ARCHIVES OF BIOCHEMISTRY AND BIOPHYSICS 86, 231-232 (1960)

On the Origin of the Free Radical Property of Melanins

H. C. LONGUET-HIGGINS
From the Department of Theoretical Chemistry, University Chemical Laboratory,
Lens$eld Road, Cambridge, England
Received August 27, 1959

The presence of unpaired electrons in melanin may be readily understood if it is

supposed that melanin is in effect a one-dimensional semiconductor, any bound pro-
tons acting as electron traps. The intense and broad optical absorption of melanin
supports this tentative view.

INTRODUCTION freedom of movement, just like the mobile

If, as suggested, the melanin molecule is a
conjugated chain of quinonoid units with a
number of additional electrons (l), then the
conventional structural formalism of organic
chemistry would allow the system to be
formulated either as a quinone-hydroquinone
copolymer, or as a quinone-semiquinone co-
polymer, or as a mixed copolymer of quinone
with both hydroquinone and semiquinone.
Between structural alternatives of this type
it is, however, impossible to choose, if only
because of the extensive resonance which
must occur between these various possibili-
ties.
THEORY
A relatively simple model of such a system
is, however, provided by the molecular or-
bital theory, in the form of the band theory
of solids. If one supposes, as seems most
likely, that the fully oxidized molecule has a
closed electron shell, then further electrons
which are added will enter a conduction
band of nonlocalized molecular orbitals
formed by interaction between the lowest
vacant orbitals of the individual quinonoid
units. (The presence of a low-lying vacant
orbital in a quinone is indicated by the ease
of reduction of such a molecule.)
Now the conduction band in question has
a capacity of 2 N electrons, where N is the
number of monomer units. Hence if the
number of surplus electrons is much less than
N, these electrons will have considerable
231
electrons in an n-type impurity semiconduc-
tor. In particular, their spins should be vir-
tually uncorrelated, and each should contrib-
ute individually to the observable spin
resonance.
At the opposite extreme, a polyquinone
which is almost fully reduced-i.e., a poly-
hydroquinone with a few electrons missing-
should, for precisely analogous reasons, be-
have as a p-type impurity semiconductor,
whose electrical conductivity arises from
positive holes in an otherwise full band.
In conclusion, a word may be said about
the effects of proton addition on the mobility
of the surplus electrons (or proton removal
on the mobility of the holes in the opposite
case). These processes are illustrated below:
-0 0. HO 0. HO OH HO 0.
Proton addition to one of the conjugated
quinone units will undoubtedly lower the
energy of its lowest vacant orbital, and may
even lead to the unit becoming an electron
trap. Indeed n-type semiconductors very of-
ten possess traps which will accommodate
one but not two electrons apiece; when such
a trap has acquired one electron, a further
electron added to the system falls into a trap
somewhere else. (Similar statements apply
to hole traps in p-type semiconductors.)
Though it is quite possible that the addition
of two protons to a quinonoid unit might
232 LONGUET-HIGGINS

create an electron-pair trap, there seems no
obvious reason why the protons should at-
tach themselves in pairs as a polyquinone is
reduced (or become detached in pairs as a
polyhydroquinone is oxidized). Neverthe-
less, it remains a possibility that most or all
of the traps are two-electron traps associated
with pairs of protons; this situation would
lead to a disappearance of the paramagne-
tism at very low temperatures.
REFERENCE
1. MASON,H. S., INGRAM,D. J. E., AND ALLEN,
B.,Arch. Biochem. Biophys. 86, 225 (1960).