One‐step synthesis of a thienylenepyridazinylenethienylene‐based coil‐rod‐coil copolymer with enhanced emission and improved fluorescence stability

Wu, Wei; Xu, Hongyao; Shen, Danfeng; Qiu, Tian; Fan, Li‐Juan

doi:10.1002/pola.26535

Cited by 6 publications

(4 citation statements)

References 52 publications

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“…The self-assembly behavior in solution of different classes of rod–coil molecules − with π-conjugated rod blocks has been reported, including polymeric or oligomeric poly(phenyl quinoline), − polythiophene, − polyfluorene, , poly(phenylene vinylene), − poly(phenylene ethynylene), and poly( p -phenylene) . However, syntheses of those polymers afford either polymers with rather broad molecular weight distributions, which is not favorable since different hydrophilic-to-hydrophobic ratios in the polymer chain result in different supramolecular structures, or low molecular weight oligomers.…”

Section: Results and Discussionmentioning

confidence: 99%

Size Control of Spherical and Anisotropic Fluorescent Polymer Nanoparticles via Precise Rigid Molecules

2015

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Highly monodisperse block copolymers allow for the preparation of luminescent particles with sizes reflecting the oligomer chain length. Self-organization in tetrahydrofuran/methanol leads to anisotropic nanorods with a thickness corresponding directly to the oligomer length (up to 14 nm for 21-mers). As a prerequisite for the realization of this concept, syntheses of defect-free poly(phenylene ethynylene)s with unprecedented chain length up to 43 repeat units were developed. Absorption and emission wavelength in solution continue to increase with increasing chain length, and do not converge until the 43-mer. ■ INTRODUCTIONConjugated polymer nanoparticles have received increased interest in the past few years due to their favorable photo-and electroluminescent properties that make them attractive candidates for e.g. optoelectronics, live cell imaging, and biosensing. 1−8 Gaining control over the particle size and shape is of fundamental interest yet remains a largely unresolved issue.The preparation of such nanoparticles most commonly involves postpolymerization dispersion techniques. 2 To obtain nanoparticles in the size regime below ca. 50 nm, which is particularly relevant e.g. for cell imaging, "nanoprecipitation" is frequently employed. A solution of the hydrophobic conjugated polymer in a water-miscible solvent (THF) is injected rapidly into an excess of water to afford highly diluted dispersions of nanoparticles. 9 Particle sizes can be varied to some extent by dilution of the polymer solution. For example, highly diluted dispersions of approximately spherical nanoparticles of high molecular weight substituted poly(phenylenevinylene) (MEH-PPV) were generated in this fashion. In these particles, the polymer chains are considered kinetically arrested and are probably randomly oriented. 10 Note that the mechanism of colloidal stabilization remains unclear here.As a concept to address the aforementioned problem of size control and to gain access to nonspherical shapes, we sought to encode particle dimensions directly via the length of the linear molecules with precise molecular dimension of these building blocks. In order to provide colloidal stability of the derived nanoparticles, these building blocks are employed in the form of block copolymers with a hydrophilic block. ■ RESULTS AND DISCUSSIONThe self-assembly behavior in solution of different classes of rod−coil molecules 11−13 with π-conjugated rod blocks has been reported, including polymeric or oligomeric poly(phenyl quinoline), 14−16 polythiophene, 17−20 polyfluorene, 21,22 poly-(phenylene vinylene), 23−25 poly(phenylene ethynylene), 26 and poly(p-phenylene). 27 However, syntheses of those polymers afford either polymers with rather broad molecular weight distributions, which is not favorable since different hydrophilicto-hydrophobic ratios in the polymer chain result in different supramolecular structures, or low molecular weight oligomers. An illustrative exception is Geng et al.'s synthesis of a polyfluorene 64-mer by Suzuki coupling in an iterativ...

