Tonga Gulen Yesilbag, Jeong Youngdo, Duncan Bradley, Mizuhara Tsukasa, Mout Rubul, Das Riddha, Kim Sung Tae, Yeh Yi-Cheun, Yan Bo, Hou Singyuk, Rotello Vincent M
Department of Chemistry, University of Massachusetts Amherst, 710 North Pleasant Street, Amherst, Massachusetts 01003, USA.
Nat Chem. 2015 Jul;7(7):597-603. doi: 10.1038/nchem.2284.
Bioorthogonal catalysis broadens the functional possibilities of intracellular chemistry. Effective delivery and regulation of synthetic catalytic systems in cells are challenging due to the complex intracellular environment and catalyst instability. Here, we report the fabrication of protein-sized bioorthogonal nanozymes through the encapsulation of hydrophobic transition metal catalysts into the monolayer of water-soluble gold nanoparticles. The activity of these catalysts can be reversibly controlled by binding a supramolecular cucurbit[7]uril 'gate-keeper' onto the monolayer surface, providing a biomimetic control mechanism that mimics the allosteric regulation of enzymes. The potential of this gated nanozyme for use in imaging and therapeutic applications was demonstrated through triggered cleavage of allylcarbamates for pro-fluorophore activation and propargyl groups for prodrug activation inside living cells.
生物正交催化拓宽了细胞内化学的功能可能性。由于细胞内环境复杂且催化剂不稳定，在细胞中有效递送和调节合成催化系统具有挑战性。在此，我们报告了通过将疏水性过渡金属催化剂封装到水溶性金纳米颗粒的单层中制备蛋白质大小的生物正交纳米酶。这些催化剂的活性可以通过将超分子葫芦[7]脲“守门人”结合到单层表面来可逆控制，提供了一种模拟酶变构调节的仿生控制机制。通过在活细胞内触发烯丙基氨基甲酸酯的裂解以激活前荧光团以及炔丙基基团以激活前药，证明了这种门控纳米酶在成像和治疗应用中的潜力。
