Skip to main content
SpringerLink
Log in

Acidity constant of pH indicators in the supramolecular systems studied by two CE-based methods compared using the RGB additive color model

  • Paper in Forefront
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Acid-base properties of methyl orange, bromocresol green, bromophenol blue, and bromothymol blue were thoroughly investigated in the past due to their application as colorimetric pH indicators. However, it is still unknown how these properties change upon the supramolecular host-guest interactions. Owing to the growing interest in using supramolecular host-guest interactions to reach expected modification of various physicochemical properties of guests, we decided to address this question in the present article. We estimated the shifts of pKa values induced by diverse hosts (cyclodextrins, cucurbiturils, calixarenes, micelles, and serum albumin) and performed a thermodynamic analysis of the selected systems. To make a deeper insight, we confronted the aforementioned dyes with the other kinds of molecules studied by us in the past. In overall, the results obtained demonstrate a large multiplicity of possible pKa behaviors, their poor predictability, and the existence of subtle structure-acidity relationships. In addition, we observed three thermodynamically different mechanisms of pKa alteration. Therefore, more studies are needed to bring closer the promising perspective of a programmable acidity’s tuning. Our methodology was based on capillary electrophoresis (CE) applied in two parallel variants: a classical method based on the fitting of a nonlinear function, and an alternative two-value method (TVM), which requires over twice less measurements to estimate pKa. To identify the optimal approach for further studies, both methods were comprehensively compared and discussed based on the RGB additive color model, a user-friendly scale that integrates three primary aspects of an analytical method: analytical performance, green chemistry, and practicality.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  1. Ma X, Zhao Y. Biomedical applications of supramolecular systems based on host−guest interactions. Chem Rev. 2015;115:7794–839.

    Article  CAS  Google Scholar 

  2. Zhou J, Yu G, Huang F. Supramolecular chemotherapy based on host–guest molecular recognition: a novel strategy in the battle against cancer with a bright future. Chem Soc Rev. 2017;46:7021–53.

    Article  CAS  Google Scholar 

  3. Bhasikuttan AC, Pal H, Mohanty J. Cucurbit[n]uril based supramolecular assemblies: tunable physico-chemical properties and their prospects. Chem Commun. 2011;47:9959–71.

    Article  CAS  Google Scholar 

  4. Ghosh I, Nau WM. The strategic use of supramolecular pKa shifts to enhance the bioavailability of drugs. Adv Drug Deliver Rev. 2012;64:764–83.

    Article  CAS  Google Scholar 

  5. Saleh N, Koner AL, Nau WM. Activation and stabilization of drugs by supramolecular pKa shifts: drug-delivery applications tailored for cucurbiturils. Angew Chem Int Ed. 2008;47:5398–401.

    Article  CAS  Google Scholar 

  6. Shaikh M, Swamy YM, Pal H. Supramolecular host–guest interaction of acridine dye with cyclodextrin macrocycles: photophysical, pKa shift and quenching study. J Photoch Photobio A. 2013;258:41–50.

    Article  CAS  Google Scholar 

  7. Gavvala K, Sengupta A, Hazra P. Modulation of photophysics and pKa shift of the anticancer drug camptothecin in the nanocavities of supramolecular hosts. ChemPhysChem. 2013;14:532–42.

    Article  CAS  Google Scholar 

  8. Barooah N, Sundararajan M, Mohanty J, Bhasikuttan AC. Synergistic effect of intramolecular charge transfer toward supramolecular pKa shift in cucurbit[7]uril encapsulated coumarin dyes. J Phys Chem B. 2014;118:7136–46.

    Article  CAS  Google Scholar 

  9. Barooah N, Mohanty J, Pal H, Bhasikuttan AC. Cucurbituril-induced supramolecular pKa shift in fluorescent dyes and its prospective applications. Proc Natl Acad Sci India Sect A Phys Sci. 2014;84:1–17.

    Article  CAS  Google Scholar 

  10. Chandra F, Pal K, Lathwal S, Koner AL. Supramolecular guest relay using host-protein nanocavities: an application of host-induced guest protonation. Mol BioSyst. 2016;12:2859–66.

    Article  CAS  Google Scholar 

  11. Basílio N, Gago S, Parola AJ, Pina F. Contrasting pKa shifts in cucurbit[7]uril host−guest complexes governed by an interplay of hydrophobic effects and electrostatic interactions. ACS Omega. 2017;2:70–5.

    Article  Google Scholar 

  12. Lazar AI, Rohacova J, Nau WM. Comparison of complexation-induced pKa shifts in the ground and excited states of dyes as well as different macrocyclic hosts and their manifestation in host-retarded excited-dye deprotonation. J Phys Chem B. 2017;121:11390–8.

    Article  CAS  Google Scholar 

  13. Shinde MN, Khurana R, Barooah N, Bhasikuttan AC, Mohanty J. Metal ion-induced supramolecular pKa tuning and fluorescence regeneration of a p-sulfonatocalixarene encapsulated neutral red dye. Org Biomol Chem. 2017;15:3975–84.

    Article  CAS  Google Scholar 

  14. Yina T, Zhang S, Lib M, Redshawc C, Nia XL. Macrocycle encapsulation triggered supramolecular pKa shift: a fluorescence indicator for detecting octreotide in aqueous solution. Sensors Actuat B-Chem. 2019;281:568–73.

    Article  Google Scholar 

  15. Yin H, Cheng Q, Rosas R, Viel S, Monnier V, Charles L, et al. A cucurbit[8]uril 2:2 complex with a negative pKa shift. Chem Eur J. 2019;25:1–9.

