najoNanosystems: Physics, Chemistry, MathematicsНаносистемы: физика, химия, математика2220-80542305-7971Университет ИТМО10.17586/2220-8054-2025-16-1-22-29najo-73Research ArticleCHEMISTRY AND MATERIALS SCIENCEХИМИЯ И НАУКА О МАТЕРИАЛАХPeroxidase-like activity of photochromic PVP-stabilized tungsten oxide nanoparticles: assessment by independent chemiluminescent and colorimetric assaysПероксидазоподобная активность фотохромных наночастиц оксида вольфрама, стабилизированных ПВП: независимый анализ хемилюминесцентным и колориметрическим методамиhttps://orcid.org/0000-0002-9811-6241ПопковM. А.PopkovM. A.

Matvei A. Popkov

Leninsky, 31, Moscow, 119991

mapopkov@igic.ras.ruhttps://orcid.org/0000-0003-3485-1842ШейченкоЕ. Д.SheichenkoE. D.

Ekaterina D. Sheichenko

Leninsky, 31, Moscow, 119991

Myasnitskaya, 20, Moscow, 101000

edsheychenko@edu.hse.ruhttps://orcid.org/0000-0002-2725-8891ФилипповаА. Д.FilippovaA. D.

Arina D. Filippova

Leninsky, 31, Moscow, 119991

arifilippova@yandex.ruhttps://orcid.org/0000-0002-0718-1911ТроневИ. В.TronevI. V.

Ilya V. Tronev

Leninsky, 31, Moscow, 119991

ivtronev@edu.hse.ruhttps://orcid.org/0009-0006-4139-1476НовоселоваК. Н.NovoselovaK. N.

Kristina N. Novoselova

Leninsky, 31, Moscow, 119991

Myasnitskaya, 20, Moscow, 101000

knnovoselova@edu.hse.ruhttps://orcid.org/0009-0009-1645-5759ТруфановаЭ. А.TrufanovaE. A.

Evelina A. Trufanova

Leninsky, 31, Moscow, 119991

Myasnitskaya, 20, Moscow, 101000

eatrufanova1@edu.hse.ruhttps://orcid.org/0009-0004-3560-4178ВасильеваД. Н.VasilyevaD. N.

Darya N. Vasilyeva

Leninsky, 31, Moscow, 119991

Myasnitskaya, 20, Moscow, 101000

dnvasileva1@edu.hse.ruhttps://orcid.org/0009-0007-0738-4974ПроценкоМ. Р.ProtsenkoM. R.

Maria R. Protsenko

Leninsky, 31, Moscow, 119991

Myasnitskaya, 20, Moscow, 101000

mrprotsenko@edu.hse.ruhttps://orcid.org/0000-0002-5868-4746СозаруковаМ. М.SozarukovaM. M.

Madina M. Sozarukova

Leninsky, 31, Moscow, 119991

smadinam@bk.ruhttps://orcid.org/0000-0002-2378-7446БаранчиковА. Е.BaranchikovA. E.

Alexander E. Baranchikov

Leninsky, 31, Moscow, 119991

Myasnitskaya, 20, Moscow, 101000

a.baranchikov@yandex.ruhttps://orcid.org/0000-0003-2343-2140ИвановВ. К.IvanovV. K.

Vladimir K. Ivanov

Leninsky, 31, Moscow, 119991

Myasnitskaya, 20, Moscow, 101000

van@igic.ras.ruKurnakov Institute of General and Inorganic Chemistry, Russian Academy of SciencesRussian FederationKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences; HSE UniversityRussian Federation2025010620251612229Copyright © Popkov M.A., Sheichenko E.D., Filippova A.D., Tronev I.V., Novoselova K.N., Trufanova E.A., Vasilyeva D.N., Protsenko M.R., Sozarukova M.M., Baranchikov A.E., Ivanov V.K., 20252025Попков M.А., Шейченко Е.Д., Филиппова А.Д., Тронев И.В., Новоселова К.Н., Труфанова Э.А., Васильева Д.Н., Проценко М.Р., Созарукова М.М., Баранчиков А.Е., Иванов В.К.Popkov M.A., Sheichenko E.D., Filippova A.D., Tronev I.V., Novoselova K.N., Trufanova E.A., Vasilyeva D.N., Protsenko M.R., Sozarukova M.M., Baranchikov A.E., Ivanov V.K.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://nanojournal.ifmo.ru/jour/article/view/73

