Departamento de Química, Pontifícia Universidade Católica do Rio de Janeiro, 22451-045, Rio de Janeiro, RJ, Brazil.
Dalton Trans. 2020 Nov 25;49(45):16252-16267. doi: 10.1039/d0dt01138j.
Although normal aging presents an accumulation of copper and iron in the brain, this becomes more relevant in neurodegeneration. α-Synuclein (α-Syn) misfolding has long been linked with the development of Parkinson's disease (PD). Copper binding promotes aggregation of α-Syn, as well as generalized oxidative stress. In this sense, the use of therapies that target metal dyshomeostasis has been in focus in the past years. Metal-Protein Attenuating Compounds (MPACs) are moderate chelators that aim at disrupting specific, abnormal metal-protein interactions. Our research group has now established that N-acylhydrazones compose a set of truly encouraging MPACs for the bioinorganic management of metal-enhanced aggregopathies. In the present work, a novel ligand, namely 1-methyl-1H-imidazole-2-carboxaldehyde isonicotinoyl hydrazone (X1INH), is reported. We describe solution studies on the interaction and affinity of this compound for copper(ii) ions showing that a fine tuning of metal-affinity was achieved. A series of in vitro biophysical NMR experiments were performed in order to assess the X1INH ability to compete with α-Syn monomers for the binding of both copper(i) and copper(ii) ions, which are central in PD pathology. A preference for copper(i) has been observed. X1INH is less toxic to human neuroglioma (H4) cells in comparison to structure-related compounds. Finally, we show that treatment with X1INH results in a higher number of smaller, less compact inclusions in a well-established model of α-Syn aggregation. Thus, X1INH constitutes a promising MPAC for the treatment of Parkinson's disease.
尽管正常衰老会导致大脑中铜和铁的积累,但在神经退行性疾病中,这种情况更为相关。α-突触核蛋白(α-Syn)错误折叠与帕金森病(PD)的发展长期相关。铜结合促进了α-Syn 的聚集以及广泛的氧化应激。从这个意义上说,过去几年的研究重点是使用针对金属动态失衡的治疗方法。金属-蛋白衰减化合物(MPAC)是一种适度的螯合剂,旨在破坏特定的、异常的金属-蛋白相互作用。我们的研究小组现已确定,N-酰腙构成了一组真正令人鼓舞的用于生物无机管理金属增强聚集病的 MPAC。在本工作中,报道了一种新的配体,即 1-甲基-1H-咪唑-2-甲酰基异烟酰腙(X1INH)。我们描述了该化合物与铜(ii)离子相互作用和亲和力的溶液研究,表明对金属亲和力进行了精细调整。进行了一系列体外生物物理 NMR 实验,以评估 X1INH 与 α-Syn 单体竞争结合铜(i)和铜(ii)离子的能力,这在 PD 病理中至关重要。观察到对铜(i)的偏好。与结构相关的化合物相比,X1INH 对人神经胶质瘤(H4)细胞的毒性较低。最后,我们表明,用 X1INH 处理会导致在建立良好的 α-Syn 聚集模型中形成更多数量的更小、更不紧凑的包含物。因此,X1INH 是治疗帕金森病的一种很有前途的 MPAC。