The Nature of Animal LightHarvey, E. Newton (Edmund Newton)
Science
The Nature of Animal Light
Harvey, E. Newton (Edmund Newton)
Phosphorescence
According to Dubois, _Pholas_ luciferase is rather readily destroyed by
chloroform and my own observations indicate that this is true also of
firefly luciferase, so that a certain amount of variation exists in the
group of luciferases.
None of the luminescent animals which I have studied are at all affected
by cyanides. The luminescence continues in extracts of _Cypridina_,
firefly, and _Cavernularia_, or in _Noctiluca_ and luminous bacteria
after addition of small or high (_m_/40) concentrations of KCN. In this
respect the luciferases are very different from many types of oxidizing
enzymes which are inhibited by exceedingly weak concentrations of
cyanide. It should be borne in mind, however, that while KCN inhibits
catalase and the catalytic decomposition of H_{2}O_{2} by Pt or Ag, it
does not affect the catalytic decomposition of H_{2}O_{2} by thallium.
OXYLUCIFERIN.--When luciferin is oxidized it must be converted into some
substance or substances and I believe this change involves no
fundamental destruction of the luciferin molecule as it is a reversible
process. I shall speak of the principal (if not the only) product formed
as _oxyluciferin_.
If we assume that the oxidation of luciferin changes the molecule but
slightly, we at once think of comparing the change luciferin ⇆
oxyluciferin with the change reduced hæmoglobin ⇆ oxyhæmoglobin. The
condition is, however, not so simple as this, for oxyhæmoglobin will
again give up its oxygen providing the partial pressure of oxygen is
made sufficiently low, whereas oxyluciferin will not do this, at least
in the dark. We can not reduce oxyluciferin solution by exhausting the
oxygen with an air-pump.
There is another oxidation-reduction system which can also be easily
reversed, but not by merely removing the oxygen from the solution--that
is, the reduction of a dye such as methylene blue to its leuco-base. I
believe the change which occurs when luciferin is oxidized is similar to
that which occurs when the leuco-base of methylene blue or sodium
indigo-sulphonate is oxidized to the blue dye. Oxidation of leuco-dye
bases occurs spontaneously in presence of oxygen and appears to consist
in the removal of hydrogen from the leuco-base with formation of water.
Reduction of these dyes may be effected in the same ways that
oxyluciferin can be reduced. In the case of methylene blue, reduction
consists in the addition of two hydrogen atoms. Whether a similar change
occurs when oxyluciferin is reduced or whether oxygen is actually added
as in formation of hæmoglobin cannot be definitely stated at present. We
may write equations representing these possibilities as follows:
C_{16}H_{20}N_{3}SCl + O ⇆ C_{16}H_{18}N_{3}SCl + H_{2}O
(leuco-methylene blue) (methylene blue)
Hæmoglobin + O ⇆ oxyhæmoglobin.
Let us now turn to the methods which may be used in reduction of
oxyluciferin. We may then endeavor to write an equation which will
represent the fundamental changes in the luminescence reaction.
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