Lanthanide Chemistry: From Coordination in Chemical Complexes Shaping Our Technology to Coordination in Enzymes Shaping Bacterial Metabolism

Abstract

Lanthanide chemistry has only been extensively studied for the last 2 decades, when it was recognized that these elements have unusual chemical characteristics including fluorescent and potent magnetic properties because of their unique 4f electrons.1,2 Chemists are rapidly and efficiently integrating lanthanides into numerous compounds and materials for sophisticated applications. In fact, lanthanides are often referred to as "the seeds of technology" because they are essential for many technological devices including smartphones, computers, solar cells, batteries, wind turbines, lasers, and optical glasses.3-6 However, the effect of lanthanides on biological systems has been understudied. Although displacement of Ca by lanthanides in tissues and enzymes has long been observed,7 only a few recent studies suggest a biological role for lanthanides based on their stimulatory properties toward some plants and bacteria.8,9 Also, it was not until 2011 that the first biochemical evidence for lanthanides as inherent metals in bacterial enzymes was published.10 This forum provides an overview of the classical and current aspects of lanthanide coordination chemistry employed in the development of technology along with the biological role of lanthanides in alcohol oxidation. The construction of lanthanide-organic frameworks will be described. Examples of how the luminescence field is rapidly evolving as more information about lanthanide-metal emissions is obtained will be highlighted, including biological imaging and telecommunications.11 Recent breakthroughs and observations from different exciting areas linked to the coordination chemistry of lanthanides that will be mentioned in this forum include the synthesis of (i) macrocyclic ligands, (ii) antenna molecules, (iii) coordination polymers, particularly nanoparticles, (iv) hybrid materials, and (v) lanthanide fuel cells. Further, the role of lanthanides in bacterial metabolism will be discussed, highlighting the discovery that lanthanides are cofactors in biology, particularly in the enzymatic oxidation of alcohols. Finally, new and developing chemical and biological lanthanide mining and recycling extraction processes will be introduced.

Functional Role of Lanthanides in Enzymatic Activity and Transcriptional Regulation of Pyrroloquinoline Quinone-Dependent Alcohol Dehydrogenases in Pseudomonas putida KT2440

“…In addition, a very recent publication described the first lanthanide-dependent ethanol dehydrogenase in Methylobacterium extorquens AM1 (16). As a consequence, REM-dependent enzymes and the microorganisms that produce them have sparked a lot of academic and commercial interest, as they might be exploited in a broad variety of biotechnological fields (35, 36). Potential applications range from the development of new biocatalysts and biosensors to the use of the associated microorganisms in REM biomining, bioleaching, and recycling processes.…”

Nucleic Acid Catalysis under Potential Prebiotic Conditions

“…Lanthanides (Ln 3+ ) are also of interest, as their interactions with nucleic acids are very different from typical divalent metal ions due to their unusual coordination chemistry. In particular, the absence of a strong ligand field allows for a high degree of structural diversity in lanthanide complexes, as ligands alone dictate the symmetry and coordination of complexes . As a result, lanthanides not only show a high affinity to the phosphate backbone of nucleic acids due to their high charge density (typically only μ m concentrations are required for binding), but they can also directly interact with the nucleobase moieties .…”

“…[77] Lanthanides( Ln 3 + )a re also of interest, as their interactions with nucleic acids are very different from typical divalent metal ions due to their unusual coordination chemistry.I np articular, the absence of as trong ligand fielda llows for ahighdegree of structurald iversity in lanthanide complexes, as ligands alone dictate the symmetry and coordination of complexes. [86] As a result, lanthanides not only show ah igh affinity to the phosphate backboneo fn ucleic acids due to their high charge density (typically only mm concentrationsa re required for binding), but they can also directly interactw ith the nucleobase moieties. [87] Because of these unusual properties, the impact of lanthanideso nn ucleic acid catalysis is rather diverse:L n 3 + ions can accelerate as mall Pb 2 + -dependentr ibozymec alled the leadzyme, [88] yet they inhibit the hammerhead [89] and hairpin [90] ribozymes,a nd the RNA-cleaving 8-17 DNAzyme.…”

Essenziell und weitverbreitet: Lanthanoid‐Metalloproteine

“…Eine 2017 verçffentliche Studie zeigte,d ass im Meerwasser um die Deep-Water-Horizon-Ölbohrplattform hauptsächlich die Konzentrationen von La, Ce,P ru nd Nd nach der Ölpest von 2010 während der Blüte von methanotrophen Bakterien (eine Klasse von methylotrophen Bakterien, die Methan als Energiequelle verwenden) abgenommen hatten. [28] Verschiedene Bakterien, z. [26] Abbildung 3z eigt, dass besonders die früheren, häufiger vorkommenden Lanthanoide das Wachstum von Bakterien, die Ln-abhängige Enzyme exprimieren, unterstützen.…”