{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,20]],"date-time":"2026-02-20T17:53:03Z","timestamp":1771609983467,"version":"3.50.1"},"reference-count":52,"publisher":"MDPI AG","issue":"2","license":[{"start":{"date-parts":[[2023,2,13]],"date-time":"2023-02-13T00:00:00Z","timestamp":1676246400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["19-73-10079"],"award-info":[{"award-number":["19-73-10079"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Symmetry"],"abstract":"<jats:p>The chirality of biopolymers and its emergence from the racemic prebiotic world is one of the key mysteries of science. There are many versions on how the total chiral balance breaking occurred, but they all face an insoluble challenge\u2014the impossibility of a total shift of the chiral balance towards the formation of biopolymers based only on D-sugars and L-amino acids. A possible solution to this problem lies in the asymmetric autocatalysis on chiral crystals. Since the reaction is heterogeneous, it is important to study the features of adsorption on the surface of crystals. In this paper, the adsorption of limonene, \u03b1-pinene, and menthol enantiomers on \u03b3-glycine and CsCuCl3 crystals was studied. Single-crystal X-ray crystallography, SEM, and porosimetry were used as auxiliary methods. The t-test was used to determine the reliability of chiral recognition. It was shown that both crystals were capable of chiral recognition at high coverages. The mechanism of supramolecular chiral recognition was identical to that of the chiral crystals studied previously. However, neither \u03b3-glycine nor CsCuCl3 showed chiral recognition with respect to all enantiomers. In fact, \u03b3-glycine crystals showed recognition for limonene enantiomers, and very high recognition in the case of menthol enantiomers. CsCuCl3 crystals showed the capability to recognize enantiomers of \u03b1-pinenes only. This led to the conclusion that the recognition of enantiomers by a supramolecular chiral surface is not universal.<\/jats:p>","DOI":"10.3390\/sym15020498","type":"journal-article","created":{"date-parts":[[2023,2,14]],"date-time":"2023-02-14T02:41:56Z","timestamp":1676342516000},"page":"498","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["Manifestation of Supramolecular Chirality during Adsorption on CsCuCl3 and \u03b3-Glycine Crystals"],"prefix":"10.3390","volume":"15","author":[{"given":"Ilya","family":"Zinovyev","sequence":"first","affiliation":[{"name":"Department of Chemistry, Ufa University of Science and Technology, 32 Zaki Validi Str., 450076 Ufa, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ekaterina","family":"Ermolaeva","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Ufa University of Science and Technology, 32 Zaki Validi Str., 450076 Ufa, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yuliya","family":"Sharafutdinova","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Ufa University of Science and Technology, 32 Zaki Validi Str., 450076 Ufa, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Elmira","family":"Gilfanova","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Ufa University of Science and Technology, 32 Zaki Validi Str., 450076 Ufa, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2095-9097","authenticated-orcid":false,"given":"Leonard","family":"Khalilov","sequence":"additional","affiliation":[{"name":"Ufa Federal Research Centre of the Russian Academy of Sciences (UFRC RAS), Institute of Petrochemistry and Catalysis RAS, 141 Oktyabrya Av., 450075 Ufa, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Irina","family":"Pavlova","sequence":"additional","affiliation":[{"name":"Ufa Federal Research Centre of the Russian Academy of Sciences (UFRC RAS), Institute of Petrochemistry and Catalysis RAS, 141 Oktyabrya Av., 450075 Ufa, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4814-5180","authenticated-orcid":false,"given":"Vladimir","family":"Guskov","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Ufa University of Science and Technology, 32 Zaki Validi Str., 450076 Ufa, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2023,2,13]]},"reference":[{"key":"ref_1","unstructured":"Viedma, C., Coquerel, G., and Cintas, P. (2015). Handbook of Crystal Growth, Elsevier."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"7304","DOI":"10.1021\/cr500671p","article-title":"Supramolecular chirality in self-assembled systems","volume":"115","author":"Liu","year":"2015","journal-title":"Chem. Rev."