A simple and green methodology to assemble poly(4-vinylpyridine) and a sulfonated azo-dye for obtaining stable polymeric nanoparticles

José Catalán-Toledo, Ariel Nenen, Gabriel A. Vallejos, Felipe Oyarzun-Ampuero, Toshimichi Shibue, Hiroyuki Nishide, Ignacio Moreno-Villoslada

Research output: Contribution to journalArticle

Abstract

A new green and simple method of synthesis of polymeric nanoparticles comprising a pH-responsive polymer and a sulfonated dye, without needing the use of any organic solvent or cross-linker, is shown. It is based on the complexation between weak basic aromatic polyelectrolytes and a strong acidic dye by means of aromatic-aromatic interactions in water at acidic pH, and subsequent fast pH change, which triggers a controlled collapse of the system in the form of nanoparticles. Poly(4-vinylpyridine) and the tetrasulfonated azo dye 4,4’-((1E,1′E)-(3,3′-dimethyl-[1,1′ biphenyl]-4,4′diyl)bis(diazen-2,1-diyl))bis(3-hidroxynaphtalen-2,7-disulfonate) form complexes at pH 3–5, undergoing short-range aromatic-aromatic interactions, as seen by 1H NMR. Subsequent and fast pH adjustment to 9–10 leads to the system collapse with faster kinetics than those for the hydration and release of the hydrophilic negatively charged dye, so that polymeric nanoparticles are formed that include the dye, which acts as stabilizer. The monomodal distributed nanoparticles showed 50–200 nm of hydrodynamic diameter, with PDI ranging between 0.1 and 0.4, and zeta potential values in the range −40 to −60 mV, resulting stable for at least 14 days. The synthesized nanoparticles have been included in calcium alginate beads, showing colorimetric sensitivity to pH changes in water. We envisage that our findings could be also applied in other hydrophilic-aromatic polymers to create stable and functional materials by using this simple and green methodology.

Original languageEnglish
Pages (from-to)289-296
Number of pages8
JournalPolymer
Volume158
DOIs
Publication statusPublished - 2018 Dec 5

Fingerprint

Azo Compounds
Azo dyes
Nanoparticles
Coloring Agents
Dyes
Aromatic polymers
Functional materials
Water
Alginate
Zeta potential
Polyelectrolytes
Complexation
Hydration
Organic solvents
Calcium
Polymers
Hydrodynamics
Nuclear magnetic resonance
poly(4-vinylpyridine)
Kinetics

Keywords

  • Aromatic-aromatic interactions
  • Aromatic-dyes
  • poly(4-vinylpyridine)
  • Polyelectrolytes
  • Polymeric nanoparticles

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry

Cite this

A simple and green methodology to assemble poly(4-vinylpyridine) and a sulfonated azo-dye for obtaining stable polymeric nanoparticles. / Catalán-Toledo, José; Nenen, Ariel; Vallejos, Gabriel A.; Oyarzun-Ampuero, Felipe; Shibue, Toshimichi; Nishide, Hiroyuki; Moreno-Villoslada, Ignacio.

In: Polymer, Vol. 158, 05.12.2018, p. 289-296.

Research output: Contribution to journalArticle

Catalán-Toledo, J, Nenen, A, Vallejos, GA, Oyarzun-Ampuero, F, Shibue, T, Nishide, H & Moreno-Villoslada, I 2018, 'A simple and green methodology to assemble poly(4-vinylpyridine) and a sulfonated azo-dye for obtaining stable polymeric nanoparticles', Polymer, vol. 158, pp. 289-296. https://doi.org/10.1016/j.polymer.2018.09.062
Catalán-Toledo, José ; Nenen, Ariel ; Vallejos, Gabriel A. ; Oyarzun-Ampuero, Felipe ; Shibue, Toshimichi ; Nishide, Hiroyuki ; Moreno-Villoslada, Ignacio. / A simple and green methodology to assemble poly(4-vinylpyridine) and a sulfonated azo-dye for obtaining stable polymeric nanoparticles. In: Polymer. 2018 ; Vol. 158. pp. 289-296.
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AU - Nenen, Ariel

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AU - Oyarzun-Ampuero, Felipe

AU - Shibue, Toshimichi

AU - Nishide, Hiroyuki

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