This paper presents a review of gas-phase detailed kinetic models developed to simulate the low temperature oxidation and autoignition of gasoline and diesel fuel components (alkanes, ethers, esters, alkenes, cycloalkanes, aromatics, including from 4 atoms of carbon) and of mixtures of several of them, which have been proposed as surrogates. The recently proposed models are summarized, as well ...

Continuous monitoring using electrospray ionisation mass spectrometry (ESI-MS) shows that Wilkinson's catalyst hydrogenates a charge-tagged alkyne to the corresponding alkene, and at only a marginally slower rate, to the alkane. No rhodium-containing intermediates were observed during the reaction, consistent with the established mechanism which points at the initial dissociation of triphenylph...

Thermodynamic studies of equilibrium chemical reactions linked with kinetic procedures are mostly impossible by traditional approaches. In this work, the new concept of generalized kinetic study of thermodynamic parameters is introduced for dynamic data. The examples of equilibria intertwined with kinetic chemical mechanisms include molecular charge transfer complex formation reactions, pH-depe...

BACKGROUND Integrative analysis between dynamical modeling of metabolic networks and data obtained from high throughput technology represents a worthy effort toward a holistic understanding of the link among phenotype and dynamical response. Even though the theoretical foundation for modeling metabolic network has been extensively treated elsewhere, the lack of kinetic information has limited t...

Through a "tag-and-modify" protein chemical modification strategy, we site-selectively phosphorylated the activation loop of protein kinase p38α. Phosphorylation at natural (180) and unnatural (172) sites created two pure phospho-forms. p38α bearing only a single phosphocysteine (pCys) as a mimic of pThr at 180 was sufficient to switch the kinase to an active state, capable of processing natura...

Kinetic isotope effects are one of the most powerful experimental techniques for establishing the nature of a chemical process. However their interpretation very often seeks support from electronic structure calculations in order to get detailed information regarding the transition state which is not experimentally available. For an example of atrazine hydrolysis we have shown how the match bet...

We show that the process of irreversible, kinetic colloid aggregation exhibits universal behavior, independent of the detailed chemical nature of the colloidal particles. Modem methods of statistical physics, applied to a kinetic growth process, provide a good basis to model the observed behavior. Two limiting regimes of colloid aggregation are identified: rapid aggregation, limited solely by t...

Even though several models for toluene oxidation have been developed [3-7], the high temperature combustion of this aromatic is not fully understood. Most high temperature studies of toluene carried out to date have involved monitoring the concentration profiles of reactants, stable intermediates, and final products in flow reactors using GC analyses. However, the ignition process of hydrocarbo...

Product contamination by particles nucleated within the processing environment often limits the deposition rate during chemical vapor deposition processes. A fundamental understanding of how these particles nucleate could allow higher growth rates while minimizing particle contamination. Here we present an extensive chemical kinetic mechanism for silicon hydride cluster formation during silane ...