Investigation of the Colorimetric Transition in Polydiacetylene Nanovesicles Induced by α-Cyclodextrin and the Inhibitory Role of Triblock Copolymer Addition

Polydiacetylene (PDA) nanovesicles are widely recognized as versatile chromatic sensing platforms, exhibiting a visible blue-to-red colorimetric transition in response to external stimuli such as temperature, pH, and molecular recognition events. In contrast to the conventional goal of amplifying this chromatic response, this work presents a supramolecular approach to inhibit the α-cyclodextrin (α-CD)-induced colorimetric transition in PDA systems. α-CD is known to interact with PDA vesicles through host–guest inclusion at the vesicle interface, triggering the characteristic chromatic change. Here, we show that the incorporation of an EO–PO–EO triblock copolymer (L64) into PDA suspensions enables controlled modulation of the α-CD-induced chromatic response, leading to a progressive attenuation of the blue-to-red transition as the L64 concentration increases. Isothermal titration calorimetry reveals a stronger affinity of α-CD for L64 (K = 11,300) than for PDA vesicles (K = 4000), with both interactions being spontaneous (ΔG° ≈ −21 kJ mol−1) and predominantly entropy-driven. Copolymer aggregation and phase separation occur without compromising the PDA vesicles, indicating that the observed chromatic modulation arises from supramolecular competition. This study introduces a strategy to regulate PDA affinity chromism using biocompatible triblock copolymers, offering a tunable and robust pathway for the design of responsive and safe chromatic sensing platforms.