Department of Chemistry , University of Texas at San Antonio , San Antonio , Texas 78249 , United States.
Department of Chemistry , University of Florida , Gainesville , Florida 32611 , United States.
J Am Chem Soc. 2019 Aug 14;141(32):12610-12618. doi: 10.1021/jacs.9b04133. Epub 2019 Aug 6.
Self-assembly of small molecules through noncovalent interactions into nanoscale architectures has been extensively studied in supramolecular chemistry. However, it is still challenging to develop a biologically inspired self-assembly system that functions in water with complex structure and dynamics by analogy with those found in nature. Here, we report a new water-soluble cationic porphyrin that undergoes adenosine triphosphate (ATP)-templated self-assembly into right-handed double-helical supramolecular structures. Direct observation of the porphyrin-ATP assembly by transmission electron microscopy has been accomplished. The assemblies consist of superhelical fibers with length greater than 1 μm and width ∼46 nm. The chiral superhelical fibers show reversible disassembly to monomers upon hydrolysis of ATP catalyzed by alkaline phosphatase (ALP), and the nanofibers can be re-formed with subsequent addition of ATP. Moreover, transient self-assembly of a chiral double helix is formed when ALP is present to consume ATP.
小分子通过非共价相互作用自组装成纳米尺度的结构在超分子化学中得到了广泛的研究。然而,开发一种受生物启发的自组装系统仍然具有挑战性,该系统能够在水中模拟自然界中存在的复杂结构和动态。在这里,我们报告了一种新的水溶性阳离子卟啉,它能够通过三磷酸腺苷(ATP)模板自组装成右手双螺旋超分子结构。通过透射电子显微镜直接观察到了卟啉-ATP 组装体。组装体由长度大于 1μm 且宽度约为 46nm 的超螺旋纤维组成。手性超螺旋纤维在碱性磷酸酶(ALP)催化的 ATP 水解作用下可逆地解组装成单体,并且纳米纤维可以通过随后添加 ATP 重新形成。此外,当存在 ALP 消耗 ATP 时,会形成瞬时的手性双链螺旋自组装。