Synthesis of cananodine by intramolecular epoxide opening

Cananodine is a guaipyridine alkaloid with activity against liver cancer. Cananodine was synthesized using a remarkable intramolecular opening of a trisubstituted epoxide as the key step in construction of the seven-membered carbocycle of the target. The epoxide opening strategy allows all four stereoisomers of cananodine to be prepared.     

New dicationic porphyrin ligands suited for intercalation into B-form DNA

This paper describes the synthesis and characterization of a new series of sterically nondemanding, dicationic porphyrins that exhibit novel DNA-binding interactions. Cationic porphyrins continue to be the focus of a great deal of effort because of the promise they have for use in photodynamic, antiviral, and anticancer therapies. The systems explored here include 5,15-di(N-methylpyridinium-4-yl)porphyrin (H2D4), 5,15-di(N-methylpyridinium-3-yl)porphyrin (H2D3), and 5,15-di(N-methylpyridinium-2-yl)porphyrin (H2D2), as well as Zn(D4) and Zn(D3), the zinc(II)-containing derivatives of H2D4 and H2D3, respectively. Viscometry studies, in conjunction with various spectroscopic techniques, reveal the nature of the adducts formed with DNA. Irrespective of the base composition, H2D4 and H2D3 bind to DNA by intercalation. The zinc derivatives Zn(D4) and Zn(D3) are also intercalators; however, the binding constants are smaller because uptake requires the loss of an axial ligand. The decisive roles that steric factors and structural rigidity play in shaping the adducts with DNA become clear. Sequences that contain mainly adenine-thymine base pairs easily depart from the canonical B-form DNA structure and generally accommodate bulky porphyrins in external binding sites. However, with the H2D3 and H2D4 systems, the steric requirements are so minimal that intercalation becomes the preferred mode of binding, even in [poly(dA-dT)]2. The intercalated form of the H2D2 isomer is less stable, probably because of frontal strain associated with the (N-methyl)pyridinium-2-yl groups. A qualitative energy-level diagram is useful for assessing the forces that influence binding and could guide the design of new porphyrin ligands.     

Librons observed in liquid acetonitrile by hyper-rayleigh scattering

Hyper-Rayleigh scattering intensity ratios I(VV)/I(VH) in the range 9-26 are observed for liquid acetonitrile (CH 3CN), inconsistent with localized modes of motion in an isotropic fluid. The observations are consistent with propagating orientational modes (librons) with frequency nu = 2 cm (-1), which scatter 71% of the light.     

Raman spectrographic system for quantitative analysis of isotopic hydrogen mixtures for muon catalysis experiments

We show that Raman spectral lines from H₂, D₂, T₂, HD, HT and DT are readily resolved, permitting an effective means to analyze isotopic hydrogen mixtures used in muon-catalyzed fusion experiments. We propose a Raman spectrographic system to allow for real-time analysis of targets involving all three isotopes of hydrogen.