Khoury Farid F, Heater Bradley S, Marzolf Daniel R, Abeyrathna Sameera, Picking Jonathan W, Kumar Piyush, Higgins Steven A, Jones Randy, Lewis Alan T, Kucharzyk Katarzyna H, Banta Scott
Department of Chemical Engineering, Columbia University New York NY 10027 USA
Battelle Memorial Research Institute Columbus OH 43201 USA
Chem Sci. 2025 May 28. doi: 10.1039/d5sc02315g.
Rare earth elements (REEs), which include the 15 lanthanides plus scandium and yttrium, are critical components commonly used in permanent magnets and play a significant role in electronics and green energy technologies. Due to the similarities of these ions, conventional separation processes are chemically- and energy-intensive and generate large quantities of waste. The lanthanides share physical and chemical similarities with calcium ions, which allow REEs to replace calcium in calcium-binding peptides and proteins. In this study, we conducted a bioinformatic search to identify calcium-binding peptides with high affinity to bind and separate REEs. Seven unique domains representing different calcium-binding geometries were selected for evaluation. The results revealed a strong correlation between the charge of the binding loop and its affinity for REEs. We concluded that highly charged, aspartic acid-rich loops exhibit greater electrostatic repulsion, which creates higher affinity due to the increased stabilization effect of ion binding. Binding affinity across the lanthanide series was highest for ions with radii similar to that of calcium (∼1 Å), consistent with the evolutionary optimization of calcium-binding proteins for selective ion recognition. While selectivity varied among proteins in solution, immobilized proteins demonstrated higher selectivity toward intermediate REEs. One notable candidate identified in the bioinformatic search was HEW5 from . We leveraged the selectivity of HEW5 in a 7 mL column to demonstrate a single-stage, chelator-free separation of an equimolar lanthanum-neodymium mixture, achieving a high purity (>90%) and yield (90%) of REEs. Additionally, immobilized HEW5 was used to remove non-REE ions from a simulated leachate stream and separate lanthanum (>90% purity) from other REEs in a single separation stage.
稀土元素(REEs)包括15种镧系元素以及钪和钇,是永磁体中常用的关键成分,在电子和绿色能源技术中发挥着重要作用。由于这些离子具有相似性,传统的分离过程在化学和能源方面都很密集,并且会产生大量废物。镧系元素与钙离子在物理和化学性质上相似,这使得稀土元素能够在钙结合肽和蛋白质中取代钙。在本研究中,我们进行了生物信息学搜索,以识别与稀土元素具有高亲和力的钙结合肽。选择了代表不同钙结合几何结构的七个独特结构域进行评估。结果表明,结合环的电荷与其对稀土元素的亲和力之间存在很强的相关性。我们得出结论,带高电荷、富含天冬氨酸的环表现出更大的静电排斥力,由于离子结合的稳定作用增强,从而产生更高的亲和力。对于半径与钙(约1 Å)相似的离子,整个镧系元素系列的结合亲和力最高,这与钙结合蛋白对选择性离子识别的进化优化一致。虽然溶液中不同蛋白质的选择性有所不同,但固定化蛋白质对中间稀土元素表现出更高的选择性。在生物信息学搜索中发现的一个值得注意的候选物是来自的HEW5。我们利用HEW5在7 mL柱中的选择性,展示了等摩尔镧 - 钕混合物的单级、无螯合剂分离,实现了稀土元素的高纯度(>90%)和高收率(90%)。此外,固定化的HEW5被用于从模拟浸出液流中去除非稀土离子,并在单个分离阶段将镧(纯度>90%)与其他稀土元素分离。