Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, UK.
Nat Chem. 2017 Sep;9(9):903-908. doi: 10.1038/nchem.2758. Epub 2017 Apr 10.
Biomolecular receptors are able to process information by responding differentially to combinations of chemical signals. Synthetic receptors that are likewise capable of multi-stimuli response can form the basis of programmable molecular systems, wherein specific input sequences create distinct outputs. Here we report a pseudo-cuboctahedral assembly capable of cooperatively binding anionic and neutral guest species. The binding of pairs of fullerene guests was observed to effect the all-or-nothing cooperative templation of an S-symmetric host stereoisomer. This bis-fullerene adduct exhibits different cooperativity in binding pairs of anions from the fullerene-free parent: in one case, positive cooperativity is observed, while in another all binding affinities are enhanced by an order of magnitude, and in a third the binding events are only minimally perturbed. This intricate modulation of binding affinity, and thus cooperativity, renders our new cuboctahedral receptor attractive for incorporation into systems with complex, programmable responses to different sets of stimuli.
生物分子受体能够通过对化学信号组合的差异响应来处理信息。同样能够对多刺激做出响应的合成受体可以构成可编程分子系统的基础，其中特定的输入序列产生不同的输出。在这里，我们报告了一种伪-cuboctahedral 组装体，能够协同结合阴离子和中性客体物种。观察到对富勒烯客体对的结合导致 S-对称主体对映异构体的全有或全无协同模板化。这种双富勒烯加合物在与富勒烯母体结合对阴离子的结合中表现出不同的协同性：在一种情况下，观察到正协同性，而在另一种情况下，所有结合亲和力都增强了一个数量级，而在第三种情况下，结合事件仅受到最小的干扰。这种结合亲和力的复杂调节，因此也调节了协同性，使我们的新型 cuboctahedral 受体成为复杂、可编程响应不同刺激集的系统的理想选择。
