Advertisement

Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

A simple, azulene-based colorimetric probe for the detection of nitrite in water

Abstract

We describe the synthesis and evaluation of an azulene-based chemodosimeter for nitrite. The probe was found to undergo two distinct color changes upon introduction of aqueous nitrite ion. A near-instant formation of a grey color provides a qualitative indication of the presence of nitrite, followed by the formation of a deep-yellow/ orange color, the endpoint from which quantitative data can be derived. The azulene probe exhibits 1:1 stoichiometry of reaction with nitrite in water, and is selective for nitrite over other anions. The azulene probe was applied to determine nitrite content in cured meat, and compared with the British Standard testing procedure (Griess test). The value obtained from the azulene-based probe agreed closely with the standard test. Our procedure only requires the preparation of one standard solution, instead of the three required for the standard Griess test.

References

  1. 1.

    Safa H, Portanguen S, Mirade P S. Reducing the levels of sodium, saturated animal fat, and nitrite in dry-cured pork meat products: A major challenge. Food and Nutrition Sciences, 2017, 8(4): 419–443

  2. 2.

    Leistner L. Properties of Water in Foods in Relation to Quality and Stability. Dordrecht: Martinus Nijhoff, 1985, 309–329

  3. 3.

    Agudo A, Cantor K P, Chan P C, Chorus I, Falconer I R, Fan A, Fujiki H, Karagas M, Lankoff A, Levallois P, et al. IARC Monographs on the Evaluation of Carcinogenic Risks to Humans Volume 94 Ingested Nitrate and Nitrite, and Cyanobacterial Peptide Toxins. Lyon: International Agency for Research on Cancer, 2010, 43–326

  4. 4.

    Hambridge T. Safety Evaluation of Food Additives—WHO Food Additives Series Number 50—JECFA Monograph Number 1059. Geneva: World Health Organisation, 2003, 1–100

  5. 5.

    National Primary Drinking Water Regulations. Washington: United States Environmental Protection Agency, 2009, 1–7

  6. 6.

    World Health Organization. Guidelines for Drinking-Water Quality, 4th Edition, Incorporating the 1st Addendum. Geneva:World Health Organization, 2017, 155–201

  7. 7.

    Commission Directive (EU)2015/1787 of 6 October 2015 Amending Annexes II and III to Council Directive 98/83/EC on the Quality of Water Intended for Human Consumption. Brussels: European Commission, 2015, 1–12

  8. 8.

    Griess J P. Remarks on the treatise of Weselsky and Benedict on some azo compounds. Berichte der Deutschen Chemischen Gesellschaft, 1879, 12(1): 426–428 (in German)

  9. 9.

    Fox J B Jr. Kinetics and mechanisms of the Griess reaction. Analytical Chemistry, 1979, 51(9): 1493–1502

  10. 10.

    Daniel WL, Han M S, Lee J S, Mirkin C A. Colorimetric nitrite and nitrate detection with gold nanoparticle probes and kinetic end points. Journal of the American Chemical Society, 2009, 131(18): 6362–6363

  11. 11.

    Xiao N, Yu C. Rapid-response and highly sensitive noncross-linking colorimetric nitrite sensor using 4-aminothiophenol modified gold nanorods. Analytical Chemistry, 2010, 82(9): 3659–3663

  12. 12.

    Zhang J, Yang C, Wang X, Yang X. Colorimetric recognition and sensing of nitrite with unmodified gold nanoparticles based on a specific diazo reaction with phenylenediamine. Analyst (London), 2012, 137(14): 3286–3292

  13. 13.

    Chen Z, Zhang Z, Qu C, Pan D, Chen L. Highly sensitive label-free colorimetric sensing of nitrite based on etching of gold nanorods. Analyst (London), 2012, 137(22): 5197–5200

  14. 14.

    Xiong Y, Li M, Liu H, Xuan Z, Yang J, Liu D. Janus PEGylated gold nanoparticles: A robust colorimetric probe for sensing nitrite ions in complex samples. Nanoscale, 2017, 9(5): 1811–1815

  15. 15.

    Kumar V V, Anthony S P. Highly selective silver nanoparticles based label free colorimetric sensor for nitrite anions. Analytica Chimica Acta, 2014, 842: 57–62

  16. 16.

    Centelles J J, Fernández-Cancio M, Imperial S. Spectrophotometric determination of nitrites in biological samples using 1,2-diaminoanthraquinone— potential application to the determination of nitric oxide synthase activity. Analytical Letters, 2003, 36(10): 2139–2149

  17. 17.

    Dey R, Chatterjee T, Ranu B C. Facile cyclization of 2-arylethynylaniline to 4(1H)-cinnolones: A new chemodosimeter for nitrite ions. Tetrahedron Letters, 2011, 52(3): 461–464

  18. 18.

    Dey R, Ranu B C. A convenient and efficient protocol for the synthesis of 4(1H)-cinnolones, 1,4-dihydrocinnolines, and cinnolines in aqueous medium: Application for detection of nitrite ions. Tetrahedron, 2011, 67(46): 8918–8924

  19. 19.

