Chemistry's Greatest Hits
What are some of the most significant accomplishments in the fifty-seven year history of the Chemistry Department? This is obviously a very subjective list, but at the clear risk of offending everyone, here we go:
Ray Davis, Solar Neutrinos, and the 2002 Nobel Prize in Physics
We are justifiably proud of our colleague, Ray Davis and his winning of the 2002 Nobel Prize in Physics. While work at Brookhaven has been associated with more than seven Nobel Prizes, this prize was the first won by a member of the BNL permanent staff. In addition, as chemists, we are pleased by the affirmation of the unity of science reflected by the awarding of the prize in physics to Ray, a chemist.
Fluorodeoxyglucose and PET
Positron Emission Tomography (PET) is a widely used technique to probe brain function, whereas most other imaging methods reveal structure. PET images are developed by geometric reconstruction of the locations at which positrons are annihilated after being emitted from radioactive compounds metabolized in the brain. Therefore, radioactive compounds must be used that pass the blood-brain barrier, are used in the brain, and are nontoxic. The method used for the discovery and synthesis of these compounds grew out of "hot atom chemistry", a field nourished by the Atomic Energy Commission, the original federal funding agency supporting Brookhaven, and a discipline in which the Chemistry Department played an important role. The synthesis and use of 18F-labeled fluorodeoxyglucose (FDG) was pioneered by researchers in the Brookhaven Chemistry Department. FDG is now the most popular compound used in PET studies worldwide.
Electron Transfer in Solution
"Oxidation-Reduction is the simplest reaction." Well, maybe. It certainly represents one of the most important classes of reactions, governing electrochemistry, which in turn provides understanding of batteries, fuel cells, corrosion, and a host of other phenomena. Experiments in electron transfer were an early fixture in the Chemistry Department, (when it needed to be shown that the rates of such rapid reactions could be measured at all), and continue today with connections to solar energy conversion and the "hydrogen economy". In addition, studies of electron transfer helped to stimulate theoretical efforts to describe these processes. The most successful theory of electron transfer is "Marcus Theory", authored over several decades by Professor Rudolph A. Marcus, now of the California Institute of Technology, and the recipient of the 1992 Nobel Prize for Chemistry, awarded for his theory of electron transfer. Much of the experimental work confirming the validity of Marcus theory was performed by researchers in the Brookhaven Chemistry Department.
The Radiation Chemistry of Water
Understanding radiation effects in water is basic to fundamental radiobiology and applications of nuclear technology depending on neutron moderation by water. The nature of the reducing and oxidizing radicals formed in water irradiation was first demonstrated in the Brookhaven chemistry Department. It was shown that the predominant reducing species has a negative charge and is a hydrated electron. This not only introduced an important new species to chemistry, but also made possible the first correct treatment of water decomposition and re-formation in nuclear applications.
Accurate measurement of absolute reaction rates of the hydroxyl and perhydroxyl radicals in irradiated water, difficult to make because of their rapidity, were also first measured in the Brookhaven Chemistry Department. A new superoxide of hydrogen, HO2, was also first discovered there.
"Hydrogen Atoms in the Radiolysis of Water" N.F. Barr and A.O. Allen, J. Phys. Chem. 63 928 (1959).
"Determination of Some Rate Constants for the Radical Processes in the Radiation Chemistry of Water" H.A. Schwarz, J. Phys. Chem. 66 255 (1962).
"The Nature of the Reducing Radical in Water Radiolysis" G. Czapski and H.A. Schwarz, J. Phys. Chem. 471 (1962).
Neutron Activation Applied to Art and Archaeology
The first application of neutron activation analysis to the study of archaeological materials was made at Brookhaven. In some Greek terra cotta figurines. It was found that the trace impurity compositions fall into patterns which are correlated to locations of origin and manufacture. Ancient commerce in Roman Aretine pottery, in South Arabian pottery, and in Mayan pottery was traced. An extensive study of ancient glass revealed many facts concerning the technology of its manufacture. This method was subsequently adopted elsewhere. At Brookhaven, activation autoradiography was applied for the first time to investigations of works of art such as paintings and to recover images from badly faded historic photographs. In paintings, the different pigments give rise to radiations decaying with different half-lives, and a sequence of radioautographs can provide information about layers of pigments used by the artist and techniques of application.
"Neutron Activation Autoradiography of Oil Paintings" E.V. Sayre and H.N. Lechtman, Studies in Conservation 13 161 (1968).
"Activation Analysis Applications in Art and Archaeology" E.V. Sayre, Adv. in Activation Analysis Vol. II, pp.156-94 (1970).
Last Modified: June 28, 2012