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Photooxidase Mimicking with Adaptive Coordination Molecular Capsules
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-09-23 , DOI: 10.1021/jacs.1c06390 Dan-Ni Yan 1, 2 , Li-Xuan Cai 1 , Pei-Ming Cheng 1 , Shao-Jun Hu 1, 2 , Li-Peng Zhou 1 , Qing-Fu Sun 1, 2
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-09-23 , DOI: 10.1021/jacs.1c06390 Dan-Ni Yan 1, 2 , Li-Xuan Cai 1 , Pei-Ming Cheng 1 , Shao-Jun Hu 1, 2 , Li-Peng Zhou 1 , Qing-Fu Sun 1, 2
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One important feature of enzyme catalysis is the induced-fit conformational change after binding substrates. Herein, we report a biomimetic water-soluble molecular capsule featuring adaptive structural change toward substrate binding, which offers an ideal platform for efficient photocatalysis. The molecular capsule was coordination-assembled from three anthracene-bridged bis-TPT [TPT = 2,4,6-tris(4-pyridyl)-1,3,5-triazine] ligands and six (bpy)Pd(NO3)2 (bpy = 2,2′-bipyridine). Once substrates bind to its hydrophobic cavity, this capsule would undergo quantitative capsule-to-bowl transformation. Visible-light absorption brought about by both the anthracene units and the charge-transfer absorption on the late-formed quintuple π–π stacked host–guest complex efficiently facilitates aerobic photooxidation for the sulfide guests by visible-light irradiation under mild conditions. Desired turnover numbers and product selectivity (sulfoxide over sulfone) have been achieved by the transformable nature of the catalyst and the hydrophilicity of the sulfoxide product. Such a photocatalytic process enabled by an adaptive coordination capsule and substrates as the allosteric effector paves the way for constructing artificial systems to mimic enzyme catalysis.
中文翻译：
利用自适应配位分子胶囊模拟光氧化酶
酶催化的一个重要特征是结合底物后诱导拟合构象变化。在此，我们报道了一种仿生水溶性分子胶囊，其具有针对底物结合的适应性结构变化，为高效光催化提供了理想的平台。该分子胶囊由三个蒽桥双-TPT [TPT = 2,4,6-三(4-吡啶基)-1,3,5-三嗪]配体和六个(bpy)Pd(NO 3 )配位组装而成2 （bpy = 2,2′-联吡啶）。一旦底物与其疏水腔结合，该胶囊就会经历定量的胶囊到碗的转变。蒽单元带来的可见光吸收和后期形成的五元π-π堆叠主客体复合物上的电荷转移吸收有效地促进了在温和条件下可见光照射下硫化物客体的有氧光氧化。通过催化剂的可转化性质和亚砜产物的亲水性，已经实现了所需的周转数和产物选择性（亚砜相对于砜）。这种由自适应协调胶囊和底物作为变构效应器实现的光催化过程为构建模拟酶催化的人工系统铺平了道路。
更新日期：2021-10-06
中文翻译：
利用自适应配位分子胶囊模拟光氧化酶
酶催化的一个重要特征是结合底物后诱导拟合构象变化。在此，我们报道了一种仿生水溶性分子胶囊，其具有针对底物结合的适应性结构变化，为高效光催化提供了理想的平台。该分子胶囊由三个蒽桥双-TPT [TPT = 2,4,6-三(4-吡啶基)-1,3,5-三嗪]配体和六个(bpy)Pd(NO 3 )配位组装而成2 （bpy = 2,2′-联吡啶）。一旦底物与其疏水腔结合，该胶囊就会经历定量的胶囊到碗的转变。蒽单元带来的可见光吸收和后期形成的五元π-π堆叠主客体复合物上的电荷转移吸收有效地促进了在温和条件下可见光照射下硫化物客体的有氧光氧化。通过催化剂的可转化性质和亚砜产物的亲水性，已经实现了所需的周转数和产物选择性（亚砜相对于砜）。这种由自适应协调胶囊和底物作为变构效应器实现的光催化过程为构建模拟酶催化的人工系统铺平了道路。
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