Specific features of the kinetics of destructive degradation of porphine and phthalocyanine derivatives in oxidizing media

Dmitry Berezin; Boris Berezin; Pavel Razgovorov

doi:10.52957/27821900_2022_03_93

UDC

544.42 544.653.2/.3 544.332

SPECIFIC FEATURES OF THE KINETICS OF DESTRUCTIVE DEGRADATION OF PORPHINE AND PHTHALOCYANINE DERIVATIVES IN OXIDIZING MEDIA Specific features of the kinetics of destructive degradation of porphine and phthalocyanine derivatives in oxidizing media

АА Аа

Published in From Chemistry Towards Technology Step-By-Step · Pages 93–105 · Rubric: Scientific articles

DOI: https://doi.org/10.52957/27821900_2022_03_93

Received: 29.08.2022 Accepted: 12.09.2022 Published: 23.09.2022

Authors

Dmitry Berezin

Boris Berezin

Pavel Razgovorov

Dmitry Berezin

Academic degree: doctor of chemical sciences

Science rang: academician author.academy_titles.37 ; professor

Ivanovo State University of Chemistry and Technology

Boris Berezin

Russian Federation

Pavel Razgovorov

Academic degree: doctor of technical sciences

Science rang: professor

Yaroslavl State Technical University Professor · Kafedra «Tehnologiya stroitel'nogo proizvodstva».

ABSTRACT

The paper presents the analysis on chemical, thermal and electrochemical stability of some aromatic macroheterocycles (MHC) of porphyrin (H2P) class as well as their benzo- and aza-analogues, establishes electronic and structural factors determining the rate of pigment destruction in the presence of oxidant. The values of redox potentials of porphyrin-, tetraaz-, tetrabenzo-porphyrin- and phthalocyanine-type MHCs correlate with the temperatures at which their thermo-oxidative degradation starts and the decomposition rates in oxidizing media. The combined benzo- and azamer substitution in H2P molecules leads to their destabilisation with respect to oxidants, the situation depending strongly on the nature of the oxidant (H2O2, S2O82- and NO3-), the solvent (H2SO4, HOAc) as well as the nature of the metal in the molecule. The polymer state or spatial distortion of the MHC has a significant influence on the resistance to oxidising agents. The reaction mechanisms of oxidation of label-free porphyrins and phthalocyanines by hydrogen peroxide are shown to be identical. In both cases, the reaction centres of MHCs are N H bonds, either in the meso-position (H2Ps) or in the coordination cavity of the H2N4 molecule (H2P), and the pigments are cleaved to colourless products.

KEYWORDS

tetrapyrrolemacroheterocyclic compounds; porphyrins; phthalocyanines; oxidative degradation, redox potentials

Funding

This work was supported by Ivanovo State University of Chemistry and Technology, Ivanovo, Russia Centre for the Collective Use of Scientific Equipment (the Russian Ministry of Education and Science, Agreement No. 075-15-2021-671)

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1. (1978) Inorganic biochemistry edited by G. Eichhorn. M.: Mir, pp. 5-113, 339-522 (in Russian).

2. Berezin, B.D. & Enikolopyan, N.S. (1988) Metalloporphyrins. M.: Nauka (in Russian).

3. Mashiko, T., Dolphin, D., Wilkinson, G., Guilard, R., McCleverty, S.A. & Permagon. (1987) Porphyrins, hydroporphyrins, azaporphyrins, phthalocyanines, corroles, corrins and related macrocycles. Comprehensive coordination chemistry. Press: Oxford, 2, pp. 813-898.

4. Kadish, K.M., Smith, K.M. & Guilard, R. (2010-2016) Handbook of porphyrin science. Singapore: World Scient. Publ., V. 1-45.

