Design Principles and Applications of Selective Lanthanide-Based Receptors for Inorganic Phosphate.
Design Principles and Applications of Selective Lanthanide-Based Receptors for Inorganic Phosphate.
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DOI：
10.3389/fchem.2022.821020
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发表时间：
2022
影响因子：
5.5
通讯作者：
Wilharm RK
中科院分区：
文献类型：
--
作者：
Pierre VC;Wilharm RK
磷酸盐是一种具有环境和医学意义的阴离子。地表水中磷酸盐含量的增加主要是由于施肥农田的径流造成的，造成了广泛的富营养化和越来越大的死区。高磷血症是一种血液中磷酸盐水平升高的疾病，是慢性或晚期肾脏疾病死亡率和发病率增加的主要原因。解决这两个问题，在一定程度上需要一种新技术，可以在中性ph下选择性地将磷酸盐隔离在水中。磷酸盐的高水合能阻碍有机受体在水中发挥足够的亲和力，可以通过与硬金属离子的配位来克服。镧系离子的硬度、亲氧性和稳定性使它们成为设计高亲和磷酸盐受体的优秀候选者。从这个角度来看，我们讨论了如何利用镧系元素配位化学原理来设计对磷酸盐敏感和选择性的受体。与许多超分子系统不同，这些寄主不能通过定向静电和氢键相互作用识别阴离子寄主。相反，我们的通量受体的选择性完全是由酸碱化学和静电力控制的。影响受体亲和力和选择性的参数包括配体和目标阴离子的碱度、镧系离子的酸度和配体的几何形状。独特的是，它们对磷酸盐的亲和力可以很容易地通过外周相互作用或镧系离子本身进行数量级的调整，而不会影响它们对碳酸氢盐和氯化物等竞争阴离子的精细选择性。
Phosphate is an anion of both environmental and medical significance. The increase in phosphate levels in surface waters due primarily to run-offs from fertilized agricultural fields causes widespread eutrophication and increasingly large dead-zones. Hyperphosphatemia, a condition in which blood phosphate levels are elevated, is a primary cause of increased mortality and morbidity in chronic or advanced kidney disease. Resolving both of these issues require, in part, new technology that could selectively sequester phosphate in water at neutral pH. The high hydration energy of phosphate, which prevents organic receptors from functioning in water with sufficient affinity, can be overcome via coordination to a hard metal ion. The hardness, oxophilicity and lability of lanthanide ions make them excellent candidates for the design of high affinity phosphate receptors. In this perspective, we discuss how the principles of lanthanide coordination chemistry can be exploited to design sensitive and selective receptors for phosphate. Unlike many supramolecular systems, these hosts do not recognize their anionic guests via directed electrostatic and hydrogen bonding interactions. Instead, the selectivity of our fluxional receptors is governed entirely by acid-base chemistry and electrostatic forces. Parameters that affect the affinity and selectivity of the receptors include the basicities of the coordinating ligand and of the targeted anion, the acidity of the lanthanide ion, and the geometry of the ligand. Uniquely, their affinity for phosphate can be readily tuned by orders of magnitude either by peripheral interactions or by the lanthanide ion itself without affecting their exquisite selectivity over competing anions such as bicarbonate and chloride.