Manganese L-Edge X-ray Absorption Spectroscopy of Manganese Catalase from <i>Lactobacillus plantarum</i> and Mixed Valence Manganese Complexes

Grush, Melissa M.; Chen, J.; Stemmler, Timothy L.; George, Simon J.; Ralston, Corie Y.; Stibrany, Robert T.; Gelasco, Andrew; Christou, George; Gorun, Sergiu M.; Penner‐Hahn, James E.; Cramer, Stephen P.

doi:10.1021/ja951614k

Cited by 73 publications

(60 citation statements)

References 27 publications

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“…Spectroscopic assignments of the C K-edge NEXAFS are based on the absorption maxima of the pure reagents, glucose (!99% purity, Sigma Aldrich), glycine (!99% purity, Sigma Aldrich) and pyrogallol (!99% purity, Sigma Aldrich), and on values reported by previous C NEXAFS studies (Myneni 2002;Urquhart and Ade 2002;Dhez et al 2003;Cooney and Urquhart 2004). Spectroscopic assignments of the Mn L-edge NEXAFS are based on the absorption maxima of the Mn reference compounds, MnCO 3 (99.99% purity, Sigma Aldrich), Mn 2 O 3 (!98% purity, Alfa Aesar), and a-MnO 2 (!99% purity, Sigma Aldrich), and are in agreement with the results of previous Mn L-edge studies (Garvie and Craven 1994;Grush et al 1996).…”

Section: Near Edge X-ray Absorption Fine Structure Spectroscopysupporting

confidence: 90%

“…The Mn L-edge spectra of the solid residues from the Maillard and integrated catechol-Maillard reaction systems show that Mn was in the divalent form in these systems ( Fig. 4a and b) and bonded to either O or N in octahedral conformation (Grush et al 1996). The minor absorption peak to the left of the maximum absorption peak (640.3 eV) is not resolved in the spectrum of the solid residue from the integrated equimolar catecholMaillard reaction system (Fig.…”

Section: Resultsmentioning

confidence: 94%

“…4. The Mn L 2,3 -edges provide a sensitive fingerprint of the valence of Mn based on the absorption maxima and shape of the spectra, and in some cases the site symmetry and ligands can also be identified (Garvie and Craven 1994;Grush et al 1996). The Mn L-edge spectra of the solid residues from the Maillard and integrated catechol-Maillard reaction systems show that Mn was in the divalent form in these systems ( Fig.…”

Section: Resultsmentioning

confidence: 99%

“…3a). The ionic character of the compound determines whether the low-energy shoulder is resolved, being only resolved in more ionic compounds (Grush et al 1996). Thus, the Mn(II) in the solid residue from the integrated catechol-Maillard system (Fig.…”

Section: Resultsmentioning

confidence: 99%

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Biomolecule-induced carbonate genesis in abiotic formation of humic substances in nature

Hardie¹,

Dynes²,

Kozak³

et al. 2009

Can. J. Soil. Sci.

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Hardie, A. G., Dynes, J. J., Kozak, L. M. and Huang, P. M. 2009. Biomolecule-induced carbonate genesis in abiotic formation of humic substances in nature. Can. J. Soil Sci. 89: 445Á453. Most soil C sequestration research has focused on organic C stabilization, while carbonate precipitation has received little attention. Mineral colloids can accelerate abiotic humification reactions of biomolecules such as amino acids, sugars, and polyphenols, derived from the breakdown of biological residues and metabolites. During these reactions CO 2 is produced as a result of the oxidation of biomolecules. However, the biomolecule-induced formation of carbonate during abiotic humification remained to be uncovered. Here we demonstrate using X-ray diffraction, Fourier transform infrared spectroscopy and C K-edge and Mn L-edge near edge X-ray absorption fine structure spectroscopy that the Maillard reaction (glucose and glycine) and the integrated polyphenol-Maillard reaction pathway (catechol, glucose and glycine), in the presence of birnessite (d-MnO 2 ) produce MnCO 3 (rhodochrosite). Increasing the molar ratio of catechol to glucose and glycine dramatically hampered carbonate formation, which is attributed to the enhanced formation of humic polymers, which increased proton generation and perturbed rhodochrosite crystallization through Mn(II)-humic complexation in the reaction systems. Thus, rhodochrosite formation was a competing reaction with humic substance formation. Our findings are of fundamental significance in understanding the vital role of the nature and relative abundance of biomolecules in abiotic carbonate formation, which merits close attention in understanding and regulating C sequestration in natural environments. . Gene`se de carbonates sous l'effet des biomole´cules durant la formation abiotique des substances humiques dans la nature. Can. J. Soil Sci. 89: 445Á453. La majeure partie des recherches sur la se´questration du C dans le sol se concentrent sur la stabilisation du C et on s'est peu attarde´a`la pre´cipitation des carbonates. Or, les colloı¨des mine´raux peuvent acce´le´rer les re´actions d'humification abiotiques des biomole´cules tels les acides amine´s, les sucres et les polyphe´nols, issues de la de´composition des re´sidus biologiques et des me´tabolites. Pendant ces re´actions, l'oxydation des biomole´cules libe`re du CO 2 . Ne´anmoins, on ne sait toujours pas grand-chose de la formation des carbonates induite par les biomole´cules durant l'humification abiotique. Les auteurs ont recouru a`la spectroscopie XRD, FTIR et NEXAFS C au seuil K pour le C et au seuil L pour le Mn afin de montrer que la re´action de Maillard (glucose et glycine) et que la voie inte´grant les polyphe´nols et la re´action de Maillard (cate´chol, glucose et glycine) produisent du MnCO 3 (rhodochrosite) en pre´sence de birnessite (d-MnO 2 ). En augmentant le rapport molaire du cate´chol avec le glucose et la glycine, on entrave conside´rablement la formation de carbonates, ce qu'on attribue a`la synthe`se accrue de polyme...