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Section: Results and Discussionmentioning

confidence: 99%

Size Control of Spherical and Anisotropic Fluorescent Polymer Nanoparticles via Precise Rigid Molecules

2015

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“…The assembly of conjugated rod-coil block molecules has been reviewed in several articles. 4,21,23,150 Several classes of p-conjugated rod-coil block molecules have been reported previously in the literature, including polyquinoline, [56][57][58] polythiophene, 33,151,152 oligomeric phenylenevinylene (OPV), [153][154][155][156][157][158][159][160] oligomeric phenylene ethylene (OPE), 62,161 oligomeric phenylene, [162][163][164] and polyfluorene (PF). 165,166 Because synthesis of the rod-like polymers is challenging, the molecular weight of the conjugated rods in the block copolymers is generally low.…”

Section: Amphiphilic Rod-coil Bcps Based On Liquid Crystalline Polymersmentioning

confidence: 99%

Tunable assembly of amphiphilic rod–coil block copolymers in solution

et al. 2013

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This review covers the recent progress in the research field of rod-coil block copolymers (BCPs) containing rigid rod-like blocks and flexible coil-like blocks. Their assembly behaviors are fundamentally different from coil-coil BCPs in morphology because of the geometric disparity between the rod and coil segments and anisotropic interactions between rod blocks to form liquid crystalline or crystalline structures. Rod-coil BCPs can self-assemble into diverse nanostructures in selective solvents, such as micelles, cylinders, vesicles, tubules, belts, and rings. This review highlights valuable contributions in the past six years on the self-assembly behavior of rod-coil BCPs controlled by the volume fraction and the composition of the blocks from both the experimental and theoretical perspectives, and their tunable self-assembled nanostructures triggered by external stimuli, such as solvent, pH, temperature, light, and chemical additives. We also briefly introduce emerging applications of rod-coil nanoparticles in the biological field.

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“…Side groups introduced onto the backbone, such as long alkyl chains or ionic functional groups, have been demonstrated to increase solubility in organic solvents or water. 5,6 Fluorescent conjugated polyelectrolytes (FCPEs) bearing positively or negatively charged groups have been developed as chemosensors to detect a variety of chemical species in both environmental and biological systems. 7−9 FCPEs have good water solubility, which is more effective for aqueous sensory applications.…”

mentioning

confidence: 99%

“…Fluorescent conjugated polymers (FCPs) have drawn growing attention for a variety of modern applications including fabrication of light-emitting diodes, photovoltaic devices, optical probes, and bio/chemo-sensors. − However, the inherently poor solubility of the conjugated backbones brings a great challenge for their practical use. Side groups introduced onto the backbone, such as long alkyl chains or ionic functional groups, have been demonstrated to increase solubility in organic solvents or water. , Fluorescent conjugated polyelectrolytes (FCPEs) bearing positively or negatively charged groups have been developed as chemosensors to detect a variety of chemical species in both environmental and biological systems. − FCPEs have good water solubility, which is more effective for aqueous sensory applications. The intrinsic energy or exciton migration along the backbones offers FCPEs with “million-fold” signal amplification.…”

mentioning

confidence: 99%

Facile Synthesis of Fluorescent Conjugated Polyelectrolytes Using Polydentate Sulfonate as Highly Selective and Sensitive Copper(II) Sensors

Chen

Tong

et al. 2017

ACS Sens.

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Fluorescent conjugated polyelectrolytes represent an exciting area of research into new chemosensors. By virtue of their rapid electron and energy transfer paths, these highly correlated, one-dimensional systems have been depicted as "molecular wires" and show "million-fold" sensitivity compared to monomolecular sensor analogs. In this paper, a novel polyelectrolyte sensor, the ttp-PPESO, has been designed by incorporating terpyridine and sulfonate functional groups into the polyelectrolyte. This specifically tailored sensor has displayed remarkable quenching response toward copper(II) with a detection limit of 14.7 nM (0.93 ppb). It is capable of selectively screening copper without interference from 12 common cations. Molecular modeling suggests that binding occurs through a coordination interaction of the terpyridine and sulfonate. The additional multidentate nature from the sulfonate offers extraordinary chelating ability to the analyte. We anticipate that this unique binding mode will provide insight for the design of future more sensitive and selective systems.

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One‐step synthesis of a thienylenepyridazinylenethienylene‐based coil‐rod‐coil copolymer with enhanced emission and improved fluorescence stability

Cited by 6 publications

References 52 publications

Size Control of Spherical and Anisotropic Fluorescent Polymer Nanoparticles via Precise Rigid Molecules

Size Control of Spherical and Anisotropic Fluorescent Polymer Nanoparticles via Precise Rigid Molecules

Tunable assembly of amphiphilic rod–coil block copolymers in solution

Facile Synthesis of Fluorescent Conjugated Polyelectrolytes Using Polydentate Sulfonate as Highly Selective and Sensitive Copper(II) Sensors

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