{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,13]],"date-time":"2026-10-13T23:44:44Z","timestamp":1791935084797,"version":"4.3.4"},"reference-count":35,"publisher":"American Chemical Society (ACS)","issue":"23","license":[{"start":{"date-parts":[[2026,6,3]],"date-time":"2026-06-03T00:00:00Z","timestamp":1780444800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,6,3]],"date-time":"2026-06-03T00:00:00Z","timestamp":1780444800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,6,3]],"date-time":"2026-06-03T00:00:00Z","timestamp":1780444800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["NSF-2018860"],"award-info":[{"award-number":["NSF-2018860"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000015","name":"U.S. Department of Energy","doi-asserted-by":"publisher","award":["DE-SC0024088"],"award-info":[{"award-number":["DE-SC0024088"]}],"id":[{"id":"10.13039\/100000015","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,6,17]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Skyrocketing demand for rare-earth elements makes their isolation and reuse from electronic waste an increasingly attractive alternative to mining. Typically, the capture of individual lanthanides from mixtures requires the iterative design of complex, macrocyclic ligands, a sometimes successful but often laborious process. Here we show that the self-assembly of rare-earth ions with a ditopic ligand, Ld, results in the selective incorporation of smaller lanthanides and gives rise to impressive separation factors. Comparison to a monotopic ligand, Lm, shows that the separation performance of ditopic Ld critically depends on the presence of two adjacent binding sites. Isothermal titration calorimetry (ITC) experiments show that the selectivity of Ld for smaller ions is thermodynamically driven and provide evidence of positive cooperativity among the two binding sites of Ld. The simplicity of the separation procedure reported here, requiring only 1 min of sonication in methanol, shows the potential applicability of this approach to real-world separations. By achieving efficient rare-earth separations in small, synthetically facile helicates, this work shows the promise of self-assembly as a mechanism to drive metal separations.<\/jats:p>","DOI":"10.1021\/jacs.6c04841","type":"journal-article","created":{"date-parts":[[2026,6,3]],"date-time":"2026-06-03T09:22:26Z","timestamp":1780478546000},"page":"24230-24239","source":"Crossref","is-referenced-by-count":2,"title":["Lanthanide Separations\nthrough Helicate Self-Assembly"],"prefix":"10.1021","volume":"148","author":[{"ORCID":"https:\/\/orcid.org\/0009-0009-2191-0330","authenticated-orcid":true,"given":"Michael R.","family":"Baptiste","sequence":"first","affiliation":[{"name":"University of Maryland, College Park , , , ,","place":["College Park, Maryland, United States, 20742"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-9166-9858","authenticated-orcid":true,"given":"Min Chieh","family":"Yang","sequence":"additional","affiliation":[{"name":"University of Maryland, College Park , , , ,","place":["College Park, Maryland, United States, 20742"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Emmanuel A.","family":"Bazan-Bergamino","sequence":"additional","affiliation":[{"name":"University of Maryland, College Park , , , ,","place":["College Park, Maryland, United States, 20742"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lina V.","family":"Gonzalez-Rey","sequence":"additional","affiliation":[{"name":"University of Maryland, College Park , , , ,","place":["College Park, Maryland, United States, 20742"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5762-3469","authenticated-orcid":true,"given":"Peter Y.","family":"Zavalij","sequence":"additional","affiliation":[{"name":"University of Maryland, College Park , , , ,","place":["College Park, Maryland, United States, 20742"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0945-766X","authenticated-orcid":true,"given":"Mercedes K.","family":"Taylor","sequence":"additional","affiliation":[{"name":"University of Maryland, College Park , , , ,","place":["College Park, Maryland, United States, 20742"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,6,3]]},"reference":[{"key":"2026073023095934700_cit1","doi-asserted-by":"publisher","first-page":"2451","DOI":"10.1039\/C3CS60440C","article-title":"Challenges\nto achievement of metal sustainability in our high-tech society","volume":"43","author":"Izatt","year":"2014","journal-title":"Chem. Soc. Rev."