Manganese electron paramagnetic resonance

Direct methods for determining the combinational form of an element or its oxidation state include infrared absorption spectrometry, X-ray diffraction and, more recently, electron paramagnetic resonance - nuclear magnetic resonance -and Mossbauer spectrometry. With such techniques the combinational forms of major elements in soil components such as clay minerals, iron, manganese and aluminium oxyhydroxides and humic materials and the chemical structures of these soil components have been elucidated over the past 50 years. These direct, mainly non-destructive, methods for speciation are dealt with in some detail in Chapter 3 and are not further discussed here. 

Kisseleva, N., Khvorova, A., Westhof, E., and Schiemann, O. (2005). Binding of manganese (II) to a tertiary stabilized hammerhead ribozyme as studied by electron paramagnetic resonance spectroscopy. RNA 11, 1—6. 

Calhoun, B. A., J. Overmeyer, and W. Sunderman Jr. Studies of trace metal metabolism Electron paramagnetic resonance of manganese in ribonucleic acids. Proc. Soc. Exptl. Biol. Med. 119, 1089 (1965). 

Fendorf, S. E., Sparks, D. L., Franz, J. A., and Camaioni, D. M. (1993). Electron-paramagnetic resonance stopped-flow kinetic-study of manganese(II) sorption desorption on Bimessite. Soil Sci. Soc. Am. J. SI, Sl-d. 

Fig. 2. EPR spectra of pellet (upper traces) and supernatant liquid (lower traces) from sucrose-washed (A) and Tris-washed chloroplasts (B), (C) Spectra of sonicated Tris-washed chloroplasts. Figure source Blankenship and Sauer (1974) Manganese in photosynthetic oxygen evolution. I. Electron paramagnetic resonance study of the environment of manganese in Tris-washed chloroplasts. Biochim Biophys Acta 357 256, 258,...

RE Blankenship and K Sauer (1974) Manganese in photosynthetic oxygen evolution I. Electron paramagnetic resonance study of the environment of manganese in Tris-washed chloroplasts. Biochim Biophys Acta 357 252-266... 

Guiles (1988) Structure and function of the manganese complex involved in photosynthetic oxygen evolution determined by X-ray absorption spectroscopy and electron paramagnetic resonance spectroscopy. Ph D dissertation, University of California, Berkeley, CA. Lawrence Berkeley Laboratory Report, LBL-25186... 

In the case where the use of mbberized cloth bags had been permitted in lieu of polyethylene material, analyses showed the presence of high concentrations of hydrolysis products and products of reaction with the drum in all regions of the drum. Electron paramagnetic resonance measurements showed the presence of iron and manganese in the lead azide lattice, although similar measurements on recently manufactured azide showed only trace amounts of iron and no manganese. The lead azide assay was also low. 

Hoffman, B. M., T. Szymanski, T. G. Brown, and F. Basolo (1978), The Dioxygen Adducts of Several Manganese(II) Porphyrins, Electron Paramagnetic Resonance Studies. J. Am. Chem. Soc. 100, 7253-7259. 

The coordination structures of enzyme-bound manganese nucleotides can in favorable cases be determined by analysis of electron paramagnetic resonance (EPR) spectra of Mn(II) coordinated to O-labeled nucleotides. When the nucleotide is stereospecifically labeled with O at one diastereotopic position of a prochiral center, either oxygen can in principle be bound to Mn(II) in the coordination complex in an enzymic site. When the coordination bond is between Mn(II) and O, the EPR signals for Mn(II) are broadened and attenuated, owing to unresolved superhyperfine coupling between the nucleus of 0 and the unpaired electrons of Mn(II) (23). No such effect is possible with 0, which has no nuclear spin. The effect is observable in samples in which all the Mn(Il) is specifically bound in one or two defined complexes of the nucleotide with the enzyme. Thus the complex Mg(Sp)-[a- 0]ADP bound at the active site of ere-... 

CcP = Cytochrome c Peroxidase BCCP = Bacterial Cytochrome c Peroxidases APX = Soybean or pea or Tobacco Ascorbate Peroxidase MNP = Manganese Peroxidase LIP = Lignin Peroxidase EPO = Eosinophil Peroxidase LPO = Lactoperoxidase MPO = Myeloperoxidase TPO = Thyroid Peroxidase ARP = Arthomyces Ramos us Peroxidase SPO = Salivary Peroxidase PGHsynthase = Prostaglandin Hsynthase KatG = Catalase-peroxidase EPR = Electron Paramagnetic Resonance RR = Resonance Raman BHA = Benzhydroxamic Acid FA = Ferulic Acid DBNBS = 3,5-dibromo-4-nitrosobenzenesulfonic acid ABTS = 2,2 -azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) MNPr = Methylnitrosopropane INH = Isoniazid. 

McDermott E, Yachandra VK, Guiles RD et al. Characterization of the manganese 02-evolving complex and the iron-quinone acceptor complex in photosystem II from a thermophilic cyanobacterium by electron paramagnetic resonance and X-ray absorption spectroscopy Biochemistry 1988 27 4021-4031. 

The structure of this complex has been investigated by electron paramagnetic resonance spectroscopy. The complex has a characteristic signal in the S2 state [1], which has suggested either a bi or tetranuclear arrangement of manganese. Unequivocal structural predictions have not been made. 

There are five main techniques of analysis that have been used to determine dissolved manganese inductively coupled plasma (ICP) (using both emission spectroscopy and mass spectrometry detection), atomic absorption spectroscopy (AAS) (using both flame and furnace atomization), electronic spectroscopy (colorimetry), electron paramagnetic resonance spectroscopy (EPR), and anodic stripping voltammetry (ASV). 

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