Skip to main content
Log in

Bray–Liebhafsky oscillatory reaction as the matrix system for the kinetic determination of microquantities of alizarin and purpurin

  • Published:
Reaction Kinetics, Mechanisms and Catalysis Aims and scope Submit manuscript

Abstract

Two hydroxyanthraquinones, alizarin and purpurin, that have been used throughout history as a natural pigment, were extracted from roots of Rubia tinctorum from Serbia. As substances with important chemical activities and, therefore, with wide applications (for example in dyeing textile fabrics as well as in pharmacy because of their anti-inflammatory, anti-cancer, antiviral, antimicrobial and antioxidant activities, etc.) they were analyzed in the kinetically very sensitive Bray–Liebhafsky (BL) oscillatory reaction. However, although they are both, hydroxyanthraquinones it is shown that their interactions with BL nonlinear reaction system differ significantly. Consequently, two different reactions were used to explain the mechanism of their chemical activities. The numerical simulations based on a standard model of the BL oscillatory reaction together with proposed reactions due to alizarin/purpurin interactions with a matrix are correlated with experimental investigations. Moreover, it is shown that very small amounts of alizarin and purpurin (from about 1 × 10–7 M) produce the response of the BL matrix such that micro-quantitative analysis based on the BL oscillatory reaction can be successfully performed in this reaction system. The linear response of the BL matrix on the presence of alizarin and purpurin (necessary for microquantitative determination) is analyzed as a function of two concentration sensitive parameters: pre-oscillatory period τ1 and potential shift after perturbation ΔE.

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

Access this article

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

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  1. Thomson RH (1971) Natural occurring quinones. Academic Press, London

    Google Scholar 

  2. Derksen GC, Naayer M, van Beek TA, Capelle A, Haaksman IK, van Doren A, de Groot A (2003) Chemical and enzymatic hydrolysis of anthraquinone glycosides from madder roots. Phytochem Anal 14:137–144

    CAS  PubMed  Google Scholar 

  3. Henderson RL, Rayner CM, Blackburn RS (2013) Isolation and extraction of lucidin primeveroside from Rubia tinctorum L. and crystal structure elucidation. Phytochemistry 95:105–108

    CAS  PubMed  Google Scholar 

  4. Chenciner R (2000) Madder red: a history of luxury and trade. Curzon Press, Caucasus World

    Google Scholar 

  5. Ford L, Rayner CM, Blackburn RS (2015) Isolation and extraction of ruberythric acid from Rubia tinctorum L. and crystal structure elucidation. Phytochemistry 117:168–173

    CAS  PubMed  Google Scholar 

  6. Bray WC (1921) A periodic reaction in homogeneous solution and its relation to catalysis. J Am Chem Soc 43:1262–1267

    CAS  Google Scholar 

  7. Bray WC, Liebhafsky HA (1931) Reactions involving hydrogen peroxide, iodine and iodate ion. I Introduction. J Am Chem Soc 53:38–44

    CAS  Google Scholar 

  8. Pejić N (2009) Analytical applications of pulse perturbation method of Bray–Liebhafsky Oscillatory reaction realized in the open reactor. Hem Ind 63:455–466 (in Serbian)

    Google Scholar 

  9. Pejić N, Anić S, Kolar-Anić Lj (2012) Analytical applications of oscillatory chemical reactions: determination of some pharmaceuticaly and biologically important compounds. Hem Ind 66:153–164 (in Serbian)

    Google Scholar 

  10. Vukojević V, Pejić N, Stanisavljev D, Anić S, Kolar-Anić Lj (1999) Determination of Cl, Br, I, malonic acid and quercetin by perturbation of a nonequilibrium stationary state in the Bray-Liebhafsky reaction. Analyst 124:47–153

    Google Scholar 

  11. Pejić N, Anić S, Kuntić V, Vukojević V, Kolar-Anić Lj (2003) Kinetic determination of microquantities of rutin by perturbation of the Bray-Liebhafsky oscillatory reaction in an open system. Microchim Acta 143:261–267

    Google Scholar 

  12. Pejić N, Blagojević S, Anić S, Vukojević V, Kolar-Anić Lj (2005) Microquantitative determination of hesperidin by pulse perturbation of the oscillatory reaction system. Bioanal Chem 381:775–780

    Google Scholar 

  13. Pejić N, Kolar-Anić Lj, Anić S, Stanisavljev D (2006) Determination of paracetamol in pure and pharmaceutical dosage forms by pulse perturbation technique. J Pharm Biomed Analy 41:610–615

    Google Scholar 

  14. Pejić N, Blagojević S, Anić S, Vukojević V, Mijatović M, Ćirić J, Marković Z, Marković S, Kolar-Anić Lj (2007) Kinetic determination of morphine by means of Bray-Liebhafsky oscillatory reaction system using analyte pulse perturbation technique. Anal Chim Acta 582(2):367–374

