Rapid Bioorthogonal Chemistry Turn-on through Enzymatic or Long Wavelength Photocatalytic Activation of Tetrazine Ligation.
Rapid Bioorthogonal Chemistry Turn-on through Enzymatic or Long Wavelength Photocatalytic Activation of Tetrazine Ligation.
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DOI：
10.1021/jacs.6b02168
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发表时间：
2016-05-11
影响因子：
15
通讯作者：
Fox JM
中科院分区：
文献类型：
--
作者：
Zhang H;Trout WS;Liu S;Andrade GA;Hudson DA;Scinto SL;Dicker KT;Li Y;Lazouski N;Rosenthal J;Thorpe C;Jia X;Fox JM
使用空气作为氧化剂，可以通过可控的催化刺激来诱导快速生物正交反应性。用红光 (660 nm) 照射的亚甲蓝 (4 μM) 催化二氢四嗪快速氧化为四嗪，从而开启对反式环辛烯亲二烯体的反应性。或者，在无过氧化物的条件下，纳摩尔水平的辣根过氧化物酶可以有效地催化二氢四嗪的空气氧化。选择在有氧水溶液中具有足够动力学稳定性的二氢四嗪/四嗪对是这些方法成功的关键。在这项工作中，携带潜在二氢四嗪的聚合物纤维被小分子、肽和蛋白质的反式环辛烯缀合物催化活化和共价修饰。除了用荧光团进行可视化之外，与细胞粘附肽缀合的纤维还表现出显着增强的介导细胞接触引导的能力。
Rapid bioorthogonal reactivity can be induced by controllable, catalytic stimuli using air as the oxidant. Methylene blue (4 μM) irradiated with red light (660 nm) catalyzes the rapid oxidation of a dihydrotetrazine to a tetrazine thereby turning on reactivity toward trans-cyclooctene dienophiles. Alternately, the aerial oxidation of dihydrotetrazines can be efficiently catalyzed by nanomolar levels of horseradish peroxidase under peroxide-free conditions. Selection of dihydrotetrazine/tetrazine pairs of sufficient kinetic stability in aerobic aqueous solutions is key to the success of these approaches. In this work, polymer fibers carrying latent dihydrotetrazines were catalytically activated and covalently modified by trans-cyclooctene conjugates of small molecules, peptides and proteins. In addition to visualization with fluorophores, fibers conjugated to a cell adhesive peptide exhibited a dramatically increased ability to mediate contact guidance of cells.