In this work, peroxidase-like activity of ultrasmall tungsten oxide nanoparticles including those stabilized with polyvinylpyrrolidone (PVP) was assessed using two independent approaches: the colorimetric method, which is based on the analysis of 3,3’,5,5’-tetramethylbenzidine (TMB) oxidation, and the luminolenhanced chemiluminescence method. It was demonstrated that bare tungsten oxide nanoparticles effectively catalyze the decomposition of hydrogen peroxide. In turn, the PVP-stabilized nanoparticles possess lower catalytic activity, which can be attributed to a decrease in the number of available active centres on the nanoparticle surface.

В данной работе пероксидазоподобную активность ультрамелких наночастиц оксида вольфрама, в том числе стабилизированных поливинилпирролидоном (ПВП), оценивали с помощью двух независимых подходов: колориметрического метода, основанного на анализе окисления 3,3',5,5'-тетраметилбензидина (ТМБ), и метода хемилюминесценции с использованием люминола в качестве молекулы-зонда. Было показано, что наночастицы нестабилизированного оксида вольфрама эффективно катализируют разложение пероксида водорода. В свою очередь, наночастицы, стабилизированные ПВП, обладают меньшей каталитической активностью, что можно объяснить уменьшением количества доступных активных центров на поверхности наночастиц.

