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The transition to university teaching
Perhaps this is
the time to ask you to explain what is meant by free radical chemistry.
Free
radicals, in solution, were first described in 1900, by an amazing pioneer
called Moses Gomberg. Chemists had tried for years beforehand to make free
radicals without success and had concluded that they didn't exist. Then Gomberg
announced that he had successfully generated them, and indeed we now know that
he had. He is also famous for a memorable footnote to the first paper, which
was published in 1900 in the American Chemical Society Journal. Having
described these new species, these free radicals, he notes, 'This work will be
continued and I reserve the field for myself.'
In fact,
he needn't have worried, because nobody else was very interested. Most
scientists didn't believe he had actually generated organic free radicals in
solution. And even at the time that I was entering the field, there were still
many chemists who had similar doubts. There were a great many polemical articles
in the scientific literature, with some chemists maintaining that organic
radicals can't exist in solution. Others were convinced that they could. There
were very few people seriously working in the field of organic radicals in
solution a couple in Great Britain, a couple in America I suppose six
people, in all, in the world.
Free
radicals are very reactive molecules. All the more familiar organic compounds,
such as sugar, alcohol and acetone, are stable; they can be stored for long
periods without change. They are stable because they possess an even number of
electrons arranged in pairs. The bonds between the atoms consist of pairs of
electrons; a pair of electrons is a stable arrangement. Furthermore, around
most of the atoms in such molecules there are eight electrons in four pairs.
This is a very stable configuration.
However,
if one of the two-electron bonds in such a molecule is broken by irradiation of
a sample with light or by otherwise applying energy then one of the ways a bond
may break is by each half taking one electron. There will then be two new
molecules each of which has an odd number of electrons. Inevitably one of those
electrons must be unpaired and that is a very unstable state. These newly
formed highly unstable, and hence highly reactive, molecules are free radicals.
Are there now two
free radicals, or one?
If a bond
in an ordinary stable molecule is broken symmetrically, two free radicals are
generated. Each new molecule has an unpaired electron, and the formal
description of a free radical is 'any atom or molecule that contains an
unpaired electron'. Hence any species that has an uneven number of electrons
must be a free radical. Indeed any
species that has an even number of electrons but has, for some reason or
another, has two of the electrons unpaired is also a free radical (a
diradical).
Because
free radicals have an unpaired electron, they are inherently extremely
reactive. To return to a stable state the unpaired electron must couple with
another electron to form an electron-pair. One of the great virtues of free
radicals is that they will often react with organic molecules at positions that
are normally resistant to attack.
Why don't we go rancid?
During your final years in Adelaide you went again to
Oxford for some months, in 1979, and made some other visits while you were
overseas. Why Oxford this time?
It was
becoming increasingly clear that radicals are very important outside of the
test tube as well as in it, and particularly in natural systems. One of the
things I used to ask my students was, 'Why don't we go rancid?' It's a good
question. Our bodies contain lots of fat. If one leaves a bit of fat lying out
in the sun for a couple of days, it smells to high heaven. Why don't you and I
go rancid? Well, we now know that fats
go rancid because of free radical attack. Indeed, free radicals are everywhere.
Whenever a chemical bond is broken by ultraviolet light, cosmic rays or beta
radiation free radicals are formed. So radicals are ubiquitous. When they
attack fats oxidative processes involving oxygen occur. The reason we don't go
rancid is that we are protected while we are alive by natural anti-oxidants
such as vitamin E and vitamin C. Because of this I became very
interested in the mechanisms of metabolic reactions possibly involving the
attack of radicals on the constituents of living organisms.
An edited transcript of the full interview can be found at http://www.science.org.au/scientists/ab.htm.
Focus questions
- Chemically speaking, what is the difference
between a stable molecule and a reactive one?
- What are free radicals and how are they formed?
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