Artificial receptors for perrhenate and pertechnetate

具有分析和生化用途的阴离子受体的设计已经成为超分子和分子识别化学中一个越来越感兴趣的领域。高铁酸盐和高铁酸盐是最难结合的阴离子，因为它们的尺寸相对较大，电荷密度较低。一方面，这些阴离子的合适受体可以为有机化合物的放射性标记提供全新的方法，而不需要经典的还原步骤，包括将Re(Vii)和Tc(Vii)转化为更容易操纵的氧化状态。另一方面，高选择性的寄主可能会解决高铁酸盐引起的修复问题。大多数已知的高铁酸盐和高锰酸盐受体是通过试错法发现的。它们在溶液中结合这些阴离子时具有纯的选择性。我们的项目致力于设计一类新型的高铁酸盐和高铁酸盐选择性受体，并了解在亲水性阴离子存在的情况下，如何高选择性地结合阴离子，如磷酸盐、硫酸盐和氯离子。在与理论家的合作中，我们计划开发一种工具，根据给定的构建块和连接子来预测受体的最佳设计。我们将借助量子化学计算，选择在主体和客体之间具有最佳几何匹配的高铁酸根阴离子的结构，并探索两类受体，它们可以结合高铁酸根或高铁酸根阴离子的所有四个氧原子。受体将具有a)非环类折叠分子结构和b)环状结构。

The design of anion receptors of analytical and biochemical utility has become an area of increased interest in supramolecular and molecular recognition chemistry. Perrhenate and pertechnetate are among the anions that are the most difficult to bind due to their relatively large size and low charge density. On the one hand, the appropriate receptors for these anions might permit completely new approaches for the radiolabeling of organic compounds without the need for the classic reduction steps involving conversion of Re(VII) and Tc(VII) to easier-to-manipulate oxidations states. On the other hand, highly selective hosts might solve remediation problems caused by pertechnetate. Most of the known receptors for pertechnetate and perrhenate were found just by trial and error approach. They possess pure selectivity in binding these anions in solution. Our project is focused on the design of a new class of selective receptors for pertechnetate and perrhenate and on understanding how to bind the anions with high selectivity in the presence of hydrophilic anions, such as phosphate, sulfate and chloride. In a collaboration with theoreticians, we plan to develop a tool to predict the best design of receptors based on given building blocks and linkers. We will select with the help of quantum chemical calculations the structures that accommodate the perrhenate anion with best geometrical fit between the host and the guest and explore two classes of receptors, which can bind all four oxygen atoms of the perrhenate or pertechnetate anions. The receptors will have a) an acyclic foldamer-like structure and b) a cyclic structure.