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Psoriasis, although non\u2010malignant, imposes a substantial physical and psychological burden. Accurate and timely detection is crucial for improving clinical outcomes. Serum metabolites, as sensitive indicators of systemic physiology, represent promising noninvasive biomarkers. Here, we developed gold\u2010modified rose\u2010like multilayer heterojunctions (G\u2010RMHJ) as an efficient matrix for laser desorption\/ionization mass spectrometry (LDI\u2010MS). The hierarchical multilayer architecture and heterojunction interfaces, combined with gold functionalization, synergistically enhance light absorption, interfacial energy transfer, and ionization efficiency, enabling sensitive and reproducible serum metabolite detection. In a cohort of 130 skin cancer and 23 psoriasis patients together with 218 healthy controls (HC), G\u2010RMHJ\u2010assisted LDI\u2010MS yielded robust serum metabolic fingerprints, and machine learning models built on these data achieved 100% test\u2010set accuracy for classifying patients vs. HC. Eight discriminative metabolites were identified that reliably differentiated four types of diseases from HC, with area under the curve values ranging from 0.933 to 1.000. This work demonstrates how hierarchical microstructured heterojunctions can directly translate materials\u2010level design into enhanced bioanalytical performance, providing a generalizable and noninvasive framework for serum metabolomics\u2013based disease classification and skin cancer subtype identification.<\/jats:p>","DOI":"10.1002\/smtd.70782","type":"journal-article","created":{"date-parts":[[2026,6,16]],"date-time":"2026-06-16T05:59:54Z","timestamp":1781589594000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Gold\u2010Functionalized Multilayer Heterojunction Microarchitectures Enable High\u2010Fidelity Serum Metabolite Profiling for Skin Cancer Subtype Classification"],"prefix":"10.1002","volume":"10","author":[{"given":"Daili","family":"Gao","sequence":"first","affiliation":[{"name":"School of Materials Science and Chemical Engineering Ningbo University  Ningbo 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