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Solution-state dynamics of sugar-connected spin probes in sucrose solution as studied multiband (L-, X-, and W-band) electron paramagnetic resonance

机译:糖连接的自旋探针在蔗糖溶液中的溶液状态动力学研究为多带(L,X和W波段)电子顺磁共振

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摘要

A multiband (L-band, 0.7 GHz; X-band, 9.4 GHz; and W-band 94 GHz) electron paramagnetic resonance (EPR) study was performed for two glycosidated spin probes, 4-(α,β-D-glucopyranosyloxy)-TEMPO (Glc-TEMPO) and 4-(α,β-D-lactopyranosyloxy)-TEMPO (Lac-TEMPO), and one non-glycosylated spin probe, 4-hydroxy-TEMPO (TEMPOL), where TEMPO=2,2,6,6-tetramethyl-1-piperidinyloxyl, to characterize fundamental hydrodynamic properties of sugar-connected spin probes. The linewidths of these spin probes were investigated in various concentrations of sucrose solutions (0-50wt%). The multiband approach has allowed full characterization of the linewidth parameters, providing insights into the molecular shapes of the spin probes in sucrose solution. The analysis based on the fast-motional linewidth theory has yielded anisotropy parameters of ρ_x ≈ 2.6 and ρ_y ≈ 0.9 for Glc-TEMPO, and ρ_x ≈ 4.2 and ρ_y ≈ 0.9 for Lac-TEMPO. These values indicate that the glycosidated spin probes have a prolate-type molecular shape elongated along the x-axis (NO axis) with Lac-TEMPO elongated more remarkably, consistent with their molecular structures. The interaction parameters k (the ratios of the effective hydrodynamic volumes to the real ones) corrected for the difference in molecular shape have been estimated and found to have the relation k(TEMPOL) < k(Glc-TEMPO) ≈ k(Lac-TEMPO). This agrees with the expectation that glycosidated spin probes can behave stronger hydrogen bonding to water. Glycosidated spin probes are expected to be useful for probing sugar-involving interactions, which commonly occur in biological systems. Thus this study will provide an indispensable basis for such spin-probe studies.
机译:对两个糖基化的自旋探针4-(α,β-D-吡喃葡萄糖基氧基)进行了多波段(L波段,0.7 GHz; X波段,9.4 GHz; W波段94 GHz)电子顺磁共振(EPR)研究。 -TEMPO(Glc-TEMPO)和4-(α,β-D-戊吡喃糖基氧基)-TEMPO(Lac-TEMPO)和一个非糖基化的自旋探针4-hydroxy-TEMPO(TEMPOL),其中TEMPO = 2,2 ,6,6-四甲基-1-哌啶基氧基,以表征糖连接的自旋探针的基本流体力学性质。在各种浓度的蔗糖溶液(0-50wt%)中研究了这些自旋探针的线宽。多频带方法已允许对线宽参数进行全面表征,从而深入了解蔗糖溶液中自旋探针的分子形状。基于快速运动线宽理论的分析得出的各向异性参数对于Glc-TEMPO为ρ_x≈2.6和ρ_y≈0.9,对于Lac-TEMPO为ρ_x≈4.2和ρ_y≈0.9。这些值表明,糖基化的旋转探针具有沿着x轴(NO轴)延伸的扁长型分子形状,而Lac-TEMPO则更明显地延伸,与其分子结构一致。已估算出针对分子形状差异校正的相互作用参数k(有效流体力学体积与实际体积的比率),并发现其关系式为k(TEMPOL)

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