.
Molecular and Cellular Radiobiology
Project Title:
Mechanisms of Action of Free Radicals and Hormones
17.
Expected Results in FY 1974:
(Cont'd,)

RX-02-02-(c)

oxidases in membranes will determine by EPR che incorporation of spin-label
precursors (free radical "traps'' such as appropriate: nitroso compounds which
can be oxidized

to

relatively

stable nitroxide

radicals in situ),

Plans are

also being considered to utilize non-linear EPR techniques and ELDOR to follow
slow motions and possible redox reactions of spin labels incorporated in

membranes both with and without stimuli for oxidative chain reactions.

In studies on free radical forms of porphyrins the cation radical work
and the anion radical experiments on metallotetraphenylbacteriochlorine will
be completed but extension of the mapping of electron spin densities of
porphyrin cation and anion radicals is planned,
Certain tetramethyl- and
propyl-substituted porphyrins synthesized by Adler of New England Research
Institute will be studied to resolve some remaining ambiguities imanalysis
and EPR splitting assignments,
The use of metal isotopes with nuclear spins

(Fe-57, Zn-67, Mg-25, Cd-113, etc.) remains an attractive possibility.

The

interesting effects of counterions on porphyrin radicals previously reported,

and the relationship of these effects to heme enzyme function may be pursued
further,

The establishment of a conjoint Brookhaven facility for on-line EPR

spectrometry during ionizing irradiation will be attempted.
Nearly ten
years ago Fessenden set up at Carnegie-Mellon a facility that permits EPR
to be done on steady-state populations of transient free radicals produced
by an electron beam from a 3-MeV Van de Graaff accelerator,
This is the

'

only on-line EPR/radiation equipment in the USA, save for a pulsed-radiation/
fast-EPR set-up built by Smaller at ANL which has been applied only to a
-

small number of special radiation problems over the last few years, yet the
laboratory does not have the in-house capability to pursue more recently
developed applications.

Highly preductive interactions between pulse radialysis optical studies
in liquids and EPR studies of irradiated single crystals or
of frozen glasses
and powders have led to significant advances in the understanding of radiation
biophysics; and it is clear that correlations of pulse radiolysis findings
with on-line EPR ofirradiated solutions would markedly accelerate this highly
productive line of inquiry.
New applications of radiochemical procedures
and/or optical pulse radiolysis techniques to "bona fide" biochemical research

(as opposed to radiochemical or radiobiological problems), especially those
invol
redox properties, electron transfers, and the like, including

proje@€s already underway in this program could be facilitated by the

cilidigeion of an on-line EPR/radiation facility.

Other deparcments at Brookhaven are also interested in utilizing such
a capability.
Radiochemists in BNL's Chemistry Department have been using
fast and slow pulse radiolysis apparatus (with the Febetron and 2-MeV Van de
Graaff, respectively) in conjunction with their more ''classical" radiochemical

(See Continuation Sheet)

1119305

RX-245

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