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The role of hydrolysis in biological effects of molybdenum cluster with DMSO ligands

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Abstract

Biological applications of octahedral molybdenum cluster complexes are complicated by their hydrolytic instability, since hydrolysis leads to irreversible changes in the structure and properties of these compounds. On the other hand, if such changes are thoroughly investigated and understood, the hydrolysis process can become an important tool for regulating specific biological effects of the clusters. In this work, we demonstrate how the luminescence and biological properties (cellular uptake, cytotoxicity in the dark and photodynamic effect) of highly unstable cluster complex [{Mo6I8}(DMSO)6](NO3)4 change along with the degree of hydrolysis. Particularly, cluster solution preliminarily aged in water demonstrated lower dark and higher photoinduced cytotoxicity and higher cellular uptake in comparison with fresh solution.

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The main data supporting the results of this study are available within the paper and its Supplementary Information files. The raw and analyzed datasets generated during the study are available for research purposes from the corresponding author on reasonable request.

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References

  1. Mikhaylov MA, Sokolov MN (2019) Molybdenum Iodides—from obscurity to bright luminescence. Eur J Inorg Chem 2019:4181–4197. https://doi.org/10.1002/ejic.201900630

    Article  CAS  Google Scholar 

  2. Evtushok DV, Melnikov AR, Vorotnikova NA, Vorotnikov YA, Ryadun AA, Kuratieva NV, Kozyr KV, Obedinskaya NR, Kretov EI, Novozhilov IN, Mironov YV, Stass DV, Efremova OA, Shestopalov MA (2017) A comparative study of optical properties and X-ray induced luminescence of octahedral molybdenum and tungsten cluster complexes. Dalton Trans 46:11738–11747. https://doi.org/10.1039/c7dt01919j

    Article  CAS  PubMed  Google Scholar 

  3. Vorotnikova NA, Alekseev AY, Vorotnikov YA, Evtushok DV, Molard Y, Amela-Cortes M, Cordier S, Smolentsev AI, Burton CG, Kozhin PM, Zhu P, Topham PD, Mironov YV, Bradley M, Efremova OA, Shestopalov MA (2019) Octahedral molybdenum cluster as a photoactive antimicrobial additive to a fluoroplastic. Mater Sci Eng C 105:artn 110150. https://doi.org/10.1016/j.msec.2019.110150

    Article  CAS  Google Scholar 

  4. Beltran A, Mikhailov M, Sokolov MN, Perez-Laguna V, Rezusta A, Revillo MJ, Galindo F (2016) A photobleaching resistant polymer supported hexanuclear molybdenum iodide cluster for photocatalytic oxygenations and photodynamic inactivation of Staphylococcus aureus. J Mater Chem B 4:5975–5979. https://doi.org/10.1039/c6tb01966h

    Article  CAS  PubMed  Google Scholar 

  5. Felip-Leon C, del Valle CA, Perez-Laguna V, Millan-Lou MI, Miravet JF, Mikhailov M, Sokolov MN, Rezusta-Lopez A, Galindo F (2017) Superior performance of macroporous over gel type polystyrene as a support for the development of photo-bactericidal materials. J Mater Chem B 5:6058–6064. https://doi.org/10.1039/c7tb01478c

    Article  CAS  PubMed  Google Scholar 

  6. Kirakci K, Zelenka J, Rumlova M, Cvacka J, Ruml T, Lang K (2019) Cationic octahedral molybdenum cluster complexes functionalized with mitochondria-targeting ligands: photodynamic anticancer and antibacterial activities. Biomater Sci 7:1386–1392. https://doi.org/10.1039/c8bm01564c

    Article  CAS  PubMed  Google Scholar 

  7. Vorotnikova NA, Bardin VA, Vorotnikov YA, Kirakci K, Adamenko LS, Alekseev AY, Meyer HJ, Kubat P, Mironov YV, Lang K, Shestopalov MA (2021) Heterogeneous photoactive antimicrobial coatings based on a fluoroplastic doped with an octahedral molybdenum cluster compound. Dalton Trans 50:8467–8475. https://doi.org/10.1039/d1dt01102b