наноматериалынанозимызолифотохромные материалыхемилюминесценцияТМБпероксидазоподобная активностьnanomaterialsnanozymessolsphotochromic materialschemiluminescenceTMBperoxidaselike activityReferencesKang T., Kim Y.G., Kim D., Hyeon T. Inorganic nanoparticles with enzyme-mimetic activities for biomedical applications. Coord. Chem. Rev., 2020, 403, P. 213092.Kang T., Kim Y.G., Kim D., Hyeon T. Inorganic nanoparticles with enzyme-mimetic activities for biomedical applications. Coord. Chem. Rev., 2020, 403, P. 213092.Liang X., Han L. White Peroxidase-Mimicking Nanozymes: Colorimetric Pesticide Assay without Interferences of O2 and Color. Adv. Funct. Mater., 2020, 30(28), P. 2001933.Liang X., Han L. White Peroxidase-Mimicking Nanozymes: Colorimetric Pesticide Assay without Interferences of O2 and Color. Adv. Funct. Mater., 2020, 30(28), P. 2001933.Gao L., Zhuang J., Nie L., et al. Intrinsic peroxidase-like activity of ferromagnetic nanoparticles. Nat. Nanotechnol., 2007, 2(9), P. 577–583.Gao L., Zhuang J., Nie L., et al. Intrinsic peroxidase-like activity of ferromagnetic nanoparticles. Nat. Nanotechnol., 2007, 2(9), P. 577–583.Gao L. Enzyme-Like Property (Nanozyme) of Iron Oxide Nanoparticles. In: Iron Oxide Nanoparticles, IntechOpen, 2022.Gao L. Enzyme-Like Property (Nanozyme) of Iron Oxide Nanoparticles. In: Iron Oxide Nanoparticles, IntechOpen, 2022.Yang Y., Mao Z., Huang W., et al. Redox enzyme-mimicking activities of CeO2 nanostructures: Intrinsic influence of exposed facets. Sci. Rep., 2016, 6(1), P. 35344.Yang Y., Mao Z., Huang W., et al. Redox enzyme-mimicking activities of CeO2 nanostructures: Intrinsic influence of exposed facets. Sci. Rep., 2016, 6(1), P. 35344.Filippova A.D., Baranchikov A.E., Ivanov V.K. Enzyme-Like Activity of Cerium Dioxide Colloidal Solutions Stabilized with L-Malic Acid. Colloid. J., 2023, 85(5), P. 782–794.Filippova A.D., Baranchikov A.E., Ivanov V.K. Enzyme-Like Activity of Cerium Dioxide Colloidal Solutions Stabilized with L-Malic Acid. Colloid. J., 2023, 85(5), P. 782–794.Filippova A.D., Sozarukova M.M., Baranchikov A.E., Kottsov S.Y., Cherednichenko K.A., Ivanov V.K. Peroxidase-like Activity of CeO2 Nanozymes: Particle Size and Chemical Environment Matter. Molecules, 2023, 28(9), P. 3811.Filippova A.D., Sozarukova M.M., Baranchikov A.E., Kottsov S.Y., Cherednichenko K.A., Ivanov V.K. Peroxidase-like Activity of CeO2 Nanozymes: Particle Size and Chemical Environment Matter. Molecules, 2023, 28(9), P. 3811.Zhao M., Tao Y., HuangW., He Y. Reversible pH switchable oxidase-like activities of MnO2 nanosheets for a visual molecular majority logic gate. Phys. Chem. Chem. Phys., 2018, 20(45), P. 28644–28648.Zhao M., Tao Y., HuangW., He Y. Reversible pH switchable oxidase-like activities of MnO2 nanosheets for a visual molecular majority logic gate. Phys. Chem. Chem. Phys., 2018, 20(45), P. 28644–28648.Lin S., Tan W., Han P., et al. A photonanozyme with light-empowered specific peroxidase-mimicking activity. Nano. Res., 2022, 15(10), P. 9073–9081.Lin S., Tan W., Han P., et al. A photonanozyme with light-empowered specific peroxidase-mimicking activity. Nano. Res., 2022, 15(10), P. 9073–9081.Deng Z., Gong Y., Luo Y., Tian Y. WO3 nanostructures facilitate electron transfer of enzyme: Application to detection of H2O2 with high selectivity. Biosens. Bioelectron., 2009, 24(8), P. 2465–2469.Deng Z., Gong Y., Luo Y., Tian Y. WO3 nanostructures facilitate electron transfer of enzyme: Application to detection of H2O2 with high selectivity. Biosens. Bioelectron., 2009, 24(8), P. 2465–2469.Kozlov D.A., Shcherbakov A.B., Kozlova T.O., et al. Photochromic and Photocatalytic Properties of Ultra-Small PVP-Stabilized WO3 Nanoparticles. Molecules, 2019, 25(1), P. 154.Kozlov D.A., Shcherbakov A.B., Kozlova T.O., et al. Photochromic and Photocatalytic Properties of Ultra-Small PVP-Stabilized WO3 Nanoparticles. Molecules, 2019, 25(1), P. 154.Lee S.