Highly Stable Upconverting Nanocrystal–Polydiacetylenes Nanoplates for Orthogonal Dual Signaling-Based Detection of Cyanide

Abstract

Although the unique optical signaling properties of polydiacetylene (PDA) have been exploited in diverse bio-chemosensors, the practical application of most PDA sensor systems is limited by their instability in harsh environments and fluorescence signal weakness. Herein, a universal design principle for a highly stable PDA sensor system with a practical dual signaling capability is developed to detect cyanide (CN) ions, which are commonly found in drinking water. Effective metal intercalation and enhanced hydrophobic intermolecular interactions between PDA–metal supramolecules are used to construct highly stacked PDA–metal nanoplates that feature unusual optical stability upon exposure to strong acids, bases, organic solvents, and thermal/mechanical stresses, and can selectively detect CN anions, concomitantly undergoing a specific supramolecular structure change. To realize the practical dual signaling capability of the PDA sensor system, upconverting nanocrystals (UCNs) are incorporated into highly stacked PDA–metal nanoplates, and practical dual signaling (orthogonal changes in luminescence and visible color) is demonstrated using a portable detection system. The presented universal design principle is expected to be suitable for the development of other highly stable and selective PDA sensor systems with practical dual signaling capability.

Protonation-Triggered Supramolecular Gel from Macrocyclic Diacetylene: Gelation Behavior, Topochemical Polymerization, and Colorimetric Response

“…An important feature of PDAs is that the chromatic property can be dynamically controlled by manipulating the assembly and disassembly behaviors by an external stimulus, making them excellent candidates for constructing stimuli-responsive materials. Since the first report by Wegner, PDA has been extensively explored for various sensing applications. − Meanwhile, protonation is a crucial factor to drive self-assembly for the PyMCDA-H + supramolecular gel formation; therefore, we speculated whether the assembly and disassembly of the PDA network could be tuned via gel–sol transition by the alternating addition of acid and base to generate a colorimetric sensory response. Accordingly, blue-phase PyMCPDA-H + gel was accessed for an assembly-related colorimetric response towards acid/base interactions.…”

“…Diacetylenes (DAs) with strong π–π stacking characteristics have attracted much interest because of their distinct ability to form noncovalently organized supramolecular structures. Importantly, these orderly arranged DA monomers can be transformed into robust covalently linked chromogenic polydiacetylene (PDA) through a UV-induced topochemical reaction. − Several self-assembling strategies have been employed, which could integrate the structural and functional features of DAs to produce ordered supramolecular PDA architectures possessing the stimuli-responsive functional properties. − The diversity of design strategies for the precise introduction of head groups to DAs has resulted in an extended library of nanoscale morphologies, including intriguing supramolecular organogels. Moreover, the characteristic property of post-cross-linking of self-organized supramolecular DA organogels into robust entangled fibrillar PDA networks has made DAs as attractive as LMOGs. − Owing to the chromogenic feature arising from the extended π-conjugated network and the synergistic interplay of non covalent interactions, PDA-based organogels can be assembled and disassembled in a controlled manner so that responsive color switching can be realized. − So far, some linear DA-based LMOGs have been reported for a gelation behavior; however, only a few examples of macrocyclic diacetylene (MCDA) as LMOGs are known despite the characteristic of self-organizing into the 1D columnar assembly. − …”

A Polydiacetylene‐based Colorimetric Adenosine Triphosphate Sensor: A Molecular Protecting Approach

“…One meritorious feature of PDA is that it displays a brilliant color change (typically blue to red) in response to physical and chemical/biochemical stimuli 2–13 . Accordingly, this stimulus‐responsive property of PDA has been extensively used for the development of colorimetric sensors 2–30 …”

Development of Polydiacetylene-Based Testosterone Detection as a Model Sensing Platform for Water-Insoluble Hormone Analytes

“…Assemblies of PDA, such as PDA liposomes in aqueous phase, react or bind with target analytes, which generates an optical transition by distorting the conjugated backbone of PDA. The liposomes consisting of amphiphilic diacetylene or/and lipid molecule are readily formulated in aqueous and the surface of the liposomes could be immobilized with various biomolecules such as peptide, enzyme and antibody [15][16][17][18][19][20]. These characteristics of simple formulation and easy-to-surface modulation enable for the PDA liposomes to be used as easily accessible and economical sensing platform.…”