2026-04-14T03:53:32Zhttps://recercat.cat/oai/request

oai:recercat.cat:10230/718132025-11-08T15:23:06Zcom_2072_6col_2072_452952

00925njm 22002777a 4500 dc Zhou, Ting author Rodríguez-Barrios, Suliany author Ruisánchez, Itziar author Rivera Gil, Pilar, 1976- author 2025-11-07T16:52:57Z 2025-11-07T16:52:57Z 2025 2025-11-07T16:52:57Z Labile Zn2+ is emerging as a quantitative driver, not just a biomarker, of metastasis, yet rapid, second-resolved intracellular measurement remains elusive. Here we engineer terpyridine-functionalised, hollow Au@SiO2 nanocapsules (NCs@TPY) and couple their SERS signal to cell-specific partial-least-squares (PLS) chemometrics, yielding an 8-log dynamic range (10-12 - 10-4 M), a low-nanomolar detection limit and ≤4.5 % cross-validated error while rejecting Ca2+/Mg2+ interference. Applying this platform to four breast-cancer lines reveals that basal cytosolic Zn2+ forms a "ladder" paralleling metastatic aggressiveness (MCF-7 25 pM < MDA 430 pM < LM2 4.7 nM < BrM2 51 nM). Manipulating extracellular zinc uncovers a biphasic switch: migration, invasion and proliferation all peak when intracellular Zn2+ rises into the nanomolar band (∼10-560 nM) and collapse once it exceeds ∼5-70 μM (line-specific). Primary-tumour-derived MDA cells are hypersensitive, reaching maximal metastatic traits at ∼0.6 μM Zn2+, whereas lung- and brain-tropic variants show partial resistance, indicating micro-environmental adaptation. The NCs@TPY-PLS assay thus provides the first tool to track intracellular zinc across eight orders of magnitude in situ and demonstrates that tightly regulated Zn2+ dyshomeostasis controls metastatic behaviour. Because the Raman ligand is exchangeable, the capsule architecture is readily extendable to multiplex ion or redox sensing, and the identified "functional window" positions zinc transporters as actionable targets for anti-metastatic therapy. PRG acknowledges the Spanish Ministry of Science, Innovation and Technology (AEI-PID2022-140423NB-100/AEI/10.13039/501100011033 and CNS2023 - 143700) for funding. TZ. and PRG appreciate the financial support from the China Scholarship Council (CSC) by a State Scholarship Fund (NSCIS no. 202008350121). With the support of the Department of Research and Universities of the Generalitat of Catalonia in the Chemometrics and Sensorics for Analytical Solutions Research Group, CHEMOSENS (Code: 2021 SGR 00705). http://hdl.handle.net/10230/71813 Labile zinc Breast neoplasms-metastasis Gold-silica nanocapsules Raman spectroscopy-SERS Plasmonic nanosensor Multivariate calibration (partial least-squares chemometrics) Intracellular ion sensing A SERS-active plasmonic nanosensor-chemometrics platform reveals a biphasic zinc switch that controls breast-cancer metastasis