    PubMed  Google Scholar 

  15. Pejić N, Blagojević S, Vukelić J, Kolar-Anić Lj, Anić S (2007) Analyte pulse perturbation tecnique for the determination of 6-monoacetylmorphine in seized street drug sample. Bull Chem Soc Jpn 80(10):1942–1948

    Google Scholar 

  16. Pejić N, Blagojević S, Anić S, Kolar-Anić Lj (2007) Determination of ascorbic acid in pharmaceutical dosage forms and urine by means of an oscillatory reaction system using the pulse perturbation technique. Anal Bioanal Chem 389:2009–2017

    PubMed  Google Scholar 

  17. Maksimović JP, Kolar-Anić LjZ, Anić SR, Ribič DD, Pejić ND (2011) Quantitative determination of some water-soluble B vitamins by kinetic analytical method based on the perturbation of an oscillatory reaction. J Braz Chem Soc 22:38–48

    Google Scholar 

  18. Pejić ND, Sarap NB, Maksimović JP, Anić SR, Kolar-Anić LjZ (2013) Pulse perturbation technique for determination of piroxicam in pharmaceuticals using an oscillatory reaction system. Cent Eur J Chem 11:180–188

    Google Scholar 

  19. Pejić ND, Maksimović JP, Blagojević SM, Anić SR, Čupić ŽD, Kolar-Anić LjZ (2012) Kinetic analytical method for determination of uric acid in human urine using analyte pulse perturbation technique. J Braz Chem Soc 23(8):1450–1459

    Google Scholar 

  20. Vukojević V, Anić S, Kolar-Anić Lj (2000) Investigation of dynamic behaviour of the Bray-Liebhafsky reaction in the CSTR. Determination of bifurcation points. J Phys Chem 104:10731–10739

    Google Scholar 

  21. Chopin-Dumas J (1978) Diagramme d'état de la reaction de Bray. C R Acad Sc Paris 287C:553

    Google Scholar 

  22. Kolar-Anić Lj, Vukojević V, Pejić N, Grozdić T, Anić S (2004) In: Boccaletti S, Gluckman BJ, Kurths J, Pecora L, Meucci R, Yordanov Q (eds) Experimental Chaos; American Institute of Physics, AIP Conference Proceedings, vol 742. Melville, New York, pp 3–3

    Google Scholar 

  23. Bubanja IN, Maćešić S, Ivanović-Šašić A, Čupić Ž, Anić S, Kolar-Anić Lj (2016) Intermittent chaos in the Bray-Liebhafsky oscillator. Temperature dependence. Phys Chem Chem Phys 18:9770–9778

    CAS  PubMed  Google Scholar 

  24. Bubanja IN, Ivanović-Šašić A, Čupić Ž, Anić S, Kolar-Anić Lj (2017) Intermittent chaos in the Bray-Liebhafsky oscillator. Dependence of dynamic states on the iodate concentration. Russ J Phys Chem A 91:2525–2529

    CAS  Google Scholar 

  25. Kolar-Anić Lj, Anić S, Čupić Ž, Ivanović-Šašić A, Pejić N, Blagojević S, Vukojević V (2017) in: Zerong Wang (ed) Uta Wille, Eusebio Juaristi (ass. eds), Chapter 23 Oscillating Reactions in Encyclopedia of Physical Organic Chemistry, 6 Volume Set, Volume 2, Part 2 Organic Rractions and Mechanisms, Wiley, New York, pp 1127–1222

  26. Tichonova LP, Zakrevskaya LN, Yatsimirrskii KB (1978) Catalytic determination of ruthenium based on an oscillating chemical reaction. J Anal Chem 33:1991–1998

    Google Scholar 

  27. Jiménez-Prieto R, Silva M, Pérez-Bendito D (1995) Analyte pulse perturbation technique: a tool for analytical determinations in far-from-equilibrium dynamic system. Anal Chem 67:729–734

    Google Scholar 

  28. Jiménez-Prieto R, Silva M, Pérez-Bendito D (1998) Approaching the use of oscillating reactions for analytical monitoring. Analyst 23:1R–8R

    Google Scholar 

  29. Gao J (2005) Application of oscillating chemical reaction to analytical chemistry: recent development. J Biol Sci 8:512–519

    CAS  Google Scholar 

  30. Wang H, Cai R, Lin Z (2006) Study and apllication of perturbation of peroxynitrite on peroxidase-oxsidase oscillation. Talanta 69:509–514

    CAS  PubMed  Google Scholar 

  31. Gao J, Lv D, Yang W, Wei X, Qu J, Chen H, Dai H, Ren J (2007) Determination of sulfanilamide based on the Mn(II)-catalyzed oscillating chemical reaction. Cen Eur J Chem 5:581–589

