Multivalent Metallosupramolecular Assemblies as Effective DNA Binding Agents

Abstract

We report the implementation of coordination chemistry onto the generation of new types of metallosupramolecular complexes with laterally appended cationic moieties for DNA binding in buffered aqueous media. Utilization of an N,N,O-type coordination pocket along with an octahedral zinc(II) metal ion allowed us to obtain mono- and tetranuclear complexes in both solution and solid state, as confirmed by NMR spectroscopy and single-crystal X-ray diffraction, respectively. By using isothermal titration calorimetry and gel electrophoresis, multiply charged cationic assemblies were observed to effectively bind to DNA through multivalent electrostatic interactions. Furthermore, we observed a correlation between the multivalency of the compounds employed and the effectiveness of DNA binding.

Tuning the Solubility of Self-Assembled Fluorescent Aromatic Cages Using Functionalized Amino Acid Building Blocks

“…The dynamic output of imine chemistry is particularly opulent (Belowich and Stoddart, 2012; Schick 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), sensors (Stefankiewicz and Lehn, 2009; Bravin et al, 2019), and self-healing materials (Roy et al, 2015; Chao et al, 2016; Drożdż et al, 2018a,b). The use of disulfide bonds, reversible through inter alia thiolate substitution, in the generation of complex supramolecular architectures has received much attention (Otto, 2012; Black et al, 2014; Sobczak et al, 2018), except those of cage topology that are still isolated cases in the literature (Sarma et al, 2007; Stefankiewicz et al, 2012; Stefankiewicz and Sanders, 2013; Naini et al, 2014).…”

Structural self-sorting of pseudopeptide homo and heterodimeric disulfide cages in water: mechanistic insights and cation sensing

“…The synthesis of functional molecular cages continues to pose an intriguing challenge due to the numerous applications of such structures 1 as chemical receptors, [2][3][4] nanocapsules for molecular transport, [5][6][7] or in molecular recognition. 8 Despite enormous progress in the development of this type of architecture, [9][10][11][12] examples of stable, yet dynamic and watersoluble structures are still very scarce. [13][14][15][16] Dynamic combinatorial chemistry (DCC) of disulfides is an effective approach to generate artificial biocompatible systems in water.…”

Intrinsic Effect of Pyridine-N-Position on Structural Properties of Cu-Based Low-Dimensional Coordination Frameworks

“…Coordination-driven self-assembly processes harness the directionality and reversibility of metal–ligand interactions to allow formation of supramolecular architectures with strictly defined shape and topology [ 1 , 2 , 3 , 4 , 5 , 6 ]. The spontaneous but controlled generation of well-defined multimetallic architectures is seen in the formation of one-, two- and three-dimensional coordination polymers (CPs) with numerous applications in, e.g., magnetism, molecular separations, dye degradation and catalysis [ 7 , 8 , 9 ].…”