},{"key":"ref_3","doi-asserted-by":"crossref","unstructured":"Bonner, W.A. (1988). Origins of Chiral Homogeneity in Nature, John Wiley&Sons, Inc.","DOI":"10.1002\/9780470147276.ch1"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"7787","DOI":"10.1039\/C7CS00555E","article-title":"Enantiomer surface chemistry: Conglomerate versus racemate formation on surfaces","volume":"46","author":"Dutta","year":"2017","journal-title":"Chem. Soc. Rev."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"363","DOI":"10.1039\/b305550g","article-title":"Supramolecular chirality of self-assembled systems in solution","volume":"33","author":"Reinhoudt","year":"2004","journal-title":"Chem. Soc. Rev."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"256","DOI":"10.3390\/sym6020256","article-title":"Supramolecular chirality in porphyrin chemistry","volume":"6","author":"Borovkov","year":"2014","journal-title":"Symmetry"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"a032540","DOI":"10.1101\/cshperspect.a032540","article-title":"The Origin of Biological Homochirality","volume":"11","author":"Blackmond","year":"2019","journal-title":"Cold Spring Harb. Perspect. Biol."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"6039","DOI":"10.1002\/adma.201302448","article-title":"Supramolecular helices: Chirality transfer from conjugated molecules to structures","volume":"25","author":"Yang","year":"2013","journal-title":"Adv. Mater."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"1107","DOI":"10.1002\/ijch.201100152","article-title":"Why are biological systems homochiral","volume":"51","author":"Percec","year":"2011","journal-title":"Isr. J. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"287","DOI":"10.1021\/ar0500158","article-title":"Molecular packing and symmetry of two-dimensional crystals","volume":"40","author":"Plass","year":"2007","journal-title":"Acc. Chem. Res."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"376","DOI":"10.1039\/C9ME00146H","article-title":"Engineering porous two-dimensional lattices via self-assembly of non-convex hexagonal platelets","volume":"5","author":"Pakalidou","year":"2020","journal-title":"Mol. Syst. Des. Eng."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"99","DOI":"10.1007\/BF01732291","article-title":"Crystallization and solid-state reaction as a route to asymmetric synthesis from achiral starting materials","volume":"6","author":"Green","year":"1975","journal-title":"J. Mol. Evol."},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"P\u00e1lyi, G., and Zucchi, C. (2017). Advances in Asymmetric Autocatalysis and Related Topics, Elsevier.","DOI":"10.1016\/j.focat.2017.05.056"},{"key":"ref_14","first-page":"359","article-title":"Chiral surfaces formed by uracil, 5-hydroxy-6-methyluracil and melamine supramolecular structures","volume":"12","author":"Gainullina","year":"2016","journal-title":"Int. J. Appl. Chem."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"13940","DOI":"10.1021\/jp903406q","article-title":"Preparing self-assembled monolayers of cyanuric acid and melamine complex on HOPG surfaces","volume":"113","author":"Zhang","year":"2009","journal-title":"J. Phys. Chem. C"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"4209","DOI":"10.1021\/jp076916a","article-title":"One-step preparation of large-scale self-assembled monolayers of cyanuric acid and melamine supramolecular species on Au(111) surfaces","volume":"112","author":"Zhang","year":"2008","journal-title":"J. Phys. Chem. C"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"8078","DOI":"10.1039\/C7NJ00890B","article-title":"Porphyrin stacks as an efficient molecular glue to induce chirality in hetero-component calixarene\u2013porphyrin assemblies","volume":"41","author":"Marino","year":"2017","journal-title":"New J. Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"18638","DOI":"10.1039\/c1jm13623b","article-title":"Sensing mechanisms of supramolecular porphyrin aggregates: A teamwork task for the detection of gaseous analytes","volume":"21","author":"Nardis","year":"2011","journal-title":"J. Mater. Chem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"628","DOI":"10.1039\/D1CE01482J","article-title":"Impact of flexible succinate connectors on the formation of tetrasulfonylcalix[4]arene based nano-sized polynuclear cages: Structural diversity and induced chirality study","volume":"24","author":"Kniazeva","year":"2022","journal-title":"CrystEngComm"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"314","DOI":"10.1002\/anie.200803578","article-title":"Heteroatom-stabilized chiral framework of aluminophosphate molecular sieves","volume":"48","author":"Song","year":"2009","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"4527","DOI":"10.1039\/b207684p","article-title":"Synthesis and structure of a novel open-framework zincophosphate with intersecting three-dimensional helical channels","volume":"24","author":"Lin","year":"2002","journal-title":"J. Chem. Soc. Dalton Trans."