Autoxidation of dopamine
to polydopamine by dissolved oxygen is
a slow process that requires highly alkaline conditions. Polydopamine
can be formed rapidly also in mildly acidic and neutral solutions
by using redox-active transition-metal ions. We present a comparative
study of polydopamine nanoparticles formed by autoxidation and aerobic
or anaerobic oxidation in the presence of Ce(IV), Fe(III), Cu(II),
and Mn(VII). The UV–vis spectra of the purified nanoparticles
are similar, and dopaminechrome is an early intermediate species.
At low pH, Cu(II) requires the presence of oxygen and chloride ions
to produce polydopamine at a reasonable rate. The changes in dispersibility
and surface charge take place at around pH 4, which indicates the
presence of ionizable groups, especially carboxylic acids, on their
surface. X-ray photoelectron spectroscopy shows the presence of three
different classes of carbons, and the carbonyl/carboxylate carbons
amount to 5–15 atom %. The N 1s spectra show the presence of
protonated free amino groups, suggesting that these groups may interact
with the π-electrons of the intact aromatic dihydroxyindole
moieties, especially in the metal-induced samples. The autoxidized
and Mn(VII)-induced samples do not contain metals, but the metal content
is 1–2 atom % in samples prepared with Ce(IV) or Cu(II), and
ca. 20 atom % in polydopamine prepared in the presence of Fe(III).
These differences in the metal content can be explained by the oxidation
and complexation properties of the metals using the general model
developed. In addition, the nitrogen content is lower in the metal-induced
samples. All of the metal oxidants studied can be used to rapidly
prepare polydopamine at room temperature, but the possible influence
of the metal content and nitrogen loss should be taken into account.