TY - JOUR
T1 - The Chemistry of Lanthanides in Biology
T2 - Recent Discoveries, Emerging Principles, and Technological Applications
AU - Cotruvo, Joseph A.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/9/25
Y1 - 2019/9/25
N2 - 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.
AB - 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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U2 - 10.1021/acscentsci.9b00642
DO - 10.1021/acscentsci.9b00642
M3 - Article
C2 - 31572776
AN - SCOPUS:85076390530
SN - 2374-7943
VL - 5
SP - 1496
EP - 1506
JO - ACS Central Science
JF - ACS Central Science
IS - 9
ER -