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Methanol soluble and stable guanosine octamers were successfully achieved via H-bond self-assembly. Through structural conformational design, we developed a new class of guanosine derivatives with modification on guanine (8-aryl) and ribose (2′,3′-isopropylidene). This unique design led to the formation of the first discrete G 8 -octamer with its structure characterized by single crystal X-ray diffraction, MS and NMR spectroscopy. The G 8 -octamer showed unique cation recognition properties, including the formation of a stable Rb + templated G-quadruplex. Based on this observation, further modification on the 8-aryl moiety was performed to incorporate a cross-layer H-bond or covalent linkage. Similar G-octamers were obtained in both cases with structures confirmed by single crystal X-ray diffraction. Furthermore, the covalently linked G-quadruplex exhibited excellent stability even in MeOH and DMSO, suggesting a promising future for this new H-bond self-assembly system in biological and material applications.
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Anion mediated, tunable isoguanosine self-assemblies: decoding the conformation influence and solvent effects
Systematic investigations were performed with various substituted groups at C8 purine and ribose. A series of isoG analogs, C8-phenyl substituted isoG were synthesized and applied for Cs + coordination. The structural proximity between purine and ribose limited pentaplex formation for C8-phenyl substituted isoG derivatives. Based on this observation, deoxy isoG derivative with modification on ribose ( tert -butyldimethylsilyl ether) was applied to assemble with the Cs + cation. Critical solvent (CDCl 3 and CD 3 CN) and anion (BPh 4 − , BARF − , and PF 6 − ) effects were revealed, leading to the controllable formation of various stable isoG pentaplexes, including singly charged decamer, doubly charged decamer, and 15-mer, etc. Finally, the X-ray crystal structure of [isoG 20 Cs 3 ] 3+ (BARF − ) 3 was successfully obtained, which is the first example of multiple-layer deoxy isoG binding with the Cs + cation, providing solid evidence of this new isoG ionophore beyond two-layer sandwich self-assembly.
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- Award ID(s):
- 1665122
- PAR ID:
- 10295412
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 12
- Issue:
- 21
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 7569 to 7574
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d1sc00988e