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"42","DOI":"10.1002\/chem.200305295","article-title":"Detection and amplification of chirality by helical polymers","volume":"10","author":"Yashima","year":"2004","journal-title":"Chem. Eur. J."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"3515","DOI":"10.1002\/chem.202000126","article-title":"Long-range chiral induction by a fully noncovalent approach in supramolecular porphyrin\u2013calixarene assemblies","volume":"26","author":"Gaeta","year":"2020","journal-title":"Chem. Eur. J."},{"key":"ref_24","doi-asserted-by":"crossref","unstructured":"Nicosia, A., Vento, F., Marletta, G., Messina, G.M.L., Satriano, C., Villari, V., Micali, N., Martino, M.T.D., Schotman, M.J.G., and Mineo, P.G. (2021). Porphyrin-based supramolecular flags in the thermal gradients\u2019 wind: What breaks the symmetry, how and why. Nanomaterials, 11.","DOI":"10.3390\/nano11071673"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1017","DOI":"10.1002\/ijch.201100066","article-title":"Achiral organic, inorganic, and metal crystals as auxiliaries for asymmetric transformations","volume":"51","author":"Weissbuch","year":"2011","journal-title":"Isr. J. Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"561","DOI":"10.1021\/ja00210a041","article-title":"Total asymmetric transformations at interfaces with centrosymmetric crystals: Role of hydrophobic and kinetic effects in the crystallization of the system glycine\/aamino acids","volume":"110","author":"Weissbuch","year":"1988","journal-title":"J. Am. Chem. Soc."},{"key":"ref_27","doi-asserted-by":"crossref","unstructured":"Davankov, V.A. (2018). Biological Homochirality on the Earth, or in the Universe? A Selective Review. Symmetry, 10.","DOI":"10.3390\/sym10120749"},{"key":"ref_28","doi-asserted-by":"crossref","unstructured":"Davankov, V.A. (2021). Chance and necessity in the evolution of matter to Life: A comprehensive hypothesis. Symmetry, 13.","DOI":"10.3390\/sym13101918"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.pbiomolbio.2019.02.001","article-title":"Symmetry breaking and functional incompleteness in biological systems","volume":"150","author":"Korenic","year":"2020","journal-title":"Prog. Biophys. Mol. Biol."},{"key":"ref_30","doi-asserted-by":"crossref","unstructured":"Takahashi, J.-I., and Kobayashi, K. (2019). Origin of terrestrial bioorganic homochirality and symmetry breaking in the universe. Symmetry, 11.","DOI":"10.3390\/sym11070919"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"12219","DOI":"10.1039\/C9CC05946F","article-title":"Spontaneous mirror-symmetry breaking coupled to top-bottom chirality transfer: From porphyrin self-assembly to scalemic Diels\u2013Alder adducts","volume":"55","author":"Arlegui","year":"2019","journal-title":"Chem. Commun."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"065504","DOI":"10.1103\/PhysRevLett.94.065504","article-title":"Chiral symmetry breaking during crystallization: Complete chiral purity induced by nonlinear autocatalysis and recycling","volume":"94","author":"Viedma","year":"2005","journal-title":"Phys. Rev. Lett."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"459","DOI":"10.1016\/0006-3002(53)90082-1","article-title":"Spontaneous asymmetric synthesis","volume":"11","author":"Frank","year":"1953","journal-title":"Biochim. Biophys. Acta"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"767","DOI":"10.1038\/378767a0","article-title":"Asymmetric autocatalysis and amplification of enatiomeric excess of a chiral molecule","volume":"378","author":"Soai","year":"1995","journal-title":"Nature"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"89","DOI":"10.2183\/pjab.95.009","article-title":"Asymmetric autocatalysis. Chiral symmetry breaking and the origins of homochirality of organic molecules","volume":"95","author":"Soai","year":"2019","journal-title":"Proc. Jpn. Acad. Ser. B"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"6723","DOI":"10.1039\/C5CS00196J","article-title":"Viedma ripening: A reliable crystallisation method to reach single chirality","volume":"44","author":"Sogutoglu","year":"2015","journal-title":"Chem. Soc. Rev."