    Article  CAS  PubMed  Google Scholar 

  8. Neaime C, Amela-Cortes M, Grasset F, Molard Y, Cordier S, Dierre B, Mortier M, Takei T, Takahashi K, Haneda H, Verelst M, Lechevallier S (2016) Time-gated luminescence bioimaging with new luminescent nanocolloids based on [Mo6I8(C2F5COO)6]2- metal atom clusters. Phys Chem Chem Phys 18:30166–30173. https://doi.org/10.1039/c6cp05290h

    Article  CAS  PubMed  Google Scholar 

  9. Vorotnikova NA, Efremova OA, Tsygankova AR, Brylev KA, Edeleva MV, Kurskaya OG, Sutherland AJ, Shestopalov AM, Mironov YV, Shestopalov MA (2016) Characterization and cytotoxicity studies of thiol-modified polystyrene microbeads doped with [{Mo6X8}(NO3)6]2- (X=Cl, Br, I). Polym Adv Technol 27:922–928. https://doi.org/10.1002/pat.3749

    Article  CAS  Google Scholar 

  10. Solovieva AO, Vorotnikov YA, Trifonova KE, Efremova OA, Krasilnikova AA, Brylev KA, Vorontsova EV, Avrorov PA, Shestopalova LV, Poveshchenko AF, Mironov YV, Shestopalov MA (2016) Cellular internalisation, bioimaging and dark and photodynamic cytotoxicity of silica nanoparticles doped by {Mo6I8}4+ metal clusters. J Mater Chem B 4:4839–4846. https://doi.org/10.1039/c6tb00723f

    Article  CAS  PubMed  Google Scholar 

  11. Svezhentseva EV, Solovieva AO, Vorotnikov YA, Kurskaya OG, Brylev KA, Tsygankova AR, Edeleva MV, Gyrylova SN, Kitamura N, Efremova OA, Shestopalov MA, Mironov YV, Shestopalov AM (2017) Water-soluble hybrid materials based on {Mo6X8}4+ (X = Cl, Br, I) cluster complexes and sodium polystyrene sulfonate. New J Chem 41:1670–1676. https://doi.org/10.1039/c6nj03469a

    Article  CAS  Google Scholar 

  12. Brandhonneur N, Hatahet T, Amela-Cortes M, Molard Y, Cordier S, Dollo G (2018) Molybdenum cluster loaded PLGA nanoparticles: an innovative theranostic approach for the treatment of ovarian cancer. Eur J Pharm Biopharm 125:95–105. https://doi.org/10.1016/j.ejpb.2018.01.007

    Article  CAS  PubMed  Google Scholar 

  13. Vorotnikov YA, Novikova ED, Solovieva AO, Shanshin DV, Tsygankova AR, Shcherbakov DN, Efremova OA, Shestopalov MA (2020) Single-domain antibody C7b for address delivery of nanoparticles to HER2-positive cancers. Nanoscale 12:21885–21894. https://doi.org/10.1039/d0nr04899b

    Article  CAS  PubMed  Google Scholar 

  14. Kirakci K, Kubat P, Kucerakova M, Sicha V, Gbelcova H, Lovecka P, Grznarova P, Ruml T, Lang K (2016) Water-soluble octahedral molybdenum cluster compounds Na2[Mo6I8(N3)6] and Na2[Mo6I8(NCS)6]: syntheses, luminescence, and in vitro studies. Inorg Chim Acta 441:42–49. https://doi.org/10.1016/j.ica.2015.10.043

    Article  CAS  Google Scholar 

  15. Vorotnikov YA, Efremova OA, Novozhilov IN, Yanshole VV, Kuratieva NV, Brylev KA, Kitamura N, Mironov YV, Shestopalov MA (2017) Hexaazide octahedral molybdenum cluster complexes: synthesis, properties and the evidence of hydrolysis. J Mol Struct 1134:237–243. https://doi.org/10.1016/j.molstruc.2016.12.052

