Chinner Kylie, Grabicki Niklas, Hamaguchi Rei, Ikeguchi Mitsunori, Kinbara Kazushi, Toyoda Sayaka, Sato Kohei, Dumele Oliver
Department of Chemistry and IRIS Adlershof, Humboldt-Universität zu Berlin Brook-Taylor-Str. 2 Berlin 12489 Germany.
School of Life Science and Technology, Tokyo Institute of Technology Yokohama Kanagawa 226-8501 Japan.
Chem Sci. 2024 Sep 11;15(39):16367-76. doi: 10.1039/d4sc03408b.
Nanohoops, an exciting class of fluorophores with supramolecular binding abilities, have the potential to become innovative tools within biological imaging and sensing. Given the biological importance of cell membranes, incorporation of macrocyclic materials with the dual capability of fluorescence emission and supramolecular complexation would be particularly interesting. A series of different-sized nanohoops-ethylene glycol-decorated []cyclo--pyrenylenes (CPYs) ( = 4-8)-were synthesised an alternate synthetic route which implements a stannylation-based precursor, producing purer material than the previous borylation approach, enabling the growth of single-crystals of the Pt-macrocycle. Reductive elimination of these single-crystals achieved significantly higher selectivity and yields towards smaller ring-sized nanohoops ( = 4-6). The supramolecular binding capabilities of these CPYs were then explored through host-guest studies with a series of polycyclic (aromatic)hydrocarbons, revealing the importance of molecular size, shape, and CH-π contacts for efficient binding. CPYs were incorporated within the hydrophobic layer of lipid bilayer membranes, as confirmed by microscopic imaging and emission spectroscopy, which also demonstrated the size-preferential incorporation of the five-fold nanohoop. Molecular dynamics simulations revealed the position and orientation within the membrane, as well as the unique non-covalent threading interaction between nanohoop and phospholipid.
纳米环是一类具有超分子结合能力的令人兴奋的荧光团，有潜力成为生物成像和传感领域的创新工具。鉴于细胞膜的生物学重要性，引入具有荧光发射和超分子络合双重能力的大环材料将特别有趣。通过一种基于锡化反应的前体的替代合成路线，合成了一系列不同尺寸的乙二醇修饰的[ ]环 - 芘（CPY）（ = 4 - 8），该路线比之前的硼化方法能产生更纯的材料，从而能够生长出铂大环的单晶。这些单晶的还原消除反应对较小环尺寸的纳米环（ = 4 - 6）实现了显著更高的选择性和产率。然后通过与一系列多环（芳香）烃的主客体研究探索了这些CPY的超分子结合能力，揭示了分子大小、形状和CH - π接触对有效结合的重要性。通过显微镜成像和发射光谱证实，CPY被纳入脂质双层膜的疏水层，这也证明了五重纳米环的尺寸优先纳入。分子动力学模拟揭示了其在膜内的位置和取向，以及纳米环与磷脂之间独特的非共价穿线相互作用。