},{"key":"2026073023095934700_cit2","doi-asserted-by":"publisher","first-page":"182","DOI":"10.1016\/j.envres.2016.05.052","article-title":"Global demand for rare earth resources\nand strategies for green mining","volume":"150","author":"Dutta","year":"2016","journal-title":"Environ. Res."},{"key":"2026073023095934700_cit3","doi-asserted-by":"publisher","first-page":"30","DOI":"10.1021\/cen-09534-cover","article-title":"A whole\nnew world for rare earths","volume":"95","author":"Ritter","year":"2017","journal-title":"C&EN"},{"key":"2026073023095934700_cit4","doi-asserted-by":"publisher","first-page":"141","DOI":"10.1002\/cite.201700098","article-title":"Demand, Supply,\nand Price Trends for Mineral Raw Materials\nRelevant to the Renewable Energy Transition Wind Energy, Solar Photovoltaic\nEnergy, and Energy Storage","volume":"90","author":"Buchholz","year":"2018","journal-title":"Chem. Ing. Technol."},{"key":"2026073023095934700_cit5","doi-asserted-by":"publisher","first-page":"153","DOI":"10.1016\/j.resourpol.2016.05.003","article-title":"National strategies\nfor securing a stable supply of rare earths in\ndifferent world regions","volume":"49","author":"Bartekova\u0301","year":"2016","journal-title":"Resour. Policy"},{"key":"2026073023095934700_cit6","doi-asserted-by":"publisher","first-page":"36","DOI":"10.1016\/j.resourpol.2012.07.001","article-title":"Rare earth elements\nas critical raw materials: Focus\non international markets and future strategies","volume":"38","author":"Massari","year":"2013","journal-title":"Resour. Policy"},{"key":"2026073023095934700_cit7","doi-asserted-by":"publisher","first-page":"94","DOI":"10.1038\/s41561-023-01350-9","article-title":"Regional\nrare-earth element supply\nand demand balanced with circular economy strategies","volume":"17","author":"Wang","year":"2024","journal-title":"Nat. Geosci."},{"key":"2026073023095934700_cit8","doi-asserted-by":"publisher","DOI":"10.1016\/j.hydromet.2023.106156","article-title":"The recovery\nof\nrare earth elements from waste electrical and electronic equipment:\nA review","volume":"222","author":"Pimassoni","year":"2023","journal-title":"Hydrometallurgy"},{"key":"2026073023095934700_cit9","doi-asserted-by":"publisher","first-page":"7965","DOI":"10.1021\/acs.chemrev.5c00103","article-title":"Electrochemical\nSeparation and Clean\nEnergy Applications of Rare Earth Elements","volume":"125","author":"Ghosh","year":"2025","journal-title":"Chem. Rev."},{"key":"2026073023095934700_cit10","doi-asserted-by":"publisher","first-page":"5751","DOI":"10.1038\/s41467-024-49981-9","article-title":"Catalytic properties of trivalent\nrare-earth oxides with intrinsic\nsurface oxygen vacancy","volume":"15","author":"Xu","year":"2024","journal-title":"Nat. Commun."},{"key":"2026073023095934700_cit11","doi-asserted-by":"publisher","first-page":"801","DOI":"10.1016\/j.jre.2020.01.012","article-title":"Advances and\nprospects of rare earth\nmetal-organic frameworks in catalytic applications","volume":"38","author":"Sun","year":"2020","journal-title":"J. Rare Earths"},{"key":"2026073023095934700_cit12","doi-asserted-by":"publisher","first-page":"220","DOI":"10.1016\/j.ccr.2017.01.011","article-title":"Systematics and surprises in lanthanide\ncoordination\nchemistry","volume":"340","author":"Cotton","year":"2017","journal-title":"Coord. Chem. Rev."