{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,16]],"date-time":"2026-10-16T03:16:41Z","timestamp":1792120601889,"version":"4.4.0"},"reference-count":45,"publisher":"Wiley","issue":"24","license":[{"start":{"date-parts":[[2023,12,28]],"date-time":"2023-12-28T00:00:00Z","timestamp":1703721600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2023,12,28]],"date-time":"2023-12-28T00:00:00Z","timestamp":1703721600000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22272146"],"award-info":[{"award-number":["22272146"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["21922202"],"award-info":[{"award-number":["21922202"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100012246","name":"Priority Academic Program Development of Jiangsu Higher Education Institutions","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100012246","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100010023","name":"Natural Science Research of Jiangsu Higher Education Institutions of China","doi-asserted-by":"publisher","award":["20KJB150028,22KJD150009"],"award-info":[{"award-number":["20KJB150028,22KJD150009"]}],"id":[{"id":"10.13039\/501100010023","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Small"],"published-print":{"date-parts":[[2024,6]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    The development of chiral nanostructures\u2010based supramolecular catalysts with satisfied enantioselectivity remains a significantly more challenging task. Herein, the synthesis and self\u2010assembly of various amino acid amphiphiles as chiral supramolecular catalysts after metal ion coordination is reported and systematically investigate their enantioselectivity in asymmetric Diels\u2013Alder reactions. In particular, the self\u2010assembly of\n                    <jats:sc>l<\/jats:sc>\n                    \/\n                    <jats:sc>d<\/jats:sc>\n                    \u2010phenylglycine\u2010based amphiphiles (\n                    <jats:sc>l<\/jats:sc>\n                    \/\n                    <jats:sc>d<\/jats:sc>\n                    \u2010PhgC\n                    <jats:sub>16<\/jats:sub>\n                    ) and Cu(II) into chiral supramolecular catalysts in the methanol\/water solution mixture is described, which features the interesting\n                    <jats:italic>M\/P<\/jats:italic>\n                    nanohelices (diameter \u22488\u00a0nm) and mostly well\u2010aligned\n                    <jats:italic>M\/P<\/jats:italic>\n                    nanoribbons (NRs). The\n                    <jats:italic>M<\/jats:italic>\n                    \/\n                    <jats:italic>P<\/jats:italic>\n                    supramolecular catalysts show both high but inverse enantioselectivity (&gt;90%\n                    <jats:italic>ee<\/jats:italic>\n                    ) in Diels\u2013Alder reactions, while their monomeric counterparts display nearly racemic products. Analysis of the catalytic results suggests the outstanding enantioselectivities are closely related to the specific stereochemical microenvironment provided by the arrangement of the amphiphiles in the supramolecular assembly. Based on the experimental evidence of chirality transfer from supramolecular nanohelices to coordinated Cu(II) and substrate aza\u2010chalcone and the molecular dynamics simulations, the enantioselective catalytic mechanisms are proposed. Moreover, the relationships between molecular structures of amino acid amphiphiles (the hydrophilic head group and hydrophobic alkyl chain length) in supramolecular catalysts and enantioselectivity in Diels\u2013Alder reactions are elaborated.\n                  <\/jats:p>","DOI":"10.1002\/smll.202310234","type":"journal-article","created":{"date-parts":[[2023,12,29]],"date-time":"2023-12-29T01:35:36Z","timestamp":1703813736000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":17,"title":["Self\u2010Assembled Metal\u2010Coordination Nanohelices as Efficient and Robust Chiral Supramolecular Catalysts for Enantioselective Reactions"],"prefix":"10.1002","volume":"20","author":[{"given":"Cong","family":"Gao","sequence":"first","affiliation":[{"name":"School of Chemistry and Chemical Engineering Yangzhou University  Yangzhou Jiangsu 225002 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shixin","family":"Li","sequence":"additional","affiliation":[{"name":"School of Bioscience and Biotechnology, Yangzhou University Yangzhou Jiangsu 225002 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Cici","family":"Zhao","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Yangzhou University  Yangzhou Jiangsu 225002 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qingqing","family":"Sun","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Yangzhou University  Yangzhou Jiangsu 225002 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaohuan","family":"Sun","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Yangzhou University  Yangzhou Jiangsu 225002 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lingling","family":"Ge","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Yangzhou University  Yangzhou Jiangsu 225002 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lei","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Yangzhou University  Yangzhou Jiangsu 225002 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zheng","family":"Xi","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Yangzhou University  Yangzhou Jiangsu 225002 