Essenziell und weitverbreitet: Lanthanoid‐Metalloproteine

Daumann, Lena J.

doi:10.1002/ange.201904090

Cited by 11 publications

(6 citation statements)

References 65 publications

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“…Further studies of XoxFs 24,43 and functional model complexes 73 metalated with different REs, native or otherwise, will enable spectroscopic analysis of the MDH reaction mechanism, about which significant questions still exist (reviewed recently 32 ). Such studies are challenging with the spectroscopically inert Ca II .…”

Section: Lanthanoenzymesmentioning

confidence: 99%

“…93−95 As a result, several investigators speculated that lanthanides might be acquired via a lanthanophore. 32,37,39,42,57,96 In Gram-negative bacteria, Fe III –siderophore complexes are typically taken up using TonB-dependent systems comprising specific outer- and inner-membrane transporters, a periplasmic binding protein, and an enzyme for siderophore degradation for iron release. 97−99…”

Section: Lanthanide Uptakementioning

confidence: 99%

“…93,94,100 For example, Mf may not require a dedicated lanthanophore because of higher RE solubility in its acidic environmental niche. 32,43 Klebensberger has recently reported that iron interferes with lanthanide uptake in Pseudomonas putida , 101 highlighting the complexity of selective metal uptake. Finally, it is possible that some previously characterized siderophores might instead (or in addition) be lanthanophores.…”

Section: Lanthanide Uptakementioning

confidence: 99%

“…Boxes are colored according to currently known biological utilization. 32 The other two REs, Y and Sc, are not shown. The ionic radius of Y is similar to that of Ho, and abundance is similar to that of La.…”

Section: Introduction: Expanding the Bioinorganic Periodic Tablementioning

confidence: 99%

“…A central theme of this Outlook (relative to other recent reviews 21,32,35−39 ) is that the above basic principles, in the context of existing knowledge about how biology handles other metal ions, 40 anticipate the key aspects of lanthanide utilization. Results so far have revealed direct analogies between Ln III acquisition, transport, utilization, and storage to the extensively described bioinorganic chemistry of Ca II and Fe III (Figure 2), and the analogies are likely to continue as more is learned.…”

Section: Introduction: Expanding the Bioinorganic Periodic Tablementioning

confidence: 99%

See 4 more Smart Citations

The Chemistry of Lanthanides in Biology: Recent Discoveries, Emerging Principles, and Technological Applications

2019

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The essential biological role of rare earth elements lay hidden until the discovery in 2011 that lanthanides are specifically incorporated into a bacterial methanol dehydrogenase. Only recently has this observation gone from a curiosity to a major research area, with the appreciation for the widespread nature of lanthanide-utilizing organisms in the environment and the discovery of other lanthanide-binding proteins and systems for selective uptake. While seemingly exotic at first glance, biological utilization of lanthanides is very logical from a chemical perspective. The early lanthanides (La, Ce, Pr, Nd) primarily used by biology are abundant in the environment, perform similar chemistry to other biologically useful metals and do so more efficiently due to higher Lewis acidity, and possess sufficiently distinct coordination chemistry to allow for selective uptake, trafficking, and incorporation into enzymes. Indeed, recent advances in the field illustrate clear analogies with the biological coordination chemistry of other metals, particularly CaII and FeIII, but with unique twists—including cooperative metal binding to magnify the effects of small ionic radius differences—enabling selectivity. This Outlook summarizes the recent developments in this young but rapidly expanding field and looks forward to potential future discoveries, emphasizing continuity with principles of bioinorganic chemistry established by studies of other metals. We also highlight how a more thorough understanding of the central chemical question—selective lanthanide recognition in biology—may impact the challenging problems of sensing, capture, recycling, and separations of rare earths.

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Section: Lanthanoenzymesmentioning

confidence: 99%

Section: Lanthanide Uptakementioning

confidence: 99%

Section: Lanthanide Uptakementioning

confidence: 99%

Section: Introduction: Expanding the Bioinorganic Periodic Tablementioning

confidence: 99%

Section: Introduction: Expanding the Bioinorganic Periodic Tablementioning

confidence: 99%

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The Chemistry of Lanthanides in Biology: Recent Discoveries, Emerging Principles, and Technological Applications

2019

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Location‐Dependent Lanthanide Selectivity Engineered into Structurally Characterized Designed Coiled Coils

et al. 2021

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Herein we report unprecedented location-dependent, size-selective binding to designed lanthanide (Ln 3+ ) sites within miniature protein coiled coil scaffolds. Not only do these engineered sites display unusual Ln 3+ selectivity for moderately large Ln 3+ ions (Nd to Tb), for the first time we demonstrate that selectivity can be location-dependent and can be programmed into the sequence. A 1 nm linear translation of the binding site towards the N-terminus can convert a selective site into a highly promiscuous one. An X-ray crystal structure, the first of a lanthanide binding site within a coiled coil to be reported, coupled with CD studies, reveal the existence of an optimal radius that likely stems from the structural constraints of the coiled coil scaffold. To the best of our knowledge this is the first report of location-dependent metal selectivity within a coiled coil scaffold, as well as the first report of locationdependent Ln 3+ selectivity within a protein.

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Selective Confinement of Rare‐Earth‐Metal Hydrates by a Capped Metallo‐Cage under Aqueous Conditions

2022

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The properties of rare‐earth‐metal ions in aqueous media often depend on their various hydration modes, which allow them to exist as monomeric or oligomeric species with different coordination numbers. Capturing rare‐earth‐metal ions in a confined cavity can fix their hydration modes and thus enable their intrinsic properties to be distinguished. However, the isolation of ionic species from bulk aqueous media is not an easy task due to competitive interaction with bulk water. Here, we report the encapsulation of hydrated rare‐earth‐metal ions in a hydrophobic cavity of a synthetic cage. Cap‐like counter anions located at the cage's portals play an important role in capturing the rare‐earth metals at a fixed position via electrostatic interactions. Preferential encapsulation of early lanthanoid (III) ions was observed even though all the rare‐earth metals have the same hydration number and geometry, as visualized by the competitive inclusion of a dye molecule. Accordingly, the early lanthanoid ion was selectively extracted from a mixture of two rare‐earth‐metal ions.

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Essenziell und weitverbreitet: Lanthanoid‐Metalloproteine

Cited by 11 publications

References 65 publications

The Chemistry of Lanthanides in Biology: Recent Discoveries, Emerging Principles, and Technological Applications

The Chemistry of Lanthanides in Biology: Recent Discoveries, Emerging Principles, and Technological Applications

Location‐Dependent Lanthanide Selectivity Engineered into Structurally Characterized Designed Coiled Coils

Selective Confinement of Rare‐Earth‐Metal Hydrates by a Capped Metallo‐Cage under Aqueous Conditions

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