Small‐Molecule‐Mediated Hierarchical Molecular Assembly of Ribbon‐Like Zein Nanofibers for Multifunctional Air Filtration

ABSTRACT Sustainable air filtration materials derived from green electrospinning of bio‐based polymers are highly desirable. However, achieving precise fiber morphology regulation and multifunctional integration in bio‐based electrospun systems remains challenging, particularly for balancing filtration performance and comfort related properties. Herein, a small‐molecule‐mediated hierarchical molecular assembly strategy is developed to engineer well‐defined ribbon‐like nanofibers in a zein system by incorporating chlorogenic acid (CA) and rutin (RU). The noncovalent interactions between CA/RU and zein regulate molecular organization through distinct yet complementary pathways, where CA promotes local β‐sheet‐rich conformational ordering while RU facilitates intermolecular association. Their competitive and cooperative molecular interactions reorganize zein chain assembly, thereby stabilizing ribbon‐like fiber architectures and optimizing filtration performance. The resulting zein/CA/RU composite nanofibrous membrane delivers 99.55% filtration efficiency for PM 0.3 with a pressure drop of 53.6 Pa and a quality factor of 0.101 Pa − 1 . Meanwhile, its reduced airflow resistance and passive radiative cooling capability provide potential benefits for thermal comfort‐related performance. This work provides a molecular‐level design strategy for morphology engineering and multifunctional integration of naturally derived nanofibers, offering a pathway toward high‐performance, low‐resistance, and sustainable air filtration materials.