DOI: 10.17586/1023-5086-2026-93-12-91-103

УДК: 535.372:536.5

Fluorescence ratiometric thermometry: elimination of key method artifacts and the thermal memory effect in porphyrins

Batishcheva Y.A., Magaryan K.A., Gorbunova Y.G., Naumov A.V.

For Russian citation (Opticheskii Zhurnal):

Батищева Ю.А., Магарян К.А., Горбунова Ю.Г., Наумов А.В. Флуоресцентная ратиотермометрия: элиминация ключевых артефактов метода и эффект термопамяти порфиринов // Оптический журнал. 2026. Т. 93. № 12. С. 91–103. http://doi.org/10.17586/1023-5086-2026-93-12-91-103

Batishcheva Yu.A., Magaryan K.A., Gorbunova Yu.G., Naumov A.V. Fluorescence ratiometric thermometry: elimination of key method artifacts and the thermal memory effect in porphyrins [in Russian] // Opticheskii Zhurnal. 2026. V. 93. № 12. P. 91–103. http://doi.org/10.17586/1023-5086-2026-93-12-91-103

For citation (Journal of Optical Technology):

Abstract:

Research subject. Photoluminescence ratiometric thermometry using tetraphenylporphyrin as a model system and the associated systematic artifacts that limit the accuracy of temperature measurements. Aim of study. Establishing the conditions for a reproducible determination of the temperature dependence of the ratio of the intensities of the fluorescent bands of tetraphenylporphyrin, taking into account the spectral sensitivity of the equipment and the thermal history of the sample. Methods. Fluorescence spectra were recorded under laser excitation over the temperature range of 25–75 °C. The spectra were corrected for the spectral response of the detection system using tungsten lamp emission and Planck’s radiation law. Spectra obtained under different conditions were compared. Main results. Neglecting the spectral response of the detection system was shown to introduce systematic errors comparable in magnitude to the temperature-induced changes. Nearly linear temperature dependences exhibiting hysteresis were obtained during a heating–cooling cycle. Scientific novelty. A procedure was developed for eliminating the key artifacts of ratiometric measurements. Temperature hysteresis was identified in the fluorescence band intensity ratio of the solution, indicating the presence of longlived, thermally induced energy states of tetraphenylporphyrin molecules. Practical significance. The conditions for the correct comparison of fluorescence spectra of a tetraphenylporphyrin solution in benzene have been determined, and limitations have been established for unambiguous determination of the solution temperature based on the ratio of the intensities at the maxima of two characteristic emission bands (FIR). The obtained results must be taken into account when using the luminescent ratiometry technique in practice, including for tasks in microfluidics, biomedical research, and diagnostics of functional materials.

Keywords:

: luminescence thermometry, ratiometric analysis, spectral calibration, photoluminescence, tetraphenylporphyrin, photobleaching, temperature dependence, hysteresis, memory

Acknowledgements:

the research was carried out within the state assignment of the Ministry of Education of the Russian Federation (theme № 126030618412-6 (“Photonic technologies in science and education: Materials, methods, and tools for ultra-high-sensitivity optical sensing and microscopy”))

OCIS codes: 300.6280, 120.6780, 120.3940, 120.6200

References:

1. Наумов А.В., Уточникова В.В. Достижения и перспективы люминесценции на Всероссийской конференции с международным участием LUMOS–2024 // Фотоника. 2024. Т. 18. № 3. С. 224–228. DOI:10.22184/1993-7296.FRos.2024.18.3.224.228

Naumov A.V., Utochnikova V.V. Achievements and perspectives of luminescence at the All-Russian Conference with International Participation LUMOS–2024 // Photonics Russia. 2024. V. 18. № 3. P. 224–228. DOI:10.22184/1993-7296.FRos.2024.18.3.224.228

2. Brites C.D.S., Lima P.P., Silva N.J.O., Millán A., Amaral V.S., Palacio F., Carlos L.D. Thermometry at the nanoscale // Nanoscale. 2012. V. 4. № 16. P. 4799–4829. DOI:10.1039/C2NR30663H

3. Jaque D., Vetrone F. Luminescence nanothermometry // Nanoscale. 2012. V. 4. № 15. P. 4301–4326. DOI:10.1039/C2NR30764B

