The beta-sandwich cupredoxin Plastocyanin (Pc) was found to self-assemble in the
presence of Zn(2+), a known mediator of protein-protein interfaces.
Diffraction-quality crystals of Pc grew from solutions containing zinc acetate
as the sole precipitant. Di- and trinuclear zinc sites contribute to the crystal
contacts in this structure. A different crystal form, also involving numerous
zinc bridging ions, was obtained in the presence of poly(ethylene glycol) 8 000.
Comparison of the two crystal forms reveals the effect of macromolecular
crowding on self-assembly. Solution-state structural characterisation of the
Zn(2+)-mediated Pc oligomers was performed by using a combination of chemical
shift perturbation mapping and small-angle X-ray scattering. The data indicate
the formation of dimers in solution. The implications for metal-mediated
assembly and crystallisation are discussed.