Controlling structure–function properties of hierarchical assemblies that feature stacks of π-conjugated building blocks represents an important challenge to engineer optoelectronic materials. In this regard, the development of new tools to navigate the free energy landscape of supramolecular assembly can lead to the creation of kinetically trapped superstructures equipped with emergent electronic properties. In the present contribution, we demonstrate that redox-assisted self-assembly of supramolecular polymers built from water-soluble perylene diimide enforces formation of superstructures with optoelectronic properties not manifested in parent assemblies. Leveraging on a theoretical model developed for H-aggregates in semiconducting polymers, free-exciton bandwidth has been calculated and increases by more than 30% in kinetically trapped superstructures (380 meV) when compared to initially prepared assemblies (290 meV). Electronic structure of intermediate assemblies is believed to perturb intermolecular interactions that regulate the conformation of initially prepared architectures. In addition to offering a means to modulate superstructure electronic properties, intermediate states can be further manipulated by thermal treatment to enable the formation of hierarchical nano-to-mesoscale materials. Investigation of their solid-state morphologies using atomic force microscopy reveals long aspect ratio nanowires spanning micro-to-mesoscale dimensions. Such morphological changes combined with novel electronic properties indicate that structure–function properties of supramolecular constructs can be modulated by redox-assisted self-assembly.

Redox-assisted assembly enforces reconfiguration of π-conjugated superstructures.

Protein phosphatase 2A (PP2A) is a ubiquitous serine/threonine phosphatase implicated in a wide variety of regulatory cellular functions. PP2A is abundant in the mammalian nervous system, and dysregulation of its cellular functions is associated with myriad neurodegenerative disorders. Additionally, PP2A has oncologic implications, recently garnering attention and emerging as a therapeutic target because of the antitumor effects of a potent PP2A inhibitor, LB100. LB100 abrogation of PP2A is believed to exert its inhibitory effects on tumor progression through cellular chemo- and radiosensitization to adjuvant agents. An updated and unifying review of PP2A biology and inhibition with LB100 as a therapeutic strategy for targeting cancers of the nervous system is needed, as other reviews have mainly covered broader applications of LB100. In this review, we discuss the role of PP2A in normal cells and tumor cells of the nervous system. Furthermore, we summarize current evidence regarding the therapeutic potential of LB100 for treating solid tumors of the nervous system.

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