Poly‐p‐phenylenevinylene‐g‐poly(2‐(methacryloyloxy)Ethyl)trimethylammonium chloride (PPV‐g‐PMETAC): A fluorescent, water‐soluble, selective anion sensor

Abstract

The photophysical and ion-sensing properties of densely grafted conjugated polymer poly-p-phenylenevinyleneg-poly(2-(methacryloyloxy)ethyl)trimethylammonium chloride (PPV-g-PMETAC) are presented herein. The grafted polymer exhibits excellent iodide-sensing which is easily observed using fluorescence spectroscopy. The iodide detection limit for PPV-g-PMETAC was found to be 10 nM and was independent of temperature and pH <12. The change in fluorescence of PPV-g-PMETAC, upon exposure to iodide, was attributed to polymer aggregation due to changes in the morphology of the grafted PMETAC side chains, which was observed using atomic force microscopic and dynamic light scattering studies.

Optical Chemical Sensing of Iodide Ions: A Comprehensive Review for the Synthetic Strategies of Iodide Sensing Probes, Challenges, and Future Aspects

“…These properties enable CPs becoming the most suitable candidates for optical chemical sensing of iodide ions. It has also been found that the shifting of responsive units from the backbone of polymer and grafting them to the brushes can result in stimulus‐responsive and smart materials of particular interest to be utilized for environmental, biological, and pharmaceutical applications [125] …”

“…It has also been found that the shifting of responsive units from the backbone of polymer and grafting them to the brushes can result in stimulus-responsive and smart materials of particular interest to be utilized for environmental, biological, and pharmaceutical applications. [125] * The new nanomaterials with enzyme-like characteristics termed nanoenzymes also have great potential in the The construction of four complexes 1-4, in which complexes 1-3 may be utilized for the fluorometric determination of iodine ions. [133] Copyright © Royal Society of Chemistry, 2015.…”

“…Alizadeh et al [124] synthesized water-soluble CPs based on N-methylpyrrole using different anionic, cationic, and nonionic surfactants. Damavandi et al [125] reported the synthesis of a water-soluble densely grafted conjugated polymer poly-p-phenylenevinylene-g-poly(2-(methaacryloxy)trimethylammonium chloride (PPV-g-PMETAC) (28). A part of the molecule, i. e., poly(2-(methaacryloxy)trimethylammonium chloride has a function of brush for CP (Figure 21).…”

Shape-Changing Bottlebrush Polymers

“…If the backbone of BBPs is a conjugated polymer, the stimuli-induced collapse of polymeric side chains can modulate the electronic structure of the backbone, resulting in changes in the optical property, which could be employed for sensing. − Using the ATRP grafting from approach, Balamurugan et al and Wang et al synthesized thermoresponsive PNIPAM-grafted (PT- g -PNIPAM) and pH-responsive PDMAEMA-grafted polythiophene BBPs (PT- g -PDMA), respectively; , noticeable shifts in the absorption wavelength of the polythiophene backbone were observed when external stimuli were applied to expand or shrink the side chains. For example, Wang et al reported that PT- g -PDMA in water showed a red shift of 18 nm in the maximal absorption (λ max,abs ) when the solution pH was decreased from 8 to 2 (Figure a,b) and the color of the solution changed from yellow to dark orange (Figure c) .…”

“…Despite the progress, more effort is still needed to further understand the coupled influences of various molecular parameters on the transitions of multicomponent BBPs between different conformations or morphologies. Almost all explicit dramatic shape transitions, such as wormlike/starlike-to-globular, reported in the literature so far are achieved with the use of the BBPs made from a flexible poly­(meth)­acrylate backbone. Stimuli-responsive BBPs composed of a conjugated polymer backbone, e.g., polythiophene, and responsive polymeric side chains have been reported; − although worm-to-globule shape transitions were proposed for the brushes to respond to environmental stimuli, the experimental verification was complicated by the intermolecular aggregation of brush molecules . If the worm/rod-to-globule shape transition is unequivocally confirmed by AFM or TEM, the family of stimuli-responsive shape-changing polymers would be greatly expanded. Synthesis of well-defined BBPs with multicomponent side chains remains a challenge.…”