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Confined Chiral Center Stacking Induced Twisted Silica Nanoribbons for Tumor Cell Proliferation Regulation
Xingjin Li1, Pei-Hang Xu2, Qianqian Lu1
1College of Smart Materials and Future Energy, Department of Chemistry, Laboratory of Advanced Materials, Fudan University, Shanghai, 200433, P.R. China.
None:
Chirality governs physiological processes across scales, yet the ambiguous link between molecular chirality and mesostructured chirality persists. Here, we show that while peptide amphiphiles with molecular chirality can assemble into achiral nanostructures, the co-assembly with silanes leads to left-handed helical-twisted nanoribbons and generates tumor cell activity inhibitory properties. The as-synthesized micrometer-long nanoribbons have a uniform morphology with a pitch of ∼340 nm, a width of ∼75 nm, and a thickness of ∼25 nm. An increase in the proportion of silane-peptide amphiphile modulates the pitch radius ratios from 4.5 to 10.4. It is proposed that the longitudinal stacking force toward the chiral centers during the silane crosslinking can successfully induce chirality transfer from the molecular to the mesostructure. Theoretical calculations confirm this mechanism reduces surface area by 35%. Without drugs, these twisted nanoribbons inhibit tumor cell activity by up to 60%, versus <30% for achiral assemblies. RNA sequencing reveals that mesostructured chirality triggers apoptosis by suppressing cell adhesion and ultimately disrupting cellular metabolism. Our study focuses on the easily overlooked molecular interactions between multiple components during mesostructured chirality formation and the biofeedback role of mesostructured chirality, providing new perspectives for understanding the evolution and significance of chirality in nature.
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