with T _i values 6 12 8 or the rhombohedrally distorted packing 6 8 6 of CaCO₃ as morphological lattice complexes can be related to cubic NaCl crystals or the cleaved rhombohedron of calcite. A different habit of crystals is expected for sphere, rod or layered packings. Many well‐defined nanoparticles can be obtained from microemulsions at variation of temperature, water content or water partial pressure. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Extended conformations of isolated molecular bottle-brushes: Influence of side-chain topology

A Monte Carlo study is presented to discuss the influence of the side-chain topology on the enhancement of the persistence length of a molecular bottle-brush in a dilute athermal solution due to the excluded volume interactions between the side chains. The structures investigated consisted of freely jointed backbones of 100 hard spheres (beads) of diameter 1 to which 50 equally flexible side chains were grafted. The diameter of the side-chain beads was varied from 1 to 3 in the same units. For every given size of the side-chain bead, the length of the side chains was varied from 4 to 20 beads. The ratio between the persistence length and the bottle-brush diameter, which is the determining factor for lyotropic behavior of conventional semi-flexible chains, was found to be almost independent of the side-chain length. At the same time, it was found to increase considerably with increasing size of the side-chain beads, suggesting that by a proper choice of the chemistry lyotropic behavior of molecular bottle-brushes due to excluded-volume interactions between the side chains might be achieved. Moreover, relatively short side chains can be used since the side chain length has only a minor influence on the ratio between the persistence length and the diameter. These findings are in a good agreement with recent experimental observations.