Department of Chemistry, University of Massachusetts Boston, 100 Morrissey Boulevard, Boston, MA 02125-3393, USA.
Biochemistry. 2013 Feb 19;52(7):1137-48. doi: 10.1021/bi3012059. Epub 2013 Feb 6.
The design and application of an effective, new class of multifunctional small molecule inhibitors of amyloid self-assembly are described. Several compounds based on the diaryl hydrazone scaffold were designed. Forty-four substituted derivatives of this core structure were synthesized using a variety of benzaldehydes and phenylhydrazines and characterized. The inhibitor candidates were evaluated in multiple assays, including the inhibition of amyloid β (Aβ) fibrillogenesis and oligomer formation and the reverse processes, the disassembly of preformed fibrils and oligomers. Because the structure of the hydrazone-based inhibitors mimics the redox features of the antioxidant resveratrol, the radical scavenging effect of the compounds was evaluated by colorimetric assays against 2,2-diphenyl-1-picrylhydrazyl and superoxide radicals. The hydrazone scaffold was active in all of the different assays. The structure-activity relationship revealed that the substituents on the aromatic rings had a considerable effect on the overall activity of the compounds. The inhibitors showed strong activity in fibrillogenesis inhibition and disassembly, and even greater potency in the inhibition of oligomer formation and oligomer disassembly. Supporting the quantitative fluorometric and colorimetric assays, size exclusion chromatographic studies indicated that the best compounds practically eliminated or substantially inhibited the formation of soluble, aggregated Aβ species, as well. Atomic force microscopy was also applied to monitor the morphology of Aβ deposits. The compounds also possessed the predicted antioxidant properties; approximately 30% of the synthesized compounds showed a radical scavenging effect equal to or better than that of resveratrol or ascorbic acid.
描述了一类有效且新型的多功能小分子淀粉样蛋白自组装抑制剂的设计和应用。设计了几种基于二芳基腙支架的化合物。使用各种苯甲醛和苯肼合成了该核心结构的 44 个取代衍生物,并对其进行了表征。评估了抑制剂候选物在多种测定中的活性,包括抑制淀粉样β(Aβ)纤维形成和寡聚体形成以及相反过程,即预制纤维和寡聚体的解聚。由于腙基抑制剂的结构模拟了抗氧化剂白藜芦醇的氧化还原特征,因此通过比色法测定化合物对 2,2-二苯基-1-苦基肼和超氧自由基的清除自由基作用来评估其清除自由基作用。腙支架在所有不同的测定中均具有活性。结构-活性关系表明,芳环上的取代基对化合物的整体活性有很大影响。抑制剂在纤维形成抑制和解聚方面表现出很强的活性,在抑制寡聚体形成和寡聚体解聚方面表现出更强的活性。支持定量荧光和比色测定,排阻色谱研究表明,最好的化合物实际上消除或大大抑制了可溶性聚集 Aβ 物质的形成。原子力显微镜也被用于监测 Aβ沉积物的形态。这些化合物还具有预测的抗氧化特性;大约 30%的合成化合物显示出的清除自由基作用与白藜芦醇或抗坏血酸相当或更好。