(214a) Mechanistic Modeling of the (Bio)Conversion of (Bio)Macromolecules

Complex reacting systems are ubiquitous, yet it is still challenging to develop quantitative models to describe them. Two main challenges are to assemble the reaction mechanism or network and to specify the quantitative parameters governing the species and reactions that comprise it. To address the first challenge, we have developed methods for automated generation of reaction mechanisms of complex systems that allow kinetic models of substantive detail to be built. Molecules are represented as graphs and matrices, and operations on these representations allow reaction to be carried out, molecule uniqueness to be determined, and properties to be calculated. We have applied our methodology to a wide range of different problems, including production of silicon nanoparticles, biochemical transformations, polymerization and depolymerization, acid-catalyzed olefin oligomerization, and tropospheric ozone formation. While the chemistries we have studied are seemingly very disparate, applying a consistent methodology to study them reveals that there are many common elements of complex reaction networks. To conquer the second issue, we have developed a hierarchical approach for specifying rate coefficients and thermodynamic properties that relies on experimental data, structure/reactivity relationships, group additivity approaches, and quantum chemical calculations. This talk will focus on the application of these approaches to a variety of different chemistries