Convergent synthesis of pyragonicin

This paper describes a second-generation synthesis of an antitumor tetrahydropyran (THP) acetogenin, pyragonicin. The key step involved an olefin cross-metathesis between the THP segment and the terminal gamma-lactone residue. The coupling reaction in the presence of Grubbs' second-generation catalyst resulted in an unseparable mixture of a desired coupling product and its one-carbon eliminated product while the use of Grubbs' first-generation catalyst afforded the former exclusively. A novel MOM-migrating reaction found in a cyclization reaction is also discussed.     

Strange behaviors of interior-point methods for solving semidefinite programming problems in polynomial optimization

We observe that in a simple one-dimensional polynomial optimization problem (POP), the ??optimal?? values of semidefinite programming (SDP) relaxation problems reported by the standard SDP solvers converge to the optimal value of the POP, while the true optimal values of SDP relaxation problems are strictly and significantly less than that value. Some pieces of circumstantial evidences for the strange behaviors of the SDP solvers are given. This result gives a warning to users of the SDP relaxation method for POPs to be careful in believing the results of the SDP solvers. We also demonstrate how SDPA-GMP, a multiple precision SDP solver developed by one of the authors, can deal with this situation correctly.     

Blends of some non-flexible and flexible polymers: Routes to molecular composites?

The definition of a molecular composite is a blend of a rigid rod polymer and a flexible coil polymer that is miscible at the molecular level. This concept has been tested using systems in which the chain flexibilities differ as widely as possible as judged by the difference in glass transition temperatures (δTg). The biggest variation (δT ∼360°C) was obtained by mixing poly benzimidazole with copolymers of poly(vinyl acetate-ran-vinyl alcohol). It was observed that the blends were distinctly two phase when the hydroxyl content was less than 50 mol %. Above this value clear blends were obtained with finely dispersed phases although it is doubtful if mixing at the molecular level takes place. Miscible blends could be obtained from combinations of the sodium salt of poly(phenylene terephthalamide) with poly(4-vinylpyridine) and mixtures of poly(phenyl imino-1,4-phenyleneoxyterephthalate) with poly(styrene-stat-hydroxylstyrene) where coulombic interactions and hydrogen bonding respectively promoted the miscibility.