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Adv."],"published-print":{"date-parts":[[2026,9,18]]},"abstract":"<jats:p>Pulsed dynamic nuclear polarization (DNP) is currently receiving substantial interest as a means to enhance the sensitivity of nuclear magnetic resonance (NMR) and magnetic resonance imaging by orders of magnitude. It has also received much attention as a central ingredient in many modalities of electron\u2013spin\u2013involved quantum sensing. Relative to spin engineering associated with NMR, the design of efficient pulsed DNP experiments with a broad experimental scope is challenged by large electron-nuclear spin systems, large electron\u2013spin\u2013involved interactions, and instrumental nonidealities and limitations. All of this may challenge traditional NMR-like theoretical and numerical pulse sequence engineering. Exploiting state-of-the-art instrumentation and taking advantage of the high sensitivity of DNP relative to NMR, we here demonstrate the use of combinations of Bayesian machine learning methods and constrained random walk procedures to design pulse sequences in situ, by experiments, directly on the spin systems responding to spectrometer instructions. For trityl and nitroxide samples, it is demonstrated that efficient broadband DNP pulse sequences can be designed in situ with experimental protocols benchmarked against in silico analogs.<\/jats:p>","DOI":"10.1126\/sciadv.aeh4467","type":"journal-article","created":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T18:02:56Z","timestamp":1789581776000},"update-policy":"https:\/\/doi.org\/10.34133\/aaas_crossmark","source":"Crossref","is-referenced-by-count":0,"title":["In situ learning-based spin engineering of pulsed dynamic nuclear polarization"],"prefix":"10.1126","volume":"12","author":[{"ORCID":"https:\/\/orcid.org\/0009-0004-1133-4193","authenticated-orcid":true,"given":"Filip V.","family":"Jensen","sequence":"first","affiliation":[{"name":"Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, DK-8000 Aarhus C, Denmark."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5648-4612","authenticated-orcid":true,"given":"Jos\u00e9 P.","family":"Carvalho","sequence":"additional","affiliation":[{"name":"Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, DK-8000 Aarhus C, Denmark."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4890-3842","authenticated-orcid":true,"given":"Nino","family":"Wili","sequence":"additional","affiliation":[{"name":"Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, DK-8000 Aarhus C, Denmark."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0007-1905-8105","authenticated-orcid":true,"given":"Asbj\u00f8rn Holk","family":"Thomsen","sequence":"additional","affiliation":[{"name":"Department of Mathematics, Aarhus University, Ny Munkegade 118, DK-8000 Aarhus C, Denmark."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9423-1106","authenticated-orcid":true,"given":"David L.","family":"Goodwin","sequence":"additional","affiliation":[{"name":"Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, DK-8000 Aarhus C, Denmark."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8969-9214","authenticated-orcid":true,"given":"Lukas","family":"Trottner","sequence":"additional","affiliation":[{"name":"Institute for Stochastics and Applications, University of Stuttgart, Wankelstrasse 5, 70563 Stuttgart, Germany."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2910-4677","authenticated-orcid":true,"given":"Claudia","family":"Strauch","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Mathematik, Ruprecht-Karls-Universit\u00e4t Heidelberg, Mathematikon, Im Neuenheimer Feld 205, 69120 Heidelberg, Germany."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anders Bodholt","family":"Nielsen","sequence":"additional","affiliation":[{"name":"Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, DK-8000 Aarhus C, Denmark."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2978-4366","authenticated-orcid":true,"given":"Niels Chr.","family":"Nielsen","sequence":"additional","affiliation":[{"name":"Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, DK-8000 Aarhus C, Denmark."}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"221","reference":[{"key":"e_1_3_2_2_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRev.70.460"},{"key":"e_1_3_2_3_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRev.80.580"},{"key":"e_1_3_2_4_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRev.78.695"},{"key":"e_1_3_2_5_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.13.567"},{"key":"e_1_3_2_6_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1697128"},{"key":"e_1_3_2_7_2","doi-asserted-by":"crossref","unstructured":"A. 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