Manganese redox cycle

W.G. Sunda, S.A. Huntsman (1990). Effects of sunlight and anthropogenic alterations in atmospheric solar attenuation on manganese redox cycles in surface seawater. In N.V. Blough and R.G. Zepp (Eds), Effects of Solar Ultraviolet Radiation on Biogeochemical Dynamics in Aquatic Environments (pp, 104-107). Technical Report No. WHOI-90-09. Woods Hole Oceanographic Institution. Woods Hole, MA. 

One-electron reduction or oxidation of organic compounds provides a useful method for the generation of anion radicals or cation radicals, respectively. These methods are used as key processes in radical reactions. Redox properties of transition metals can be utilized for the efficient one-electron reduction or oxidation (Scheme 1). In particular, the redox function of early transition metals including titanium, vanadium, and manganese has been of synthetic potential from this point of view [1-8]. The synthetic limitation exists in the use of a stoichiometric or excess amount of metallic reductants or oxidants to complete the reaction. Generally, the construction of a catalytic redox cycle for one-electron reduction is difficult to achieve. A catalytic system should be constructed to avoid the use of such amounts of expensive and/or toxic metallic reagents. 

There is evidence that it is a manganese complex that acts as a mediator in supplying the electrons [through the Mn(II)/Mn(III)/Mn(IV) redox cycle] necessary to return the photo-oxidized chlorophylls back to their reduced state. The manganese centre is able to provide the four electrons produced in the oxidation of water in four successive steps. 

This chapter discusses the chemical mechanisms influencing the fate of trace elements (arsenic, chromium, and zinc) in a small eutrophic lake with a seasonally anoxic hypolimnion (Lake Greifen). Arsenic and chromium are redox-sensitive trace elements that may be directly involved in redox cycles, whereas zinc is indirectly influenced by the redox conditions. We will illustrate how the seasonal cycles and the variations between oxic and anoxic conditions affect the concentrations and speciation of iron, manganese, arsenic, chromium, and zinc in the water column. The redox processes occurring in the anoxic hypolimnion are discussed in detail. Interactions between major redox species and trace elements are demonstrated. 

Electron transfer from the substrates to 02 proceeds by a redox cycle that consists of copper(II) and copper(I). The high catalytic activity of the copper complex can be explained as follows (1) The redox potential of Cu(I)/Cu(II) fits the redox reaction. (2) The high affinity of Cu(I) to 02 results in rapid reoxidation of the catalyst. (3) Monomers can coordinate to, and dissociate from, the copper complex, and inner-sphere electron transfer proceeds in the intermediate complex. (4) The complex remains stable in the reaction system. It may be possible to investigate other catalysts whose redox potentials can be controlled by the selection of ligands and metal species to conform with these requisites several other suitable catalysts for oxidative polymerization of phenols, such as manganese and iron complexes, are candidates on the basis of their redox potentials. 

Dinuclear Manganese Complexes as Models for the Manganese Catalase. As discussed previously, the manganese catalase has a dinuclear active site that is thought to function by cycling redox states between Mn(II)2 and Mn(III)2. Although the [Mn(IV)(salpn)(/z2-0)]2 chemistry nicely explains the alternate catalase reactions of the OEC, this system is an inappropriate model for the Mn catalase because the redox cycle in that enzyme is lower and the core structure is believed to be dramatically different. In fact, a [Mn(III/IV)(/z2-0)]2 superoxidized state of the Mn catalase has been identified and shown to be inactive. 

Sunda W. G. and Huntsman S. A. (1988) Effect of sunlight on redox cycles of manganese in the southwestern Sargasso Sea. Deep-Sea Res. 35, 1297-1317. 

A similar photochemically catalyzed redox cycle most likely occurs also for manganese. Since Mn(IV) apparently does not occur as a soluble species, the uptake of manganese occurs as Mn (Sunda and Kieber, 1994). 

Fig. 7. (A) The oxidation states of Mn in the various S-states. The model incorporates a histidine radical formation in the Sj-state with no oxidation of Mn in the Sj- Sa transition the model also accommodates the 1 0 1 2 proton-release pattern in the Kok cycle (B) a proposed topological model for the photosynthetic water-oxidizing Mn-complex based on XAS and EPR studies. Figure source (A) [adapted] and (B) Sauer, Yachandra, Britt and Klein (1992) The photosynthetic water oxidation complex studied by EPR and X-ray absorption spectroscopy. In VL Pecararo (ed) Manganese Redox Enzymes, pp 141-175. VCH Publ.

Mn CATs from Thermus thermophilus and Lactobacillus plantarum contain a binuclear manganese cluster. The mechanism of catalysis involves two-electron redox cycling of the binuclear manganese cluster between the divalent and trivalent states Mn -Mn oMn +-Mn + [205] ... 

In natural systems microbiological oxidation may offer a faster pathway, particularly at pH < 8 and low concentrations (<5 jlM) of particulate oxides. Hastings and Emerson (17) showed that sporulated cultures of marine bacillus SG-1 at pH 7.5 accelerated the oxidation of Mn(II) by a factor of 104 with respect to the abiotic catalysis on a colloidal MnOz surface. A radiotracer study of microbial Mn oxidation in a marine fjord revealed half-lives as short as 2 days (18). Perhaps microorganisms can use the entire redox cycle of manganese. A study indicates that the vegetative cells of spores that mediate Mn(II) oxidation also reduce manganese oxides (19). 

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