    Article  Google Scholar 

  16. Zhang YM, Yang Y, Zhang YH, Liu Y. Polysaccharide nanoparticles for efficient siRNA targeting in cancer cells by supramolecular pKa shift. Sci Rep. 2016;6:28848. https://doi.org/10.1038/srep28848.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  17. Nowak P, Garnysz M, Mitoraj MP, Sagan F, Woźniakiewicz M, Kościelniak P. Analytical aspects of achiral and cyclodextrin-mediated capillary electrophoresis of warfarin and its two main derivatives assisted by theoretical modeling. J Chromatogr A. 2015;1377:106–13.

    Article  CAS  Google Scholar 

  18. Sabnis RW. Handbook of acid-base indicators. San Francisco; USA; CRC Press Taylor & Francis Group; 2007.

  19. Nowak P, Woźniakiewicz M, Mitoraj MP, Garnysz M, Kościelniak P. Modulation of pKa by cyclodextrins; subtle structural changes induce spectacularly different behaviors. RSC Adv. 2015;5:77545–52.

    Article  CAS  Google Scholar 

  20. Nowak P, Woźniakiewicz M, Piwowarska M, Kościelniak P. Determination of acid dissociation constant of 20 coumarinderivatives by capillary electrophoresis using the amine capillary and two different methodologies. J Chromatogr A. 2016;1446:149–57.

    Article  CAS  Google Scholar 

  21. Nowak PM, Sagan F, Mitoraj MP. Origin of remarkably different acidity of hydroxycoumarins–joint experimental and theoretical studies. J Phys Chem B. 2017;121:4554–61.

    Article  CAS  Google Scholar 

  22. Nowak PM, Woźniakiewicz M, Janus M, Kościelniak P. Enhancing effectiveness of capillary electrophoresis as an analytical tool in the supramolecular acidity modification. Anal Bioanal Chem. 2017;409:3633–43.

    Article  CAS  Google Scholar 

  23. Woźniakiewicz M, Nowak PM, Gołąb M, Adamowicz P, Kała M, Kościelniak P. Acidity of substituted cathinones studied by capillary electrophoresis using the standard and fast alternative approaches. Talanta. 2018;180:193–8.

    Article  Google Scholar 

  24. Nowak PM, Woźniakiewicz M, Mitoraj M, Sagan F, Kościelniak P. Thermodynamics of acid-base dissociation of several cathinones and1-phenylethylamine, studied by an accurate capillary electrophoresis method free from the Joule heating impact. J Chromatogr A. 2018;1539:78–86.

    Article  CAS  Google Scholar 

  25. Nowak PM, Olesek K, Woźniakiewicz M, Mitoraj M, Sagan F, Kościelniak P. Cyclodextrin-induced acidity modification of substituted cathinones studied by capillary electrophoresis supported by density functional theory calculations. J Chromatogr A. 2018;1580:142–51.

    Article  CAS  Google Scholar 

  26. Nowak PM, Kościelniak P. What color is your method? Adaptation of the RGB additive color model to analytical method evaluation. Anal Chem. 2019;91:10343–52.

    Article  CAS  Google Scholar 

  27. Nowak PM, Woźniakiewicz M, Kościelniak P. Seven approaches to elimination of the inherent systematic errors in determination of electrophoretic mobility by capillary electrophoresis. Anal Chem. 2017;89:3630–8.

    Article  CAS  Google Scholar 

  28. Nowak P, Woźniakiewicz M, Mitoraj MP, Sagan F, Kościelniak P. Enthalpy–entropy relations in the acid–base equilibrium of warfarin and 10-hydroxywarfarin; joint experimental and theoretical studies. RSC Adv. 2015;5:74562–9.

    Article  CAS  Google Scholar 

  29. Datta S, Panja S, Halder M. Detailed scenario of the acid−base behavior of prototropic molecules in the subdomain-IIA pocket of serum albumin: results and prospects in drug delivery. J Phys Chem B. 2014;118:12153–67.

    Article  CAS  Google Scholar 

  30. Tobiszewski M, Mechlińska A, Namieśnik J. Green analytical chemistry – theory and practice. Chem Soc Rev. 2010;39:2869–78.

    Article  CAS  Google Scholar 

  31. Tobiszewski M. Metrics for green analytical chemistry. Anal Methods. 2016;8:2993–9.

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The study was carried out with equipment purchased thanks to the European Regional Development Fund within framework of the Polish Innovation Economy Operational Program (contract no. POIG.0 2.01.00-12-0 23/08).

Funding

This work received financial support from the National Science Centre, Poland (Preludium, 2016–2019, grant no. 2015/17/N/ST4/03792).

Author information

Authors and Affiliations

  1. Faculty of Chemistry, Department of Analytical Chemistry, Jagiellonian University in Kraków, Gronostajowa St. 2, 30-387, Kraków, Poland

    Paweł Mateusz Nowak, Patrycja Leszczenko, Jagoda Zarusińska & Paweł Kościelniak

Authors
  1. Paweł Mateusz Nowak
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Patrycja Leszczenko
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jagoda Zarusińska
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Paweł Kościelniak
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Paweł Mateusz Nowak.

Ethics declarations

Conflict of interest

The authors declare that they have no competing interests.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

ESM 1

(DOCX 348 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Nowak, P.M., Leszczenko, P., Zarusińska, J. et al. Acidity constant of pH indicators in the supramolecular systems studied by two CE-based methods compared using the RGB additive color model. Anal Bioanal Chem 412, 577–588 (2020). https://doi.org/10.1007/s00216-019-02289-w

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-019-02289-w

Keywords

Search

Navigation