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<p>Polyphenol-mediated Cu-phosphate hybrid nanoflowers (hNFs) are emerging organic-inorganic platforms for biomedical applications, yet the ligand-level structural rules that connect polyphenol architecture with nanoflower assembly and biological performance remain insufficiently defined. Here, we systematically synthesized hNFs using structurally diverse polyphenols, caffeic acid, catechin, epicatechin, hesperidin, quercetin, and naringenin, to determine how coordination topology, stereochemistry, hydroxyl distribution, and glycosylation govern morphology and function. SEM-EDS analyses showed that ligand architecture directed divergent assembly pathways, producing well-defined hierarchical nanoflowers for caffeic acid, catechin, epicatechin, and hesperidin, but irregular aggregates for quercetin and naringenin. FTIR, XRD, and XPS confirmed successful incorporation of the polyphenolic ligands into Cu-phosphate frameworks while preserving the inorganic scaffold, and DLS/zeta-potential measurements revealed ligand-dependent aqueous dispersion behavior. In MTT assays, the hNFs displayed ligand- and cell line-dependent cytotoxicity against A549 and MCF-7 cells, with epicatechin-mediated hNFs showing the strongest activity, followed by caffeic acid. Time-dependent MTT analysis in MCF-7 cells further showed generally enhanced hNF cytotoxicity at 48&#xa0;h compared with 24&#xa0;h, whereas the corresponding free ligands remained non-cytotoxic within the tested concentration range. DAPI staining supported apoptosis-associated nuclear alterations, while DPPH assays showed that hybridization markedly attenuated the intrinsic radical-scavenging activity of the free ligands. These findings establish ligand architecture as a central design parameter linking coordination chemistry, hierarchical morphology, antioxidant behavior, and anticancer performance, providing a novel ligand-level framework for engineering polyphenol-based Cu-phosphate hybrid nanomaterials.</p>

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Engineering Cu-Phosphate Hybrid Nanoflowers via Polyphenol Coordination: Ligand Architecture Dictates Morphology and Biological Performance

  • 期刊论文

  • 发表日期：

    2026年8月4日

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  • Berna Kavakcıoğlu Yardımcı,
  • Mine Sulak,
  • Arif Akköylü

摘要

Polyphenol-mediated Cu-phosphate hybrid nanoflowers (hNFs) are emerging organic-inorganic platforms for biomedical applications, yet the ligand-level structural rules that connect polyphenol architecture with nanoflower assembly and biological performance remain insufficiently defined. Here, we systematically synthesized hNFs using structurally diverse polyphenols, caffeic acid, catechin, epicatechin, hesperidin, quercetin, and naringenin, to determine how coordination topology, stereochemistry, hydroxyl distribution, and glycosylation govern morphology and function. SEM-EDS analyses showed that ligand architecture directed divergent assembly pathways, producing well-defined hierarchical nanoflowers for caffeic acid, catechin, epicatechin, and hesperidin, but irregular aggregates for quercetin and naringenin. FTIR, XRD, and XPS confirmed successful incorporation of the polyphenolic ligands into Cu-phosphate frameworks while preserving the inorganic scaffold, and DLS/zeta-potential measurements revealed ligand-dependent aqueous dispersion behavior. In MTT assays, the hNFs displayed ligand- and cell line-dependent cytotoxicity against A549 and MCF-7 cells, with epicatechin-mediated hNFs showing the strongest activity, followed by caffeic acid. Time-dependent MTT analysis in MCF-7 cells further showed generally enhanced hNF cytotoxicity at 48 h compared with 24 h, whereas the corresponding free ligands remained non-cytotoxic within the tested concentration range. DAPI staining supported apoptosis-associated nuclear alterations, while DPPH assays showed that hybridization markedly attenuated the intrinsic radical-scavenging activity of the free ligands. These findings establish ligand architecture as a central design parameter linking coordination chemistry, hierarchical morphology, antioxidant behavior, and anticancer performance, providing a novel ligand-level framework for engineering polyphenol-based Cu-phosphate hybrid nanomaterials.