DOPA melanins
A cautionary note: a large amount of work has been published
on human melanin, which we will refer to as DOPA
melanin, since DOPA (dihydroxyphenylalanine, an oxidation
product of tyrosine) is its monomer. The involvement of
DOPA melanin in skin cancers (malignant melanoma) and in
brain disorders such as Parkinson’s disease accounts for the
sustained volume of research and publishing on the structure
and biochemistry of DOPA melanins. A book by Prota
(1992) provides a comprehensive discussion of DOPA
melanins.
The melaninology neophyte must apply caution in assuming
that a fungal melanin is of DOPA origin. There are many
fungi that are never known to produce any form of melanin
under normal growth conditions but will produce DOPA
melanin if DOPA is fed to colonies on agar. DOPA will
spontaneously oxidize to form melanin when in mildly alkaline
solution without any enzymatic intervention. There are
also numerous enzymes, such as laccase, polyphenoloxidases,
and perhaps peroxidases and catalases, that are
found in the cell walls and environs of normally
nonmelanized fungi that will form black polymers from applied
solutions of DOPA. This may lead to erroneous assumptions
about the nature of the monomer of fungal
melanins. The native melanin of the black yeast
Phaeococcomyces, for instance, is known to be of DHN origin
(Butler 1987; Butler et al. 1989), but albino mutant colonies
on agar will blacken when overlaid with drops of
L-DOPA solution. Numerous fungi now known to produce
DHN melanin were previously reported to produce DOPA
melanins (Bell and Wheeler 1986).
It has been claimed for many years that mushroomproducing
fungi produce DOPA melanins; indeed, mushroom
tyrosinase has been a common term applied to the
phenoloxidase that is routinely used for the formation of
synthetic DOPA melanin by enzymatic oxidation (e.g., Prota
1992). The fungal genus Tuber (of truffle fame) is reported
to synthesise DOPA melanin (Miranda et al. 1992).
The yeast Cryptococcus neoformans causes potentially fatal
meningoencephalitis in 5–10% of AIDS patients and may
form DOPA melanin from dopamine, a brain neurotransmitter
(Wang and Casadevall 1994). This yeast apparently
forms melanin at the cell wall using laccase and, curiously,
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seems to be a rare example of a melanin-forming fungus that
does not synthesize the monomer to its own integrated cell
wall melanin but forms the melanin at the cell wall from exogenously
supplied substrate (i.e., the yeast does not have its
own melanin precursor pathway). Perhaps this attests to the
parasitic nature of this yeast, since theft of needed molecules
from the host, rather than going to the expense of synthesis,
is a tactic of parasites