    Article  CAS  Google Scholar 

  16. Pronin AS, Yarovoy SS, Gayfulin YM, Ryadun AA, Brylev KA, Samsonenko DG, Eltsov IV, Mironov YV (2020) Cyanide complexes based on {Mo6I8}4+ and {W6I8}4+ cluster cores. Molecules 25:artn 5796. https://doi.org/10.3390/molecules25245796

    Article  CAS  Google Scholar 

  17. Kirakci K, Pozmogova TN, Protasevich AY, Vavilov GD, Stass DV, Shestopalov MA, Lang K (2021) A water-soluble octahedral molybdenum cluster complex as a potential agent for X-ray induced photodynamic therapy. Biomater Sci 9:2893–2902. https://doi.org/10.1039/d0bm02005b

    Article  CAS  PubMed  Google Scholar 

  18. Marchuk MV, Vorotnikova NA, Vorotnikov YA, Kuratieva NV, Stass DV, Shestopalov MA (2021) Optical property trends in a family of Mo6I8 aquahydroxo complexes. Dalton Trans 50:8794–8802. https://doi.org/10.1039/d1dt01293b

    Article  CAS  PubMed  Google Scholar 

  19. Svezhentseva EV, Vorotnikov YA, Solovieva AO, Pozmogova TN, Eltsov IV, Ivanov AA, Evtushok DV, Miroshnichenko SM, Yanshole VV, Eling CJ, Adawi AM, Bouillard JSG, Kuratieva NV, Fufaeva MS, Shestopalova LV, Mironov YV, Efremova OA, Shestopalov MA (2018) From photoinduced to dark cytotoxicity through an octahedral cluster hydrolysis. Chem Eur J 24:17915–17920. https://doi.org/10.1002/chem.201804663

    Article  CAS  PubMed  Google Scholar 

  20. Kirakci K, Demel J, Hynek J, Zelenka J, Rumlova M, Ruml T, Lang K (2019) Phosphinate apical ligands: a route to a water-stable octahedral molybdenum cluster complex. Inorg Chem 58:16546–16552. https://doi.org/10.1021/acs.inorgchem.9b02569

    Article  CAS  PubMed  Google Scholar 

  21. Spreckelmeyer S, Orvig C, Casini A (2014) Cellular transport mechanisms of cytotoxic metallodrugs: an overview beyond cisplatin. Molecules 19:15584–15610. https://doi.org/10.3390/molecules191015584

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  22. Levina A, Crans DC, Lay PA (2017) Speciation of metal drugs, supplements and toxins in media and bodily fluids controls in vitro activities. Coord Chem Rev 352:473–498. https://doi.org/10.1016/j.ccr.2017.01.002

    Article  CAS  Google Scholar 

  23. Sanna D, Ugone V, Micera G, Buglyó P, Bíró L, Garribba E (2017) Speciation in human blood of Metvan, a vanadium based potential anti-tumor drug. Dalton Trans 46:8950–8967. https://doi.org/10.1039/C7DT00943G

    Article  CAS  PubMed  Google Scholar 

  24. Yeo CI, Ooi KK, Tiekink ERT (2018) Gold-based medicine: a paradigm shift in anti-cancer therapy? Molecules 23:artn 1410. https://doi.org/10.3390/molecules23061410

    Article  CAS  Google Scholar 

  25. Kiss T, Enyedy ÉA, Jakusch T, Dömötör O (2019) Speciation of metal complexes of medicinal interest: relationship between solution equilibria and pharmaceutical properties. Curr Med Chem 26:580–606. https://doi.org/10.2174/0929867325666180307113435

