In this paper, we presented the unique optical properties of monodispersed and uniform luminescence nanothermometers (LNTs), composed of core (NaYF4:Yb3+,Er3+) and core-shell (NaYF4:Yb3+,Er3+@NaYF4) upconverting nanoparticles (UCNPs). We observed a significant influence of the NaYF4 shell on the reduction of the luminescence energy loss, which appeared as a steeper temperature vs. luminescence intensity ratio (I G2/I G1) curve. Moreover, the addition of nonionic IGEPAL CO-520 surfactant and a small amount of deionized water led to the additional improvement of the nanothermometer's sensitivity, especially in the physiological temperature range between 35 and 40 °C. Such behavior was explained by the physical and chemical interactions of the surfactant molecules with the particle surface, which led to a significant reduction in luminescent energy loss. The developed method of lanthanide-based LNT synthesis and characterization is suitable for the preparation of in vitro nanothermometers and could be applied, for example, in microelectronics or environmental monitoring.

Adam Mickiewicz University in Poznań NanoBioMedical Centre ul Wszechnicy Piastowskiej 3 61 614 Poznań Poland

Department of Biochemistry Molecular Biology and Biotechnology Wrocław University of Science and Technology ul C K Norwida 4 6 50 373 Wrocław Poland

Department of Experimental Physics Wrocław University of Science and Technology wyb Stanisława Wyspiańskiego 27 50 370 Wrocław Poland

Department of Polymer Particles Institute of Macromolecular Chemistry Czech Academy of Sciences Heyrovského nám 2 162 00 Prague 6 Czech Republic

Department of Semiconductor Materials Engineering Wrocław University of Science and Technology wyb Stanisława Wyspiańskiego 27 50 370 Wrocław Poland

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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;4:4799–4829. doi: 10.1039/c2nr30663h. PubMed DOI

Savchuk O. A., Silvestre O. F., Adão R. M., Nieder J. B.. GFP fluorescence peak fraction analysis based nanothermometer for the assessment of exothermal mitochondria activity in live cells. Sci. Rep. 2019;9:7535. doi: 10.1038/s41598-019-44023-7. PubMed DOI PMC

Mohammed L. J., Omer K. M.. Carbon dots as new generation materials for nanothermometer: Review. Nanoscale Res. Lett. 2020;15:182. doi: 10.1186/s11671-020-03413-x. PubMed DOI PMC

Vetrone F., Naccache R., Zamarrón A., Juarranz de la Fuente A., Sanz-Rodríguez F., Maestro L. M., Rodriguez E. M., Jaque D., Solé J. G., Capobianco J. A.. Temperature sensing using fluorescent nanothermometers. ACS Nano. 2010;4:3254–3258. doi: 10.1021/nn100244a. PubMed DOI

Tan M., Li F., Cao N., Li H., Wang X., Zhang Ch., Jaque D., Chen G.. Accurate in vivo nanothermometry through NIR-II lanthanide luminescence lifetime. Small. 2020;16:e2004118. doi: 10.1002/smll.202004118. PubMed DOI

Kriszt R., Arai S., Itoh H., Lee M. H., Goralczyk A. G., Ang X. M., Cypess A. M., White A. P., Shamsi F., Xue R., Lee J. Y., Lee S.-C., Hou Y., Kitaguchi T., Sudhaharan T., Ishiwata S., Lane E. B., Chang Y.-T., Tseng Y.-H., Suzuki M., Raghunath M.. Optical visualisation of thermogenesis in stimulated single-cell brown adipocytes. Sci. Rep. 2017;7:1383. doi: 10.1038/s41598-017-00291-9. PubMed DOI PMC

Xie T.-R., Liu C.-F., Kang J.-S.. Dye-based mito-thermometry and its application in thermogenesis of brown adipocytes. Biophys. Rep. 2017;3:85–91. doi: 10.1007/s41048-017-0039-6. PubMed DOI PMC

Nakano M., Arai Y., Kotera I., Okabe K., Kamei Y., Nagai T.. Genetically encoded ratiometric fluorescent thermometer with wide range and rapid response. PLoS One. 2017;12:e0172344. doi: 10.1371/journal.pone.0172344. PubMed DOI PMC

Christofferson J., Maize K., Ezzahri Y., Shabani J., Wang X., Shakouri A.. Microscale and nanoscale thermal characterization techniques. J. Electron. Packag. 2008;130:041101. doi: 10.1115/1.2993145. DOI

Chatterjee D. K., Rufaihah A. J., Zhang Y.. Upconversion fluorescence imaging of cells and small animals using lanthanide doped nanocrystals. Biomater. 2008;29:937–943. doi: 10.1016/j.biomaterials.2007.10.051. PubMed DOI

