Alcoholic Fermentation: Second Edition, 1914Harden, Arthur
Science
Alcoholic Fermentation: Second Edition, 1914
Harden, Arthur
Fermentation
The spontaneous production of ketonic aldehydes from amino-acids and
from hydroxy-acids in aqueous solution, which has been demonstrated by
Dakin and Dudley [1913], points however to the possibility that the
ketonic acid may be a secondary product derived from the corresponding
ketonic aldehyde [see also Dakin, 1908; Neuberg, 1908, 1909]. This
itself may either arise directly from the amino-acid or from a
previously formed hydroxy-acid, the latter alternative being, however,
improbable in view of the small yield of alcohol obtained from
hydroxy-acids by the action of yeast in the experiments of Neubauer
and Fromherz.
R·CH(NH{2})·COOH → R·CH(OH)·COOH
R·CH(NH{2})·COOH ⇌ R·CO·CHO
R·CO·CHO ⇌ R·CH(OH)·COOH
2R·CO·CHO + O{2} → 2R·CO·COOH
(2) Whatever be the exact mode by which the ketonic acid is formed,
it appears most probable that a compound of this nature forms the
starting-point for the next stage in the production of the alcohols.
The researches of Neuberg, which have already been discussed on p.
81, have revealed a mechanism in yeast--the enzyme carboxylase--by
which these α-ketonic acids are rapidly broken up into an aldehyde and
carbon dioxide:
R·CO·COOH = R·CHO + CO{2}
and it can scarcely be doubted that this is the actual course of the
reaction.
(3) The final conversion of the aldehyde into the corresponding
alcohol is also a change which it has been proved can be effected
by yeast [Neuberg and Rosenthal, 1913] probably by the aid of the
reductase which is one of the weapons in its armoury of enzymes.
Yeast is capable of producing many vigorous reducing actions and
rapidly reduces methylene blue and sodium selenite. It is in all
probability due to a reaction of this kind that the iso-amylaldehyde
and isovaleraldehyde were reduced to the alcohols in Neuberg and
Steenbock's experiments [1913, 1914], and that considerable quantities
of ethyl alcohol are formed in the sugar free fermentation of pyruvic
acid [Neuberg and Kerb, 1913, 1] (see later p. 110 for a discussion of
this question).
A further possibility exists that in some cases the aldehyde may
[p094] be simultaneously oxidised and reduced or the molecule of one
aldehyde reduced and that of another oxidised with production of the
corresponding acid and alcohol by an "aldehydo-mutase," similar to
that which has been observed by Parnas [1910] in many animal tissues.
Finally the aldehyde may simply be converted into the corresponding
acid by oxidation as appears to take place in the formation of
succinic acid.
The intermediate production of an aldehyde would thus be consistent
both with the production of alcohols and acids from amino-acids.
Fusel oil would be formed by the reduction of the aldehydes arising
from the simple monobasic amino-acids, succinic acid would be produced
by oxidation of the aldehyde derived from the dibasic glutamic acid.
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