4. Suta M., Antić Ž., Đorđević V., Kuzman S., Dramićanin M.D., Meijerink A. Making Nd³⁺ a sensitive luminescent thermometer for physiological temperatures — an account of pitfalls in Boltzmann thermometry // Nanomaterials. 2020. V. 10. № 3. P. 543. DOI:10.3390/nano10030543

5. Kumar P., Patel R., Shrivastava N., Patel M., Rondeau-Gagné S., Selopal G.S. Aspects of luminescence nanoprobes for thermometry: Progress and outlook // Appl. Mater. Today. 2023. V. 35. P. 101931. DOI:10.1016/j.apmt.2023.101931

6. Mazza M.M.A., Raymo F.M. Structural designs for ratiometric temperature sensing with organic fluorophores // J. Mater. Chem. C. 2019. V. 7. № 18. P. 5333–5342. DOI:10.1039/C9TC00993K

7. Kolesnikov I.E., Kalinichev A.A., Kurochkin M.A., Kolesnikov E.Yu., Lähderanta E. Porphyrins as efficient ratiometric and lifetime-based contactless optical thermometers // Mater. Des. 2019. V. 184. P. 108188. DOI:10.1016/j.matdes.2019.108188

8. Bispo-Jr A.G., Saraiva L.F., Lima S.A.M., Pires A.M., Mazali I.O., Sigoli F.A. Lanthanide coordination polymers as luminescent thermometers: Integrating theoretical modeling with experimental analysis to tune the thermal response // J. Mater. Chem. C. 2025. V. 13. № 7. P. 3320–3330. DOI:10.1039/D4TC04537H

9. Polikovskiy T.A., Gontcharenko V.E., Lishova-Dvoretskaya S.D., Islamov M.M., Belousov Y.A., Taydakov I.V. Sensitivity-Range Integral (SRI): A novel approach to evaluating and optimizing luminescent thermometers. A case study of thermometric properties governed by intermolecular CT states in isomeric Eu/Tb coordination compounds // J. Mater. Chem. C. 2026. V. 14. № 11. P. 4539–4555. DOI:10.1039/D5TC03645C

10. Tcelykh L.O., Kozhevnikova V.Yu., Goloveshkin A.S., Latipov E.V., Gordeeva E.O., Utochnikova V.V. Sensing temperature with Tb-Eu-based luminescent thermometer: A novel approach to increase the sensitivity // Sens. Actuators A: Phys. 2022. V. 345. P. 113787. DOI:10.1016/j.sna.2022.113787

11. Ivanova A.A., Polikovskiy T.A., Gontcharenko V.E., Korshunov V.M., Kiskin M.A., Taydakov I.V., Belousov Yu.A. Precision across temperatures: Eu/Tb luminescent thermometer with exceptionally high and stable sensitivity from 180 to 320 K // Sens. Actuators A: Phys. 2024. V. 379. P. 115969. DOI:10.1016/j.sna.2024.115969

12. Савостьянов А.О., Еремчев И.Ю., Наумов А.В. Люминесцентная нанотермометрия с одиночными органическими молекулами: влияние электрон-фононного взаимодействия // Фотоника. 2023. Т. 17. № 7. С. 508–515. DOI:10.22184/1993-7296.FRos.2023.17.7.508.514

Savostianov A.O., Eremchev I.Yu., Naumov A.V. Luminescence nanothermometry by single organic molecules: Manifestation of electron-phonon interaction // Photonics Russia. 2023. V. 17. № 7. P. 508–515. DOI:10.22184/1993-7296.FRos.2023.17.7.508.514

13. Krylov I.V., Akasov R.A., Rocheva V.V., Sholina N.V., Khochenkov D.A., Nechaev A.V., Melnikova N.V., Dmitriev A.A., Ivanov A.V., Generalova A.N., Khaydukov E.V. Local overheating of biotissue labeled with upconversion nanoparticles under Yb³⁺ resonance excitation // Front. Chem. 2020. V. 8. P. 295. DOI:10.3389/fchem.2020.00295