5. Shelton, R.A. (1994) Metalloporphyrins in catalytic oxidations. Marcel Dekker: New York.

6. Tarasevich, M.R. & Radiushkina, K.A. (1982) Catalysis and electrocatalysis by porphyrins. M.: Nauka (in Russian).

7. Barona-Castaño, J.C., Carmona-Vargas, Ch.C., Brocksom, T.J. & De Oliveira, K.T. (2016) Porphyrins as catalysts in scalable organic reactions, Molecules, 21(3), pp. 310. DOI:https://doi.org/10.3390/molecules21030310.

8. Gonsalves, A.M.A.R. & Pereira, M.M. (1996) State of the art in the development ofbiomimetic oxidation catalysts, J. of Molec. Catal. A: Chem., 113(1-2), pp. 209-221. DOI:https://doi.org/10.1016/S1381-1169(96)00050-7.

9. Feng, L., Wang, K.-Yu., Joseph, E. & Zhou, H.-K. (2020) Catalytic porphyrin framework compounds, Trends in Chem., 2(6), pp. 555-568. DOI:https://doi.org/10.1016/j.trechm.2020.01.003.

10. Simonova, O.R., Zaitseva, S.V. & Koifman, O.I. (2008) Oxidation kinetics of Zn-5,15 bis(ortho-methoxyphenyl)-2,3,7,8,12,13,17,18-octamethylporphyrin with organic peroxides in o-xylene, Russ. J. Gen. Chem., (78), pp. 1260-1267. DOI:https://doi.org/10.1134/S1070363208060285.

11. Denis, T.G.St., Huang, Y.-Y. & Hamblin, M.R. (2013) Cyclic tetrapyrroles in photodynamic therapy: the chemistry of porphyrins and related compounds in medicine. Singapore: World Scient. Publ., 27, pp. 255-301.

12. Giancola, C., Caterino, M., D'Aria, F., Kustov, A.V., Belykh, D.V., Khudyaeva, I.S., Starseva, O.M., Berezin, D.B., Pylina, Y.I., Usacheva, T. & Amato, J. (2020) Selective binding of a bioactive porphyrin-based photosensitizer to the G-quadruplex from the KRAS oncogene promoter, Int. J. Biol. Macromol, (145), pp. 244-251. DOI:https://doi.org/10.1016/j.ijbiomac.2019.12.152.

13. Karimov, D.R., Berezin, D.B. & Tomilova, I.K. (2020) Corroles as aromatic analogues of corrinoids and vitamin B12: synthesis, structural features and properties of macroheterocycles, prospects for chemistry of materials based on them, From Chemistry Towards Technology Step-By-Step, 1(1), pp. 9-56. DOI:https://doi.org/10.52957/27821900_2020_01_9 [online]. Available at: http://chemintech.ru/index.php/tor/2020tom1no1 (in Russian).

14. Koifman, O.I., Ageeva, T.A., Beletskaya, I.P. et al. (2020) Macroheterocyclic compounds - a key building block in new functional materials and molecular devices, Macroheterocycles, 13(4), pp. 311-467. DOI:https://doi.org/10.6060/mhc200814k.

15. Kustov, A.V., Morshnev, P.K., Kukushkina, N.V. et al. (2022) Solvation, cancer cell photoinactivation and the interaction of chlorin photosensitizers with a potential passive carrier non-ionic surfactant Tween 80, Int. J. Mol. Sci., (23), pp. 5294. DOI:https://doi.org/10.3390/ijms23105294.

16. Kustov, A.V., Smirnova, N.L., Berezin, D.B. & Berezin, M.B. (2015) Blood porphyrins in binary mixtures of N,N-dimethylformamide with 1-octanol and chloroform: the energetic of salvation, solute-cosolvent interactions and model calculations, J. Chem. Thermodyn, (83), pp. 104-109. DOI:https://doi.org/10.1016/j.jct.2014.12.013.

17. Kustov, A.V., Smirnova, N.L., MorshnevPh.K. et al. (2022) Transurethral resection of non-muscle invasive bladder tumors combined with fluorescence diagnosis and photodynamic therapy with chlorin e6-type photosensitizers, J. Clin. Med., 11(1), pp. 233. DOI:https://doi.org/10.3390/jcm11010233.