-H., Deshpande R., Parilla P.A., et al. Crystalline WO3 Nanoparticles for Highly Improved Electrochromic Applications. Adv. Mater., 2006, 18(6), P. 763–766.Lee S.-H., Deshpande R., Parilla P.A., et al. Crystalline WO3 Nanoparticles for Highly Improved Electrochromic Applications. Adv. Mater., 2006, 18(6), P. 763–766.Aliannezhadi M., Abbaspoor M., Shariatmadar Tehrani F., Jamali M. High photocatalytic WO3 nanoparticles synthesized using Sol-gel method at different stirring times. Opt. Quantum Electron., 2023, 55(3), P. 250.Aliannezhadi M., Abbaspoor M., Shariatmadar Tehrani F., Jamali M. High photocatalytic WO3 nanoparticles synthesized using Sol-gel method at different stirring times. Opt. Quantum Electron., 2023, 55(3), P. 250.Huang Z., Song J., Pan L., Zhang X., Wang L., Zou J. Tungsten Oxides for Photocatalysis, Electrochemistry, and Phototherapy. Adv. Mater., 2015, 27(36), P. 5309–5327.Huang Z., Song J., Pan L., Zhang X., Wang L., Zou J. Tungsten Oxides for Photocatalysis, Electrochemistry, and Phototherapy. Adv. Mater., 2015, 27(36), P. 5309–5327.Dong X., Lu Y., Liu X., Zhang L., Tong Y. Nanostructured tungsten oxide as photochromic material for smart devices, energy conversion, and environmental remediation. J. Photochem. Photobiol. C Photochem. Rev., 2022, 53, P. 100555.Dong X., Lu Y., Liu X., Zhang L., Tong Y. Nanostructured tungsten oxide as photochromic material for smart devices, energy conversion, and environmental remediation. J. Photochem. Photobiol. C Photochem. Rev., 2022, 53, P. 100555.Zeb S., Sun G., Nie Y., Xu H., Cui Y., Jiang X. Advanced developments in nonstoichiometric tungsten oxides for electrochromic applications. Mater. Adv., 2021, 2(21), P. 6839–6884.Zeb S., Sun G., Nie Y., Xu H., Cui Y., Jiang X. Advanced developments in nonstoichiometric tungsten oxides for electrochromic applications. Mater. Adv., 2021, 2(21), P. 6839–6884.George J.M., Antony A., Mathew B. Metal oxide nanoparticles in electrochemical sensing and biosensing: a review. Microchim. Acta, 2018, 185(7), P. 358.George J.M., Antony A., Mathew B. Metal oxide nanoparticles in electrochemical sensing and biosensing: a review. Microchim. Acta, 2018, 185(7), P. 358.Can F., Courtois X., Duprez D. Tungsten-Based Catalysts for Environmental Applications. Catalysts, 2021, 11(6), P. 703.Can F., Courtois X., Duprez D. Tungsten-Based Catalysts for Environmental Applications. Catalysts, 2021, 11(6), P. 703.Kameneva S.V., Popkov M.A., Tronev I.V., Kottsov S.Y., Sozarukova M.M., Ivanov V.K. Photochromic aerogels based on cellulose and chitosan modified with WO3 nanoparticles. Nanosyst. Physics., Chem., Math, 2022, 13(4), P. 404–413.Kameneva S.V., Popkov M.A., Tronev I.V., Kottsov S.Y., Sozarukova M.M., Ivanov V.K. Photochromic aerogels based on cellulose and chitosan modified with WO3 nanoparticles. Nanosyst. Physics., Chem., Math, 2022, 13(4), P. 404–413.Staerz A., Somacescu S., Epifani M., Russ T., Weimar U., Barsan N. WO3 Based Gas Sensors. In: EUROSENSORS 2018. MDPI, 2019, P. 826.Staerz A., Somacescu S., Epifani M., Russ T., Weimar U., Barsan N. WO3 Based Gas Sensors. In: EUROSENSORS 2018. MDPI, 2019, P. 826.Zhou Y., She X.,Wu Q., Xiao J., Peng T. MonoclinicWO3 nanosheets-carbon nanotubes nanocomposite based electrochemical sensor for sensitive detection of bisphenol A. J. Electroanal. Chem., 2022, 915, P. 116355.Zhou Y., She X.,Wu Q., Xiao J., Peng T. MonoclinicWO3 nanosheets-carbon nanotubes nanocomposite based electrochemical sensor for sensitive detection of bisphenol A. J. Electroanal. Chem., 2022, 915, P. 