Fixing zein at the fibrillar carboxymethyl cellulose toward an amphiphilic nano-network

•Zein-CMC complexes (ZCs) were dispersible in water.•Interfacial properties of ZCs could be controlled by charge properties of CMC.•The nano-network structures of ZCs enhanced the emulsion stability.•Droplet size and stability of the emulsions could be tailored. In this study, co-assembled protein-polysaccharide complexes (ZCs) were prepared by fixing zein nanoparticles at the fibrillar carboxymethyl cellulose (CMC) by pH-driven anti-solvent precipitation. The complexation boosted the dispersity of zein from 17.3% to 88.6%. Scanning electron microscopy and atomic force microscopy confirmed the formation of network structures where the fibrous polysaccharides inserted into the interval of granular proteins. Circular dichroism spectrum, fluorescence spectrum, and X-ray diffraction verified the electrostatic interaction pattern between zein and CMC. Besides, the ZCs presented favorable amphiphilic properties, and the electrostatic interaction between zein and CMC can be fine-tuned by the substitution degree (DS) of carboxymethyl in CMC. Therefore, the Pickering emulsions stabilized by ZCs had controllable size and long-term stability using DS as a stimulus. Our study offers a novel strategy developing bio-based materials as novel stabilizers of Pickering emulsions.