14. Liu S., Gao D., Wang L., Song W., Zhang Z., Zhu Y., Xiao P., Gao S., Zhang Q. Synthesis and luminescence tunability studies in new upconverting BaGeTeO₆:Yb³⁺/Ho³⁺ phosphors [на англ. яз.] // Оптический журнал. 2026. Т. 93. № 7. С. 88–100. DOI: 10.17586/1023-5086-2026-93-07-88-100

Liu S., Gao D., Wang L., Song W., Zhang Z., Zhu Y., Xiao P., Gao S., Zhang Q. Synthesis and luminescence tunability studies in new upconverting BaGeTeO₆:Yb³⁺/Ho³⁺ phosphors [in English] // Opticheskii Zhurnal. 2026. V. 93. № 7. P. 88–100. DOI: 10.17586/1023-5086-2026-93-07-88-100

15. Переседова Д.А., Рипенко В.С., Липатов Е.И., Бураченко А.Г. Аномальная температурная зависимость спектров катодолюминесценции центра 3H синтетических алмазов после радиационно-термической обработки // Оптический журнал. 2026. Т. 93. № 1. С. 34–41. DOI:10.17586/1023-5086-2026-93-01-34-41

Peresedova D.A., Ripenko V.S., Lipatov E.I., Burachenko A.G. Anomalous temperature dependence of cathodoluminescence spectra of 3H center of synthetic diamond after radiation-thermal treatment // Journal of Optical Technology. 2026. V. 93(1). P. 22–26. DOI:10.1364/JOT.93.000022

16. Успенская Ю.А., Гурин А.С., Учаев М.В., Бундакова А.П., Музафарова М.В., Мохов Е.Н., Нагалюк С.С., Солтамов В.А., Баранов П.Г., Бабунц Р.А., Килин С.Я. NV^–-центры в алмазе и карбиде кремния как основа мазеров, работающих при комнатной температуре // Физика твердого тела. 2025. Т. 67. № 9. С. 1647–1653. DOI:10.61011/FTT.2025.09.61616.233-25

Uspenskaya Yu.A., Gurin A.S., Uchaev M.V., Bundakova A.P., Muzafarova M.V., Mokhov E.N., Nagalyuk S.S., Soltamov V.A., Baranov P.G., Babunts R.A., Kilin S.Ya. NV^–-centers in diamond and silicon carbide as the basis for room-temperature masers [in Russian] // Physics of the Solid State. 2025. V. 67. № 9. P. 1647–1653. DOI:10.61011/FTT.2025.09.61616.233-25

17. Neliubov A.Yu., Eremchev I.Yu., Drachev V.P., Kosolobov S.S., Ekimov E.A., Arzhanov A.I., Tarasevich A.O., Naumov A.V. Enigmatic color centers in microdiamonds with bright, stable, and narrow-band fluorescence // Phys. Rev. B. 2023. V. 107. № 8. P. L081406. DOI:10.1103/PhysRevB.107.L081406

18. Кучеренко М.Г., Налбандян В.М., Чмерева Т.М. Люминесценция комплекса «квантовая точка — слоистая плазмонная наночастица» в магнитном поле // Оптический журнал. 2021. Т. 88. № 9. С. 9–19. DOI:10.17586/1023-5086-2021-88-09-09-19

Kucherenko M.G., Nalbandyan V.M., Chmereva T.M. Luminescence of a complex composed of a quantum dot and a layered plasmon nanoparticle in a magnetic field // Journal of Optical Technology. 2021. V. 88(9). P. 489–496. DOI:10.1364/JOT.88.000489

19. Батталова Э.И., Харинцев С.С. Термометрия разупорядоченных твердых тел на основе электронного комбинационного рассеяния света // Письма в ЖЭТФ. 2024. Т. 120. № 10. С. 760–764. DOI:10.31857/S0370274X24110154

Battalova E.I., Kharintsev S.S. Electronic Raman scattering thermometry of disordered solids // JETP Lett. 2024. V. 120. № 10. P. 727–731. DOI:10.1134/S0021364024603737

20. Nexha A., Carvajal J.J., Pujol M.C., Díaz F., Aguiló M. Lanthanide doped luminescence nanothermometers in the biological windows: Strategies and applications // Nanoscale. 2021. V. 13. № 17. P. 7913–7987. DOI:10.1039/D0NR09150B

