{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,27]],"date-time":"2026-10-27T04:32:58Z","timestamp":1793075578924,"version":"4.5.0"},"reference-count":27,"publisher":"Wiley","issue":"11","license":[{"start":{"date-parts":[[2026,10,26]],"date-time":"2026-10-26T00:00:00Z","timestamp":1792972800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,10,26]],"date-time":"2026-10-26T00:00:00Z","timestamp":1792972800000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["analyticalsciencejournals.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Journal of Chemometrics"],"published-print":{"date-parts":[[2026,11]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    Calibration models can improve agreement between calculated and experimental\n                    <jats:sup>13<\/jats:sup>\n                    C NMR shifts without necessarily transferring to a new compound. We reanalyzed a literature\u2010derived finite\u2010cluster GIAO\u2010DFT benchmark comprising carbamazepine (CBZ), theophylline (THP), and ibuprofen (IBP) using compound\u2010blocked validation and added an independent protocol\u2010heterogeneous external challenge using lamivudine Form II. Uncalibrated predictions, a one\u2010parameter offset, two\u2010parameter affine scaling, and a three\u2010parameter quadratic model were compared. Across the 20 primary sites, raw RMSE was 1.311\u2009ppm. Leave\u2010one\u2010compound\u2010out aggregate RMSE was 1.065\u2009ppm for offset correction, 1.113\u2009ppm for affine scaling, and 1.052\u2009ppm for quadratic calibration; macro\u2010averaged RMSE was 0.915, 0.986, and 0.916\u2009ppm, respectively. Offset correction was lower than affine scaling in all three internal folds. In the locked lamivudine challenge (eight\n                    <jats:sup>13<\/jats:sup>\n                    C sites), however, raw RMSE was 4.174\u2009ppm, and all three transferred calibrations worsened error: 4.643\u2009ppm offset, 4.623\u2009ppm affine, and 4.592\u2009ppm quadratic. Thus the external API does not support generalization of the internally favorable calibration behavior. Because the external calculation used a published Gaussian09 GIAO workflow rather than the historical finite\u2010cluster protocol, it is an out\u2010of\u2010domain robustness challenge rather than like\u2010for\u2010like validation. Fbias is interpreted only retrospectively. The results support a bounded conclusion: Calibration rankings in this small benchmark are fragile to API and protocol domain shift and require prospective validation under a harmonized computational workflow.\n                  <\/jats:p>","DOI":"10.1002\/cem.70186","type":"journal-article","created":{"date-parts":[[2026,10,27]],"date-time":"2026-10-27T03:56:12Z","timestamp":1793073372000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Compound\u2010Blocked Calibration Transfer in a Three\u2010API Finite\u2010Cluster GIAO\u2010DFT\n                    <sup>13<\/sup>\n                    C NMR Benchmark"],"prefix":"10.1002","volume":"40","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1674-9705","authenticated-orcid":false,"given":"Khaldoun A.","family":"Al\u2010Sou'od","sequence":"first","affiliation":[{"name":"Department of Chemistry Al al\u2010Bayt University  Mafraq Jordan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9271-6943","authenticated-orcid":false,"given":"Raed","family":"Ghanem","sequence":"additional","affiliation":[{"name":"Department of Chemistry Al al\u2010Bayt University  Mafraq 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