{"title":"葡萄糖醛酸的合成凝集素","authors":"Canjia Zhai, , , Chengkai Xu, , , Yunpeng Cui, , , Lukasz Wojtas, , , Jianfeng Cai, , and , Wenqi Liu*, ","doi":"10.1021/acscentsci.5c00951","DOIUrl":null,"url":null,"abstract":"<p >The selective recognition of hydrophilic carbohydrates in water remains a longstanding challenge in supramolecular chemistry due to solvent competition and the lack of a strong driving force comparable to the hydrophobic effect. Herein, we report the design, synthesis, and characterization of a water-soluble tetralactam macrocycle, MPNT<sup>2+</sup>·2Cl<sup>–</sup>, as a highly effective synthetic lectin for glucuronate. MPNT<sup>2+</sup>·2Cl<sup>–</sup> features two dimethylnaphthalene panels, pyridinium spacers, and morpholine side chains, forming a rigid, preorganized cavity with convergent hydrogen bond donors, polarized C–H donors, and complementary electrostatic interactions. The receptor achieves a binding affinity of 103,000 M<sup>–1</sup> for glucuronate in water, over 19-fold higher than previous synthetic systems, along with excellent selectivity over structurally similar carbohydrates. Single-crystal X-ray analysis, DFT calculation, and IGMH analysis reveal a dense network of [N–H···O], [C–H···O], and [C–H···π] interactions, highlighting the role of stereoelectronic complementarity in complex formation. Moreover, MPNT<sup>2+</sup>·2Cl<sup>–</sup> acts as a chiroptical sensor, producing binding-induced circular dichroism signals that enable sensitive detection of glucuronic acid at physiologically relevant concentrations. This work presents a generalizable strategy for designing synthetic lectins that recognize carbohydrates in aqueous solutions and opens up new possibilities for developing molecular sensors and diagnostic tools for biologically important anionic sugars.</p><p >A synthetic macrocyclic lectin recognizes glucuronate in water, enabling strong, selective binding and chiroptical sensing of a biologically important sugar.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 9","pages":"1753–1761"},"PeriodicalIF":10.4000,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscentsci.5c00951","citationCount":"0","resultStr":"{\"title\":\"A Synthetic Lectin for Glucuronate\",\"authors\":\"Canjia Zhai, , , Chengkai Xu, , , Yunpeng Cui, , , Lukasz Wojtas, , , Jianfeng Cai, , and , Wenqi Liu*, \",\"doi\":\"10.1021/acscentsci.5c00951\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The selective recognition of hydrophilic carbohydrates in water remains a longstanding challenge in supramolecular chemistry due to solvent competition and the lack of a strong driving force comparable to the hydrophobic effect. Herein, we report the design, synthesis, and characterization of a water-soluble tetralactam macrocycle, MPNT<sup>2+</sup>·2Cl<sup>–</sup>, as a highly effective synthetic lectin for glucuronate. MPNT<sup>2+</sup>·2Cl<sup>–</sup> features two dimethylnaphthalene panels, pyridinium spacers, and morpholine side chains, forming a rigid, preorganized cavity with convergent hydrogen bond donors, polarized C–H donors, and complementary electrostatic interactions. The receptor achieves a binding affinity of 103,000 M<sup>–1</sup> for glucuronate in water, over 19-fold higher than previous synthetic systems, along with excellent selectivity over structurally similar carbohydrates. Single-crystal X-ray analysis, DFT calculation, and IGMH analysis reveal a dense network of [N–H···O], [C–H···O], and [C–H···π] interactions, highlighting the role of stereoelectronic complementarity in complex formation. Moreover, MPNT<sup>2+</sup>·2Cl<sup>–</sup> acts as a chiroptical sensor, producing binding-induced circular dichroism signals that enable sensitive detection of glucuronic acid at physiologically relevant concentrations. This work presents a generalizable strategy for designing synthetic lectins that recognize carbohydrates in aqueous solutions and opens up new possibilities for developing molecular sensors and diagnostic tools for biologically important anionic sugars.</p><p >A synthetic macrocyclic lectin recognizes glucuronate in water, enabling strong, selective binding and chiroptical sensing of a biologically important sugar.</p>\",\"PeriodicalId\":10,\"journal\":{\"name\":\"ACS Central Science\",\"volume\":\"11 9\",\"pages\":\"1753–1761\"},\"PeriodicalIF\":10.4000,\"publicationDate\":\"2025-08-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/pdf/10.1021/acscentsci.5c00951\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Central Science\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acscentsci.5c00951\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Central Science","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acscentsci.5c00951","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
The selective recognition of hydrophilic carbohydrates in water remains a longstanding challenge in supramolecular chemistry due to solvent competition and the lack of a strong driving force comparable to the hydrophobic effect. Herein, we report the design, synthesis, and characterization of a water-soluble tetralactam macrocycle, MPNT2+·2Cl–, as a highly effective synthetic lectin for glucuronate. MPNT2+·2Cl– features two dimethylnaphthalene panels, pyridinium spacers, and morpholine side chains, forming a rigid, preorganized cavity with convergent hydrogen bond donors, polarized C–H donors, and complementary electrostatic interactions. The receptor achieves a binding affinity of 103,000 M–1 for glucuronate in water, over 19-fold higher than previous synthetic systems, along with excellent selectivity over structurally similar carbohydrates. Single-crystal X-ray analysis, DFT calculation, and IGMH analysis reveal a dense network of [N–H···O], [C–H···O], and [C–H···π] interactions, highlighting the role of stereoelectronic complementarity in complex formation. Moreover, MPNT2+·2Cl– acts as a chiroptical sensor, producing binding-induced circular dichroism signals that enable sensitive detection of glucuronic acid at physiologically relevant concentrations. This work presents a generalizable strategy for designing synthetic lectins that recognize carbohydrates in aqueous solutions and opens up new possibilities for developing molecular sensors and diagnostic tools for biologically important anionic sugars.
A synthetic macrocyclic lectin recognizes glucuronate in water, enabling strong, selective binding and chiroptical sensing of a biologically important sugar.
期刊介绍:
ACS Central Science publishes significant primary reports on research in chemistry and allied fields where chemical approaches are pivotal. As the first fully open-access journal by the American Chemical Society, it covers compelling and important contributions to the broad chemistry and scientific community. "Central science," a term popularized nearly 40 years ago, emphasizes chemistry's central role in connecting physical and life sciences, and fundamental sciences with applied disciplines like medicine and engineering. The journal focuses on exceptional quality articles, addressing advances in fundamental chemistry and interdisciplinary research.