21. Sun Y., Kong M., Ke J., Gu Y., Li F., Feng W. Rare earth luminescent nanothermometers for biological thermal sensing // Coord. Chem. Rev. 2025. V. 523. P. 216222. DOI:10.1016/j.ccr.2024.216222

22. Kolesnikov I.E., Kalinichev A.A., Solomatina A.I., Kurochkin M.A., Meshkov I.N., Kolesnikov E.Yu., Gorbunova Yu.G. Thermosensitive phosphorus(V) porphyrin: Toward subcellular ratiometric optical temperature sensing // Sens. Actuators A: Phys. 2022. V. 347. P. 113917. DOI:10.1016/j.sna.2022.113917

23. Kurochkin M.A., Kalinichev A.A., Silonov S.A., Efimova I.A., Safonova E.A., Kolesnikov E.Yu., Gorbunova Yu.G., Kolesnikov I.E. Unlocking precise optical thermometry with water-soluble phosphorus(V) porphyrins: A multiparametric study // Sens. Actuators A: Phys. 2026. V. 406. P. 117900. DOI:10.1016/j.sna.2026.117900

24. Sotoma S., Zhong C., Kah J.C.Y., Yamashita H., Plakhotnik T., Harada Y., Suzuki M. In situ measurements of intracellular thermal conductivity using heater-thermometer hybrid diamond nanosensors // Sci. Adv. 2021. V. 7. № 3. P. eabd7888. DOI:10.1126/sciadv.abd7888

25. Đačanin Far L., Dramićanin M.D. Luminescence thermometry with nanoparticles: A review // Nanomaterials. 2023. V. 13. № 21. P. 2904. DOI:10.3390/nano13212904

26. Marciniak L., Kniec K., Elżbieciak-Piecka K., Trejgis K., Stefanska J., Dramićanin M. Luminescence thermometry with transition metal ions. A review // Coord. Chem. Rev. 2022. V. 469. P. 214671. DOI:10.1016/j.ccr.2022.214671

27. Liu M., Liang J., Vetrone F. Toward accurate photoluminescence nanothermometry using rare-earth doped nanoparticles for biomedical applications // Acc. Chem. Res. 2024. V. 57. № 18. P. 2653–2664. DOI:10.1021/acs.accounts.4c00342

28. Касимов Р.Х., Аржанов А.И., Седых К.О., Голиков А.Д., Галанова В.С., Гладуш Ю.Г., Ковалюк В.В., Наумов А.В., Гольцман Г.Н. Источник одиночных фотонов с использованием коллоидных квантовых точек CdSe/CdS/ZnS на волноводах из нитрида кремния // Оптический журнал. 2026. Т. 93. № 1. С. 80–86. DOI:10.17586/1023-5086-2026-93-01-80-86

Kasimov R.Kh., Arzhanov A.I., Sedykh K.O., Golikov A.D., Galanova V.S., Gladush Y.G., Kovalyuk V.V., Naumov A.V., Goltsman G.N. Single photon source based on CdSe/CdS/ZnS quantum dots on silicon nitride waveguides // Journal of Optical Technology. 2026. V. 93(1). P. 50–53. DOI:10.1364/JOT.93.000050

29. Dmitrieva O.A., Mamardashvili N.Z. Porphyrin dimer as efficient optical thermometer: Experimental and computational evaluation of the barrier to torsional rotation // J. Lumin. 2021. V. 235. P. 117986. DOI:10.1016/j.jlumin.2021.117986

30. Kolesnikov I.E., Kurochkin M.A., Meshkov I.N., Akasov R.A., Kalinichev A.A., Kolesnikov E.Yu., Gorbunova Yu.G., Lähderanta E. Water-soluble multimode fluorescent thermometers based on porphyrins photosensitizers // Mater. Des. 2021. V. 203. P. 109613. DOI:10.1016/j.matdes.2021.109613

31. Поволоцкий А.В., Смирнова О.С., Солдатова Д.А., Лукьянов Д.А. Флуоресцентные ратиометрические термометры на основе диад тетрафенилпорфирина и металлированного цинком тетрафенилпорфирина // Изв. РАН. Сер. физ. 2023. Т. 87. № 11. С. 1631–1636. DOI:10.31857/S0367676523702824

