Pulse radiolysis experiments demonstrate how unpaired electrons at one end of a molecule can initiate chemistry at 'distant' locations. Researchers at the Brookhaven National Laboratory of the U.S. Department of Energy (DOE) helped in measuring how unpaired electrons in atoms at one end of a molecu
Journal of the American Chemical Society
This research relied on the combined resources of a Princeton University-led DOE Energy Frontier Research Center focused on Bio-Inspired Light Escalated Chemistry . Co-authors included Matthew Bird , Robert Knowles , and Nick Shin . Credit: Brookhaven National Laboratory and Princeton University Robert Knowles, who led Princeton’s role in this research, said, “This project is an example of how BioLEC’s combined expertise enabled the team to quantify an important physical property of these radical species, that in turn allowed us to design the resulting synthetic methodology.”
“We use the Laser Electron Accelerator Facility —part of the Accelerator Center for Energy Research in Brookhaven’s Chemistry Division—to generate intense high-energy electron pulses,” Bird explained. “These pulses allow us to add or subtract electrons from molecules to make reactive species that might be difficult to make using other techniques, including short-lived reaction intermediates. With this technique, we can step into one part of a reaction and monitor what happens.
The Brookhaven scientists found the acidity had to be high to enable proton capture, meaning the oxygen radical was a very strong electron-withdrawing group. That was good news for the Princeton team. They then demonstrated that it’s possible to exploit the “electron-withdrawing” effect of oxygen radicals by making parts of molecules that are generally inert more chemically reactive.
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