Tang Jian-Hong, Luo Minrui, Tsao Wilhelmina, Waters Emily Alexandria, Parigi Giacomo, Luchinat Claudio, Meade Thomas J
Departments of Chemistry, Molecular Biosciences, Neurobiology, and Radiology, Northwestern University, Evanston, Illinois 60208, United States.
Department of Chemistry and Magnetic Resonance Center (CERM), University of Florence, and Consorzio Interuniversitario Risonanze Magnetiche Metallo Proteine (CIRMMP), Via L. Sacconi 6, Sesto Fiorentino 50019, Italy.
Inorg Chem. 2024 Dec 30;63(52):24662-24671. doi: 10.1021/acs.inorgchem.4c03878. Epub 2024 Dec 16.
Glycoconjugates forming from the conjugation of carbohydrates to other biomolecules, such as proteins, lipids, or other carbohydrates, are essential components of mammalian cells and are involved in numerous biological processes. Due to the capability of sugars to form multiple hydrogen bonds, many synthetic glycoconjugates are desirable biocompatible platforms for imaging, diagnostics, drugs, and supramolecular self-assemblies. Herein, we present a multimeric galactose functionalized paramagnetic gadolinium (Gd(III)) chelate that displays spontaneous dynamic aggregation in aqueous conditions. The dynamic aggregation of the Gd(III) complex was shown by the concentration-dependent magnetic resonance (MR) relaxation measurements, nuclear magnetic resonance dispersion (NMRD) analysis, and dynamic light scattering (DLS). Notably, these data showed a nonlinear relationship between magnetic resonance relaxation rate and concentrations (0.03-1.35 mM), and a large DLS hydrodynamic radius was observed in the high-concentration solutions. MR phantom images were acquired to visualize real-time dynamic aggregation behaviors in aqueous solutions. The visualization of the dynamic self-assembling process of multivalent glycoconjugates has rarely been reported.
由碳水化合物与其他生物分子（如蛋白质、脂质或其他碳水化合物）结合形成的糖缀合物是哺乳动物细胞的重要组成部分，并参与众多生物过程。由于糖类能够形成多个氢键，许多合成糖缀合物是用于成像、诊断、药物和超分子自组装的理想生物相容性平台。在此，我们展示了一种多聚体半乳糖功能化的顺磁性钆（Gd(III)）螯合物，其在水性条件下呈现出自发的动态聚集。通过浓度依赖性磁共振（MR）弛豫测量、核磁共振频散（NMRD）分析和动态光散射（DLS）证明了Gd(III)配合物的动态聚集。值得注意的是，这些数据显示磁共振弛豫率与浓度（0.03 - 1.35 mM）之间存在非线性关系，并且在高浓度溶液中观察到较大的DLS流体动力学半径。采集MR体模图像以可视化水溶液中的实时动态聚集行为。多价糖缀合物动态自组装过程的可视化报道很少。
