A perspective on the role of lanthanides in biology: Discovery, open questions and possible applications

Daumann, Lena J.; Pol, Arjan; Camp, Huub J. M. Op den; Martinez‐Gomez, N. Cecilia

doi:10.1016/bs.ampbs.2022.06.001

Cited by 11 publications

(14 citation statements)

References 94 publications

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“…SI Sections 3 and 6). The ADF calculations report −0.06 Å shorter Sm−C 9 H 9 bond length going from Sm 4f 6 to Sm 4f 5 5d 1 electronic configuration (cf. Figure 6a and Tables S2 and S3).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Photon-Modulated Bond Covalency of [Sm(II)(η⁹-C₉H₉)₂]

Vitova,

Ramanantoanina,

Schacherl

et al. 2024

J. Am. Chem. Soc.

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Lanthanides are widely assumed not to form covalent bonds due to the localized nature of their 4f valence electrons. This work demonstrates that the ionic bond of Sm(II) with cyclononatetraenyl (η 9 -C 9 H 9 − ) in [Sm(η 9 -C 9 H 9 ) 2 ] can be modulated and becomes more covalent by photon-induced transfer of Sm 4f electrons to Sm 5d orbitals. This photon-induced change in bonding properties facilitates a subsequent reconfiguration of [Sm(η 9 -C 9 H 9 ) 2 ]. As a result, Sm−C bond length contraction is detected and the local Sm coordination environment exhibits more extensive disorder. Both Sm 4f and 5d electrons have increased participation in covalent Sm−ligand interactions. The Sm L 3 -edge valence band resonant inelastic X-ray scattering (VB-RIXS), high-resolution X-ray absorption near-edge structure (HR-XANES), and quantum chemical computations showcase a spectroscopic methodology for in-depth studies of bond covalency of lanthanide atoms.

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Section: ■ Results and Discussionmentioning

confidence: 99%

“…Figure 4b). In order to demonstrate this more clearly, we simulated Sm L 3 -edge HR-XANES spectra, which are linear combinations of [Sm(η 9 -C 9 H 9 ) 2 ] 4f 6 and the Sm 2 O 3 spectra (cf. S6, Figures S8 and S9).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Photon-Modulated Bond Covalency of [Sm(II)(η⁹-C₉H₉)₂]

Vitova,

Ramanantoanina,

Schacherl

et al. 2024

J. Am. Chem. Soc.

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“…However, it should be noted that strains with lanM deletions did not exhibit obvious phenotypes during REE‐dependent growth, which may imply that LanM fulfils a different role (Fujitani et al., 2022 ). The phylogenetic distribution of LanM is also somewhat limited compared to the distribution of XoxF‐like proteins (found only in Methylobacterium , Methylorubrum and Bradyrhizobium species), suggesting that there may be alternative REE scavengers (whether protein or small molecule metallophores) in other genera (Daumann et al., 2022 ).…”

Section: Uptake Bioaccumulation and Homeostasis Of Reesmentioning

confidence: 99%

Rare earth elements in biology: From biochemical curiosity to solutions for extractive industries

Rocha,

Alexandrov,

Scott

2024

Microbial Biotechnology

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Rare earth elements (REEs) are critical for our modern lifestyles and the transition to a low‐carbon economy. Recent advances in our understanding of the role of REEs in biology, particularly methylotrophy, have provided opportunities to explore biotechnological innovations to improve REE mining and recycling. In addition to bacterial accumulation and concentration of REEs, biological REE binders, including proteins (lanmodulin, lanpepsy) and small molecules (metallophores and cofactors) have been identified that enable REE concentration and separation. REE‐binding proteins have also been used in several mechanistically distinct REE biosensors, which have potential application in mining and medicine. Notably, the role of REEs in biology has only been known for a decade, suggesting their considerable scope for developing new understanding and novel applications.

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“…In another example, the mining of lanthanide elements required for electronic devices requires industrial processes that degrade the environment (Chakhmouradian & Wall, 2012 ). Recent findings that microbes specifically acquire and utilize various lanthanide elements is leading to investigations into more environmentally friendly bio‐recovery processes (Daumann et al, 2022 ).…”

Section: Chemical Recyclingmentioning

confidence: 99%

A microbial evolutionary approach for a sustainable future

Wackett

2023

Microbial Biotechnology

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With the continued population increase, more sustainable use of water, land, air and chemicals is imperative. Microorganisms will need to be called upon to aid in many sustainability efforts. Prokaryotes are the fastest‐evolving cellular life, and most manipulatable via synthetic biology. Moreover, their natural diversity in processing organic and inorganic chemicals, and their survivability in extreme niches, make them prime agents to enlist for solving many of society's pressing problems.

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A perspective on the role of lanthanides in biology: Discovery, open questions and possible applications

Cited by 11 publications

References 94 publications

Photon-Modulated Bond Covalency of [Sm(II)(η⁹-C₉H₉)₂]

Photon-Modulated Bond Covalency of [Sm(II)(η⁹-C₉H₉)₂]

Rare earth elements in biology: From biochemical curiosity to solutions for extractive industries

A microbial evolutionary approach for a sustainable future

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A perspective on the role of lanthanides in biology: Discovery, open questions and possible applications

Cited by 11 publications

References 94 publications

Photon-Modulated Bond Covalency of [Sm(II)(η9-C9H9)2]

Photon-Modulated Bond Covalency of [Sm(II)(η9-C9H9)2]

Rare earth elements in biology: From biochemical curiosity to solutions for extractive industries

A microbial evolutionary approach for a sustainable future

Contact Info

Product

Resources

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Photon-Modulated Bond Covalency of [Sm(II)(η⁹-C₉H₉)₂]

Photon-Modulated Bond Covalency of [Sm(II)(η⁹-C₉H₉)₂]