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0050-7509","authenticated-orcid":false,"given":"Jie","family":"Han","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Yangzhou University  Yangzhou Jiangsu 225002 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rong","family":"Guo","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Yangzhou University  Yangzhou Jiangsu 225002 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,12,28]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-020-00528-3"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr050311y"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr4001226"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1226132"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/b811349c"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b01306"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr500671p"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c04182"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.0c00604"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b03309"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.8b00312"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202209806"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.0c00012"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9QM00571D"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202013790"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b08808"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/la203110z"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5NR03699B"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.langmuir.9b01745"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201904884"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsnano.7b06484"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-019-11840-3"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsmaterialslett.2c00761"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja408860s"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsnano.1c05489"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201302662"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.9b00509"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5RA04437E"},{"key":"e_1_2_7_29_1","unstructured":"We performed the CD and catalytic experiments of the assemblies of L\u2010 and D\u2010PhgC16 formed at different time intervals in the 4\/6 methanol\/water solution respectively. (Figure S34 and Figure S40) The result showed that the intensity of CD signal obtained at 5\u00a0min was lower than that at 10\u00a0min which did not experience noticeable changes with extended time. Interestingly similar enantioselectivity (92% ee) for the Diels\u2010Alder reaction was achieved by the Cu(II)\u2010assemblies formed at 10 15 30 and 60\u00a0min while lower ee (83\u201085%) was obtained by the assemblies formed at 5\u00a0min. These results suggested that the self\u2010assembly process of L\u2010 and D\u2010PhgC16 was completed after 10\u00a0min."},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1039\/c4cc00311j"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202103809"},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.201905667"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201800251"},{"key":"e_1_2_7_34_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201103187"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201301539"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1002\/adom.202000173"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsnano.9b07307"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsnano.0c00352"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201704431"},{"key":"e_1_2_7_40_1","unstructured":"The Diels\u2010Alder reaction catalyzed by Cu(II) alone showed the retention times of the endo and exo isomers and the formation of endo\u2010dominated products (Figure S53 Supporting Information). In the presence of the metal\u2010coordinated chiral supramolecular assemblies the ratio of endo:exo calculated by integrating the peak areas appeared at distinct retention times was revealed to be larger than 90% (Figure S54 Supporting Information)."},{"key":"e_1_2_7_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja960318k"},{"key":"e_1_2_7_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja972772"},{"key":"e_1_2_7_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja984273u"},{"key":"e_1_2_7_44_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202101499"},{"key":"e_1_2_7_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c12907"}],"container-title":["Small"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/smll.202310234","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/smll.202310234","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/smll.202310234","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,3,8]],"date-time":"2026-03-08T21:15:54Z","timestamp":1773004554000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/smll.202310234"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,12,28]]},"references-count":45,"journal-issue":{"issue":"24","published-print":{"date-parts":[[2024,6]]}},"alternative-id":["10.1002\/smll.202310234"],"URL":"https:\/\/doi.org\/10.1002\/smll.202310234","archive":["Portico"],"relation":{},"ISSN":["1613-6810","1613-6829"],"issn-type":[{"value":"1613-6810","type":"print"},{"value":"1613-6829","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,12,28]]},"assertion":[{"value":"2023-11-09","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2023-12-28","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"2310234"}}