This dissertation explores the capacity of direct chemical modification of existing aptamer structures for the discovery of novel functional applications using a closely related family of fluorescent aptamers as a model system. Further, this dissertation explores the merits of reusing validated structural motifs for the accelerated discovery of novel aptamer utility. This work additionally raises broad questions about the influence of sequence identity and proximity of structure in G-quadruplex-cation interactions, and its relationship to G-Quadruplex behavior with implications for rational tuning, and the merits of structural recycling and functional reprogramming of aptamers as a conceptual alternative to de novo aptamer generation.