116355.Anithaa A.C., Lavanya N., Asokan K., Sekar C.WO3 nanoparticles based direct electrochemical dopamine sensor in the presence of ascorbic acid. Electrochim. Acta, 2015, 167, P. 294–302.Anithaa A.C., Lavanya N., Asokan K., Sekar C.WO3 nanoparticles based direct electrochemical dopamine sensor in the presence of ascorbic acid. Electrochim. Acta, 2015, 167, P. 294–302.Sharma A., Saini A.K., Kumar N., et al. Methods of preparation of metal-doped and hybrid tungsten oxide nanoparticles for anticancer, antibacterial, and biosensing applications. Surfaces and Interfaces, 2022, 28, P. 101641.Sharma A., Saini A.K., Kumar N., et al. Methods of preparation of metal-doped and hybrid tungsten oxide nanoparticles for anticancer, antibacterial, and biosensing applications. Surfaces and Interfaces, 2022, 28, P. 101641.Bashir A., Khan S.R., Aqib A.I., Shafique L., Ataya F.S. Multifunctional integration of tungsten oxide (WO3) coating: A versatile approach for enhanced performance of antibiotics against single mixed bacterial infections. Microb. Pathog., 2024, 189, P. 106571.Bashir A., Khan S.R., Aqib A.I., Shafique L., Ataya F.S. Multifunctional integration of tungsten oxide (WO3) coating: A versatile approach for enhanced performance of antibiotics against single mixed bacterial infections. Microb. Pathog., 2024, 189, P. 106571.Popov A.L., Han B., Ermakov A.M., et al. PVP-stabilized tungsten oxide nanoparticles: pH sensitive anti-cancer platform with high cytotoxicity. Mater. Sci. Eng. C, 2020, 108, P. 110494.Popov A.L., Han B., Ermakov A.M., et al. PVP-stabilized tungsten oxide nanoparticles: pH sensitive anti-cancer platform with high cytotoxicity. Mater. Sci. Eng. C, 2020, 108, P. 110494.Jiang X., Liu W., Li Y., et al. WO3 nanosheets with peroxidase-like activity and carbon dots based ratiometric fluorescent strategy for xanthine oxidase activity sensing and inhibitor screening. Talanta, 2024, 267, P. 125129.Jiang X., Liu W., Li Y., et al. WO3 nanosheets with peroxidase-like activity and carbon dots based ratiometric fluorescent strategy for xanthine oxidase activity sensing and inhibitor screening. Talanta, 2024, 267, P. 125129.Sadashivanna R.H., Krishna H., Shivakumar A., Gangadhara N.Y., Mahesh Lohith K.S., Krishnegowda A. Oxalic acid capped tungsten oxide nanozyme mimicking peroxidase activity, its synthesis characterization, and kinetic data validation via spectrophotometric studies. Nano-Structures & Nano-Objects, 2024, 40, P. 101340.Sadashivanna R.H., Krishna H., Shivakumar A., Gangadhara N.Y., Mahesh Lohith K.S., Krishnegowda A. Oxalic acid capped tungsten oxide nanozyme mimicking peroxidase activity, its synthesis characterization, and kinetic data validation via spectrophotometric studies. Nano-Structures & Nano-Objects, 2024, 40, P. 101340.Robert A., Meunier B. How to Define a Nanozyme. ACS Nano, 2022, 16(5), P. 6956–6959.Robert A., Meunier B. How to Define a Nanozyme. ACS Nano, 2022, 16(5), P. 6956–6959.Zandieh M., Liu J. Nanozymes: Definition, Activity, and Mechanisms. Adv. Mater., 2024, 36(10), P. 2211041.Zandieh M., Liu J. Nanozymes: Definition, Activity, and Mechanisms. Adv. Mater., 2024, 36(10), P. 2211041.Popov A.L., Savintseva I.V., Popova N.R., et al. PVP-stabilized tungsten oxide nanoparticles (WO3) nanoparticles cause hemolysis of human erythrocytes in a dose-dependent manner. Nanosyst. Physics., Chem., Math, 2019, 10(2), P. 199–205.Popov A.L., Savintseva I.V., Popova N.R., et al. PVP-stabilized tungsten oxide nanoparticles (WO3) nanoparticles cause hemolysis of human erythrocytes in a dose-dependent manner. Nanosyst. Physics., Chem., Math, 2019, 10(2), P. 199–205.Basha M.A.F. Magnetic and optical studies on polyvinylpyrrolidone thin films doped with rare