Locke Andrea K, Cummins Brian M, Abraham Alexander A, Coté Gerard L
Department of Biomedical Engineering, Texas A&M University , College Station, Texas 77843, United States.
Anal Chem. 2014 Sep 16;86(18):9091-7. doi: 10.1021/ac501791u. Epub 2014 Aug 27.
Competitive binding assays utilizing concanavalin A (ConA) have the potential to be the basis of improved continuous glucose monitoring devices. However, the efficacy and lifetime of these assays have been limited, in part, by ConA's instability due to its thermal denaturation in the physiological environment (37 °C, pH 7.4, 0.15 M NaCl) and its electrostatic interaction with charged molecules or surfaces. These undesirable interactions change the constitution of the assay and the kinetics of its behavior over time, resulting in an unstable glucose response. In this work, poly(ethylene glycol) (PEG) chains are covalently attached to lysine groups on the surface of ConA (i.e., PEGylation) in an attempt to improve its stability in these environments. Dynamic light scattering measurements indicate that PEGylation significantly improved ConA's thermal stability at 37 °C, remaining stable for at least 30 days. Furthermore, after PEGylation, ConA's binding affinity to the fluorescent competing ligand previously designed for the assay was not significantly affected and remained at ~5.4 × 10(6) M(-1) even after incubation at 37 °C for 30 days. Moreover, PEGylated ConA maintained the ability to track glucose concentrations when implemented within a competitive binding assay system. Finally, PEGylation showed a reduction in electrostatic-induced aggregation of ConA with poly(allylamine), a positively charged polymer, by shielding ConA's charges. These results indicate that PEGylated ConA can overcome the instability issues from thermal denaturation and nonspecific electrostatic binding while maintaining the required sugar-binding characteristics. Therefore, the PEGylation of ConA can overcome major hurdles for ConA-based glucose sensing assays to be used for long-term continuous monitoring applications in vivo.
利用伴刀豆球蛋白A(ConA)的竞争性结合测定法有潜力成为改进的连续血糖监测设备的基础。然而,这些测定法的功效和寿命受到了限制,部分原因是ConA在生理环境(37°C,pH 7.4,0.15 M NaCl)中因热变性而不稳定,以及它与带电分子或表面的静电相互作用。这些不良相互作用会随时间改变测定法的组成及其行为动力学,导致葡萄糖反应不稳定。在这项工作中,聚乙二醇(PEG)链被共价连接到ConA表面的赖氨酸基团上(即聚乙二醇化),试图提高其在这些环境中的稳定性。动态光散射测量表明,聚乙二醇化显著提高了ConA在37°C时的热稳定性,至少可稳定30天。此外,聚乙二醇化后,ConA与先前为该测定法设计的荧光竞争配体的结合亲和力没有受到显著影响,即使在37°C孵育30天后仍保持在约5.4×10⁶ M⁻¹。此外,聚乙二醇化的ConA在竞争性结合测定系统中实施时仍保持跟踪葡萄糖浓度的能力。最后,聚乙二醇化通过屏蔽ConA的电荷,减少了ConA与带正电的聚合物聚烯丙胺的静电诱导聚集。这些结果表明,聚乙二醇化的ConA可以克服热变性和非特异性静电结合引起的不稳定性问题,同时保持所需的糖结合特性。因此,ConA的聚乙二醇化可以克服基于ConA的葡萄糖传感测定法在体内用于长期连续监测应用的主要障碍。