Fractals: optical susceptibility and giant raman scattering

A theory is developed which describes the optical properties of fractal clusters (i.e. of aggregates of non-trivial Hausdorff dimension consisting of interacting monomer particles). It is shown that with respect to these properties fractal clusters differ significantly from both gases and condensed media. The interaction between the monomers is assumed to be dipole-dipole. The theory is based on the self-consistent field equations; it takes into account the fluctuation nature of the fractal cluster (considerable probability for approach of monomers to each other despite an asymptotically zero integral density). An expression is obtained for the linear susceptibility. Combination of the monomers with the formation of a cluster entails the splitting, shift and broadening of the monomer spectra. These changes depend strongly on the fractal (Hausdorff) dimension of the cluster but do not depend on the number of monomers in it (for a cluster of non-trivial dimension). On the other hand, the monomers partially retain their individuality and the susceptibility — its quasi-resonance nature. Broadening, like the imaginary part of the susceptibility, does not depend on dissipation in an individual monomer. It is predicted that giant Raman scattering may occur at an impurity particle fixed near one of the cluster monomers when excitation takes place in the absorption band of the cluster. The enhancement factor for the scattering is also determined by the fractal dimension.     

Fluorine-NMR competition binding experiments for high-throughput screening of large compound mixtures

High-throughput ligand-based NMR screening with competition binding experiments is extended to (19)F detection. Fluorine is a favorable nucleus for these experiments because of the significant contribution of the Chemical Shift Anisotropy (CSA) to the (19)F transverse relaxation of the ligand signal when bound to a macromolecular target. A low to moderate affinity ligand containing a fluorine atom is used as a reference molecule for the detection and characterization of new ligands. Titration NMR experiments with the selected reference compound are performed for finding the optimal set-up conditions for HTS and for deriving the binding constants of the identified NMR hits. Rapid HTS of large chemical mixtures and plant or fungi extracts against the receptor of interest is possible due to the high sensitivity of the (19)F nucleus and the absence of overlap with the signals of the mixtures to be screened. Finally, a novel approach for HTS using a reference molecule in combination with a control molecule is presented.     

A two-directional synthesis of (+/-)-perhydrohistrionicotoxin

An entirely two-directional synthesis of (+/-)-perhydrohistrionicotoxin is presented, utilizing a tandem oxime formation/Michael addition/[3 + 2] cycloaddition as the key step. This approach also constitutes formal syntheses of (+/-)-histrionicotoxin and (+/-)-histrionicotoxin 235A.