    CAS  Google Scholar 

  32. Gao J, Lv D, Sun H, Yang W (2009) Determination of L-aspartic acid by using the Cu(II)-catalyzed oscillating reaction. J Braz Chem Soc 10:1827–1832

    Google Scholar 

  33. Hu G, Chen L, Zhang J, Chen P, Wang W, Song J, Qiu L, Song J, Hu L (2009) Determination of alizarin red S using a novel B-Z oscillation system catalyzed by a tetraazamacrocyclic complex. Cent Eur J Chem 7:291–297

    CAS  Google Scholar 

  34. Strizhak PE, Khavrus V (2000) Determination of gases (NO, CO, Cl2) using mixed-mode regimes in the Belousov-Zhabotinskii oscillating chemical reaction. Talanta 51:935–947

    CAS  PubMed  Google Scholar 

  35. Gao J, Chen X, Ren J, Yang W (2011) Determination of p-phenylenediamine by perturbation of a non-equilibrium stationary state in the B-Z reaction. J Braz Chem Soc 22(648):651

    Google Scholar 

  36. Zeng Q, Chen L, Song X, Hu G, Hu L (2014) Determination of vitamin B6 (pyridoxine hydrochloride) based on a novel BZ oscillating reaction system catalyzed by a macrocyclic complex. Cent Eur J Chem 12:325–331

    CAS  Google Scholar 

  37. Maia LFO, Reis EL, Reis C, Reis CDG, Damasceno OIC, dos Reis LGT (2019) Potentiometric determination of paracetamol in pharmaceutical formulations by the analyte pulse perturbation technique using Belousov-Zhabotinskii oscillating chemical reaction. J Anal Chem 74(12):1232–1238

    CAS  Google Scholar 

  38. Dar Farhad NA, Peerzada GM, Ganaie NB, Rashid S (2017) Effect of different chemical species on the behavior of tyrosine in a typical BR oscillatory chemical reaction. Chem Select 2(34):11293–11301

    CAS  Google Scholar 

  39. Riyaz S, Peerzada GM, Ganaie NB, Gull U (2017) Kinetics of acetaminophen based oscillatory chemical reaction with and without ferroin as catalyst: an inorganic prototype model for paracetamol-ethanol syndrome. Prog React Kinet Mec 42(2):163–181

    CAS  Google Scholar 

  40. Cervellati R, Höner K, Furrow SD, Neddens C, Costa S (2002) The Briggs-Rauscher reaction as a test to measure the activity of antioxidants. Helv Chim Acta 84:3533–3547

    Google Scholar 

  41. Cervellati R, Renzulli C, Guerra MC, Speroni E (2002) Evaluation of antioxidant activity of some natural polyphenolic compounds using the Briggs-Rauscher reaction method. J Agric Food Chem 50(26):7504–7509

    CAS  PubMed  Google Scholar 

  42. Höner K, Cervellati R (2002) Measurements of the antioxidant capacity of fruits and vegetables using the BR reaction method. Eur Food Res Technol 215(5):437–442

    Google Scholar 

  43. Höner K, Cervellati R (2002) Measurements of the in vitro antioxidant activity of German white wines using a novel method. Eur Food Res Technol 214(4):356–360

    Google Scholar 

  44. Cervellati R, Höner K, Furrow SD, Mazzanti F (2002) Inhibitory effects by antioxidants on the oscillations of the Briggs-Rauscher reaction in mixed EtOH/H2O medium. Helv Chim Acta 85(8):2523–2537

    CAS  Google Scholar 

  45. Anić S, Maksimović J, Lončarević D, Pejić N, Čupić Ž (2009) Activity of polymer supported cobalt catalyst in the Bray-Liebhafsky oscillator. Russ J Phys Chem A 83:1468–1472

    Google Scholar 

  46. Maksimović JP, Čupić ŽD, Lončarević D, Pejić N, Vasiljević-Radović D, Anić S (2011) Kinetics of the Bray-Liebhafsky oscillatory reaction perturbed by polymer supported cobalt catalyst. Sci Sinter 43:55–62

    Google Scholar 

  47. Schmitz G (1987) Cinetique de la reaction de Bray. J Chim Phys 84:957–965 (in French)

    CAS  Google Scholar 

  48. Kolar-Anić Lj, Schmitz G (1992) Mechanism of the Bray-Liebhafsky reaction: effect of the oxidation of iodous acid by hydrogen peroxide. J Chem Soc Faraday Trans 88:2343–2349

    Google Scholar 

  49. Kolar-Anić Lj, Mišljenović Đ, Anić S, Nicolis G (1995) The influence of the reduction of iodate ion by hydrogen peroxide on the model of the Bray-Liebhafsky reaction. React Kinet Catal Lett 54:35–41

