Paramagnetic resonance investigation of mono- and di-manganese-containing systems in biochemistry.

Although not as important as iron, manganese is one of the key transition metal (d block) elements in biochemistry. The role of Mn in photosynthesis is perhaps its "starring role," but has been extensively covered elsewhere and will not be discussed in this chapter. In contrast to iron, for which Fe Mӧssbauer effect (nuclear gamma resonance) spectroscopy is available, Mn (100% abundant) lacks this ability. Instead, the defining technique for Mn is electron paramagnetic resonance (EPR) spectroscopy, as Mn(II), Mn(IV), and even Mn(III), as well as certain di-Mn systems are generally EPR active. This chapter describes how EPR and its advanced derivatives, electron spin echo envelope modulation (ESEEM) and electron-nuclear/electron-electron double resonance (ENDOR/ELDOR) spectroscopies, provide valuable biochemical information on many Mn-containing systems. These include endogenous Mn in mono- and di-Mn (protein) enzymes as well as brief mention of applications to Mn in non-protein biological systems.