},{"key":"2026073023095934700_cit13","doi-asserted-by":"publisher","first-page":"751","DOI":"10.1107\/S0567739476001551","article-title":"Revised\neffective ionic radii and systematic studies of interatomic distances\nin halides and chalcogenides","volume":"32","author":"Shannon","year":"1976","journal-title":"Acta Crystallogr."},{"key":"2026073023095934700_cit14","doi-asserted-by":"publisher","first-page":"25669","DOI":"10.1021\/jacs.4c07332","article-title":"Tetradentate\nLigand\u2019s Chameleon-Like Behavior\nOffers Recognition of Specific Lanthanides","volume":"146","author":"Pramanik","year":"2024","journal-title":"J. Am. Chem. Soc."},{"key":"2026073023095934700_cit15","doi-asserted-by":"publisher","first-page":"16327","DOI":"10.1021\/acsami.9b22902","article-title":"Molecular Recognition at Mineral Interfaces: Implications\nfor the Beneficiation of Rare Earth Ores","volume":"12","author":"Sutton","year":"2020","journal-title":"ACS\nAppl. Mater. Interfaces"},{"key":"2026073023095934700_cit16","doi-asserted-by":"publisher","first-page":"6326","DOI":"10.1002\/chem.201806443","article-title":"Efficient Separation of Light Lanthanides(III)\nby Using Bis-Lactam Phenanthroline Ligands","volume":"25","author":"Healy","year":"2019","journal-title":"Chem.-Eur. J."},{"key":"2026073023095934700_cit17","doi-asserted-by":"publisher","first-page":"17620","DOI":"10.1021\/acs.inorgchem.0c02861","article-title":"Structure\nActivity Relationship Approach toward the Improved Separation of Rare-Earth\nElements Using Diglycolamides","volume":"59","author":"Stamberga","year":"2020","journal-title":"Inorg. Chem."},{"key":"2026073023095934700_cit18","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202410233","article-title":"Chelator-Assisted\nPrecipitation-Based Separation of the Rare Earth Elements Neodymium\nand Dysprosium from Aqueous Solutions","volume":"63","author":"Gao","year":"2024","journal-title":"Angew.\nChem., Int. Ed."},{"key":"2026073023095934700_cit19","doi-asserted-by":"publisher","first-page":"22666","DOI":"10.1021\/jacs.5c04150","article-title":"Macrocyclic Chelators for Aqueous Lanthanide Separations\nvia Precipitation: Toward Sustainable Recycling of Rare-Earths from\nNdFeB Magnets","volume":"147","author":"Jones","year":"2025","journal-title":"J. Am. Chem. Soc."},{"issue":"6","key":"2026073023095934700_cit20","doi-asserted-by":"publisher","first-page":"1222","DOI":"10.1021\/acs.bioconjchem.2c00190","article-title":"H2 BZmacropa-NCS: A Bifunctional\nChelator for Actinium-225 Targeted Alpha Therapy","volume":"33","author":"Kadassery","year":"2022","journal-title":"Bioconjugate Chem."},{"key":"2026073023095934700_cit21","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2022.214786","article-title":"Design\nof lanthanide based metal\u2013organic\npolyhedral cages for application in catalysis, sensing, separation\nand magnetism","volume":"472","author":"Bell","year":"2022","journal-title":"Coord. Chem. Rev."},{"key":"2026073023095934700_cit22","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2022.214612","article-title":"Coordination\/metal\u2013organic\ncages inside out","volume":"467","author":"Tateishi","year":"2022","journal-title":"Coord. Chem. Rev."},{"key":"2026073023095934700_cit23","doi-asserted-by":"publisher","first-page":"6374","DOI":"10.1021\/acs.chemrev.1c00602","article-title":"Coordination-Directed\nSelf-Assembly\nof Functional Polynuclear Lanthanide Supramolecular Architectures","volume":"122","author":"Li","year":"2022","journal-title":"Chem. Rev."},{"key":"2026073023095934700_cit24","doi-asserted-by":"publisher","first-page":"168","DOI":"10.1038\/s41570-020-00246-1","article-title":"Metal-organic\ncages\nfor molecular separations","volume":"5","author":"Zhang","year":"2021","journal-title":"Nat. Rev. Chem."},{"key":"2026073023095934700_cit25","doi-asserted-by":"publisher","first-page":"528","DOI":"10.1039\/D0CS00443J","article-title":"The rise of\nmetal\u2013organic polyhedral","volume":"50","author":"Lee","year":"2021","journal-title":"Chem. Soc.\nRev."