Conjugated Nanowire Sensors via High-Energy Single-Particle-Induced Linear Polymerization of 9,9′-Spirobi[9H-fluorene] Derivatives

Abstract

Nanostructures composed of conjugated polymers or π-conjugated molecules provide sensing platforms with large specific surface areas. One of the feasible approaches to accessing such nanostructured miniaturized sensors with ultrahigh sensitivity is to develop a network of organic nanowires with optical/electronic properties that can measure signals upon interacting with the analytes at their surfaces. In this work, organic nanowires with controlled number density and uniform length were fabricated by one-dimensional solid-state polymerization of 9,9'-spirobi[9 H-fluorene] (SBF) derivatives triggered by high-energy single particles. SBF was chosen as a conjugated molecular motif with the interplay of high density of π-electrons, high solubility, and uniform solid-state structures, allowing us to fabricate sensing platforms via solution processing. The as-deposited energy density in linear polymerization nanospace was theoretically analyzed by a collision model, interpreting nanowire sizes at subnanometer levels. The substitution of bromine atoms was confirmed to be effective not only for the higher collision probability of the incident particles but also for the remarkable increase in radiolytic neutral radical yield via C-Br cleavages or electron-dissociative attachments onto the bromine atoms. The fluorescence spectra of SBF-based nanowires were different from those of SBF derivatives due to extended bond formation as a result of polymerization reactions. Fluorescence was quenched by the addition of nitrobenzene, indicating the potential use of our nanowires for fluorometric sensing applications. Microwave-based conductivity measurements revealed that the SBF-based nanowires exhibited charge carrier transport property upon photoexcitation, and that the conductivity was changed upon treatment with nitrobenzene vapors. The presented strategy of bromination of aromatic rings for efficient fabrication of controlled nanowire networks with favorable fluorescent and charge transport properties of nanowires advances the development of nanostructured sensing systems.

Highly Efficient Solid-State Intra-Track Polymerization of Ethynyl-Substituted Spirobifluorenes Triggered by Swift Heavy Ion Irradiations

“…We previously reported that SBF frameworks were likely to be reacted upon irradiation of high LET charged particles and formed into clear and uniform nanowires by the STLiP process [16]. Halogenation of aromatic rings of SBF enhances the overall polymerization reactions mediated by free radicals remarkably due to DEA.…”

“…1). The key factor in the STLiP technique is to achieve gelation with high enough insolubility against successive wet development process with strong solvent for initial target molecules [15][16][17][18], and thus to trigger efficiently the initiation reactions and promote propagation reactions in a charged particle track.…”

Electrical percolation and dynamic piezoresistivity of silver nanoparticle/polydimethylsiloxane films

“…This indicates a transition percolation stage with a relatively wide range, i.e., 0.16 mg cm −2 m d 0.32 mg cm −2 , a distinctive feature of nano-particle percolation [17,18]. In this transition stage the main conduction mechanism switches from electron tunneling at m d =0.16 mg cm −2 to contact conductance at m d =0.32 mg cm −2 [17,18]. R changes rapidly with m d in the transition stage.…”

“…Specifically, the electrical percolation threshold of AgNPs on the PDMS surface is found to be around m d =0.16 mg cm −2 as R decreases rapidly from 59 Ω to 1.04 Ω by nearly 60 times when m d grow from 0.16 mg cm −2 to 0.32 mg cm −2 by a factor of 2. This indicates a transition percolation stage with a relatively wide range, i.e., 0.16 mg cm −2 m d 0.32 mg cm −2 , a distinctive feature of nano-particle percolation [17,18]. In this transition stage the main conduction mechanism switches from electron tunneling at m d =0.16 mg cm −2 to contact conductance at m d =0.32 mg cm −2 [17,18].…”

Interactions of Single Particle with Organic Matters: A Facile Bottom-Up Approach to Low Dimensional Nanostructures

“…Further analyses from the mechanistic and quantitative aspects were performed by employing 9,9 -spirobi[9H-fluorene] (SBF) and its brominated derivatives [114]. Spin-coated films of SBF, 2-bromo-SBF (2Br-SBF), 4-bromo-SBF (4Br-SBF), 2,2 -dibromo-SBF (2,2 Br 2 -SBF), 2,7-dibromo-SBF (2,7Br 2 -SBF), 2,2 ,7,7 -tetrabromo-SBF (Br 4 -SBF), 2,2 -bi-9,9'-spirobi[9H-fluorene] (SBF 2 ), and 2,2 :7 ,2 -ter-9,9 -spirobi[9H-fluorene] (SBF 3 ) were irradiated with 350 MeV 129 Xe 26+ ions, and their nanowires were isolated after development with toluene.…”