A SERS-active plasmonic nanosensor-chemometrics platform reveals a biphasic zinc switch that controls breast-cancer metastasis

Zhou, Ting; Rodríguez-Barrios, Suliany; Ruisánchez, Itziar; Rivera Gil, Pilar, 1976-

A SERS-active plasmonic nanosensor-chemometrics platform reveals a biphasic zinc switch that controls breast-cancer metastasis

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dc.contributor.author Zhou, Ting
dc.contributor.author Rodríguez-Barrios, Suliany
dc.contributor.author Ruisánchez, Itziar
dc.contributor.author Rivera Gil, Pilar, 1976-
dc.date.accessioned 2025-11-07T16:52:57Z
dc.date.available 2025-11-07T16:52:57Z
dc.date.issued 2025
dc.date.updated 2025-11-07T16:52:57Z
dc.description.abstract 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.
dc.description.sponsorship 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).
dc.format.mimetype application/pdf
dc.identifier.citation Zhou T, Rodriguez-Barrios S, Ruisanchez I, Rivera-Gil P. A SERS-active plasmonic nanosensor-chemometrics platform reveals a biphasic zinc switch that controls breast-cancer metastasis. Biosens Bioelectron. 2025 Dec 1;289:117897. DOI: 10.1016/j.bios.2025.117897
dc.identifier.doi http://dx.doi.org/10.1016/j.bios.2025.117897
dc.identifier.issn 0956-5663
dc.identifier.uri http://hdl.handle.net/10230/71813
dc.language.iso eng
dc.publisher Elsevier
dc.relation.ispartof Biosensors and Bioelectronics. 2025;289:117897
dc.relation.projectID info:eu-repo/grantAgreement/ES/3PE/PID2022-140423NB-100
dc.rights.accessRights info:eu-repo/semantics/openAccess
dc.rights.uri http://creativecommons.org/licenses/by-nc/4.0/
dc.subject.keyword Labile zinc
dc.subject.keyword Breast neoplasms-metastasis
dc.subject.keyword Gold-silica nanocapsules
dc.subject.keyword Raman spectroscopy-SERS
dc.subject.keyword Plasmonic nanosensor
dc.subject.keyword Multivariate calibration (partial least-squares chemometrics)
dc.subject.keyword Intracellular ion sensing
dc.title A SERS-active plasmonic nanosensor-chemometrics platform reveals a biphasic zinc switch that controls breast-cancer metastasis
dc.type info:eu-repo/semantics/article
dc.type.version info:eu-repo/semantics/publishedVersion

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