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However, precise modulation of their activity remains a significant obstacle to biomedical applications. Herein, we uncovered a cyclization-provoked, size-reliant topological barrier that suppresses the catalytic core folding of DNAzymes, thereby governing their catalytic activity. Leveraging this underlying topological insight, we engineered a catalytically inert, minimal-sequence circular DNAzyme bearing a cleavable apurinic\/apyrimidinic (AP) site and revealed that its substrate-cleavage potential could be restored through miRNA-10b-responsive circular-to-linear switching. The smallest circular size confers the strongest topological barrier for catalytic activity self-blocking in the circular DNAzyme, providing the most effective means for stimuli-specific activity restoration. This topology-informed strategy facilitated the design of an orthogonally activated circular DNAzyme-metal nanohybrid via Zn2+-mediated coordination self-assembly of the circular DNAzyme with its substrates. The nanohybrid allowed accurate discrimination of metastatic triple-negative breast cancer in various complex biological settings, including a heterogeneous population of cell subtypes, an in vivo subcutaneous tumor model, an in vivo sentinel lymph node metastasis model, and clinical human breast tissue samples. Our findings provide a flexible and robust framework for conditional manipulation of DNAzyme activity, enabling more accurate, spatiotemporal regulation for future therapeutic interventions.<\/jats:p>","DOI":"10.1021\/acs.analchem.6c03059","type":"journal-article","created":{"date-parts":[[2026,8,4]],"date-time":"2026-08-04T13:15:47Z","timestamp":1785849347000},"page":"23209-23221","source":"Crossref","is-referenced-by-count":2,"title":["A Topology-Programmed\nCircular DNAzyme Enables High-Precision\nDiagnosis of Metastatic Triple-Negative Breast Cancer"],"prefix":"10.1021","volume":"98","author":[{"given":"Kun","family":"Yuan","sequence":"first","affiliation":[{"name":"Zhengzhou University , , ,","place":["Zhengzhou, P.R. China, 450001"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yiwen","family":"Yan","sequence":"additional","affiliation":[{"name":"Zhengzhou University , , ,","place":["Zhengzhou, P.R. 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