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Using Diffusion NMR To Characterize Guanosine Self-Association:Insights into Structure and Mechanism

机译:使用扩散NMR表征鸟苷的自缔合:结构和机理的见解

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This paper presents results from a series of pulsed field gradient(PFG)NMR studies on lipophilic gua-nosine nucleosides that undergo cation-templated assembly in organic solvents.The use of PFG-NMR to measure diffusion coefficients for the different aggregates allowed us to observe the influences of cation,solvent and anion on the self-assembly process.Three case studies are presented.In the first study,diffusion NMR confirmed formation of a hexadecameric G-quadru-plex[Gl]_16-4K~+.4pic~-in CD_3CN.Furthermore,hexadecamer formation from 5'-TBDMS-2',3'-isopropylidene.Gl and K~+ picrate was shown to be a cooperative process in CD_3CN.In the second study,diffusion NMR studies on 5'-(3,5-bis(methoxy)benzoyl)-2',3'-isopropylidene G4 showed that hierarchical self-association of G_8-octamers is controlled by the K~+ cation.Evidence for formation of both discrete G_8-octamers and G16-hexadecamers in CD_2Cl_2 was obtained.The position of this octamer-hexadecamer equilibrium was shown to depend on the K~+ concentration.In the third case,diffusion NMR was used to determine the size of a guanosine self-assembly where NMR signal integration was ambiguous.Thus,both diffusion NMR and ESI-MS show that 5'-O-acetyl-2',3'-0-isopropylidene G7 and Na~+ picrate form a doubly charged octamer[G7]_8-2Na~+-2pkT 9 in CD_2Cl_2.The anion's role in stabilizing this particular complex is discussed.In all three cases the information gained from the diffusion NMR technique enabled us to better understand the self-assembly processes,especially regarding the roles of cation,anion and solvent.
机译:本文介绍了一系列脉冲场梯度(PFG)NMR研究的结果,该研究对在有机溶剂中经过阳离子模板组装的亲脂性胍基核苷进行了研究.PFG-NMR用于测量不同聚集体的扩散系数使我们能够观察到阳离子,溶剂和阴离子对自组装过程的影响。进行了三个案例研究。在第一项研究中,扩散NMR证实了十六聚体G-quadru-plex [Gl] _16-4K〜+ .4pic〜-的形成。此外,在CD_3CN中,由5'-TBDMS-2',3'-异亚丙基.G1和K〜+苦味酸盐形成六聚体是一个协同过程。在第二项研究中,对5'-(的扩散NMR研究3,5-双(甲氧基)苯甲酰基)-2',3'-异亚丙基G4表明G_8-八聚体的层级自缔合受K〜+阳离子的控制。离散的G_8-八聚体和G16-形成的证据得到了CD_2Cl_2中的六聚体。该八聚体-六聚体平衡的位置取决于在第三种情况下,使用扩散NMR来确定鸟苷自组装体的大小,其中NMR信号的积分模棱两可。因此,扩散NMR和ESI-MS均显示5'-O-乙酰基- 2',3'-0-异亚丙基G7和Na〜+苦味酸盐在CD_2Cl_2中形成双电荷八聚物[G7] _8-2Na〜+ -2pkT9。讨论了阴离子在稳定该特定络合物中的作用。在所有三种情况下,从扩散核磁共振技术获得的信息使我们能够更好地了解自组装过程,特别是关于阳离子,阴离子和溶剂的作用。

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