A coopetition-driven strategy of parallel/perpendicular aromatic stacking enabling metastable supramolecular polymerization
Abstract Metastable supramolecular polymerization under kinetic control has recently been recognized as a closer way to biosystem than thermodynamic process. While impressive works on metastable supramolecular systems have been reported, the library of available non-covalent driving modes is still s...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-12-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-55106-z |
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| author | Zhao Gao Xuxu Xie Juan Zhang Wei Yuan Hongxia Yan Wei Tian |
| author_facet | Zhao Gao Xuxu Xie Juan Zhang Wei Yuan Hongxia Yan Wei Tian |
| author_sort | Zhao Gao |
| collection | DOAJ |
| description | Abstract Metastable supramolecular polymerization under kinetic control has recently been recognized as a closer way to biosystem than thermodynamic process. While impressive works on metastable supramolecular systems have been reported, the library of available non-covalent driving modes is still small and a simple yet versatile solution is highly desirable to design for easily regulating the energy landscapes of metastable aggregation. Herein, we propose a coopetition-driven metastability strategy for parallel/perpendicular aromatic stacking to construct metastable supramolecular polymers derived from a class of simple monomers consisting of lateral indoles and aromatic core. By subtly increasing the stacking strength of aromatic cores from phenyl to anthryl, the parallel face-to-face stacked aggregates are competitively formed as metastable products, which spontaneously transform into thermodynamically favorable species through the cooperativity of perpendicular edge-to-face stacking and parallel offset stacking. The slow kinetic-to-thermodynamic transformation could be accelerated by adding seeds for realizing the desired living supramolecular polymerization. Besides, this transformation of parallel/perpendicular aromatic stacking accompanied by time-dependent emission change from red to yellow is employed to dynamic cell imaging, largely avoiding the background interferences. The coopetition relationship of different aromatic stacking for metastable supramolecular systems is expected to serve as an effective strategy towards pathway-controlled functional materials. |
| format | Article |
| id | doaj-art-eaf6f9572c924969a2e79f573cdf1869 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-12-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-eaf6f9572c924969a2e79f573cdf18692025-01-05T12:36:42ZengNature PortfolioNature Communications2041-17232024-12-0115111310.1038/s41467-024-55106-zA coopetition-driven strategy of parallel/perpendicular aromatic stacking enabling metastable supramolecular polymerizationZhao Gao0Xuxu Xie1Juan Zhang2Wei Yuan3Hongxia Yan4Wei Tian5School of Chemistry and Chemical Engineering, Northwestern Polytechnical UniversitySchool of Chemistry and Chemical Engineering, Northwestern Polytechnical UniversitySchool of Chemistry and Chemical Engineering, Northwestern Polytechnical UniversityDivision of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological UniversitySchool of Chemistry and Chemical Engineering, Northwestern Polytechnical UniversitySchool of Chemistry and Chemical Engineering, Northwestern Polytechnical UniversityAbstract Metastable supramolecular polymerization under kinetic control has recently been recognized as a closer way to biosystem than thermodynamic process. While impressive works on metastable supramolecular systems have been reported, the library of available non-covalent driving modes is still small and a simple yet versatile solution is highly desirable to design for easily regulating the energy landscapes of metastable aggregation. Herein, we propose a coopetition-driven metastability strategy for parallel/perpendicular aromatic stacking to construct metastable supramolecular polymers derived from a class of simple monomers consisting of lateral indoles and aromatic core. By subtly increasing the stacking strength of aromatic cores from phenyl to anthryl, the parallel face-to-face stacked aggregates are competitively formed as metastable products, which spontaneously transform into thermodynamically favorable species through the cooperativity of perpendicular edge-to-face stacking and parallel offset stacking. The slow kinetic-to-thermodynamic transformation could be accelerated by adding seeds for realizing the desired living supramolecular polymerization. Besides, this transformation of parallel/perpendicular aromatic stacking accompanied by time-dependent emission change from red to yellow is employed to dynamic cell imaging, largely avoiding the background interferences. The coopetition relationship of different aromatic stacking for metastable supramolecular systems is expected to serve as an effective strategy towards pathway-controlled functional materials.https://doi.org/10.1038/s41467-024-55106-z |
| spellingShingle | Zhao Gao Xuxu Xie Juan Zhang Wei Yuan Hongxia Yan Wei Tian A coopetition-driven strategy of parallel/perpendicular aromatic stacking enabling metastable supramolecular polymerization Nature Communications |
| title | A coopetition-driven strategy of parallel/perpendicular aromatic stacking enabling metastable supramolecular polymerization |
| title_full | A coopetition-driven strategy of parallel/perpendicular aromatic stacking enabling metastable supramolecular polymerization |
| title_fullStr | A coopetition-driven strategy of parallel/perpendicular aromatic stacking enabling metastable supramolecular polymerization |
| title_full_unstemmed | A coopetition-driven strategy of parallel/perpendicular aromatic stacking enabling metastable supramolecular polymerization |
| title_short | A coopetition-driven strategy of parallel/perpendicular aromatic stacking enabling metastable supramolecular polymerization |
| title_sort | coopetition driven strategy of parallel perpendicular aromatic stacking enabling metastable supramolecular polymerization |
| url | https://doi.org/10.1038/s41467-024-55106-z |
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