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Determination of Cu2+ in drinking water using a hydroxyjulolidine-dihydroperimidine colorimetric sensor

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Abstract

A new and highly efficient colorimetric Cu2+ chemosensor HL, synthesized by condensation between 8-hydroxyjulolidine-9-carboxaldehyde and 1,8-diaminonaphthalene, has been rationally designed and thoroughly studied. In a buffered aqueous methanol mixture, interactions between HL and Cu2+ produce an intense visible band at 421 nm, considerably red-shifted (~ 100 nm) from the peak maxima of HL (320 nm). Absorbance spectrophotometry experiments pointed to an exceptional 2.3 nM limit of detection (LoD) calculated from the ratiometric response upon Cu2+ binding. Furthermore, without the aid of instrumentation an impressive 0.5 µM LoD is possible by naked-eye observations, far below the 31.5 µM (2 mg/L) guidelines for drinking water established by the World Health Organization. Spectrophotometric pH titrations allowed the determination of the equilibrium constants and speciation plots for the formation of the various chemical species of HL in the absence and presence of Cu2+, with only mononuclear complexes being found. Additional studies highlighted the selectivity of HL to Cu2+ when in the presence of other metal ions, and a 1:1 (M:L) binding stoichiometry has also been confirmed with results from Cu2+ titrations, Job’s plot and ESI-HRMS in good agreement. The Cu2+ sensing mechanism was also found to be reversible by cycling with H2Na2EDTA.

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Acknowledgements

The authors would like to thank Western Sydney University (WSU), Dr Laurel George and Dr Richard Wuhrer from the WSU Advance Material Characterisation Facility, and Dr Meena Mikhael from the WSU Mass Spectrometry Facility for instrument access. The authors would also like to thank the Australian Synchrotron (Clayton, Victoria, Australia) and their beamline scientists for assistance and access to the MX1 beamline where crystallographic data acquisition was undertaken. DJF would also like to acknowledge and thank WSU for a Postgraduate Research Award and CSIRO for a PhD top-up award. LMPL is grateful for financial support from project LISBOA-01-0145-FEDER-007660 (Microbiologia Molecular, Estrutural e Celular) funded by FEDER funds through COMPETE2020-Programa Operacional Competitividade e Internacionalização (POCI) and by national funds through Fundação para a Ciência e a Tecnologia (FCT), and also for a postdoctoral fellowship (SFRH/BPD/73361/2010) from FCT.

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Authors and Affiliations

  1. School of Science and Health, Western Sydney University, Locked Bag 1797, Penrith, NSW 2751, Australia

    Daniel J. Fanna, Alexander R. Craze, Jason K. Reynolds & Feng Li

  2. Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, Av. da República, 2780-157, Oeiras, Portugal

    Luís M. P. Lima

  3. CSIRO Manufacturing, Private Bag 33, Clayton, VIC, 3169, Australia

    Adrian Trinchi

  4. CSIRO Manufacturing, P.O. Box 218, Lindfield, NSW 2070, Australia

    Daniel J. Fanna & Gang Wei

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  1. Daniel J. Fanna
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  2. Luís M. P. Lima
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This paper is dedicated to Professor Karsten Gloe on the occasion of his 70th Birthday.

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Fanna, D.J., Lima, L.M.P., Craze, A.R. et al. Determination of Cu2+ in drinking water using a hydroxyjulolidine-dihydroperimidine colorimetric sensor. J Incl Phenom Macrocycl Chem 94, 141–154 (2019). https://doi.org/10.1007/s10847-018-0862-5

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