History of Chemistry, Volume 2 (of 2): From 1850 to 1910Thorpe, T. E. (Thomas Edward)
History
History of Chemistry, Volume 2 (of 2): From 1850 to 1910
Thorpe, T. E. (Thomas Edward)
Chemistry -- History
The ferments known as _enzymes_ are also found to possess the power
of selection, behaving differently towards the different optically
active modifications of the same substance. It is frequently observed
that an optically active substance may be rendered inactive by the
conversion of half the substance into its enantiomorph. This operation
was first performed by Pasteur, and may be brought about by heating
the substance, either alone or with water, under pressure. Indeed, it
is occasionally observed to take place at the ordinary temperature
(_autoracemisation_).
By the action of various reagents the derivatives of an optically
active substance are found not unfrequently to change the direction of
their optical activity. Indeed, by such means one enantiomorph may be
changed into another. Thus _lævo_-menthol may be converted into the
_dextro_-modification by treatment with sulphuric acid.
The rotatory power of a substance is frequently modified by the
character of its solvent, and varies with the temperature and
concentration of the solution. Landolt and Oudemans found that the
specific rotation of dilute solutions of tartrates and of salts of the
active alkaloids was independent of the nature of the base and acid
respectively present—a fact which finds its explanation in the theory
of electrolytic dissociation. It has been known for some years past
that the specific rotation of solutions of certain sugars changes with
time, being sometimes less and sometimes more than the initial amount.
This phenomenon is now known as _multirotation_, or _mutarotation_. It
seems to be connected with an alteration in the configuration of the
molecules.
There is a special case of stereo-isomerism, differing from that
of optical isomerism and of structural isomerism (with which we
have hitherto been alone concerned), which was predicted by Van ’t
Hoff in his remarkable work _La Chimie dans l’Espace_, published in
1877—noteworthy as being the first serious attempt to grapple with
the problem of spatial molecular grouping, foreshadowed by Wollaston,
Berzelius, and, indeed, all the early philosophic thinkers who accepted
the atomic theory. The special form of stereo-isomerism now referred
to, which has been more particularly investigated by Wislicenus, is
distinguished as _geometrical isomerism_; not, perhaps, a sufficiently
descriptive term, since, comprehensively, all forms of isomerism are
really cases of geometrical isomerism. Instances of it are to be
met with among the isomeric acids existing as glycerides in certain
fats, in cinnamic acid, in stilbene and its derivatives, etc. It was
first observed in _maleic_ and _fumaric acids_—isomeric acids of the
empirical formula C2H2 (COOH)2, obtained by the distillation of malic
acid, the characteristic acid met with in the apple and other fruits
and in certain other vegetal products. These acids may be represented
by the following space formulæ:
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