NEAR DIFFUSION-LIMITED REACTIONS

Project: Research project

Project Details

Description

The project is concerned with the investigation of reactions of
reactive intermediates with a potential use in photoaffinity
labeling techniques. It addresses the need for development of new
photoreactive reagents for studies of macromolecules important in
many areas of medical and biological research. The understanding
of reaction mechanisms of such reagents, which includes their
kinetics and selectivity, is crucial to the optimization of the
photolabeling. Such optimization should lead to more precise
information about the interactions between small molecules of
biological interest and macromolecules and macroassemblies such as
enzymes, receptors and membranes.

A simple test is proposed for the study of such photogenerated
reactive intermediates. It allows one to estimate reaction rates
of these species without absolute rate measurements. In this test
two substrates with known diffusive properties and containing a
different number of reactive sites compete for a reactive
intermediate of interest. The approach uses diffusion rate as an
internal clock for rapid reactions. The test is being used to
estimate reaction rates of some of the least selective nitrenes and
carbenes known. It provides data on C-H bond insertion,
intersystem crossing, and complexation with solvents for these
reactive intermediates.
StatusFinished
Effective start/end date7/1/906/30/91

Funding

  • National Institute of General Medical Sciences

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