The first definite discovery of a lichen-acid was made towards the
beginning of the nineteenth century and is due to the researches of C.
H. Pfaff[813]. He was engaged in an examination of _Cetraria islandica_,
the Iceland Moss, which in his time was held in high repute, not only as
a food but as a tonic. He wished to determine the chemical properties
of the bitter principle contained in it, which was so much prized by
the Medical Faculty of the period, though the bitterness had to be
removed to render palatable the nutritious substance of the thallus. He
succeeded in isolating an acid which he tested and compared with other
organic acids and found that it was a new substance, nearest in chemical
properties to succinic acid. In a final note, he states that the new
“lichen-acid,” as he named it, approached still nearer to boletic acid,
a constituent of a fungus, though it was distinct from that substance
also in several particulars. The name “cetrarin” was proposed, at a
later date, by Herberger[814] who described it as a “subalkaloidal
substance, slightly soluble in cold water to which it gives a bitter
taste; soluble in hot water, but, on continued boiling, throwing down a
brown powder which is slightly soluble in alcohol and readily soluble in
ether.” Knop and Schnederman[815] found that Herberger’s “cetrarin” was
a compound substance and contained besides other substances “cetraric
acid” and lichesterinic acid. It has now been determined by Hesse[816] as
fumarprotocetraric acid (C₆₂H₅₀O₃₅), a derivative of which is cetraric
acid or triaethylprotocetraric acid with the formula C₅₄H₃₉O₂₄(OC₂H₅)₃
and not C₂₀H₁₈O₉ as had been supposed. Cetraric acid has not yet been
isolated with certainty from any lichen[817].
After this first isolation of a definite chemical substance, further
research was undertaken, and gradually a number of these peculiar acids
were recognized, the lichens examined being chiefly those that were of
real or supposed economic value either in medicine or in the arts. In
late years a wider chemical study of lichen products has been vigorously
carried on, and the results gained have been recently arranged and
published in book form by Zopf[818]. Many of the statements on the
subject included here are taken from that work. Zopf gives a description
of all the acids that had been discovered up to the date of publication,
and the methods employed for extracting each substance. The structural
formulae, the various affinities, derivatives and properties of the
acids, with their crystalline form, are set forth along with a list of
the lichens examined and the acids peculiar to each species. In many
instances outline figures of the crystals obtained by extraction are
given. For a fuller treatment of the subject, the student is referred to
the book itself, as only a general account can be attempted here.
Public-domain text, read in full here on John Shaqi.
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