With the increasing demand for the co-encapsulation and controlled delivery of bioactive compounds, the design of liquid-based carriers has garnered considerable attention. Vitamin D3 and riboflavin sodium phosphate (RP) suffer from poor stability and low bioavailability; nevertheless, high internal phase Pickering emulsions (HIPPEs) feature a tunable microstructure that allows for effective compartmentalization of multiple components. In this study, HIPPEs stabilized by egg white peptide (EWP)-konjac glucomannan (KGM) co-assemblies were constructed as a versatile vehicle for the co-delivery of vitamin D3 and RP. EWP-KGM co-assemblies were comprehensively characterized using multispectral techniques and structural analyses. The EWP@KGM co-assembly (mass ratio 10:5) exhibited enhanced emulsifying activity index (EAI: 15.12 m2/g, 3.74-fold higher than EWP) and emulsifying stability index (ESI: 736.60 min, 53-fold higher than EWP), attributed to increased interfacial thickness and steric hindrance. All HIPPEs demonstrated shear-thinning behavior, gel-like viscoelasticity (G′ > G″), and long-term storage stability. Under simulated gastrointestinal digestion, EWP-KGM-HIPPEs protected RP integrity and improved vitamin D3 bioaccessibility. FFA release kinetics followed Korsmeyer-Peppas model, indicating anomalous transport driven by diffusion and matrix relaxation. This study presents a promising platform for the dual encapsulation of bioactives with contrasting polarities, paving the way for applications in nutraceuticals.
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