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Here, we present an intelligent enzymatic microneedle platform that achieves calibration\u2010efficient, matrix\u2010adaptive, and drift\u2010resilient high\u2010fidelity sensing through a Nafion\u2010shielded dual\u2010mode architecture and an explainable feedforward neural network (FFNN). Using glucose as a representative model analyte, the platform integrates 2T\/4T impedance acquisition with a functionalized Nafion interface to improve robustness against contact\u2010related and biofluid\u2010induced perturbations. SHapley Additive exPlanations were used to interpret the internal decision logic of the FFNN, revealing that the model learns physics\u2010aligned feature relationships rather than relying solely on statistical fitting. Specifically, the network identifies matrix\u2010dependent compensation patterns associated with contact impedance and leverages phase \u2013 impedance coupling to evaluate interfacial integrity before processing glucose\u2010related electrochemical responses. This interpretability analysis suggests that the model can distinguish glucose\u2010associated enzymatic signals from nonspecific environmental and interfacial perturbations. After few\u2010shot domain adaptation, the platform achieved a mean absolute relative difference (MARD) of 2.55% in whole blood, demonstrating high prediction fidelity in a complex biological matrix. Supported by ablation studies and principal component analysis, this work bridges electrochemical interface engineering and explainable machine learning, offering a highly scalable and robust framework for minimally invasive metabolic\u00a0monitoring.<\/jats:p>","DOI":"10.1002\/smll.74708","type":"journal-article","created":{"date-parts":[[2026,7,22]],"date-time":"2026-07-22T06:16:58Z","timestamp":1784701018000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Matrix\u2010Aware Electrochemical Sensing: A Neural Network Approach to Deciphering Medium\u2010Specific Surface Dynamics"],"prefix":"10.1002","volume":"22","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-5310-2022","authenticated-orcid":false,"given":"Honglin","family":"Piao","sequence":"first","affiliation":[{"name":"Department of Materials Science and Engineering Yonsei University Seoul Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0009-5090-6330","authenticated-orcid":false,"given":"Daerl","family":"Park","sequence":"additional","affiliation":[{"name":"Department of Materials Science and Engineering Yonsei University Seoul Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0002-5019-8097","authenticated-orcid":false,"given":"Jaehyun","family":"Kim","sequence":"additional","affiliation":[{"name":"Department of Materials Science and Engineering Yonsei University Seoul Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0007-4448-3154","authenticated-orcid":false,"given":"Mingu","family":"Song","sequence":"additional","affiliation":[{"name":"Department of Materials Science and Engineering Yonsei University Seoul Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0003-6866-7039","authenticated-orcid":false,"given":"Jeongwon","family":"Rho","sequence":"additional","affiliation":[{"name":"Department of Materials Science and Engineering Yonsei University Seoul Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-4875-3894","authenticated-orcid":false,"given":"Seonghoon","family":"Park","sequence":"additional","affiliation":[{"name":"Department of Materials Science and Engineering Yonsei University Seoul Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5540-5433","authenticated-orcid":false,"given":"Hyung\u2010Ho","family":"Park","sequence":"additional","affiliation":[{"name":"Department of Materials Science and Engineering Yonsei University Seoul Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4656-2095","authenticated-orcid":false,"given":"Heon\u2010Jin","family":"Choi","sequence":"additional","affiliation":[{"name":"Department of Materials Science and Engineering Yonsei University Seoul Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,7,21]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1149\/2.F08193IF"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.analchem.1c03827"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/advs.202306560"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bios.2023.115506"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1038\/s44222-023-00108-7"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41551-022-00887-1"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202403758"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.analchem.1c04401"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1149\/1945-7111\/ad6b4a"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1109\/JSEN.2023.3291423"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1163\/156856208X386273"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bios.2015.07.036"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.201707146"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.34133\/2022\/9892340"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41578-020-00255-y"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41524-017-0056-5"},{"key":"e_1_2_8_18_1","doi-asserted-by":"crossref","unstructured":"A. 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