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Carbon Dots Detect Water-to-Ice Phase Transition and Act as Alcohol Sensors via Fluorescence Turn-Off/On Mechanism

  • Sergii Kalytchuk*
    Sergii Kalytchuk
    Regional Centre of Advanced Technologies and Materials, Czech Advanced Technology and Research Institute, Palacký University Olomouc, Šlechtitelů 27, Olomouc 783 71, Czech Republic
    *Email: [email protected]
    More by Sergii Kalytchuk
    Orcidhttp://orcid.org/0000-0002-6371-8795
  • , 
  • Lukáš Zdražil
    Lukáš Zdražil
    Regional Centre of Advanced Technologies and Materials, Faculty of Science, Palacký University Olomouc, Šlechtitelů 27, Olomouc 783 71, Czech Republic
    Department of Physical Chemistry, Faculty of Science, Palacký University Olomouc, 17. listopadu 12, Olomouc 771 46, Czech Republic
    More by Lukáš Zdražil
    Orcidhttp://orcid.org/0000-0002-5284-9845
  • , 
  • Zdeněk Bad’ura
    Zdeněk Bad’ura
    Regional Centre of Advanced Technologies and Materials, Faculty of Science, Palacký University Olomouc, Šlechtitelů 27, Olomouc 783 71, Czech Republic
    Department of Experimental Physics, Faculty of Science, Palacký University Olomouc, 17. listopadu 12, Olomouc 786 41, Czech Republic
    More by Zdeněk Bad’ura
  • , 
  • Miroslav Medved’
    Miroslav Medved’
    Regional Centre of Advanced Technologies and Materials, Faculty of Science, Palacký University Olomouc, Šlechtitelů 27, Olomouc 783 71, Czech Republic
    More by Miroslav Medved’
    Orcidhttp://orcid.org/0000-0001-8599-1031
  • , 
  • Michal Langer
    Michal Langer
    Regional Centre of Advanced Technologies and Materials, Faculty of Science, Palacký University Olomouc, Šlechtitelů 27, Olomouc 783 71, Czech Republic
    Department of Physical Chemistry, Faculty of Science, Palacký University Olomouc, 17. listopadu 12, Olomouc 771 46, Czech Republic
    More by Michal Langer
    Orcidhttp://orcid.org/0000-0003-2574-0980
  • , 
  • Markéta Paloncýová
    Markéta Paloncýová
    Regional Centre of Advanced Technologies and Materials, Faculty of Science, Palacký University Olomouc, Šlechtitelů 27, Olomouc 783 71, Czech Republic
    More by Markéta Paloncýová
    Orcidhttp://orcid.org/0000-0002-6811-7761
  • , 
  • Giorgio Zoppellaro
    Giorgio Zoppellaro
    Regional Centre of Advanced Technologies and Materials, Faculty of Science, Palacký University Olomouc, Šlechtitelů 27, Olomouc 783 71, Czech Republic
    More by Giorgio Zoppellaro
  • , 
  • Stephen V. Kershaw
    Stephen V. Kershaw
    Department of Materials Science and Engineering, and Center for Functional Photonics (CFP), City University of Hong Kong, 83 Tat Chee Avenue, Hong Kong S.A.R., China
    More by Stephen V. Kershaw
    Orcidhttp://orcid.org/0000-0003-0408-4902
  • , 
  • Andrey L. Rogach
    Andrey L. Rogach
    Department of Materials Science and Engineering, and Center for Functional Photonics (CFP), City University of Hong Kong, 83 Tat Chee Avenue, Hong Kong S.A.R., China
    More by Andrey L. Rogach
    Orcidhttp://orcid.org/0000-0002-8263-8141
  • , 
  • Michal Otyepka
    Michal Otyepka
    Regional Centre of Advanced Technologies and Materials, Faculty of Science, Palacký University Olomouc, Šlechtitelů 27, Olomouc 783 71, Czech Republic
    More by Michal Otyepka
    Orcidhttp://orcid.org/0000-0002-1066-5677
  • , and 
  • Radek Zbořil*
    Radek Zbořil
    Regional Centre of Advanced Technologies and Materials, Czech Advanced Technology and Research Institute, Palacký University Olomouc, Šlechtitelů 27, Olomouc 783 71, Czech Republic
    Nanotechnology Centre, VŠB−Technical University of Ostrava, 17. listopadu 2172/15, Ostrava-Poruba 708 00, Czech Republic
    *Email: [email protected]
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    Orcidhttp://orcid.org/0000-0002-3147-2196
Cite this: ACS Nano 2021, 15, 4, 6582–6593
Publication Date (Web):March 16, 2021
https://doi.org/10.1021/acsnano.0c09781
Copyright © 2021 American Chemical Society
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    Abstract

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    Highly fluorescent carbon nanoparticles called carbon dots (CDs) have been the focus of intense research due to their simple chemical synthesis, nontoxic nature, and broad application potential including optoelectronics, photocatalysis, biomedicine, and energy-related technologies. Although a detailed elucidation of the mechanism of their photoluminescence (PL) remains an unmet challenge, the CDs exhibit robust, reproducible, and environment-sensitive PL signals, enabling us to monitor selected chemical phenomena including phase transitions or detection of ultralow concentrations of molecular species in solution. Herein, we report the PL turn-off/on behavior of aqueous CDs allowing the reversible monitoring of the water–ice phase transition. The bright PL attributable to molecular fluorophores present on the CD surface was quenched by changing the liquid aqueous environment to solid phase (ice). Based on light-induced electron paramagnetic resonance (LEPR) measurements and density functional theory (DFT) calculations, the proposed kinetic model assuming the presence of charge-separated trap states rationalized the observed sensitivity of PL lifetimes to the environment. Importantly, the PL quenching induced by freezing could be suppressed by adding a small amount of alcohols. This was attributed to a high tendency of alcohol to increase its concentration at the CD/solvent interface, as revealed by all-atom molecular dynamics simulations. Based on this behavior, a fluorescence “turn-on” alcohol sensor for exhaled breath condensate (EBC) analysis has been developed. This provided an easy method to detect alcohols among other common interferents in EBC with a low detection limit (100 ppm), which has a potential to become an inexpensive and noninvasive clinically useful diagnostic tool for early stage lung cancer screening.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsnano.0c09781.

    • AFM topography images, FTIR spectrum, XPS analysis of CDs; dependence of radiative and nonradiative recombination rates for CDs in liquid and solid (frozen) states; optical properties of N,S-CDs synthesized using citric acid and l-cysteine; synthesis and optical properties of CDs synthesized using citric-acid and triethanolamine; optical properties and light-induced EPR of citrazinic acid; results of reversibility experiments; MD simulations; EPR of CDs recorded without illumination; light-induced EPR of CDs without molecular states; light-induced EPR of CDs in the presence of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical; excitation–emission map of CDs in a frozen state; steady-state and time-resolved photoluminescence od CDs as a function of solvent composition (water-2-propanol, water–methanol); structures of model species representing carbon core, hydrophilic surface, and IPCA; optimized parameters for kinetic model; vertical ionization potentials and electron affinities; estimated relative energies (ΔECT) of the [D+···A–] state; details of PL decay fitting data for time-resolved photoluminescence measurements; relations between kinetic parameters; MD simulation protocol; composition of MD simulation boxes; topology of the IPCA anion (PDF)

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    This article is cited by 29 publications.

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