18. Shukhto, O.V., Khudyaeva, I.S., Belykh, D.V. & Berezin, D.B. (2021) Aggregation of hydrophobic chlorines with antimicrobial fragments in aqueous solutions of ethanol and Tween 80, Izvestiya vuzov. Khimiya i khim. tekhnol., 64(11), pp. 86-96. DOI:https://doi.org/10.6060/ivkkt.20216411.6500 (in Russian).

19. Berezin, D.B., Makarov, V.V., Znoyko, S.A., Mayzlish, V.E. & Kustov, A.V. (2020) Aggregation water soluble octaanionic phthalocyanines behavior and their photoinactivation antimicrobial effect in vitro, Mend. Commun., 30(5), pp. 621-623. DOI:https://doi.org/10.1016/j.mencom.2020.09.023.

20. Kustov, A.V., Belykh, D.V., Startseva, O.M., Kruchin, S.O., Venediktov, E.A. & Berezin, D.B. (2016) New photosensitizers developed on a methylpheophorbidea platform for photodynamic therapy: Synthesis, singlet oxygen generation and modeling of passive membrane transport, Pharmaceutica Analytica Acta, 7(5), pp. 480 484. DOI:https://doi.org/10.4172/2153-2435.1000480.

21. Kustov, A.V., Smirnova, N.L., Berezin, D.B. & Berezin, M.B. (2015) Thermodynamics of solution of proto- and mezoporphyrins in N,N-dimethylformamide, J. Chem. Thermodyn, (89), pp. 123-126. DOI:https://doi.org/10.1016/j.jct.2015.05.016.

22. Berezin, B.D. (1981) Coordination compounds of porphyrins and phthalocyanines. Wiley: Toronto.

23. Kadish, K.M., Smith, K.M. & Guilard R. (2000) Electrochemistry of metalloporphyrins in non-aqueous media. The porphyrin handbook. Acad. Press: New York, (8), pp. 1-114.

24. Kadish, K.M., Royal, G., Van Caemelbecke, E. & Gueletti, L. (2000) Metalloporphyrins in non-aqueous media: database of redox potentials. The porphyrin handbook. Acad. Press: New York, 9, pp. 1-219.

25. Sidorov, A.N. & Maslov, V.G. (1975) Negative ions of tetrapyrrole compounds, Uspekhi khimii, 44(4), pp. 577 601 (in Russian).

26. Berezin, B.D. & Berezin, D.B. (2003) A course in modern organic chemistry. M.: Vysshaya shkola, pp. 242-248 (in Russian).

27. Wolfson, S.V., Kalia, O.L., Lebedev, O.L. & Lukyanets, E.A. (1974) Redox reactions of phthalocyanines and related compounds. Kinetics and mechanism of interaction of phthalocyanines with benzoyl peroxide Zhurn. org. khimii, 44(8), pp. 1757-1763 (in Russian).

28. Li, R., Zhang, X., Zhu, P., Ng, D.K.P., Kobayashi, N. & Jiang, J. (2006) Electron-donating or withdrawing nature of substituents revealed by the electrochemistry of metal-free phthalocyanines, Inorg. Chem., 45(5), pp. 2327-2334. DOI:https://doi.org/10.1021/ic051931k.

29. Berezin, D.B. (2010) Macrocyclic effect and structural chemistry of porphyrins. M.: Krasand (in Russian).

30. Berezin, B.D. & Sennikova, G.V. (1969) Kinetics of oxidative degradation of phthalocyanine and pheophytin complexes, Zhurn. fiz. khimii, 43(10), pp. 2499-2504 (in Russian).

31. Potapova, T.I., Petrova, T.A., Lisova, N.N. & Berezin, B.D. (1989) Oxidative degradation of tetrabenzoporphyrin and its substitutes, Izvestiya vuzov. Khimiya i khim. tekhnol., 32(1), pp. 42-45 (in Russian).

