Characterization of a nitrogen-rich fulvic acid and its precursor algae from solid state NMR

作者: Jingdong Mao , Rose M. Cory , Diane M. McKnight , Klaus Schmidt-Rohr

DOI: 10.1016/J.ORGGEOCHEM.2007.04.005

关键词: AlkylHeteroatomCarbon-13 NMRSolid-state nuclear magnetic resonanceNuclear magnetic resonance spectroscopyNitrogenChemistryCrystallographyAromaticityStereochemistrySpin diffusion

摘要: Abstract A nitrogen-rich fulvic acid (FA) from Pony Lake, a coastal pond in Antarctica, was investigated using advanced solid state nuclear magnetic resonance (NMR) techniques and compared with the precursor algal material. significant fraction of non-protonated alkyl carbons, some bonded to nitrogen, detected; most must be humification products, since they were undetectable lake algae. The corresponding branched structures account for 25–50% carbon FA. Spectral editing detected methylenes (20% all C) ethyl groups attached branch point. COOH are also enriched (∼10% C); 15N NMR spectral CH CN indicates peptides (∼1/4 C, ∼2/5 N), but spectrum exhibits bands up- downfield peptide signal; these associated 157 ppm sp2-hybridized three heteroatoms, which at least two N, according 13C{14N} SPIDER (saturation pulse induced dipolar exchange recoupling) NMR. This component, possibly degradation product penguin guano, accounts nearly half N. OCH, O–CH–O OCH2 moieties, typically found sugar rings, identified (∼12% C). quantitative 13C shows an aromaticity 8%; many aromatic carbons 1H–13C 1H spin diffusion that components within 1 nm non-polar segments, excludes polysaccharide or domains. Overall, structural differences between FA striking.

参考文章(35)
S. B. Clark, J. S. Gaffney, N. A. Marley, Humic and fulvic acids: isolation, structure, and environmental role. Proceedings of a symposium at the 210th American Chemical Society's National Meeting, Chicago, Illinois, USA, August 1995. Humic and fulvic acids: isolation, structure, and environmental role. Proceedings of a symposium at the 210th American Chemical Society's National Meeting, Chicago, Illinois, USA, August 1995.. ,(1996)
Vanessa Jane Killops, Stephen Douglas Killops, An introduction to organic geochemistry ,(1993)
Andrew E. Bennett, Chad M. Rienstra, Michèle Auger, K. V. Lakshmi, Robert G. Griffin, Heteronuclear decoupling in rotating solids The Journal of Chemical Physics. ,vol. 103, pp. 6951- 6958 ,(1995) , 10.1063/1.470372
Maria E. Uhle, Yu-Ping Chin, George R. Aiken, Diane M. McKnight, Binding of Polychlorinated Biphenyls to Aquatic Humic Substances: The Role of Substrate and Sorbate Properties on Partitioning Environmental Science & Technology. ,vol. 33, pp. 2715- 2718 ,(1999) , 10.1021/ES9808447
Wei-Guo Hu, Jingdong Mao, Baoshan Xing, Klaus Schmidt-Rohr, Poly(methylene) Crystallites in Humic Substances Detected by Nuclear Magnetic Resonance Environmental Science & Technology. ,vol. 34, pp. 530- 534 ,(2000) , 10.1021/ES990506L
Rose M. Cory, Diane M. McKnight, Fluorescence spectroscopy reveals ubiquitous presence of oxidized and reduced quinones in dissolved organic matter. Environmental Science & Technology. ,vol. 39, pp. 8142- 8149 ,(2005) , 10.1021/ES0506962
Alexandra Brown, Diane M McKnight, Yu-Ping Chin, Emily C Roberts, Maria Uhle, Chemical characterization of dissolved organic material in Pony lake, a saline coastal pond in Antarctica Marine Chemistry. ,vol. 89, pp. 327- 337 ,(2004) , 10.1016/J.MARCHEM.2004.02.016
G.R. Aiken, D.M. McKnight, K.A. Thorn, E.M. Thurman, Isolation of hydrophilic organic acids from water using nonionic macroporous resins Organic Geochemistry. ,vol. 18, pp. 567- 573 ,(1992) , 10.1016/0146-6380(92)90119-I