    Article  CAS  PubMed  Google Scholar 

  26. Anthony EJ, Bolitho EM, Bridgewater HE, Carter OWL, Donnelly JM, Imberti C, Lant EC, Lermyte F, Needham RJ, Palau M, Sadler PJ, Shi H, Wang F-X, Zhang W-Y, Zhang Z (2020) Metallodrugs are unique: opportunities and challenges of discovery and development. Chem Sci 11:12888–12917. https://doi.org/10.1039/D0SC04082G

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  27. Merlino A (2021) Recent advances in protein metalation: structural studies. Chem Commun 57:1295–1307. https://doi.org/10.1039/D0CC08053E

    Article  CAS  Google Scholar 

  28. Pessoa JC, Correia I (2021) Misinterpretations in evaluating interactions of vanadium complexes with proteins and other biological targets. Inorganics 9:17. https://doi.org/10.3390/inorganics9020017

    Article  CAS  Google Scholar 

  29. Kostova I (2006) Platinum complexes as anticancer agents. Recent Pat Anticancer Drug Discov 1:1–22. https://doi.org/10.2174/157489206775246458

    Article  CAS  PubMed  Google Scholar 

  30. Vorotnikov YA, Efremova OA, Vorotnikova NA, Brylev KA, Edeleva MV, Tsygankova AR, Smolentsev AI, Kitamura N, Mironov YV, Shestopalov MA (2016) On the synthesis and characterisation of luminescent hybrid particles: Mo6 metal cluster complex/SiO2. RSC Adv 6:43367–43375. https://doi.org/10.1039/c6ra04321f

    Article  CAS  Google Scholar 

  31. Mikhaylov MA, Abramov PA, Komarov VY, Sokolov MN (2017) Cluster aqua/hydroxocomplexes supporting extended hydrogen bonding networks. preparation and structure of a unique series of cluster hydrates [Mo6I8(OH)4(H2O)2]·nH2O (n= 2, 12, 14). Polyhedron 122:241–246. https://doi.org/10.1016/j.poly.2016.11.011

    Article  CAS  Google Scholar 

  32. Aubert T, Burel A, Esnault MA, Cordier S, Grasset F, Cabello-Hurtado F (2012) Root uptake and phytotoxicity of nanosized molybdenum octahedral clusters. J Hazard Mater 219–220:111–118. https://doi.org/10.1016/j.jhazmat.2012.03.058

    Article  CAS  PubMed  Google Scholar 

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Acknowledgements

This research was supported by the Russian Foundation for Basic Research (Grant no. 20-33-90087). The NIIC team thanks the Ministry of Science and Higher Education of the Russian Federation (No. 121031700321-3).

Funding

Funding was provided by the Russian Foundation for Basic Research (Grant no. 20-33-90087) and Ministry of Science and Higher Education of the Russian Federation (No. 121031700321-3).

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Authors and Affiliations

  1. Nikolaev Institute of Inorganic Chemistry SB RAS, 3 Acad. Lavrentiev Ave., 630090, Novosibirsk, Russia

    Ekaterina V. Pronina, Tatiana N. Pozmogova, Yuri A. Vorotnikov, Anton A. Ivanov & Michael A. Shestopalov

  2. SPF-Vivarium, Institute of Cytology and Genetics SB RAS, 10 Acad. Lavrentieva ave., 630090, Novosibirsk, Russia

    Tatiana N. Pozmogova

  3. Novosibirsk State University, 1 Pirogova st., 630090, Novosibirsk, Russia

    Tatiana N. Pozmogova

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  1. Ekaterina V. Pronina
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  2. Tatiana N. Pozmogova
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  3. Yuri A. Vorotnikov
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  4. Anton A. Ivanov
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  5. Michael A. Shestopalov
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Correspondence to Yuri A. Vorotnikov.

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Pronina, E.V., Pozmogova, T.N., Vorotnikov, Y.A. et al. The role of hydrolysis in biological effects of molybdenum cluster with DMSO ligands. J Biol Inorg Chem 27, 111–119 (2022). https://doi.org/10.1007/s00775-021-01914-3

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