Povolotskiy A.V., Smirnova O.S., Soldatova D.A., Lukyanov D.A. Fluorescent ratiometric thermometers based on dyads of tetraphenylporphyrin and zinc metalated tetraphenylporphyrin // Bull. Russ. Acad. Sci. Phys. 2023. V. 87. № 11. P. 1691–1696. DOI:10.3103/S1062873823703902

32. Starukhin A.S., Panarin A.Yu. The internal heavy atom effect on the deactivation of triplet states of porphyrins in the presence of molecular oxygen // J. Appl. Spectrosc. 2023. V. 90. № 5. P. 1037–1042. DOI:10.1007/s10812-023-01629-0

33. Старухин А.С., Ковгар В.В., Шершень В.С., Павич Т.А. Зависимость величин квантовых выходов флуоресценции порфиринов и фталоцианинов от эффектов реабсорбции // Изв. РАН. Сер. физ. 2024. Т. 88. № 6. С. 935–940. DOI:10.31857/S0367676524060143

Starukhin A.S., Kouhar V.V., Shershan V.S., Pavich T.A. Dependence of fluorescence quantum yields on the effects of reabsorption for porphyrins and phthalocyanines // Bull. Russ. Acad. Sci. Phys. 2024. V. 88. № 6. P. 891–895. DOI:10.1134/S1062873824706792

34. Gladkov L.L., Klenitsky D.V., Kruk M.M. Mechanisms of bathochromic band shifts in absorption spectra of N-substituted porphine derivatives // J. Appl. Spectrosc. 2023. V. 90. № 4. P. 754–760. DOI:10.1007/s10812-023-01592-w

35. Koifman O.I., Ageeva T.A., Kuzmina N.S., et al. Synthesis strategy of tetrapyrrolic photosensitizers for their practical application in photodynamic therapy // Macroheterocycles. 2022. V. 15. № 4. P. 207–302. DOI:10.6060/mhc224870k

36. Jacinto C., Silva W.F., Garcia J., Zaragosa G.P., Ilem C.N.D., Sales T.O., Santos H.D.A., Conde B.I.C., Barbosa H.P., Malik S., Sharma S.K. Nanoparticles based image-guided thermal therapy and temperature feedback // J. Mater. Chem. B. 2025. V. 13. № 1. P. 54–102. DOI:10.1039/D4TB01416B

37. Uttamlal M., Holmes-Smith A.S. The excitation wavelength dependent fluorescence of porphyrins // Chem. Phys. Lett. 2008. V. 454. № 4–6. P. 223–228. DOI:10.1016/j.cplett.2008.02.012

38. Adler A.D., Longo F.R., Finarelli J.D., Goldmacher J., Assour J., Korsakoff L. A simplified synthesis for meso-tetraphenylporphine // J. Org. Chem. 1967. V. 32. № 2. P. 476. DOI:10.1021/jo01288a053

39. Resch-Genger U., DeRose P.C. Characterization of photoluminescence measuring systems (IUPAC Technical Report) // Pure Appl. Chem. 2012. V. 84. № 8. P. 1815–1835. DOI:10.1351/PAC-REP-10-07-07

40. Resch-Genger U., Bremser W., Pfeifer D., Spieles M., Hoffmann A., DeRose P.C., Zwinkels J.C., Gauthier F., Ebert B., Taubert R.D., Monte C., Voigt J., Hollandt J., Macdonald R. State-of-the-art comparability of corrected emission spectra. 1. Spectral correction with physical transfer standards and spectral fluorescence standards by expert laboratories // Anal. Chem. 2012. V. 84. № 9. P. 3889–3898. DOI:10.1021/ac2034503

41. Marunchenko A., Kumar J., Kiligaridis A., Tatarinov D., Pushkarev A., Vaynzof Y., Scheblykin I.G. Memlumor: A luminescent memory device for energy-efficient photonic neuromorphic computing // ACS Energy Lett. 2024. V. 9. № 5. P. 2075–2082. DOI:10.1021/acsenergylett.4c00691