Development of low-cost colourimetric and pH sensors based on PMMA@Cyanine polymers

• Published in: Dyes and pigments 2022-04, Vol.200, p.110154, Article 110154
• Main Authors: Galhano, Joana, Marcelo, Gonçalo A., Kurutos, Atanas, Bértolo, Emilia, Capelo-Martinez, Jose Luis, Lodeiro, Carlos, Oliveira, Elisabete
• Format: Article
• Language: English
• Subjects: Colourimetric; Cyanine dyes; Fluorimetric; Low-cost polymers; Low-pH sensor polymers; Metal ions; Temperature
• ISSN: 0143-7208; 1873-3743
• DOI: 10.1016/j.dyepig.2022.110154

Cyanine derivatives 1–3 were successfully characterized and their sensorial ability studied against Zn2+, Co2+, Cd2+, Ni2+, Cu2+, Hg2+ and Ag+ metal ions. All dyes revealed a colourimetric selectivity towards Cu2+ metal ions, with the formation of mononuclear species. Cyanine 2 can detect and quantify the lowest concentrations of Cu2+ in aqueous media, 0.3 and 0.6 μM. With the aim of exploring the optical properties of these dyes, solid-supported devices were designed by the synthesis of polymethylmethacrylate (PMMA) polymers doped with dyes 1, 2, and 3 and their copper complexes. All PMMA_doped polymers were tested as temperature and low-pH sensors. PMMA_1 and PMMA_1@Cu2+ showed to be reversible fluorimetric thermoresponsive polymers, while PMMA_2, PMMA_3, PMMA_2@Cu2+ and PMMA_3@Cu2+ irreversible colourimetric and fluorimetric thermoresponsive polymers. From all acids tested, HCl, HBr, HClO4, H3PO4, HCOOH and CH3SO3H, the best results were obtained for PMMA_3 and PMMA_3@Cu2+ with HCl. After activation in 12 M HCl, both polymers were capable of sensing 8 M, 10 M, 11 M and 12 M HCl: their color changed from green to yellow and they showed an increase in their emission maxima at 805 nm in seconds. The capability to reversibly sense higher acid concentrations in seconds, after activation, for more than 10 cycles, make PMMA_3 and PMMA_3@Cu2+ good candidates for superacid sensing, allowing for a real-time follow up of contaminated affluents, or their incorporation in quality control in industrial processes. [Display omitted] •Cyanine derivatives 1–3 showed a colourimetric selectivity towards Cu2+ metal ions.•Cyanine 2 can detect and quantify, 0.3 and 0.6 μM of Cu2+ in aqueous media.•PMMA_1 and PMMA_1@Cu2+ are reversible fluorimetric thermoresponsive polymers.•PMMA_2, PMMA_3, PMMA_2@Cu2+ and PMMA_3@Cu2+ are irreversible colourimetric and fluorimetric thermoresponsive polymers.•PMMA_3 and PMMA_3@Cu2+ are good candidates for superacid sensing.