Catalytic site-selective substrate processing within a tubular nanoreactor
Catalytic site-selective substrate processing within a tubular nanoreactor
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DOI：
10.1038/s41565-019-0579-7
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发表时间：
2019-12-01
影响因子：
38.3
通讯作者：
Bayley, Hagan
中科院分区：
文献类型：
--
作者：
Qing, Yujia;Tamagaki-Asahina, Hiroko;Bayley, Hagan
化学家们长期以来一直在寻找当存在几个具有相似反应性的位点时精确修饰分子的能力。我们推断，纳米结构内的基板的限制可能允许在本体溶液中无法实现的位点选择性反应，即使使用复杂的试剂。特别是，纳米管内聚合物的拉伸和排列可能允许位点特异性裂解或修饰。为了探索这一命题，大分子二硫化物底物内的管状蛋白质纳米反应器，其中包含位于不同位置的半胱氨酸残基沿着沿着每个管的长度的集合的成员延长。对于每个纳米反应器，我们通过使用一组聚合物基质（位点选择性）和两个硫原子中的哪一个被攻击（区域选择性）来定义反应位置，并发现二硫键交换以原子精度发生。我们的策略具有选择性加工多种生物大分子的潜力，并且可以通过使用替代纳米管来进一步推广化学和基底。
Chemists have long sought the ability to modify molecules precisely when presented with several sites of similar reactivity. We reasoned that the confinement of substrates within nanostructures might permit site-selective reactions unachievable in bulk solution, even with sophisticated reagents. In particular, the stretching and alignment of polymers within nanotubes might allow site-specific cleavage or modification. To explore this proposition, macromolecular disulfide substrates were elongated within members of a collection of tubular protein nanoreactors, which contained cysteine residues positioned at different locations along the length of each tube. For each nanoreactor, we defined the reactive location by using a set of polymer substrates (site-selectivity) and which of the two sulfur atoms was attacked (regioselectivity), and found that disulfide interchange occurs with atomic precision. Our strategy has potential for the selective processing of a wide variety of biomacromolecules, and the chemistry and substrates might be generalized yet further by using alternative nanotubes.