    Adarsh N, Shanmugasundaram M, Ramaiah D. Efficient reaction based colorimetric probe for sensitive detection, quantification, and on-site analysis of nitrite ions in natural water resources. Analytical Chemistry, 2013, 85(21): 10008–10012

  20. 20.

    Zhu J, Li C, Liu S, Liu Z, Yang J, Tian J, Hu X. A non-diazotizationcoupling reaction-based colorimetric determination of nitrite in tap water and milk. European Food Research and Technology, 2014, 238(5): 889–894

  21. 21.

    Sawicki E, Stanley T W, Pfaff J, Johnson H. Sensitive new methods for autocatalytic spectrophotometric determination of nitrite through free-radical chromogens. Analytical Chemistry, 1963, 35(13): 2183–2191

  22. 22.

    Shu Q, Bats J W, Schmittel M. Two closely related iridium(III) complexes as colorimetric and fluorometric chemodosimeters for nitrite in aqueous solution operating along different modes of action. Inorganic Chemistry, 2011, 50(21): 10531–10533

  23. 23.

    Yang S, Wo Y, Meyerhoff M E. Polymeric optical sensors for selective and sensitive nitrite detection using cobalt(III) corrole and rhodium(III) porphyrin as ionophores. Analytica Chimica Acta, 2014, 843: 89–96

  24. 24.

    Liu R S H. Colorful azulene and its equally colorful derivatives. Journal of Chemical Education, 2002, 79(2): 183–185

  25. 25.

    Liu R S H, Asato A E. Tuning the color and excited state properties of the azulenic chromophore: NIR absorbing pigments and materials. Journal of Photochemistry and Photobiology A Chemistry, 2003, 4(3): 179–194

  26. 26.

    Ghazvini Zadeh E H, Tang S, Woodward A W, Liu T, Bondar M V, Belfield K D. Chromophoric materials derived from a natural azulene: Syntheses, halochromism and one-photon and two-photon microlithography. Journal of Materials Chemistry. C, Materials for Optical and Electronic Devices, 2015, 3(33): 8495–8503

  27. 27.

    Lichosyt D,Wasiłek S, Dydio P, Jurczak J. The influence of binding site geometry on anion-binding selectivity: A case study of macrocyclic receptors built on the azulene skeleton. Chemistry (Weinheim an der Bergstrasse, Germany), 2018, 24(45): 11683–11692

  28. 28.

    Buica G O, Lazar I G, Birzan L, Lete C, Prodana M, Enachescu M, Tecuceanu V, Stoian A B, Ungureanu E M. Azulene-ethylenediaminetetraacetic acid: A versatile molecule for colorimetric and electrochemical sensors for metal ions. Electrochimica Acta, 2018, 263: 382–3902

  29. 29.

    López-Alled C M, Sanchez-Fernandez A, Edler K J, Sedgwick A C, Bull S D, McMullin C L, Kociok-Köhn G, James T D, Wenk J, Lewis S E. Azulene-boronate esters: Colorimetric indicators for fluoride in drinking water. Chemical Communications, 2017, 53 (93): 12580–12583

  30. 30.

    Wakabayashi S, Uchida M, Tanaka R, Habata Y, Shimizu M. Synthesis of azulene derivatives that have an azathiacrown ether moiety and their selective color reaction towards silver ions. Asian Journal of Organic Chemistry, 2013, 2(9): 786–791

  31. 31.

    Tang T, Lin T, Erden F, Wang F K, He C. Configuration-dependent optical properties and acid susceptibility of azulene compounds. Journal of Materials Chemistry. C, Materials for Optical and Electronic Devices, 2018, 6(19): 5153–5160

  32. 32.

    Lichosyt D, Dydio P, Jurczak J. Azulene-based macrocyclic receptors for recognition and sensing of phosphate anions. Chemistry (Weinheim an der Bergstrasse, Germany), 2016, 22 (49): 17673–17680

  33. 33.

    Gai L, Chen J, Zhao Y, Mack J, Lu H, Shen Z. Synthesis and properties of azulene-functionalized BODIPYs. RSC Advances, 2016, 6(38): 32124–32129

  34. 34.

    Zieliński T, Kędziorek M, Jurczak J. The azulene moiety as a chromogenic building block for anion receptors. Tetrahedron Letters, 2005, 46(37): 6231–6234

  35. 35.

    Cowper P, Pockett A, Kociok-Köhn G, Cameron P J, Lewis S E. Azulene-thiophene-cyanoacrylic acid dyes with donor-π-acceptor structures: Synthesis, characterisation and evaluation in dyesensitized solar cells. Tetrahedron, 2018, 74(22): 2775–2786

  36. 36.

    Gee A P, Cosham S D, Johnson A L, Lewis S E. Phosphorussubstituted azulenes accessed via direct Hafner reaction of a phosphino cyclopentadienide. Synlett, 2017: 973–975

  37. 37.

