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The Earlier the Better: Structural Analysis and Separation of Lanthanides with Pyrroloquinoline Quinone
Author(s) -
Lumpe Henning,
Menke Annika,
Haisch Christoph,
Mayer Peter,
Kabelitz Anke,
Yusenko Kirill V.,
Guilherme Buzanich Ana,
Block Theresa,
Pöttgen Rainer,
Emmerling Franziska,
Daumann Lena J.
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202002653
Subject(s) - pyrroloquinoline quinone , chemistry , lanthanide , europium , cofactor , dimer , infrared spectroscopy , mass spectrometry , context (archaeology) , crystallography , enzyme , organic chemistry , chromatography , ion , paleontology , biology
Lanthanides (Ln) are critical raw materials, however, their mining and purification have a considerable negative environmental impact and sustainable recycling and separation strategies for these elements are needed. In this study, the precipitation and solubility behavior of Ln complexes with pyrroloquinoline quinone (PQQ), the cofactor of recently discovered lanthanide (Ln) dependent methanol dehydrogenase (MDH) enzymes, is presented. In this context, the molecular structure of a biorelevant europium PQQ complex was for the first time elucidated outside a protein environment. The complex crystallizes as an inversion symmetric dimer, Eu 2 PQQ 2 , with binding of Eu in the biologically relevant pocket of PQQ. LnPQQ and Ln1Ln2PQQ complexes were characterized by using inductively coupled plasma mass spectrometry (ICP‐MS), infrared (IR) spectroscopy, 151 Eu‐Mössbauer spectroscopy, X‐ray total scattering, and extended X‐ray absorption fine structure (EXAFS). It is shown that a natural enzymatic cofactor is capable to achieve separation by precipitation of the notoriously similar, and thus difficult to separate, lanthanides to some extent.