{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,12,9]],"date-time":"2025-12-09T12:46:43Z","timestamp":1765284403065,"version":"3.46.0"},"reference-count":29,"publisher":"MDPI AG","issue":"24","license":[{"start":{"date-parts":[[2025,12,9]],"date-time":"2025-12-09T00:00:00Z","timestamp":1765238400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100004329","name":"Slovenian research agency","doi-asserted-by":"publisher","award":["P1\u2013153"],"award-info":[{"award-number":["P1\u2013153"]}],"id":[{"id":"10.13039\/501100004329","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Hydrophilic interaction liquid chromatography (HILIC) is widely used for the analysis of glycans and oligosaccharides, yet the molecular basis of retention remains incompletely understood. In this study, we investigated dextran ladders labelled with 2-aminobenzamide (2-AB) and Rapifluor-MS\u2122 (Waters, Milford, MA, USA) across a wide range of degrees of polymerization (DP 2\u201315), temperature conditions (10 \u00b0C to 70 \u00b0C), and gradient programs using a Acquity\u2122 Premier Glycan BEH Amide column (Bridged Ethylene Hybrid, Waters, Milford, MA, USA). Van\u2019t Hoff analysis revealed distinct enthalpic and entropic contributions to retention, allowing identification of a mechanistic transition from enthalpy-dominated docking interactions at low DP to entropy-driven dynamic adsorption at higher DP. This transition occurred reproducibly between DP 4\u20136, depending on the fluorescent label, while gradient steepness primarily influenced the location of the minimum enthalpy. Molecular dynamics simulations provided additional evidence, showing increased conformational flexibility and end-to-end distance variability for longer oligomers. This finding is consistent with entropy-dominated adsorption accompanied by displacement of structured interfacial water. Together, these results establish a molecular-level framework linking retention thermodynamics, conformational behavior, and solvation effects, thereby advancing our mechanistic understanding of glycan separation in HILIC.<\/jats:p>","DOI":"10.3390\/molecules30244711","type":"journal-article","created":{"date-parts":[[2025,12,9]],"date-time":"2025-12-09T12:42:43Z","timestamp":1765284163000},"page":"4711","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Molecular and Thermodynamic Insights into the Enthalpy-Entropy Shift Governing HILIC Retention of Labelled Dextrans"],"prefix":"10.3390","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0009-0008-3458-9905","authenticated-orcid":false,"given":"Matja\u017e","family":"Gr\u010dman","sequence":"first","affiliation":[{"name":"Faculty of Chemistry and Chemical Technology, University of Ljubljana, Ve\u010dna pot 113, SI-1000 Ljubljana, Slovenia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8429-0273","authenticated-orcid":false,"given":"\u010crtomir","family":"Podlipnik","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Chemical Technology, University of Ljubljana, Ve\u010dna pot 113, SI-1000 Ljubljana, Slovenia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Matev\u017e","family":"Pompe","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Chemical Technology, University of Ljubljana, Ve\u010dna pot 113, SI-1000 Ljubljana, Slovenia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6835-840X","authenticated-orcid":false,"given":"Drago","family":"Ko\u010dar","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Chemical Technology, University of Ljubljana, Ve\u010dna pot 113, SI-1000 Ljubljana, Slovenia"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2025,12,9]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"465232","DOI":"10.1016\/j.chroma.2024.465232","article-title":"Understanding Retention and Intra-Particle Diffusivity of Alkylsulfobetaine-Bonded Ethylene Bridged Particles with Different Mesopore Sizes for Hydrophilic Interaction Liquid Chromatography Applications","volume":"1733","author":"Gritti","year":"2024","journal-title":"J. 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