The mineralization
of collagen via synthetic procedures has been
extensively investigated for hydroxyapatite as well as for silica
and calcium carbonate. From a fundamental point of view, it is interesting
to investigate whether collagen could serve as a generic mineralization
template for other minerals, like iron oxides. Here, bio-inspired
coprecipitation reaction, generally leading to the formation of magnetite,
is used to mineralize collagen with iron hydroxides. Platelet-shaped
green rust crystals form outside the collagen matrix, while inside
the collagen, nanoparticles with a size of 2.6 nm are formed, which
are hypothesized to be iron (III) hydroxide. Mineralization with nanoparticles
inside the collagen solely occurs in the presence of poly(aspartic
acid) (pAsp). In the absence of pAsp, magnetite particles are formed
around the collagen. Time-resolved cryo-TEM shows that during the
coprecipitation reaction, initially a beam-sensitive phase is formed,
possibly an Fe
3+
–pAsp complex. This beam-sensitive
phase transforms into nanoparticles. In a later stage, sheet-like
crystals are also found. After 48 h of mineralization, ordering of
the nanoparticles around one of the collagen sub-bands (the a-band)
is observed. This is very similar to the collagen–hydroxyapatite
system, indicating that mineralization with iron hydroxides inside
collagen is possible and proceeds via a similar mechanism as hydroxyapatite
mineralization.