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Poly-l-Lysine-functionalized fluorescent diamond particles: pH triggered fluorescence enhancement via surface charge modulation

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Abstract

Recently, the interest in applying fluorescent diamond particles (FDPs) containing nitrogen-vacancy (NV) centers for enhancing the mechanical and chemical properties of some materials, biological imaging, and sensing has been expanding rapidly. The unique properties of NV centers such as intensive, time-stable fluorescence, and an electron spin, which exhibits long coherence time and may be manipulated using external stimuli, such as pH, make them a perfect candidate for a quantum-effect-based sensing platform. However, monitoring of the local changes with the use of the nonmodified diamond particles has certain limitations; therefore, to enhance their sensing properties, in this article, the covalent functionalization of the FDPs’ surfaces with poly-l-Lysine (pLys) (NV-pLys) is presented. The FDPs’ surface is functionalized in an anhydrous environment, and successful attachment is confirmed by Fourier transform infrared spectroscopy (FTIR). As the pLys undergoes pH-triggered changes of conformation, it also induces changes in the diamonds’ surface charge, therefore modulating the fluorescence, and finally as a result enhances NV-pLys pH-sensitivity. Further investigation of the zeta potential, particle size, and contact angle reveals remarkable colloidal stability and superior wettability of the NV-pLys over a wide range of pH, which also may significantly affect NV-pLys biocompatibility. These findings open new possibilities for the construction of biocompatible, stable, and highly sensitive nanosensors.

Impact statement

Fluorescent diamond particles (FDPs) containing negatively charged nitrogen-vacancy (NV) color centers due to their distinctive nature are widely used in many disciplines, including biomedicine. Therefore, it becomes increasingly important to find and ascertain the aspects of NV centers’ behavior in a variety of environments before utilizing them as biosensors, or imaging agents. In this article, we have analyzed the NV centers’ behavior in a wide pH range. To improve the FDPs’ sensing properties (widen the measurable pH range), we have covalently functionalized the FDPs’ surface using poly-l-Lysine (pLys). Apart from enhanced pH sensitivity, further investigation reveals remarkable colloidal stability and superior wettability of the pLys-functionalized FDPs over a wide range of pH, which indicated improved biocompatibility. Presented here, surface modification may prepare the diamonds to work in the cellular environment (e.g., as part of an implant), favoring early stages of cell adhesion. Furthermore, it opens new possibilities for the construction of biocompatible, stable, and highly sensitive nanosensors with great potential for use in high-impact medical applications.

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Data availability

Data supporting the findings of this study are available within the and from the corresponding authors upon reasonable request.

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Acknowledgments

This research work is supported by the National Science Centre, Poland, under Grant No. 2016/21/B/ST7/01430, and the Foundation for Polish Science within the “TEAM-NET” project carried out within the POIR.04.04.00-00-1644/18 programme co-financed by the European Union under the European Regional Development Fund. R.B. gratefully acknowledges financial support from the National Science Centre under Project No. UMO-2020/01/0/ST7/00104. M.J. acknowledges the support from the Foundation for Polish Science within the START 2021 program. The authors would like to gratefully acknowledge R. Carano and C. Dessy from Testa Analytical Solutions (Germany) for carrying out the measurements of the zeta potential of carboxylated diamonds.

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Authors and Affiliations

  1. Department of Metrology and Optoelectronics, Faculty of Electronics, Telecommunications and Informatics, Gdańsk University of Technology, Gdańsk, Poland

    Monika Janik, Maciej J. Głowacki, Mateusz Ficek & Robert Bogdanowicz

  2. Institute of Microelectronics and Optoelectronics, Warsaw University of Technology, Warsaw, Poland

    Monika Janik

  3. Center for Plasma and Laser Engineering, The Szewalski Institute of Fluid-Flow Machinery, Polish Academy of Sciences, Gdańsk, Poland

    Mirosław Sawczak

  4. Department of Analytical Chemistry, Faculty of Chemistry, University of Gdańsk, Gdańsk, Poland

    Anna Wcisło & Paweł Niedziałkowski

  5. Department of Electrochemistry, Corrosion and Materials Engineering, Faculty of Chemistry, Gdańsk University of Technology, Gdańsk, Poland

    Kacper Jurak

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  1. Monika Janik
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  2. Maciej J. Głowacki
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Janik, M., Głowacki, M.J., Sawczak, M. et al. Poly-l-Lysine-functionalized fluorescent diamond particles: pH triggered fluorescence enhancement via surface charge modulation. MRS Bulletin 47, 1011–1022 (2022). https://doi.org/10.1557/s43577-022-00326-1

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