Interfacial Engineering of Clay-Based Nanohybrids with pH-Responsive Network-like Behavior for Hair Photoprotection...

The interfacial behavior of hybrid nanoparticles on biological substrates governs their functional performance. Here, we investigate how surface properties and colloidal stability dictate the pH-dependent adhesion of oxybenzone-loaded palygorskite nanohybrids to hair-a model biological interface. A series of hybrids with 5-50% oxybenzone loadings were prepared via melt impregnation. XRD and FTIR analyses confirm hydrogen bonding between oxybenzone and palygorskite, forming stable organic-inorganic hybrids. The colloidal stability of these nanohybrids varies non-monotonically with oxybenzone loading, governed by surface hydrophilicity and zeta potential, exhibiting a network-like behavior upon pH change. Optimal stability is achieved at an intermediate loading with a favorable balance of surface properties. While pristine hybrids show no affinity for hair, surface modification with cationic polyquaternium-7 (PQ-7) or non-ionic polyvinylpyrrolidone (PVP) enables effective deposition through distinct pH-dependent mechanisms: PQ-7 operates optimally at pH 10 via electrostatic attraction, whereas PVP performs best at pH 4 through hydrogen bonding, forming a protective coating layer on the hair surface. Deposition fails for PVP-modified hybrids at 50% loading due to excessive surface hydrophobicity. The deposited hybrids provide exceptional UV protection, significantly mitigating cuticle damage, suppressing photo-yellowing, and minimizing protein oxidation. Among the hybrids, hybrid-35 exhibited the best colloidal stability, whereas PQ-7-modified hybrid-50 gave the highest UV protection (color difference ΔE reduced from 10.51 to 1.60). The adhesion rates of the two best-performing hybrids were 2.70% and 2.85%, respectively. Beyond hair protection, we evaluate the environmental interface of these materials. While free oxybenzone is highly toxic to Chlorella vulgaris, hybridization drastically reduces its ecotoxicity. Remarkably, palygorskite and the hybrids promote algal growth, likely by acting as nutrient adsorbents and attachment sites. This work provides fundamental insights into particle-biointerface interactions and offers a strategy for designing functional hybrid materials with tailored surface properties for bio-related applications.