Abstract
<jats:p>Materials with well-defined permeation pathways are of interest for protective garments in hazardous environments where they must permit high water vapor, oxygen and carbon dioxide transmission, while rejecting harmful small organic molecules. Nanostructured polymers with 1 nm scale pores formed by crosslinking self-assembled lyotropic mesophases have emerged as promising semipermeable membranes for a variety of molecular separations. Here, we examine their ability to selectively impede the penetration of chemical warfare agent (CWA) simulants while permitting the passage of water vapor. We investigate systems with ordered direct hexagonal (CYL) and lamellar (LAM) nanostructures featuring glycerol-filled pores. Both systems were prepared as membranes with thicknesses of ~500 nm. The CYL materials feature transport limiting dimensions, or pore sizes, of 0.87 nm, while the LAM has 1.45 nm domains. Despite its smaller pore size, the CYL nanostructure exhibited a markedly higher vapor flux than the LAM, and both systems outperformed commercial breathable garments. Their water to CWA simulant molar selectivity was ~ 4 to 100 times higher than dense hydrophilic polymer coatings. These glycerol-filled nanostructured membranes with 1 nm scale pores provide a new route to engineering highly breathable materials that can be used in protective garments.</jats:p>