Glycoluril-Derived Molecular Clips are Potent and Selective Receptors for Cationic Dyes in Water.
Glycoluril-Derived Molecular Clips are Potent and Selective Receptors for Cationic Dyes in Water.
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DOI：
10.1002/chem.201601796
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发表时间：
2016-10-17
影响因子：
4.3
通讯作者：
Isaacs, Lyle
中科院分区：
文献类型：
--
作者：
She, Nengfang;Moncelet, Damien;Gilberg, Laura;Lu, Xiaoyong;Sindelar, Vladimir;Briken, Volker;Isaacs, Lyle
分子片段1在水中保持单体，并与合适的客人参与主客识别过程。我们报告了用1H NMR， UV/Vis和荧光滴定测量的32个1•客体配合物的Ka值。1的空腔由具有负静电电位的芳香表面形成，因此对平面和阳离子芳香客体表现出高亲和力和选择性，这与CB[n]受体相比，CB[n]受体更喜欢脂肪族而不是芳香客体。静电效应在识别过程中起主导作用，其中离子偶极相互作用可能发生在铵离子与C=O基团之间，1的SO3 -基团与客体上的阳离子基团之间，以及1的空腔内通过阳离子-π相互作用。宿主1对具有大平面芳香表面的定向客体（如萘二亚胺NDI+和苝二亚胺PDI+）和由吖啶衍生的阳离子染料（如亚甲基蓝和天青A）具有高亲和力。通过比较类似的中性和阳离子客体（如亚甲基紫与亚甲基蓝；喹啉与n-甲基喹啉；吖啶与n-甲基吖啶；中性红与中性红H+），确定了阳离子-π相互作用的关键重要性，其亲和度相差高达380倍。我们证明了1对亚甲基蓝的高亲和力（Ka = 3.92 × 107 M−1;Kd = 25 nM）允许选择性地隔离和染色亚甲基蓝染色的U87细胞。
Molecular clip 1 remains monomeric in water and engages in host•guest recognition processes with suitable guests. We report the Ka values for 32 1•guest complexes measured by 1H NMR, UV/Vis, and fluorescence titrations. The cavity of 1 is shaped by aromatic surfaces of negative electrostatic potential and therefore displays high affinity and selectivity for planar and cationic aromatic guests which distinguishes it from CB[n] receptors that prefer aliphatic over aromatic guests. Electrostatic effects play a dominant role in the recognition process whereby ion-dipole interactions may occur between ammonium ions and the C=O groups of 1, between the SO3− groups of 1 and pendant cationic groups on the guest, and within the cavity of 1 by cation-π interactions. Host 1 displays high affinity toward dicationic guests with large planar aromatic surfaces (e.g. naphthalene diimide NDI+ and perylene diimide PDI+) and cationic dyes derived from acridine (e.g. methylene blue and azure A). The critical importance of cation-π interactions was ascertained by a comparison of analogous neutral and cationic guests (e.g. methylene violet vs. methylene blue; quinoline vs. N-methylquinolinium; acridine vs. N-methylacridinium; neutral red vs. neutral red H+) whose affinities differ by up to 380-fold. We demonstrate that the high affinity of 1 toward methylene blue (Ka = 3.92 × 107 M−1; Kd = 25 nM) allows for the selective sequestration and destaining of U87 cells stained with methylene blue.
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