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Here we report an autonomous solid-state nanopore in which voltage-driven precipitation and dissolution repeatedly create and erase transient conductive pathways under constant bias. This reaction cycle generates stochastic ionic spikes and converts the pore into a chemically stateful nanofluidic element whose conductance reflects recent history. As nucleotides and amino acids traverse these transient openings, they reshape the evolving pore state and produce distinct spike amplitudes, durations, and firing statistics. Learning these state-dependent fingerprints enables discrimination of four nucleotides, quantitative readout of mixed populations, and extension to seven amino acids without active gating. Our results reposition the solid-state nanopore as a reaction-programmed molecular interface that integrates sensing, memory, and signal generation within chemically dynamic nanoscale environments for molecular analytics and iontronic information processing.<\/jats:p>","DOI":"10.1021\/acsnano.6c08258","type":"journal-article","created":{"date-parts":[[2026,8,4]],"date-time":"2026-08-04T13:02:40Z","timestamp":1785848560000},"page":"22104-22115","source":"Crossref","is-referenced-by-count":1,"title":["Autonomous\nMolecular Sensing with a Chemically Stateful\nSolid-State Nanopore"],"prefix":"10.1021","volume":"20","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4552-1163","authenticated-orcid":true,"given":"Makusu","family":"Tsutsui","sequence":"first","affiliation":[{"name":"The University of Osaka , , 8-1 Mihogaoka, Ibaraki , ,","place":["Osaka, Japan, 567-0047"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9004-3797","authenticated-orcid":true,"given":"Yuki","family":"Komoto","sequence":"additional","affiliation":[{"name":"The University of Osaka , , 8-1 Mihogaoka, Ibaraki , ,","place":["Osaka, Japan, 567-0047"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8590-2737","authenticated-orcid":true,"given":"Kazumichi","family":"Yokota","sequence":"additional","affiliation":[{"name":"National Institute of Advanced Industrial Science and Technology , , ,","place":["Takamatsu, Kagawa, Japan, 761-0395"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5451-4301","authenticated-orcid":true,"given":"Wei-Lun","family":"Hsu","sequence":"additional","affiliation":[{"name":"The University of Tokyo , , 7-3-1 , , ,","place":["Hongo, Bunkyo-ku, Tokyo, Japan, 113-8656"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5418-7494","authenticated-orcid":true,"given":"Denis","family":"Garoli","sequence":"additional","affiliation":[{"name":"Istituto Italiano di Tecnologia , Morego 30 , ,","place":["Genova, Italy, 16163"]},{"name":"Dip. di Scienze e Metodi dell\u2019Ingegneria Universita\u0300 di Modena e Reggio Emilia via Amendola 2 , ,","place":["Reggio Emilia, Italy, 42122"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ali","family":"Douaki","sequence":"additional","affiliation":[{"name":"Istituto Italiano di Tecnologia , Morego 30 , ,","place":["Genova, Italy, 16163"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Germa\u0301n","family":"Lanzavecchia","sequence":"additional","affiliation":[{"name":"Istituto Italiano di Tecnologia , Morego 30 , ,","place":["Genova, Italy, 16163"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ryuichiro","family":"Abe","sequence":"additional","affiliation":[{"name":"The University of Osaka , , 3-1 Yamadaoka, Suita , ,","place":["Osaka, Japan, 565-0871"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6896-3282","authenticated-orcid":true,"given":"Hirofumi","family":"Daiguji","sequence":"additional","affiliation":[{"name":"The University of Tokyo , , 7-3-1 , , ,","place":["Hongo, Bunkyo-ku, Tokyo, Japan, 113-8656"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tomoji","family":"Kawai","sequence":"additional","affiliation":[{"name":"The University of Osaka , , 8-1 Mihogaoka, Ibaraki , ,","place":["Osaka, Japan, 567-0047"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,30]]},"reference":[{"key":"2026081111142101900_cit1","doi-asserted-by":"publisher","first-page":"314","DOI":"10.1038\/s41557-023-01322-x","article-title":"Nanopore DNA Sequencing Technologies and Their Applications\ntowards Single-Molecule Proteomics","volume":"16","author":"Dorey","year":"2024","journal-title":"Nat. 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