Ghosh Debasis, Konar Mouli, Mondal Tanmay, Govindaraju Thimmaiah
Bioorganic Chemistry Laboratory, New Chemistry Unit and School of Advanced Materials (SAMat), Jawaharlal Nehru Centre for Advanced Scientific Research Jakkur P.O. Bengaluru 560064 Karnataka India
Nanoscale Adv. 2022 Mar 31;4(9):2196-2200. doi: 10.1039/d2na00161f. eCollection 2022 May 3.
Orchestration of differential architectures of designer peptidomimetics that modulate metal oxidation states to perform multiple chemical transformations remains a challenge. Cu-chelation and self-assembly properties of amyloid β (Aβ14-23) peptide were tuned by the incorporation of cyclic dipeptide (CDP) and pyrene (Py) as the assembly directing and reporting units, respectively. We explore the molecular architectonics of Aβ14-23 derived peptidomimetics (AkdPy) to form differential architectures that stabilize distinct Cu oxidation states. The fibrillar self-assembly of AkdPy is modulated to form nanosheets by the one-off addition of Cu. Notably, the serial addition of Cu resulted in the formation of micelle-like core-shell architectures. The micelle-like and nanosheet architectures were found to differentially stabilize Cu and Cu states and catalyze tandem oxidative-hydrolysis and alkyne-azide cycloaddition reactions, respectively.
设计能够调节金属氧化态以执行多种化学转化的拟肽的不同结构编排仍然是一项挑战。分别通过引入环二肽（CDP）和芘（Py）作为组装导向和报告单元，对淀粉样β（Aβ14 - 23）肽的铜螯合和自组装特性进行了调整。我们探索了源自Aβ14 - 23的拟肽（AkdPy）的分子结构，以形成稳定不同铜氧化态的不同结构。通过一次性添加铜，AkdPy的纤维状自组装被调节形成纳米片。值得注意的是，连续添加铜导致形成类似胶束的核壳结构。发现类似胶束和纳米片的结构分别以不同方式稳定铜（I）和铜（II）状态，并分别催化串联氧化水解和炔烃 - 叠氮环加成反应。
