Ultrafast pump–probe measurements
can discriminate the two forms of melanin found in biological tissue
(eumelanin and pheomelanin), which may be useful for diagnosing and
grading melanoma. However, recent work has shown that bound iron content
changes eumelanin’s pump–probe response, making it more
similar to that of pheomelanin. Here we record the pump–probe
response of these melanins at a wider range of wavelengths than previous
work and show that with shorter pump wavelengths the response crosses
over from being dominated by ground-state bleaching to being dominated
by excited-state absorption. The crossover wavelength is different
for each type of melanin. In our analysis, we found that the mechanism
by which iron modifies eumelanin’s pump–probe response
cannot be attributed to Raman resonances or differences in melanin
aggregation and is more likely caused by iron acting to broaden the
unit spectra of individual chromophores in the heterogeneous melanin
aggregate. We analyze the dependence on optical intensity, finding
that iron-loaded eumelanin undergoes irreversible changes to the pump–probe
response after intense laser exposure. Simultaneously acquired fluorescence
data suggest that the previously reported “activation”
of eumelanin fluorescence may be caused in part by the dissociation
of metal ions or the selective degradation of iron-containing melanin.
As the most common pitfall in diagnosing adrenal cortical carcinoma is mistaking it for pheochromocytoma or vice versa, GATA3 may be useful in narrowing the differential diagnosis as a part of a panel of immunohistochemical markers. However, occasional GATA3 expression in the most common source of metastases within the adrenal gland, metastatic pulmonary adenocarcinoma, may confound the diagnosis due to the overlapping expression with pheochromocytoma and other carcinomas.
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