Asymmetric ultrafiltration membranes derived from block copolymer self-assembly have seen growing attention as a result of their ordered pore structures and scalable fabrication process. One route to extend their utility is to provide, through the molecular architecture of the block copolymer, covalent binding sites for facile attachment of foreign functional molecules. Here, we report the synthesis of triblock terpolymer poly­(styrene)-block-poly­(4-vinylpyridine)-block-poly­(propylene sulfide) (SVPS) and its fabrication into isoporous ultrafiltration membranes. Final SVPS membrane top surfaces exhibit narrowly dispersed mesopores with 6-fold symmetry. Membranes show a switchable response to pH changes demonstrating the potential as a chemical gate. Membrane pore surfaces are decorated with thiol groups providing active covalent binding sites via versatile thiol–ene click chemistry. The work may open pathways to produce high-performance multifunctional membranes for chem- and bio-sensing and for separation and as membrane reactors.

Asymmetric poly(isoprene-b-styrene-b-4-vinylpyridine) (ISV) block copolymer membranes fabricated via self-assembly and non-solvent induced phase separation (SNIPS) process have drawn significant attention due to the simple processing method and the generation of highquality isoporous ultrafiltration membranes. With the present study on SNIPS membrane substructure, we systematically varied membrane casting parameters to tune the cross-sectional morphologies of SNIPS membranes while simultaneously preserving top surface structure. Parameters such as polymer concentration, evaporation time, solvent ratio, and coagulation bath temperature were investigated to control transformation of commonly produced sponge-like cross-sectional morphologies into more open and permeable finger-like substructures. Membranes with sponge-like and finger-like substructures were then integrated onto nylon supports for enhanced mechanical properties. Hydraulic permeability tests at various pH conditions gave distinct open-state flux values for SNIPS membranes with different sublayer

No abstract

The functionalization with phosphotriesterase of poly(isoprene-b-styrene-b-4-vinylpyridine)-based nanoporous membranes fabricated by self-assembly and nonsolvent induced phase separation (SNIPS) is shown to enable dynamically responsive membranes capable of substrate-specific and localized gating response. Integration of the SNIPS process with macroporous nylon support layers yields mechanically robust textile-type films with high moisture vapor transport rates that display rapid and local order-of-magnitude modulation of permeability. The simplicity of the fabrication process that is compatible with large-area fabrication along with the versatility and efficacy of enzyme reactivity offers intriguing opportunities for engineered biomimetic materials that are tailored to respond to a complex range of external parameters, providing sensing, protection, and remediation capabilities.

In recent years, responsive polymer-based structures have been studied extensively due to their unique ability to alter their physical properties upon exposure to external stimuli. Despite this, the nanoscale Q-resolved dynamic properties of these materials have barely been explored, which is limiting the development and applications of these materials. To address this issue, we used inelastic Xray scattering (IXS) and found evidence for van der Waals mediated molecular vibration-responsive rattling dynamics in bulk poly(isoprene-block-styrene) (SI) and poly(styreneblock-ethylene oxide) (SO) stacked thin film block copolymers. Their cylinder-forming hexagonally arranged static structures were characterized using small-angle X-ray scattering (SAXS) and grazing incidence small-angle X-ray scattering (GISAXS), complemented by scanning electron microscopy (SEM). Specifically, we observed that the longitudinal vibrational mode in bulk SI experiences a strong phonon attenuation as temperature increases from 30 to 90 °C, while the transverse phonon excitations are nonexistent in the measured Q-range due to anharmonicity-mediated symmetry breaking in phonon interactions. Furthermore, the emergent transverse acoustic phonon modes in both the bulk SI and SO thin films exhibited a nondispersive behavior with a nearly zero slope in the hydrodynamic limit (Q → 0), mimicking optical phonon excitations (i.e., standing waves). In summary, these findings point to the use of polymeric materials for Q-resolved nanoacoustic sensing, and the visualization of THz phonons.

Deviating from the traditional formation of block copolymer derived isoporous membranes from one block copolymer chemistry, here asymmetric membranes with isoporous surface structure are derived from two chemically distinct block copolymers blended during standard membrane fabrication. As a first proof of principle, the fabrication of asymmetric membranes is reported, which are blended from two chemically distinct triblock terpolymers, poly(isoprene-b-styrene-b-(4-vinyl)pyridine) (ISV) and poly(isoprene-b-styrene-b-(dimethylamino)ethyl methacrylate) (ISA), differing in the pH-responsive hydrophilic segment. Using block copolymer self-assembly and nonsolvent induced phase separation process, pure and blended membranes are prepared by varying weight ratios of ISV to ISA. Pure and blended membranes exhibit a thin, selective layer of pores above a macroporous substructure. Observed permeabilities at varying pH values of blended membranes depend on relative triblock terpolymer composition. These results open a new direction for membrane fabrication through the use of mixtures of chemically distinct block copolymers enabling the tailoring of membrane surface chemistries and functionalities.

No abstract