},{"key":"2026073023095934700_cit26","doi-asserted-by":"publisher","first-page":"547","DOI":"10.1038\/s41467-018-02940-7","article-title":"A supramolecular\nlanthanide separation approach based on multivalent\ncooperative enhancement of metal ion selectivity","volume":"9","author":"Li","year":"2018","journal-title":"Nat. Commun."},{"issue":"47","key":"2026073023095934700_cit27","doi-asserted-by":"publisher","first-page":"17723","DOI":"10.1021\/ja409882k","article-title":"Cooperative\nThermodynamic Control of Selectivity in the Self-Assembly of Rare\nEarth Metal\u2013Ligand Helices","volume":"135","author":"Johnson","year":"2013","journal-title":"J. Am. Chem.\nSoc."},{"key":"2026073023095934700_cit28","doi-asserted-by":"publisher","first-page":"5394","DOI":"10.1073\/pnas.90.12.5394","article-title":"Self-recognition in helicate self-assembly:\nspontaneous formation of helical metal complexes from mixtures of\nligands and metal ions","volume":"90","author":"Kramer","year":"1993","journal-title":"Proc. Natl. Acad. Sci.\nU.S.A."},{"key":"2026073023095934700_cit29","doi-asserted-by":"publisher","first-page":"4784","DOI":"10.1039\/D4CC05827E","article-title":"Selective\nbinding of rare-earth ions in polymerizable\ncages","volume":"61","author":"Ou","year":"2025","journal-title":"Chem. Commun."},{"key":"2026073023095934700_cit30","unstructured":"Rowan, L. R.\n          \n          Critical Mineral Resources:\nNational Policy and Critical Minerals List; Congressional Research Service, 2026."},{"issue":"4","key":"2026073023095934700_cit31","doi-asserted-by":"publisher","first-page":"1495","DOI":"10.1016\/j.fmre.2023.01.004","article-title":"Yttrium separation\nby phosphorylcarboxylic acid and the underlying\ntetrad effect along lanthanide unveiled from different microscopic\ninteractions","volume":"5","author":"Zhang","year":"2025","journal-title":"Fundamental Research"},{"key":"2026073023095934700_cit32","doi-asserted-by":"publisher","DOI":"10.1063\/1.1839852","article-title":"Introducing ONETEP:\nLinear-scaling density functional simulations on parallel computers","volume":"122","author":"Skylaris","year":"2005","journal-title":"J. Chem. Phys."},{"key":"2026073023095934700_cit33","doi-asserted-by":"publisher","first-page":"4457","DOI":"10.1021\/acs.inorgchem.6b00244","article-title":"Periodic Trends in Lanthanide Compounds\nthrough the Eyes of Multireference ab Initio Theory","volume":"55","author":"Aravena","year":"2016","journal-title":"Inorg. Chem."},{"key":"2026073023095934700_cit34","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.98.205101","article-title":"First-principles calculation of Coulomb\ninteraction\nparameters for lanthanides: Role of self-consistence and screening\nprocesses","volume":"98","author":"More\u0301e","year":"2018","journal-title":"Phys. Rev. B"},{"key":"2026073023095934700_cit35","doi-asserted-by":"publisher","first-page":"324","DOI":"10.1103\/PhysRevB.33.324","article-title":"Magnetic ground\nstate of metallic hydrogen and lithium in the low-density limit","volume":"33","author":"Min","year":"1986","journal-title":"Phys. Rev. B"}],"container-title":["Journal of the American\nChemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacs.6c04841","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/23\/24230\/66271344\/jacs.6c04841.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/23\/24230\/66271344\/jacs.6c04841.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,7,31]],"date-time":"2026-07-31T03:10:05Z","timestamp":1785467405000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jacsat\/article\/148\/23\/24230\/5233450\/Lanthanide-Separations-through-Helicate-Self"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,6,3]]},"references-count":35,"journal-issue":{"issue":"23","published-online":{"date-parts":[[2026,6,3]]},"published-print":{"date-parts":[[2026,6,17]]}},"URL":"https:\/\/doi.org\/10.1021\/jacs.6c04841","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,6,3]]}}}