32. Akopov, A.S., Bykova, V.V. & Berezin, B.D. (1983) Kinetics of oxidative degradation of tetra-2,3-pyridinporphyrazine and its complexes in reaction with hydrogen peroxide, Sbornik "Problemy khimii rastvorov i tekhnologii zhidkofaznykh materialov", 19(3), pp. 581-585 (in Russian).

33. Antina, E.V., Barannikov, V.P., Berezin, M.B. & Vjugin, A.I. (2001) Physical Chemistry of Solutions of Macroheterocyclic Compounds, Sbornik "Problemy khimii rastvorov i tekhnologii zhidkofaznykh materialov". Ivanovo: IKhR RAS, pp. 217-248 (in Russian).

34. Pop, S.-F., Ion, R.-M., Corobea, M.C. & Raditoiu, V. (2011) Spectral and thermal investigations of porphyrin and phthalocyaninenanomaterials, J. Optoelectr. Adv. Mater., 13(7), pp. 906-911.

35. Berezin, D.B., Karimov, D.R., Barannikov, V.P. & Semeykin, A.S. (2011) Investigation of the thermal stability of porphyrins with chemically active NH-bonding and their associates with electron-donating solvents, Zhurn. fiz. khimii, 85(12), pp. 2325-2330. DOI:https://doi.org/10.1134/S0036024411120041 (in Russian).

36. Shormanova, L.P. & Berezin, B.D. (1970) Oxidative degradation of polymeric phthalocyanine and its complex compounds, Visokomolekulyarnie soedineniya, 12(3), pp. 692-696 (in Russian).

37. Senge, M.O., Kadish, K.M., Smith, K.M. & Guilard, R. (2000) Highly substituted porphyrins. The porphyrin handbook. Acad. Press: New York, (1), pp. 239-347.

38. Flitsch, W. (1988) Hydrogenated porphyrin derivatives: hydroporphyrins, Adv. Heterocycl. Chem., (43), pp. 73-126. DOI:https://doi.org/10.1016/S0065-2725(08)60253-6.

39. Veyrat, M., Ramasseul, R., Turowska-Tyrk, I., Scheidt, W.R., Autret, M., Kadish, K.M. & Marchon, J.-C. (1999) Nickel(II) and Zinc(II) meso-tetracyclohexylporphyrins. Structural and electronic effects induced by meso-cyclohexyl substitution in metalloporphyrins, Inorg. Chem., 38(8), pp. 1772-1779. DOI:https://doi.org/10.1021/ic981233i.

40. Berezin, D.B. (2012) N-substituted porphyrinoids: structure, spectroscopy, reactivity. LAMBERT Acad. Publ.: Saarbrucken (in Russian).

41. Berezin, D.B., Andrianov, V.G. & Semeykin, A.S. (1996) Manifestation of structural features of porphyrin molecules in their ESP, Opt. cpektroskopiya, 80(4), pp. 618-626 (in Russian).

42. Kustov, A.V., Berezin, D.B., Strelnikov, A.I. & Lapochkina, N.P. (2020) Antitumor and antimicrobial photodynamic therapy: mechanisms, targets, clinical and laboratory studies. Practical guide. M.: Largo (in Russian).

43. Kustov, A.V., Morshnev, Ph.K., Kukushkina, N.V., Krestyaninov, M.A., Smirnova, N.L., Berezin, D.B., Kokurina, G.N. & Belykh, D.V. (2022) The effect of molecular structure of chlorin photosensitizers on photo-bleaching of 1,3-diphenylisobenzofurane – the possible evidence of iodine reactive species formation, Comptes Rendus Chimie, (25), pp. 97-102. DOI:https://doi.org/10.5802/crchim.158.

44. Venediktov, E.A., Tulikova, E.Yu., Rozhkova, E.P., Belykh, D.V., Khudyaeva, I.S. & Berezin, D.B. (2017) Synthesis, spectral-luminescent and photochemical properties of the tricationic chlorine derivative e6 with trimethylammonium groups, Makrogeterotsikly, 10(3), pp. 295-300. DOI:https://doi.org/10.6060/mhc170404v (in Russian).

