Hande E. Cingil

Polydiacetylenes (PDAs) are renowned for their exceptional optical properties intricately linked to the polymer conformation, yet they exhibit poor conductivity in their undoped state. Despite this drawback, PDAs have garnered significant interest as sensing materials owing to their ability to undergo colorimetric shifts from blue to red in response to external stimuli. However, the irreversible nature of this transition has limited their utility in dynamic environments. In this study, we augment the sensing capabilities of PDA films beyond their irreversible optical response by inducing a reversible electronic response through conductivity modulation. We investigated polyamine‐substituted PDAs with enriched hydrogen‐bonding interaction sites for the concurrent changes in colorimetry and conductivity upon acetic acid (AA) vapor exposure. Coated on a flexible interdigitated electrode (IDE), we monitor the conductivity change throughout the blue‐to‐red phase transition. Remarkably, AA molecules act as dopants, significantly amplifying the system's conductivity. Although the PDA coating retains its red phase at postdopant removal, the electronic response reverts to its initial state, demonstrating reversibility. This reversible electronic response offers invaluable real‐time insights into the specific triggers within dynamic environments, underscores the adaptability of responsive conjugated polymers, and highlights a promising avenue for their utilization in various sensing and monitoring applications.

Polydiacetylenes are chromatic conjugated polymers formed upon the photopolymerization of self-assembled diacetylenes. They exhibit conformation-dependent colorimetric responses, usually irreversible, to external triggers. Here, we presented an approach to obtain a reversible colorimetric response to a pH change through structural modifications on the monomer and extended photopolymerization time. Both factors, enhanced hydrogen bond forming headgroups and longer UV exposure, impacted the rotational freedom of polydiacetylene conformation. Such a restricted conformation state reduced colorimetric response efficiency but enabled reversible colorimetric response to a pH change. These results highlight the possibility of obtaining a reversible colorimetric pH response of polydiacetylenes for customized sensing applications through monomer-level tailoring combined with tuning the photopolymerization time.

Correction for ‘A study on the conformation-dependent colorimetric response of polydiacetylene supramolecules to external triggers’ by Hande E. Cingil et al. , Mater. Chem. Front. , 2023, https://doi.org/10.1039/d2qm01006b.

Polydiacetylene (PDA) supramolecules exhibit a conformation-dependent colorimetric response to external triggers.

Responsive materials, which can adapt and operate autonomously under dynamic conditions, are a stepping stone towards functional, life‐like systems inspired by fueled self‐assembly processes in nature. Complex coacervate core micelles (C3Ms) comprising oppositely charged macromolecules constitute a novel class of polymeric micelles ideally suited for use as responsive nanoscopic delivery vehicles of hydrophilic and hydrophobic cargo. To fully exploit their potential, it is important that the C3Ms form and fall apart in an autonomous fashion as orchestrated by dynamic cues in their environment. Herein a means to temporally program the self‐regulated C3M coassembly pathway, using a modulated base‐catalyzed feedback system, is presented. Incorporated in the C3Ms is a pH responsive polyfluorene‐based conjugated polyelectrolyte (CPF) as a building block and trace amounts of a molecular sensor (doxorubicin HCl) as cargo, both of which report on micellar coassembly and disassembly via binding‐induced fluorescence quenching. CPF additionally reports on the pH of its microenvironment as its pH‐dependent conformational states are mirrored in the transitions of its vibronic bands. This experimental design enables one to monitor solution pH, C3M disassembly and reassembly, as well as cargo release and recapture noninvasively in a closed system with real time florescence experiments.

Complex coacervate core micelles (C3Ms) form upon complexation of oppositely charged copolymers. These co‐assembled structures are widely investigated as promising building blocks for encapsulation, nanoparticle synthesis, multimodal imaging, and coating technology. Here, the impact on ice growth is investigated of C3Ms containing poly(vinyl alcohol), PVA, which is well known for its high ice recrystallization inhibition (IRI) activity. The PVA‐based C3Ms are prepared upon co‐assembly of poly(4‐vinyl‐N‐methyl‐pyridinium iodide) and poly(vinyl alcohol)‐block‐poly(acrylic acid). Their formation conditions, size, and performance as ice recrystallization inhibitors are studied. It is found that the C3Ms exhibit IRI activity at PVA monomer concentrations as low as 1 × 10⁻³m. The IRI efficacy of PVA‐C3Ms is similar to that of linear PVA and PVA graft polymers, underlining the influence of vinyl alcohol monomer concentration rather than polymer architecture.

The coassembly of well-defined biological nanostructures relies on a delicate balance between attractive and repulsive interactions between biomolecular building blocks. Viral capsids are a prototypical example, where coat proteins exhibit not only self-interactions but also interact with the cargo they encapsulate. In nature, the balance between antagonistic and synergistic interactions has evolved to avoid kinetic trapping and polymorphism. To date, it has remained a major challenge to experimentally disentangle the complex kinetic reaction pathways that underlie successful coassembly of biomolecular building blocks in a noninvasive approach with high temporal resolution. Here we show how macromolecular force sensors, acting as a genome proxy, allow us to probe the pathways through which a viromimetic protein forms capsids. We uncover the complex multistage process of capsid assembly, which involves recruitment and complexation, followed by allosteric growth of the proteinaceous coat. Under certain conditions, the single-genome particles condense into capsids containing multiple copies of the template. Finally, we derive a theoretical model that quantitatively describes the kinetics of recruitment and growth. These results shed new light on the origins of the pathway complexity in biomolecular coassembly.

Attractive electrostatic forces between polymers can be exploited to create well‐defined and responsive nanoscale structures. In the process of charge‐driven coassembly, the polymers involved undergo subtle conformational changes. However, ascertaining these conformational transitions, and relating this to the nanostructures that are formed, has remained elusive to date. Here it is shown how the force‐optical response of tailored mechanochromic polymers can be used to detect structural transitions that occur at the nanoscale during assembly. It is shown that at low‐charge stoichiometry, electrostatic binding causes individual macromolecules to stretch and stiffen. Remarkably, at stoichiometries close to full charge compensation a gradual transition from single molecular complexes to multimolecular micelles is observed. Moreover, the same macromolecular sensors reveal how the assembly pathways are fully reversible as the binding strength is weakened. These results highlight how mechanochromic polymer sensors can be used to detect the molecular transitions occur during supramolecular structure formation with high precision.