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Section: Near Edge X-ray Absorption Fine Structure Spectroscopysupporting

confidence: 90%

Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Biomolecule-induced carbonate genesis in abiotic formation of humic substances in nature

Hardie¹,

Dynes²,

Kozak³

et al. 2009

Can. J. Soil. Sci.

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“…[6][7][8][9][10][11][12][13][14][15] For Mn see Refs. 16 Here we focus on the crystal field generated by the negatively charged N atoms surrounding the central metal ion of porphyrins and phthalocyanines. Usually, the HOMO is located at the metal atom and the LUMO is delocalized over the N atoms and the surrounding π -system.…”

Section: Introductionmentioning

confidence: 99%

Crystal fields of porphyrins and phthalocyanines from polarization-dependent 2p-to-3d multiplets

Johnson

Garcı́a-Lastra

Kennedy

et al. 2014

The Journal of Chemical Physics

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Polarization-dependent X-ray absorption spectroscopy is combined with density functional calculations and atomic multiplet calculations to determine the crystal field parameters 10Dq, Ds, and Dt of transition metal phthalocyanines and octaethylporphyrins (Mn, Fe, Co, Ni). The polarization dependence facilitates the assignment of the multiplets in terms of in-plane and out-of-plane orbitals and avoids ambiguities. Crystal field values from density functional calculations provide starting values close to the optimum fit of the data. The resulting systematics of the crystal field can be used for optimizing electron-hole separation in dye-sensitized solar cells. © 2014 AIP Publishing LLC.

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Absorption Techniques inX‐Ray Spectrometry

Kawai

2000

Encyclopedia of Analytical Chemistry

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X‐ray absorbance depends on the wavelength of the X‐rays, atomic number, chemical environment, and concentration of analyte. X‐ray absorption spectrometry is a technique for analyzing the chemical environment of an element in an unknown material. This method is closely related to photoelectron spectroscopy, Auger electron spectroscopy, and X‐ray fluorescence spectroscopy. Chemical information in the chemical shift and line shape of XANES (X‐ray absorption near‐edge structure) spectra is described. The history and theory of EXAFS (extended X‐ray absorption fine structure) are discussed in relation to other experimental techniques. Data analysis methods, databases, software packages, instrumentation, and synchrotron radiation facilities for X‐ray absorption analysis are overviewed. Alternative methods such as electron energy loss spectroscopy (EELS), self‐absorption effect, extended X‐ray emission fine structure (EXEFS), X‐ray Raman scattering, diffraction anomalous fine structure (DAFS), β‐environment fine structure (BEFS), and inverse photoemission spectroscopy (IPES) are also described.

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Manganese L-Edge X-ray Absorption Spectroscopy of Manganese Catalase from Lactobacillus plantarum and Mixed Valence Manganese Complexes

Cited by 73 publications

References 27 publications

Biomolecule-induced carbonate genesis in abiotic formation of humic substances in nature

Biomolecule-induced carbonate genesis in abiotic formation of humic substances in nature

Crystal fields of porphyrins and phthalocyanines from polarization-dependent 2p-to-3d multiplets

Absorption Techniques inX‐Ray Spectrometry

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