    Google Scholar 

  50. Schmitz G (2010) Iodine oxidation by hydrogen peroxide in acidic solutions, Bray-Liebhafsky reaction and other related reactions. Phys Chem Chem Phys 12:6605–6615

    CAS  PubMed  Google Scholar 

  51. Maćešić S, Čupić Ž, Kolar-Anić Lj (2016) Bifurcation analysis of the reduced model of Bray-Liebhafsky reaction. Reac Kinet Mech Cat 118(1):39–55 Erratum 57–57

  52. Kolar-Anić Lj, Mišljenović Đ, Stanisavljev D, Anić S (1990) On the applicability of the Schmitz’s model to dilution-reinitiated oscillations in the Bray-Liebhafsky reaction. J Phys Chem 94:8144–8146

    Google Scholar 

  53. Kolar-Anić Lj, Čupić Ž, Anić S, Schmitz G (1997) The pseudo-steady states in the model of the Bray-Liebhafsky oscillatory reaction. J Chem Soc Faraday Trans 93:2147–2152

    Google Scholar 

  54. Schmitz G, Lj K-A, Anić S, Grozdić T, Vukojević V (2006) Complex and chaotic oscillations in a model for the catalytic hydrogen peroxide decomposition under open reactor conditions. J Phys Chem A 110:10361–10368

    CAS  PubMed  Google Scholar 

  55. Ivanović A, Čupić ŽD, Janković MM, LjZ K-A, Anić SR (2008) The chaotic sequences in the Bray-Liebhafsky reaction in an open reactor. Phys Chem Chem Phys 10:5848–5858

    PubMed  Google Scholar 

  56. Kolar-Anić Lj, Čupić Ž, Schmitz G, Anić S (2010) Improvement of the stoichiometric network analysis for determination of instability conditions of complex nonlinear reaction systems. Chem Eng Sci 65:3718–3728

    Google Scholar 

  57. Ivanović-Šašić A, Marković VM, Anić SR, Kolar-Anić LjZ, Čupić ŽD (2011) Structures of chaos in open reaction systems. Phys Chem Chem Phys 13:20162–20171

    PubMed  Google Scholar 

  58. Stanković B, Čupić Ž, Maćešić S, Pejić N, Kolar-Anić  Lj (2016) Complex bifurcations in the oscillatory reaction model. Chaos Soliton Fract 87:84–91

    Google Scholar 

  59. Artists’ Pigments. (1997) A Handbook of Their History and Characteristics, Vol 3: E.W. Fitzhugh (Ed.) Oxford University Press

  60. Gear CW (1971) Numerical initial value problems in ordinary differential equations. Prentice-Hall Inc., Englewood Cliffs

    Google Scholar 

  61. Anić S, Kolar-Anić Lj (1986) The oscillatory decomposition of H2O2 monitored by the potentiometric method with Pt and Ag+/S2- indicator electrode. Ber Bunsenges Phys Chem 90:1084–1086

    Google Scholar 

  62. Anić S (1987) PhD Thesis, Usmeravanje razvoja oscilatornog razlaganja vodonikperoksida, University of Belgrade, Faculty of Physical Chemistry (in Serbian)

  63. Maksimović JP, Tošović J, Pagnacco MC (2020) Insight into the origin of pyrocatechol inhibition on oscillating Bray-Liebhafsky reactions: combined experimental and theoretical study. Bull Chem Soc Jpn 93(5):676–684. https://doi.org/10.1246/bcsj.20190296

    Article  CAS  Google Scholar 

  64. Furrow SD, Cervellati R, Amadori G (2002) New substrates for the oscillating Briggs-Rauscher reaction. J Phys Chem A 106:5841–5850

    CAS  Google Scholar 

  65. Stanisavljev DR, Milenković MC, Popović-Bijelić AD, Mojović MD (2013) Radicals in the Bray-Liebhafsky oscillatory reaction. J Phys Chem A 117:3292–3295

    CAS  PubMed  Google Scholar 

Download references

Acknowledgements

This work was partially supported by the Ministry of Education, Science and Technological Development of Republic of Serbia (Grant Numbers OI 172015 and III 45001, and Contract numbers 451-03-68/2020-14/200026, 451-03-68/2020-14/200111 and 451-03-68/2020-14/200146). We are grateful to Prof. N. Pejić for fruitful discussion.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Željko Čupić.

Additional information

Publisher's Note

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

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Maksimović, J., Čupić, Ž., Manojlović, N. et al. Bray–Liebhafsky oscillatory reaction as the matrix system for the kinetic determination of microquantities of alizarin and purpurin. Reac Kinet Mech Cat 130, 655–668 (2020). https://doi.org/10.1007/s11144-020-01798-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11144-020-01798-5

Keywords

Navigation