    Cowper P, Jin Y, Turton M D, Kociok-Köhn G, Lewis S E. Azulenesulfonium salts: Accessible, stable, and versatile reagents for cross-coupling. Angewandte Chemie International Edition, 2016, 55(7): 2564–2568

  38. 38.

    Wu D, Sedgwick A C, Gunnlaugsson T, Akkaya E U, Yoon J, James T D. Fluorescent chemosensors: The past, present and future. Chemical Society Reviews, 2017, 46(23): 7105–7123

  39. 39.

    Sawicki E, Stanley T W, Pfaff J, D’Amico A. Comparison of fiftytwo spectrophotometric methods for the determination of nitrite. Talanta, 1963, 10(6): 641–655

  40. 40.

    Garcia E E. Determination of nitrite ion using the reaction with p-nitroaniline and azulene. Analytical Chemistry, 1967, 39(13): 1605–1607

  41. 41.

    Fang H, Gan Y, Wang S, Tao T. A selective and colorimetric chemosensor for fluoride based on dimeric azulene boronate ester. Inorganic Chemistry Communications, 2018, 95: 17–21

  42. 42.

    Nefedov V A, German N A, Nikishin G I. Anomalous orientation in the nitration of azulene by copper(II) nitrite in pyridine: Preparation of 2-nitroazulene. Zhurnal Organicheskoi Khimii, 1983, 9: 1123–1124

  43. 43.

    Anderson A G Jr, Haddock R D. The reaction of azulene and azupyrene with silver nitrite and of azupyrene with nitrogen dioxide/dinitrogen tetroxide. New Journal of Chemistry, 1992, 16: 919–922

  44. 44.

    Nozoe T, Seto S, Matsumura S. Synthesis of 2-substituted azulenes by nucleophilic substitution reactions of 2-haloazulene derivatives. Bulletin of the Chemical Society of Japan, 1962, 35(12): 1990–1998

  45. 45.

    Nozoe T, Takase K, Kato M, Nogi T. Reaction of 2-arylsulfonyloxytropones and active methylene compounds: Formation of 8-hydroxy-2H-cyclohepta[b]furan-2-one and 2-amino-8H-cyclohepta[b]furan-8-one derivatives. Tetrahedron, 1971, 27(24): 6023–6035

  46. 46.

    Wang Y W, Hua Y X, Wu H H, Sun X, Peng Y. A solvent-tuning fluorescence sensor for In(III) and Al(III) ions and its bioimaging application. Chinese Chemical Letters, 2017, 28(10): 1994–1996

  47. 47.

    Wang Y W, Liu S B, Ling W J, Peng Y. A fluorescent probe for relay recognition of homocysteine and Group IIIA ions including Ga (III). Chemical Communications, 2016, 52(4): 827–830

  48. 48.

    Ma T H, Dong M, Dong Y M, Wang Y W, Peng Y. A unique watertuning dual-channel fluorescence-enhanced sensor for aluminum ions based on a hybrid ligand from a 1,1′-binaphthyl scaffold and an amino acid. Chemistry (Weinheim an der Bergstrasse, Germany), 2010, 16(34): 10313–10318

  49. 49.

    Nozoe T, Asao T, Susumago H, Ando M. The diazotization of 2-aminoazulene derivatives: The formation of 2-diazo-2,6-azulenoquinone derivatives. Bulletin of the Chemical Society of Japan, 1974, 47(6): 1471–1476

  50. 50.

    Romański J, Piątek P. Selective ammonium nitrate recognition by a heteroditopic macrotricyclic ion-pair receptor. Journal of Organic Chemistry, 2013, 78(9): 4341–4347

  51. 51.

    Methods of Test for Meat and Meat Products. Part 8. Determination of Nitrite Content; BS 4401–8: 1976. London: British Standards Institute, 2011, 1–10

Download references

Acknowledgements

We are grateful for Ph.D. funding to C.M.L.-A. from the EU Horizon 2020 research and innovation programme under grant agreement H2020-MSCA-CO-FUND, #665992. The Centre for Sustainable Chemical Technologies is supported by EPSRC under grant EP/L016354/1. We also thank EPSRC for DTP Ph.D. funding to L.C.M. T.D.J. wishes to thank the Royal Society for a Wolfson Research Merit Award. NMR and MS facilities were provided through the Material and Chemical Characterisation Facility (MC2) at the University of Bath.

Author information

Correspondence to Jannis Wenk or Tony D. James or Simon E. Lewis.

Electronic supplementary material

Rights and permissions

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Murfin, L.C., López-Alled, C.M., Sedgwick, A.C. et al. A simple, azulene-based colorimetric probe for the detection of nitrite in water. Front. Chem. Sci. Eng. 14, 90–96 (2020). https://doi.org/10.1007/s11705-019-1790-7

Download citation

Keywords

  • azulene
  • nitrite
  • diazoquinone