Multiaddressable molecular rectangles with reversible host-guest interactions: Modulation of pH-controlled guest release and capture
Multiaddressable molecular rectangles with reversible host-guest interactions: Modulation of pH-controlled guest release and capture
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DOI：
10.1073/pnas.1423709112
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发表时间：
2015-01-20
影响因子：
11.1
通讯作者：
Yam, Vivian Wing-Wah
中科院分区：
文献类型：
--
作者：
Chan, Alan Kwun-Wa;Lam, Wai Han;Yam, Vivian Wing-Wah
通过用不同的双炔基配体封端U形双铂（II）三联吡啶部分，合成了一系列具有不同刚性和空腔尺寸的多地址铂（II）分子矩形.已经进行了与各种正方形平面铂（II）、钯（II）和金（III）配合物以及相关的低维金（I）配合物的主-客体缔合的研究，其中大部分是潜在的抗癌治疗剂。矩形结构的优异的客体限制和选择性已经被示出。将pH响应性官能团引入配体骨架产生多功能分子矩形，其在添加酸和碱时表现出可逆的客体释放和捕获，表明其在pH调节的受控治疗剂递送中的潜力。发现可逆的主-客体相互作用受到金属-金属相互作用和p-p相互作用的强烈扰动，在一定程度上，静电相互作用，根据客体分子的性质产生各种光谱变化。通过二维核磁共振和范特霍夫分析确定了它们的结合模式和热力学参数，并得到了计算研究的支持。
A series of multiaddressable platinum(II) molecular rectangles with different rigidities and cavity sizes has been synthesized by endcapping the U-shaped diplatinum(II) terpyridine moiety with various bis-alkynyl ligands. The studies of the host-guest association with various square planar platinum(II), palladium(II), and gold(III) complexes and the related low-dimensional gold(I) complexes, most of which are potential anticancer therapeutics, have been performed. Excellent guest confinement and selectivity of the rectangular architecture have been shown. Introduction of pH-responsive functionalities to the ligand backbone generates multifunctional molecular rectangles that exhibit reversible guest release and capture on the addition of acids and bases, indicating their potential in controlled therapeutics delivery on pH modulation. The reversible host-guest interactions are found to be strongly perturbed by metal-metal and p-p interactions and to a certain extent, electrostatic interactions, giving rise to various spectroscopic changes depending on the nature of the guest molecules. Their binding mode and thermodynamic parameters have been determined by 2D NMR and van't Hoff analysis and supported by computational study.