The Nature of Animal LightHarvey, E. Newton (Edmund Newton)
Science
The Nature of Animal Light
Harvey, E. Newton (Edmund Newton)
Phosphorescence
Since oxyluciferin can be reduced by palladium and sodium hypophosphite
(Harvey, 1918), it is probable that we can write the equation for
reduction of oxyluciferin and oxidation of luciferin in a similar manner
to that of methylene blue:
Luciferin + O ⇆ Oxyluciferin + H_{2}O
Briefly--LH_{2} + O ⇆ L + H_{2}O.
Just as in the case of methylene blue the reaction proceeds in the right
hand direction spontaneously if the pressure of O is sufficiently high.
If luciferase is also present we have luminescence.
LH_{2} + O + luciferase ⇆ L + H_{2}O + luciferase (luminescence)
The reaction proceeds in the left hand direction under low oxygen
pressure, in the presence of nascent hydrogen or with some catalyzer
which is able to split water, transferring the H_{2} to oxyluciferin and
the O to an acceptor (A). NaH_{2}PO_{2} plays the part of the acceptor.
L + H_{2}O + A + Pd = LH_{2} + AO + Pd.
This appears to be the way in which the reducing enzymes or
perhydridases (comparable to the Pd) of living tissues act (Bach,
1911-13) and the action of yeast cells, bacteria, muscle suspensions,
etc., in reducing oxyluciferin must occur in the same manner.
If we assume that the LH_{2} (luciferin) compound is dissociated to even
the slightest extent into L and hydrogen, the hydrogen ion will shift
the equilibrium toward the formation of that substance which involves
the taking up of hydrogen. Consequently we may obtain a partial
formation of luciferin by adding an acid to oxyluciferin. Reduction of
the H-ion concentration tends to shift the equilibrium in the opposite
direction. Consequently, addition of alkali favors the oxidation of
luciferin, and it is quite generally true that biological oxidations are
favored by an alkaline reaction. In addition oxygen in alkaline medium
has a higher oxidation potential than in neutral or acid media. I
believe this is the explanation of the action of acid in formation of
luciferin from oxyluciferin.
Addition of acid is not the only means of favoring the formation of
luciferin from oxyluciferin. Any reaction which proceeds in one
direction with evolution of light should, theoretically, proceed in the
opposite direction under the influence of light. So far as I know the
case of a reaction, photogenic in one direction and photochemical in the
other direction, has never been described, unless we are to accept the
cases of phosphorescence, for instance, the absorption of light by CaS
and its emission in the dark. However, the reaction which occurs during
phosphorescence cannot be stated.
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