45. Berezin, D.B. & Likhonina, A.E. (2018) Influence of the medium on the fluorescence characteristics, photo- and heat stability of porphyrins of different structure proper, Zhurn. obshchey khimii, 88(10), pp. 1651-1658. DOI:https://doi.org/10.1134/S0044460X18100116 (in Russian).

46. Takeda, J., Ohya, T. & Sato, M. (1992 ) A ferrochelatase transition-state model. Rapid incorporation of copper (II) into nonplanardodecaphenylporphyrin, Inorg. Chem., 31(13), pp. 2877-2880. DOI:https://doi.org/10.1021/ic00039a038.

47. Sazanovich, I.V., Van, Hoek A., Panarin, A.Yu., Bolotin, V.L., Semeykin, A.S., Berezin, D.B. & Chirvony, V.S. (2005) The photophysical and metal coordination properties of the N-CH3 substituted porphyrins: H(NCH3)TPP vs H(NCH3)OEP, J. Porph. Phthaloc, 9(1), pp. 59-67. DOI:https://doi.org/10.1142/S1088424605000113.

48. Berezin, D.B. (2022) The role of the entropic factor in the complexation kinetics of nonplanarporphyrins with localized and delocalized type of NH-bonding, From Chemistry Towards Technology Step-By-Step, 3(1), pp. 48 57. DOI:https://doi.org/10.52957/27821900_2022_01_48 [online]. Available at: http://chemintech.ru/index.php/tor/2022tom3no1 (in Russian).

49. Ongayi, O., Fronczek, F.R. & Vicente, M.G.H. (2003) Benzoylbiliverdins from chemical oxidation of dodeca-substituted porphyrins, Chem. Comm., 9(18), pp. 2298-2299. DOI:https://doi.org/10.1039/B306586C.

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Berezin D. B., Berezin B. D., Razgovorov P. B. Specific features of the kinetics of destructive degradation of porphine and phthalocyanine derivatives in oxidizing media // From Chemistry Towards Technology Step-By-Step. 2022. no. 3. pp. 93-105. DOI: https://doi.org/10.52957/27821900_2022_03_93. (Date of access 12.09.2026).

MLA

Dmitry Berezin, Berezin B. D., Razgovorov P. B.. "Specific features of the kinetics of destructive degradation of porphine and phthalocyanine derivatives in oxidizing media." From Chemistry Towards Technology Step-By-Step 3.3 (2022): 93-105. DOI: https://doi.org/10.52957/27821900_2022_03_93.

APA

Berezin D. B., Berezin B. D., Razgovorov P. B. (2022). Specific features of the kinetics of destructive degradation of porphine and phthalocyanine derivatives in oxidizing media. From Chemistry Towards Technology Step-By-Step, 3(3), 93-105. https://doi.org/10.52957/27821900_2022_03_93

Chicago

Dmitry Berezin, Berezin B. D., Razgovorov P. B.. "Specific features of the kinetics of destructive degradation of porphine and phthalocyanine derivatives in oxidizing media." From Chemistry Towards Technology Step-By-Step 3, no. 3 (2022): 93-105. https://doi.org/10.52957/27821900_2022_03_93.

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{{cite journal | author = Berezin D. B., Berezin B. D., Razgovorov P. B. | title = Specific features of the kinetics of destructive degradation of porphine and phthalocyanine derivatives in oxidizing media | journal = From Chemistry Towards Technology Step-By-Step | year = 2022 | volume = 3 | issue = 3 | pages = 93-105 | doi = 10.52957/27821900_2022_03_93 }}

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SPECIFIC FEATURES OF THE KINETICS OF DESTRUCTIVE DEGRADATION OF PORPHINE AND PHTHALOCYANINE DERIVATIVES IN OXIDIZING MEDIA Specific features of the kinetics of destructive degradation of porphine and phthalocyanine derivatives in oxidizing media

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