Abstract
We previously reported novel fluorescent aromatic cages that are self-produced using a set of orthogonal dynamic covalent reactions, operating simultaneously in one-pot, to assemble up to 10 components through 12 reactions into a single cage-type structure. We now introduce N-functionalized amino acids as new building blocks that enable tuning the solubility and analysis of the resulting cages. A convenient divergent synthetic approach was developed to tether different side chains on the N-terminal of a cysteine-derived building block. Our studies show that this chemical functionalization does not prevent the subsequent self-assembly and effective formation of desired cages. While the originally described cages required 94% DMSO, the new ones bearing hydrophobic side chains were found soluble in organic solvents (up to 75% CHCl3), and those grafted with hydrophilic side chains were soluble in water (up to 75% H2O). Fluorescence studies confirmed that despite cage functionalization the aggregation-induced emission properties of those architectures are retained. Thus, this work significantly expands the range of solvents in which these self-assembled cage compounds can be generated, which in turn should enable new applications, possibly as fluorescent sensors.
Highlights
Due to the unique physicochemical properties and a wide range of applications, cagetype architectures enjoy unflagging interest (Hasell and Cooper, 2016; Markiewicz et al, 2017; Beuerle and Gole, 2018; Mastalerz, 2018)
Molecular cages based on dynamic imine bonds and boronic esters have been the most frequently used among chemists (Beuerle and Gole, 2018; Acharyya and Mukherjee, 2019; Kołodziejski et al, 2019)
Supramolecular architectures based on imine and/or acyl-hydrazone bonds have already found number of applications as biomolecular recognition receptors (Nial et al, 2007; Ulrich, 2019), nanocapsules (Durot et al, 2014; Eichstaedt et al, 2019; Jedrzejewska and Szumna, 2019), Multi-Component Doubly Dynamic Molecular Cages sensors (Stefankiewicz and Lehn, 2009; Bravin et al, 2019), and self-healing materials (Roy et al, 2015; Chao et al, 2016; Drozdzet al., 2018a,b)
Summary
Due to the unique physicochemical properties and a wide range of applications, cagetype architectures enjoy unflagging interest (Hasell and Cooper, 2016; Markiewicz et al, 2017; Beuerle and Gole, 2018; Mastalerz, 2018). Molecular cages based on dynamic imine bonds (and/or acyl-hydrazones) and boronic esters have been the most frequently used among chemists (Beuerle and Gole, 2018; Acharyya and Mukherjee, 2019; Kołodziejski et al, 2019). Supramolecular architectures based on imine and/or acyl-hydrazone bonds have already found number of applications as biomolecular recognition receptors (Nial et al, 2007; Ulrich, 2019), nanocapsules (Durot et al, 2014; Eichstaedt et al, 2019; Jedrzejewska and Szumna, 2019), Multi-Component Doubly Dynamic Molecular Cages sensors (Stefankiewicz and Lehn, 2009; Bravin et al, 2019), and self-healing materials (Roy et al, 2015; Chao et al, 2016; Drozdzet al., 2018a,b). The nature of dynamic systems based on imine and disulfide bonds is well-known separately but multi-dynamic systems that employs them simultaneously are an enduring challenge (Sarma et al, 2007; Orrillo et al, 2019; Reuther et al, 2019)
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