Reactions of Weinreb amides: formation of aldehydes by Wittig reactions

Aldehydes are prepared in excellent yield by Wittig reactions of phosphoranes on the Weinreb amide of formic acid followed by in situ hydrolysis.     

Synthesis and optical properties of metal-centered dimeric fullerene macromolecules

Dimeric fullerene macromolecules were prepared via the complexation of two fullerenylated 2,2′:6′,2″-terpyridine ligands with Fe(II) and Co(II) ions. The solubility of these macromolecules in some organic solvents allowed both their structural characterization and a study of their optical properties. The electronic absorption and emission of the macromolecules in solution were evaluated; and the results indicated no meaningful ground-state and excited singlet state intramolecular charge transfer interactions. However, the laser flash photolysis results could be explained in terms of the electron transfer quenching of the excited triplet methanofullerene moiety by the center metal–ligand complex in the macromolecules. The optical limiting properties of the macromolecules in solution were also investigated in comparison with those of the ligands for an evaluation of the complexation effects.     

Global and local optimization using radial basis function response surface models

The focus of this paper is the optimization of complex multi-parameter systems. We consider systems in which the objective function is not known explicitly, and can only be evaluated through computationally intensive numerical simulation or through costly physical experiments. The objective function may also contain many local extrema which may be of interest. Given objective function values at a scattered set of parameter values, we develop a response surface model that can dramatically reduce the required computation time for parameter optimization runs. The response surface model is developed using radial basis functions, producing a model whose objective function values match those of the original system at all sampled data points. Interpolation to any other point is easily accomplished and generates a model which represents the system over the entire parameter space. This paper presents the details of the use of radial basis functions to transform scattered data points, obtained from a complex continuum mechanics simulation of explosive materials, into a response surface model of a function over the given parameter space. Response surface methodology and radial basis functions are discussed in general and are applied to a global optimization problem for an explosive oil well penetrator.     

Time-Resolved Photoacoustic Calorimetry: From Carbenes to Proteins

Why have molecules only been seen but not heard? For over a century chemists have probed reactions with various spectroscopic methods to learn about structures, dynamics, and reactivities of their molecules. What they have not done is to listen to their molecules react. Although the photoacoustic phenomenon has been known since 1880, it is only in the last twenty years that technology has developed to the point where sound waves produced by reacting molecules can be time resolved and the information contained within the waves deciphered. The information content within the photoacoustic wave is indeed rich, for one can learn about the dynamics and the magnitude of enthalpy changes associated with the reaction as well as the changes in molecular volume. This review article chronicles the development of time-resolved photoacoustic calorimetry and its application to a variety of reactions encountered in organic and organometallic chemistry and biochemistry.