earth metal salts. Polym. J.., 2010, 42(9), P. 728–734.Basha M.A.F. Magnetic and optical studies on polyvinylpyrrolidone thin films doped with rare earth metal salts. Polym. J.., 2010, 42(9), P. 728–734.Pacheco M.L., Pinto T.V., Sousa C.M., et al. Tuning the Photochromic Properties of WO3 -Based Materials toward High-Performance Light- Responsive Textiles. ACS Appl. Opt. Mater., 2023, 1(8), P. 1434–1451.Pacheco M.L., Pinto T.V., Sousa C.M., et al. Tuning the Photochromic Properties of WO3 -Based Materials toward High-Performance Light- Responsive Textiles. ACS Appl. Opt. Mater., 2023, 1(8), P. 1434–1451.Hussain M., Kalulu M., Ahmad Z., Ejeromedoghene O., Fu G. Rapid fabrication of polyoxometalate-enhanced photo responsive films from ethyl cellulose (EC) and polyvinylpyrrolidone (PVP). Int. J. Biol. Macromol., 2024, 280, P. 136051.Hussain M., Kalulu M., Ahmad Z., Ejeromedoghene O., Fu G. Rapid fabrication of polyoxometalate-enhanced photo responsive films from ethyl cellulose (EC) and polyvinylpyrrolidone (PVP). Int. J. Biol. Macromol., 2024, 280, P. 136051.Jiang B., Duan D., Gao L., et al. Standardized assays for determining the catalytic activity and kinetics of peroxidase-like nanozymes. Nat. Protoc., 2018, 13(7), P. 1506–1520.Jiang B., Duan D., Gao L., et al. Standardized assays for determining the catalytic activity and kinetics of peroxidase-like nanozymes. Nat. Protoc., 2018, 13(7), P. 1506–1520.Zheng J.J., Zhu F., Song N., et al. Optimizing the standardized assays for determining the catalytic activity and kinetics of peroxidase-like nanozymes. Nat. Protoc., 2024, 19, 3470–3488.Zheng J.J., Zhu F., Song N., et al. Optimizing the standardized assays for determining the catalytic activity and kinetics of peroxidase-like nanozymes. Nat. Protoc., 2024, 19, 3470–3488.Feng K.,Wang G.,Wang S., et al. Breaking the pH Limitation of Nanozymes: Mechanisms, Methods, and Applications. Adv. Mater., 2024, 36(31), P. 2401619.Feng K.,Wang G.,Wang S., et al. Breaking the pH Limitation of Nanozymes: Mechanisms, Methods, and Applications. Adv. Mater., 2024, 36(31), P. 2401619.Eroi S.N., Ello A.S., Diabat´e D., Ossonon D.B. Heterogeneous WO3/H2O2 system for degradation of Indigo Carmin dye from aqueous solution. South African J. Chem. Eng., 2021, 37, P. 53–60.Eroi S.N., Ello A.S., Diabat´e D., Ossonon D.B. Heterogeneous WO3/H2O2 system for degradation of Indigo Carmin dye from aqueous solution. South African J. Chem. Eng., 2021, 37, P. 53–60.Shi R., Wei S., Cheng S., Zeng J., Wang Y., Shu X. Colorimetric Detection of Glucose Using WO3 Nanosheets as Peroxidase-mimetic Enzyme. Chem. Res. Chinese Univ., 2022, 38(4), P. 985–990.Shi R., Wei S., Cheng S., Zeng J., Wang Y., Shu X. Colorimetric Detection of Glucose Using WO3 Nanosheets as Peroxidase-mimetic Enzyme. Chem. Res. Chinese Univ., 2022, 38(4), P. 985–990.Yang J., Cheng S.Q., Shi R., Ying Qin S., Huang L., Lin Wang Y. Spectrophotometric detection of uric acid with enzyme-like reaction mediated 3,3’,5,5’-tetramethylbenzidine oxidation. Bull. Chem. Soc. Ethiop., 2022, 37(1), P. 11–21.Yang J., Cheng S.Q., Shi R., Ying Qin S., Huang L., Lin Wang Y. Spectrophotometric detection of uric acid with enzyme-like reaction mediated 3,3’,5,5’-tetramethylbenzidine oxidation. Bull. Chem. Soc. Ethiop., 2022, 37(1), P. 11–21.Li Z., Liu X., Liang X.H., Zhong J., Guo L., Fu F. Colorimetric determination of xanthine in urine based on peroxidase-like activity of WO3 nanosheets. Talanta, 2019, 204, P. 278–284.Li Z., Liu X., Liang X.H., Zhong J., Guo L., Fu F. Colorimetric determination of xanthine in urine based on peroxidase-like activity of WO3 nanosheets. Talanta, 2019, 204, P. 278–284.

The authors declare that there are no conflicts of interest present.