{"title":"通过多平衡 GFN2-xTB 量子方法实现 α-CD 对葑酮和樟脑的手性识别","authors":"Cleber Paulo Andrada Anconi","doi":"10.1007/s10847-024-01219-3","DOIUrl":null,"url":null,"abstract":"<div><p>Binding constants for host-guest cyclodextrin systems have been estimated recently through the small-cost GFN2-xTB semiempirical quantum method in a multi-equilibrium scope. This work applied such an approach to investigate the inclusion of fenchone and camphor into α-cyclodextrin. The computational cost associated with GFN2-xTB and the supramolecular arrangements automated obtained by UD-APARM allowed the investigation of an unprecedented 18,615 starting systems (8640 for 1:1 guest/CD and 5184 + 2232 + 2559 for 1:2 guest/CD stoichiometry). According to the present study, only 18 (0.21%) for 1:1 associations and 45 (0.45%) for 1:2 associations contribute to the binding constants. The chiral recognition was achieved for the four inclusion compounds investigated: (−)-fenchone@(α-CD)<sub>2</sub>, (+)-fenchone@(α-CD)<sub>2</sub>, and (−)-camphor@(α-CD)<sub>2</sub> and (+)-camphor@(α-CD)<sub>2</sub>. When experimental and theoretical GFN2-xTB (ALPB) binding constants were compared, a linear correlation with an R<sup>2</sup> equal to 0.9933 was obtained. Estimated error varied from 1 to 3% to adjusted GFN2-xTB values. Furthermore, the theoretical data supported the experimental information that two CD units encapsulate camphor guests, increasing their stabilities. The procedure adopted can be expanded to investigate other 1:1 and 1:2 chiral host-guest systems for which it was addressed that finding out representative host-guest systems correspond to the bottleneck in the use of the discussed GFN2-xTB/UD-APARM multi-equilibrium approach.</p><h3>Graphical abstract</h3>\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":638,"journal":{"name":"Journal of Inclusion Phenomena and Macrocyclic Chemistry","volume":"104 3-4","pages":"83 - 98"},"PeriodicalIF":2.3000,"publicationDate":"2024-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Chiral recognition of fenchone and camphor by α-CD through the multi-equilibrium GFN2-xTB quantum approach\",\"authors\":\"Cleber Paulo Andrada Anconi\",\"doi\":\"10.1007/s10847-024-01219-3\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Binding constants for host-guest cyclodextrin systems have been estimated recently through the small-cost GFN2-xTB semiempirical quantum method in a multi-equilibrium scope. This work applied such an approach to investigate the inclusion of fenchone and camphor into α-cyclodextrin. The computational cost associated with GFN2-xTB and the supramolecular arrangements automated obtained by UD-APARM allowed the investigation of an unprecedented 18,615 starting systems (8640 for 1:1 guest/CD and 5184 + 2232 + 2559 for 1:2 guest/CD stoichiometry). According to the present study, only 18 (0.21%) for 1:1 associations and 45 (0.45%) for 1:2 associations contribute to the binding constants. The chiral recognition was achieved for the four inclusion compounds investigated: (−)-fenchone@(α-CD)<sub>2</sub>, (+)-fenchone@(α-CD)<sub>2</sub>, and (−)-camphor@(α-CD)<sub>2</sub> and (+)-camphor@(α-CD)<sub>2</sub>. When experimental and theoretical GFN2-xTB (ALPB) binding constants were compared, a linear correlation with an R<sup>2</sup> equal to 0.9933 was obtained. Estimated error varied from 1 to 3% to adjusted GFN2-xTB values. Furthermore, the theoretical data supported the experimental information that two CD units encapsulate camphor guests, increasing their stabilities. The procedure adopted can be expanded to investigate other 1:1 and 1:2 chiral host-guest systems for which it was addressed that finding out representative host-guest systems correspond to the bottleneck in the use of the discussed GFN2-xTB/UD-APARM multi-equilibrium approach.</p><h3>Graphical abstract</h3>\\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>\",\"PeriodicalId\":638,\"journal\":{\"name\":\"Journal of Inclusion Phenomena and Macrocyclic Chemistry\",\"volume\":\"104 3-4\",\"pages\":\"83 - 98\"},\"PeriodicalIF\":2.3000,\"publicationDate\":\"2024-02-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Inclusion Phenomena and Macrocyclic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s10847-024-01219-3\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"Agricultural and Biological Sciences\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Inclusion Phenomena and Macrocyclic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s10847-024-01219-3","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"Agricultural and Biological Sciences","Score":null,"Total":0}
Chiral recognition of fenchone and camphor by α-CD through the multi-equilibrium GFN2-xTB quantum approach
Binding constants for host-guest cyclodextrin systems have been estimated recently through the small-cost GFN2-xTB semiempirical quantum method in a multi-equilibrium scope. This work applied such an approach to investigate the inclusion of fenchone and camphor into α-cyclodextrin. The computational cost associated with GFN2-xTB and the supramolecular arrangements automated obtained by UD-APARM allowed the investigation of an unprecedented 18,615 starting systems (8640 for 1:1 guest/CD and 5184 + 2232 + 2559 for 1:2 guest/CD stoichiometry). According to the present study, only 18 (0.21%) for 1:1 associations and 45 (0.45%) for 1:2 associations contribute to the binding constants. The chiral recognition was achieved for the four inclusion compounds investigated: (−)-fenchone@(α-CD)2, (+)-fenchone@(α-CD)2, and (−)-camphor@(α-CD)2 and (+)-camphor@(α-CD)2. When experimental and theoretical GFN2-xTB (ALPB) binding constants were compared, a linear correlation with an R2 equal to 0.9933 was obtained. Estimated error varied from 1 to 3% to adjusted GFN2-xTB values. Furthermore, the theoretical data supported the experimental information that two CD units encapsulate camphor guests, increasing their stabilities. The procedure adopted can be expanded to investigate other 1:1 and 1:2 chiral host-guest systems for which it was addressed that finding out representative host-guest systems correspond to the bottleneck in the use of the discussed GFN2-xTB/UD-APARM multi-equilibrium approach.
期刊介绍：
The Journal of Inclusion Phenomena and Macrocyclic Chemistry is the premier interdisciplinary publication reporting on original research into all aspects of host-guest systems. Examples of specific areas of interest are: the preparation and characterization of new hosts and new host-guest systems, especially those involving macrocyclic ligands; crystallographic, spectroscopic, thermodynamic and theoretical studies; applications in chromatography and inclusion polymerization; enzyme modelling; molecular recognition and catalysis by inclusion compounds; intercalates in biological and non-biological systems, cyclodextrin complexes and their applications in the agriculture, flavoring, food and pharmaceutical industries; synthesis, characterization and applications of zeolites.
The journal publishes primarily reports of original research and preliminary communications, provided the latter represent a significant advance in the understanding of inclusion science. Critical reviews dealing with recent advances in the field are a periodic feature of the journal.
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