7 research outputs found
A Quantum Yield Map for Synthetic Eumelanin
The quantum yield of synthetic eumelanin is known to be extremely low and it
has recently been reported to be dependent on excitation wavelength. In this
paper, we present quantum yield as a function of excitation wavelength between
250 and 500 nm, showing it to be a factor of 4 higher at 250 nm than at 500 nm.
In addition, we present a definitive map of the steady-state fluorescence as a
function of excitation and emission wavelengths, and significantly, a
three-dimensional map of the specific quantum yield: the fraction of photons
absorbed at each wavelength that are subsequently radiated at each emission
wavelength. This map contains clear features, which we attribute to certain
structural models, and shows that radiative emission and specific quantum yield
are negligible at emission wavelengths outside the range of 585 and 385 nm (2.2
and 3.2 eV), regardless of excitation wavelength. This information is important
in the context of understanding melanin biofunctionality, and the quantum
molecular biophysics therein.Comment: 10 pages, 6 figure
Quantitative photoluminescence of broad band absorbing melanins: A procedure to correct for inner filter and re-absorption effects
We report methods for correcting the photoluminescence emission and
excitation spectra of highly absorbing samples for re-absorption and inner
filter effects. We derive the general form of the correction, and investigate
various methods for determining the parameters. Additionally, the correction
methods are tested with highly absorbing fluorescein and melanin (broadband
absorption) solutions; the expected linear relationships between absorption and
emission are recovered upon application of the correction, indicating that the
methods are valid. These procedures allow accurate quantitative analysis of the
emission of low quantum yield samples (such as melanin) at concentrations where
absorption is significant.Comment: 20 pages, 13 figure
Quantitative scattering of melanin solutions
The optical scattering coefficient of a dilute, well solubilised eumelanin
solution has been accurately measured as a function of incident wavelength, and
found to contribute less than 6% of the total optical attenuation between 210
and 325nm. At longer wavelengths (325nm to 800nm) the scattering was less than
the minimum sensitivity of our instrument. This indicates that UV and visible
optical density spectra can be interpreted as true absorption with a high
degree of confidence. The scattering coefficient vs wavelength was found to be
consistent with Rayleigh Theory for a particle radius of 38+-1nm.Comment: 23 pages, 5 figure
Towards Structure-Property-Function Relationships for Eumelanin
We discuss recent progress towards the establishment of important
structure-property-function relationships in eumelanins - key functional
bio-macromolecular systems responsible for photo-protection and immune response
in humans, and implicated in the development of melanoma skin cancer. We focus
on the link between eumelanin's secondary structure and optical properties such
as broad band UV-visible absorption and strong non-radiative relaxation; both
key features of the photo-protective function. We emphasise the insights gained
through a holistic approach combining optical spectroscopy with first
principles quantum chemical calculations, and advance the hypothesis that the
robust functionality characteristic of eumelanin is related to extreme chemical
and structural disorder at the secondary level. This inherent disorder is a low
cost natural resource, and it is interesting to speculate as to whether it may
play a role in other functional bio-macromolecular systems.Comment: 19 pages, 8 figures, Invited highlight article for Soft Matte