Division of Molecular Biology, Instituto Potosino de Investigación Científica y Tecnológica, San Luis Potosí, Mexico.
Division of Advanced Materials, Instituto Potosino de Investigación Científica y Tecnológica, San Luis Potosí, Mexico.
PLoS One. 2018 Jul 20;13(7):e0201028. doi: 10.1371/journal.pone.0201028. eCollection 2018.
Flavin-binding photoreceptor proteins sense blue-light (BL) in diverse organisms and have become core elements in recent optogenetic applications. The light-oxygen-voltage (LOV) protein Vivid (VVD) from the filamentous fungus Neurospora crassa is a classic BL photoreceptor, characterized by effecting a photocycle based on light-driven formation and subsequent spontaneous decay of a flavin-cysteinyl adduct. Here we report that VVD presents alternative outcomes to light exposure that result in protein self-oxidation and, unexpectedly, rise of stability through kinetic control. Using optical absorbance and mass spectrometry we show that purified VVD develops amorphous aggregates with the presence of oxidized residues located at the cofactor binding pocket. Light exposure increases oxidative levels in VVD and specific probe analysis identifies singlet oxygen production by the flavin. These results indicate that VVD acts alternatively as a photosensitizer, inducing self-oxidative damage and subsequent aggregation. Surprisingly, BL illumination has an additional, opposite effect in VVD. We show that light-induced adduct formation establishes a stable state, delaying protein aggregation until photoadduct decay occurs. In accordance, repeated BL illumination suppresses VVD aggregation altogether. Furthermore, photoadduct formation confers VVD stability against chemical denaturation. Analysis of the aggregation kinetics and testing of stabilizers against aggregation reveal that aggregation in VVD proceeds through light-dependent kinetic control and dimer formation. These results uncover the aggregation pathway of a photosensor, where light induces a remarkable interplay between protein damage and stability.
黄素结合光感受器蛋白在各种生物中感知蓝光 (BL),并已成为最近光遗传学应用的核心元素。丝状真菌粗糙脉孢菌的光氧电压 (LOV) 蛋白 Vivid (VVD) 是一种经典的 BL 光感受器,其特点是基于黄素-半胱氨酸加合物的光驱动形成和随后的自发衰减来进行光循环。在这里,我们报告 VVD 对光暴露有替代的反应,导致蛋白质自氧化,并通过动力学控制出人意料地提高稳定性。使用光学吸收和质谱我们表明,纯化的 VVD 会形成无定形聚集体,同时存在位于辅因子结合口袋的氧化残基。光暴露会增加 VVD 中的氧化水平,并且特定探针分析确定了黄素产生的单线态氧。这些结果表明,VVD 可以作为一种光敏剂,诱导自氧化损伤和随后的聚集。令人惊讶的是,BL 光照在 VVD 中具有另外的相反效果。我们表明,光诱导加合物的形成建立了一种稳定状态,延迟了蛋白质聚集,直到光加合物的衰减发生。相应地,重复的 BL 照射完全抑制了 VVD 聚集。此外,光加合物的形成赋予了 VVD 对化学变性的稳定性。对聚集动力学的分析和对聚集抑制剂的测试表明,VVD 中的聚集通过光依赖性动力学控制和二聚体形成进行。这些结果揭示了光传感器的聚集途径,其中光诱导了蛋白质损伤和稳定性之间的显著相互作用。