Lopes Dahabada H J, Attar Aida, Nair Gayatri, Hayden Eric Y, Du Zhenming, McDaniel Kirsten, Dutt Som, Bravo-Rodriguez Kenny, Mittal Sumit, Klärner Frank-Gerrit, Wang Chunyu, Sanchez-Garcia Elsa, Schrader Thomas, Bitan Gal
∥Department of Biology, Rensselaer Polytechnic Institute, Troy, New York 12180, United States.
⊥Institute of Organic Chemistry, University of Duisburg-Essen, 45141 Essen, Germany.
ACS Chem Biol. 2015 Jun 19;10(6):1555-69. doi: 10.1021/acschembio.5b00146. Epub 2015 Apr 16.
In type-2 diabetes (T2D), islet amyloid polypeptide (IAPP) self-associates into toxic assemblies causing islet β-cell death. Therefore, preventing IAPP toxicity is a promising therapeutic strategy for T2D. The molecular tweezer CLR01 is a supramolecular tool for selective complexation of K residues in (poly)peptides. Surprisingly, it inhibits IAPP aggregation at substoichiometric concentrations even though IAPP has only one K residue at position 1, whereas efficient inhibition of IAPP toxicity requires excess CLR01. The basis for this peculiar behavior is not clear. Here, a combination of biochemical, biophysical, spectroscopic, and computational methods reveals a detailed mechanistic picture of the unique dual inhibition mechanism for CLR01. At low concentrations, CLR01 binds to K1, presumably nucleating nonamyloidogenic, yet toxic, structures, whereas excess CLR01 binds also to R11, leading to nontoxic structures. Encouragingly, the CLR01 concentrations needed for inhibition of IAPP toxicity are safe in vivo, supporting its development toward disease-modifying therapy for T2D.
在2型糖尿病(T2D)中,胰岛淀粉样多肽(IAPP)会自我缔合形成有毒聚集体,导致胰岛β细胞死亡。因此,预防IAPP毒性是一种很有前景的T2D治疗策略。分子钳CLR01是一种用于选择性络合(多)肽中K残基的超分子工具。令人惊讶的是,即使IAPP在第1位只有一个K残基,它也能在亚化学计量浓度下抑制IAPP聚集,而有效抑制IAPP毒性则需要过量的CLR01。这种特殊行为的原因尚不清楚。在这里,生化、生物物理、光谱和计算方法相结合,揭示了CLR01独特双重抑制机制的详细机理。在低浓度下,CLR01与K1结合,可能形成非淀粉样但有毒的结构,而过量的CLR01也与R11结合,形成无毒结构。令人鼓舞的是,抑制IAPP毒性所需的CLR01浓度在体内是安全的,这支持了其朝着T2D疾病改善疗法的方向发展。