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"2235","DOI":"10.1021\/jacsau.2c00394","article-title":"Identifying a hidden conglomerate chiral pool in the CSD","volume":"2","author":"Walsh","year":"2022","journal-title":"JACS Au"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"7","DOI":"10.1016\/j.jphotochemrev.2005.02.002","article-title":"Introduction to chiral crystallization of achiral organic compounds. Spontaneous generation of chirality","volume":"6","author":"Matsuura","year":"2005","journal-title":"J. Photochem. Photobiol. C Photochem. Rev."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"3573","DOI":"10.1021\/acs.cgd.6b00547","article-title":"Enantiomer-specific oriented attachment of guanidine carbonate crystals","volume":"16","author":"Sivakumar","year":"2016","journal-title":"Cryst. Growth Des."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"17769","DOI":"10.1039\/D0NJ03912H","article-title":"Supramolecular chiral surface of nickel sulfate hexahydrate crystals and its ability to chiral recognition by enantiomers adsorption data","volume":"44","author":"Allayarova","year":"2020","journal-title":"New J. Chem."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"11968","DOI":"10.1039\/D1CP01265G","article-title":"Mechanism of chiral recognition by enantiomorphous cytosine crystals during enantiomer adsorption","volume":"23","author":"Shayakhmetova","year":"2021","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"26785","DOI":"10.1039\/D2CP01212J","article-title":"Possibility of chiral recognition by adsorption on enantiomorphous crystals: The impact of crystal surface polarity","volume":"24","author":"Gallyamova","year":"2022","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"1513","DOI":"10.1039\/C4CE02434F","article-title":"Attrition-induced spontaneous chiral amplification of the \u03b3 polymorphic modification of glycine","volume":"17","author":"Tarasevych","year":"2015","journal-title":"CrystEngComm"},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"4200","DOI":"10.1039\/C9OB00345B","article-title":"Achiral amino acid glycine acts as an origin of homochirality in asymmetric autocatalysis","volume":"17","author":"Matsumoto","year":"2019","journal-title":"Org. Biomol. Chem."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"339","DOI":"10.1107\/S0021889808042726","article-title":"OLEX2: A Complete Structure Solution, Refinement and Analysis Program","volume":"42","author":"Dolomanov","year":"2009","journal-title":"J. Appl. Cryst."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1107\/S2053229614024218","article-title":"Crystal structure refinement with SHELXL","volume":"71","author":"Sheldrick","year":"2015","journal-title":"Acta Crystallogr. Sect. C Struct. Chem."},{"key":"ref_47","doi-asserted-by":"crossref","unstructured":"Kiselev, A.V., and Yashin, Y.I. (1969). Gas Adsorption Chromatography, Plenum Press.","DOI":"10.1007\/978-1-4899-6503-5"},{"key":"ref_48","doi-asserted-by":"crossref","unstructured":"Rudzinski, W., Steele, W.A., and Zgrablich, G. (1997). Equilibria and Dynamics of Gas Adsorption on Heterogeneous Solid Surfaces, Elsevier.","DOI":"10.1016\/S0167-2991(97)80062-6"},{"key":"ref_49","unstructured":"Dodge, Y. (2008). The Concise Encyclopedia of Statistics, Springer."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"6031","DOI":"10.1039\/c2cc30549f","article-title":"Absolute chirality of the c-polymorph of glycine: Correlation of the absolute structure with the optical rotation","volume":"48","author":"Ishikawa","year":"2012","journal-title":"Chem. Commun."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"277","DOI":"10.1021\/ic50036a025","article-title":"A Redetermination of the Crystal Structure of CsCuCl3","volume":"5","author":"Schlueter","year":"1966","journal-title":"Inorg. Chem."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"14637","DOI":"10.1039\/c0cp00512f","article-title":"Chiral supramolecular self-assembly of rubrene","volume":"12","author":"Wang","year":"2010","journal-title":"Phys. Chem. Chem. Phys."}],"container-title":["Symmetry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-8994\/15\/2\/498\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T18:33:51Z","timestamp":1760121231000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-8994\/15\/2\/498"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,2,13]]},"references-count":52,"journal-issue":{"issue":"2","published-online":{"date-parts":[[2023,2]]}},"alternative-id":["sym15020498"],"URL":"https:\/\/doi.org\/10.3390\/sym15020498","relation":{},"ISSN":["2073-8994"],"issn-type":[{"value":"2073-8994","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,2,13]]}}}