Bio-Templated Chiral Zeolitic Imidazolate Framework for Enantioselective Chemoresistive Sensing

Chiral metal-organic frameworks (MOFs) have gained rising attention as ordered nanoporous materials for enantiomer separations, chiral catalysis, and sensing. Among those, chiral MOFs are generally obtained through complex synthetic routes by using a limited choice of reactive chiral organic precursors as the primary linkers or auxiliary ligands. Here, we report a template-controlled synthesis of chiral MOFs from achiral precursors grown on chiral nematic cellulose-derived nanostructured bio-templates. We demonstrate that chiral MOFs, specifically, zeolitic imidazolate framework (ZIF), unc-[Zn(2-MeIm)(2), 2-MeIm=2-methylimidazole], can be grown from regular precursors within nanoporous organized chiral nematic nanocelluloses via directed assembly on twisted bundles of cellulose nanocrystals. The template-grown chiral ZIF possesses tetragonal crystal structure with chiral space group of P4(1), which is different from traditional cubic crystal structure of I-43 m for freely grown conventional ZIF-8. The uniaxially compressed dimensions of the unit cell of templated ZIF and crystalline dimensions are signatures of this structure. We observe that the templated chiral ZIF can facilitate the enantiotropic sensing. It shows enantioselective recognition and chiral sensing abilities with a low limit of detection of 39 mu M and the corresponding limit of chiral detection of 300 mu M for representative chiral amino acid, D- and L- alanine.

Automated summary

In this study, a method for the synthesis of chiral metal-organic frameworks (MOFs) from achiral precursors was reported by utilizing chiral nematic cellulose-derived bio-templates. It was demonstrated that chiral MOFs, specifically zeolitic imidazolate frameworks (ZIF), can be grown from regular precursors on twisted bundles of cellulose nanocrystals, resulting in a tetragonal crystal structure with chiral space group of P4(1). The templated chiral ZIF also exhibited enantioselective recognition and chiral sensing abilities.