Sticky-Ends-Guided Creation of Functional Hollow Nanopores for Guest Encapsulation and Water Transport

Commercial uses of water-transporting aquaporins for seawater desalination and wastewater reclamation/reuse are being investigated in both academia and the industry. Presently, structural complexity, stability, scalability, and activity reconstitution of these costly channel proteins still present substantial challenges to scientists and engineers. An attractive strategy is to develop robust synthetic water channels able to mimic the water-transporting function of aquaporins for utility in the making of next generation of water channel based biomimetic porous membranes for various water purification applications. In sharp contrast to burgeoning development in constructing synthetic ion channels over the past four decades, very limited progress has been made in the area of synthetic water channels. A handful of such examples include the first report by Percec in 2007 (Percec et al. J. Am. Chem. Soc. 2007, 129, 11698-11699), which was followed by Barboiu in 2011 (Barboiu et al. Angew. Chem., Int. Ed. 2011, SO, 11366-11372), Gong and Hou in 2012 (Gong et al. Nat. Commun. 2012, 3, 949; Hou et al. J. Am. Chem. Soc. 2012, 134, 8384-8387), and Zeng in 2014 (Zeng et al. J. Am. Chem. Soc. 2014, 136, 14270-14276). Radically deviating from the fact that the discovery of novel synthetic channel systems with desired transport selectivity is most often empirical and very often serendipitous, we have instead adopted a. more rational designer approach whereby molecular building blocks have been carefully designed from scratch to perform their intended built-in functions. Our designer journey started in 2008, two years after I started leading a group at the National University of Singapore. Since then, we have been actively investigating the use of designed water-binding aquafoldamers to construct synthetic water channels for the rapid and selective transport of water molecules ideally with the exclusion of all other nonproton molecular species. Toward this goal, we designed and characterized, by an experimental-theoretical synergy, a new class of modular, H-bonded, and crescent-shaped oligopyridine amide foldamers, enclosing a sizable cavity of about 2.8 angstrom in diameter. Matching well with the diameter of water molecules and decorated by interior-pointing H-bond donors (amide H atoms) and acceptors (pyridine N atoms) for water binding, this sizable cavity experimentally proves to be suitable for water recognition. In particular, helically folded oligomers are found to be capable of binding two water molecules that are vertically aligned in parallel with helical axis. However, the existence of two repulsive groups at the two helical ends prevents the formation of 1D hollow tubular cavity, via self-assembly, for encapsulating 1D water chains. Subsequently, we introduced two electrostatically complementary functional groups that act as sticky ends at helical ends. These feeble sticky ends faithfully and seamlessly align short cavity-containing helices one dimensionally to create hollow tubular aquapores. To our delight, these aquapores demonstrate their excellent ability of highly selectively hosting a chain of single file H-bonded water molecules and allow for selective transport of both protons and water molecules with exclusion of metal ions including Na+ and N+ ions across the lipid membranes.