Membranes with Functionalized Nanopores for Aromaticity-Based Separation of Small Molecules

Abstract

Membranes that can separate molecules of similar size based on chemical features could transform chemical manufacturing. We demonstrate membranes with functional, 1–3 nm pores prepared using a simple and scalable approach: coating a porous support with random copolymer micelles in alcohol, followed by precipitation in water and functionalization of pore surfaces. This approach was used to prepare membranes that can separate two hormones of similar size and charge, differentiated by aromaticity, mediated through π–π interactions between the aromatic solute and pore walls functionalized with phenol groups. The aromatic molecule permeates more slowly in single-solute experiments. In competitive diffusion experiments, however, it permeates 7.1 times faster than its nonaromatic analogue. This approach can be used to manufacture membranes for complex separations based on various intermolecular interactions.

Interaction-based ion selectivity exhibited by self-assembled, cross-linked zwitterionic copolymer membranes

“…This enhanced mixed-salt selectivity was due to the lower retention of Cl − during mixed-salt filtration (SI Appendix, Table S6). While the underlying mechanism is not yet clear, it is consistent with previous studies of membranes with nanoscale, functionalized pores (9,18). These results motivate further study of the synergistic use of nanoconfinement and chemical interactions to achieve previously inaccessible membrane separations (6).…”

“…However, the relatively large size of BCP membrane pores (>2 to 3 nm) limits its use for ion separations. Membranes formed from packed arrays of random copolymer micelles have demonstrated selectivity based on solute charge (9) and aromaticity (18), but the pore size of these membranes is also too large to separate salt ions. It has been shown that the transport properties of ion exchange membranes are affected by the compatibility between the ions and fixed charge groups (19,20), but this approach has not been utilized to design advanced membrane filters.…”

Physics of the nuclear pore complex: Theory, modeling and experiment

“…The rudimentary NPC-like affinity-based selectivity is also observed in completely synthetic nanopores that use synthetic polymers [25], and provide a link to a wider field of design of polymer functionalized nanochannels for various nanotechnology applications such as protein sorting, DNA sequencing and ''smart'' materials [146,[188][189][190][191][192][193][194][195][196][197][198][199]. Such artificial nanopores, although not the direct focus of this review, can also serve as experimental venues for testing the conceptual models of NPC transport.…”

“…Yet these are efficiently filtered out, without clogging the NPC. In the more general context, the question of specificity and throughput in the presence of non-specific competition is important for the design of artificial nano-channels and biosensors that are capable of molecular sorting and detection under realistic conditions without fouling [193,301,302].…”

Sustainable nano-pesticide platform based on Pyrethrins II for prevention and control Monochamus alternatus

“…In recently years, nanotechnology has gradually been applied in the agriculture and forestry pest control [ 9 , 10 ]. Especially, nanotechnology shows excellent properties in the transportation of agrochemicals, including fertilizers [ 11 ], pesticides [ 12 ] and hormones [ 13 ]. In 2019, International Union of Pure and Applied Chemistry (IUPAC) ranked nano-pesticides as the top ten emerging chemical technologies that could change the world [ 14 ].…”