Alcoholic Fermentation: Second Edition, 1914Harden, Arthur
Science
Alcoholic Fermentation: Second Edition, 1914
Harden, Arthur
Fermentation
(/a/) A small portion of this is converted by a reaction which may be
variously interpreted as a Cannizzaro transformation or a reductase
reaction into glycerol and pyruvic acid.
CH{2}:C(OH)·CHO + H{2}O H{2} CH{2}(OH)·CH(OH)·CH{2}(OH)
│ glycerol
+ │ = +
CH{2}:C(OH)·CHO O CH{2}:C(OH)·COOH
Pyruvic acid
(/b/) The pyruvic acid is then decomposed by carboxylase yielding
aldehyde and carbon dioxide (equation 2, p. 109). [p114]
(/c/) The aldehyde and a molecule of glyoxal then undergo a Cannizzaro
reaction and yield alcohol and pyruvic acid,
CH{3}·CO·CHO O CH{3}·CO·COOH
+ │ = +
CH{3}·CHO H{2} CH{3}·CH{2}(OH)
and the latter then undergoes reaction (/b/).
A small amount of glycerol is thus necessarily formed, as is actually
found to be the case.
The experimental foundation for stages (/a/) and (/c/) will be awaited
with great interest, as well as the proof that methylglyoxal is
readily fermentable (see p. 104).
THE FORMIC ACID THEORY.
An interesting interpretation of the phenomena of fermentation was
attempted by Schade [1906] based upon the conception that glucose
under the influence of catalytic agents readily decomposes into
acetaldehyde and formic acid. It was subsequently found that the
experimental evidence upon which this conclusion was founded had
been wrongly interpreted [Buchner, Meisenheimer, and Schade, 1906;
Schade, 1907], but Schade has succeeded in devising an interesting
series of reactions by means of which alcohol and carbon dioxide can
be obtained from sugar by the successive action of various catalysts.
The following are the stages of this series: (1) Glucose, fructose,
and mannose are converted by alkalis into lactic acid along with other
products. (2) Lactic acid when heated with dilute sulphuric acid
yields a mixture of acetaldehyde and formic acid:--
CH{3}·CH(OH)·COOH = CH{3}·CHO + H·COOH.
(3) It has long been known that formic acid is catalysed by metallic
rhodium at the ordinary temperature into hydrogen and carbon dioxide,
and Schade has found that when a mixture of acetaldehyde and formic
acid is submitted to the action of rhodium the acetaldehyde is reduced
to alcohol at the expense of the hydrogen and the carbon dioxide is
evolved:--
CH{3}·CHO + H·COOH = CH{3}·CH{2}(OH) + CO{2}.
Schade suggests [1908] that the fermentation of sugar may proceed by a
similar series of reactions catalysed by enzymes, the acetaldehyde and
formic acid being derived not from the relatively stable lactic acid
but more probably from a labile substance capable of undergoing change
either into lactic acid or into aldehyde and formic acid.
Public-domain text, read in full here on John Shaqi.
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