Haemocyanin models

Tolman, W. B., Reactivity of dioxygen-copper systems , Chem. Rev. 2004,104, 1047-1076. 

---

Catechol oxidase and tyrosinase are among the enzymes that have Type 3 dinuclear centres. However, the prototype of this class of proteins is the invertebrate oxygen transport protein, haemocyanin (Figure 14.5), for which structures of the oxy and deoxy forms have been determined at high resolution and confirm, as predicted from model compounds, that the... 

As previously discussed, the binuclear Cu(I) haemocyanins constitute another important class of dioxygen carriers. The first model compound whose structure in the oxygenated form resembles most closely that of oxyhaemocyanin is the dicopper(II) complex with the tris(3,5-diisopro-pylpyrazolyl)borate ligand shown in Figure 26.29... 

Fig. 15. Modelling of j3-haemocyanin (H. pomatia) constructed from 160 spheres of radius 2.5 nm with overall dimensions of 39 tun (height) and 34 nm (diameter). For clarity, the 20 subunits at the inner side of the bottom are not drawn. The spheres corresponding to the one-twentieth dissociation product are shown connected by lines to indicate three adjacent units [119]. The comparison between the theoretical...

Many model compounds have been studied in attempts to understand the binding of O2 in haemocyanin, and often involve imidazole or pyrazole derivatives to represent His residues. In the light of the crystallographic data (Figure 29.8),... 

It is now known, through the modelling studies of Kitajima and the solving of the X-ray crystal structure of oxy-haemocyanin by Magnus, that there is no endogenous bridge and that the site structure is as that shown schematically in Figure 4. Therefore it is... 

---