Shi Z., Duan Y., Zhu X., Wang Q., Li D. D., Hu K., Feng W., Li F., Xu C.. Dual functional NaYF4:Yb3+, Er3+@NaYF4:Yb3+, Nd3+ core-shell nanoparticles for cell temperature sensing and imaging. Nanotechnology. 2018;29:094001. doi: 10.1088/1361-6528/aaa44a. PubMed DOI

Wen S., Zhou J., Zheng K., Bednarkiewicz A., Liu X., Jin D.. Advances in highly doped upconversion nanoparticles. Nat. Commun. 2018;9:2415. doi: 10.1038/s41467-018-04813-5. PubMed DOI PMC

Zhu X., Feng W., Chang J., Tan Y.-W., Li J., Chen M., Sun Y., Li F.. Temperature-feedback upconversion nanocomposite for accurate photothermal therapy at facile temperature. Nat. Commun. 2016;7:10437. doi: 10.1038/ncomms10437. PubMed DOI PMC

Wu S., Han G., Milliron D. J., Aloni S., Altoe V., Talapin D. V., Cohen B. E., Schuck P. J.. Non-blinking and photostable upconverted luminescence from single lanthanide-doped nanocrystals. Biophys. And Comput. Biol. 2009;106:10917–10921. doi: 10.1073/pnas.0904792106. PubMed DOI PMC

Puccini A., Liu N., Hemmer E.. Lanthanide-based nanomaterials for temperature sensing in the near-infrared spectral region: Illuminating progress and challenges. Nanoscale. 2024;16:10975–10993. doi: 10.1039/D4NR00307A. PubMed DOI

van Ravenhorst I. K., Geitenbeek R. G., van der Eerden M. J., van Omme J. T., Peréz Garza H. H., Meirer F., Meijerink A., Weckhuysen B. M.. In situ local temperature mapping in microscopy nano-reactors with luminescence thermometry. ChemCatChem. 2019;11:5505–5512. doi: 10.1002/cctc.201900985. DOI

Geitenbeek R. G., Vollenbroek J. C., Weijgertze H. M. H., Tregouet C. B. M., Nieuwelink A.-E., Kennedy Ch. L., Weckhuysen B. M., Lohse D., van Blaaderen A., van der Berg A., Odijk M., Meijerink A.. Luminescence thermometry for: In situ temperature measurements in microfluidic devices. Lab Chip. 2019;19:1236–1246. doi: 10.1039/C8LC01292J. PubMed DOI

Wang C., Xu R., Tian W., Jiang X., Cui Z., Wang M., Sun H., Fang K., Gu N.. Determining intracellular temperature at single-cell level by a novel thermocouple method. Cell Res. 2011;21:1517–1519. doi: 10.1038/cr.2011.117. PubMed DOI PMC

Okabe K., Inada N., Gota Ch., Harada Y., Funatsu T., Uchiyama S.. Intracellular temperature mapping with a fluorescent polymeric thermometer and fluorescence lifetime imaging microscopy. Nat. Commun. 2012;3:705. doi: 10.1038/ncomms1714. PubMed DOI PMC

Jaque D., Vetrone F.. Luminescence nanothermometry. Nanoscale. 2012;4:4301–4326. doi: 10.1039/c2nr30764b. PubMed DOI

del Rosal B., Ximendes E., Rocha U., Jaque D.. In vivo luminescence nanothermometry: From materials to applications. Adv. Opt. Mater. 2017;5:1600508. doi: 10.1002/adom.201600508. DOI

Di X., Wang D., Zhou J., Zhang L., Stenzel M. H., Su Q. P., Jin D.. Quantitatively monitoring in situ mitochondrial thermal dynamics by upconversion nanoparticles. Nano Lett. 2021;21:1651–1658. doi: 10.1021/acs.nanolett.0c04281. PubMed DOI PMC

Homma M., Takei Y., Murata A., Inoue T., Takeoka S.. A ratiometric fluorescent molecular probe for visualization of mitochondrial temperature in living cells. Chem. Commun. 2015;51:6194–6197. doi: 10.1039/C4CC10349A. PubMed DOI

Bu C., Mu L., Cao X., Chen M., She G., Shi W.. Silver nanowire-based fluorescence thermometer for a single cell. ACS Appl. Mater. Interfaces. 2018;10:33416–33422. doi: 10.1021/acsami.8b09696. PubMed DOI

Chen M., Xue S., Liu L., Li Z., Wang H., Tan Ch., Yang J., Hu X., Jiang X.-F., Cheng Y., Wang H., Xing X., He S.. A highly stable optical humidity sensors based on nano-composite film. Sens. Actuators B: Chem. 2019;287:329–337. doi: 10.1016/j.snb.2019.02.051. DOI

Macairan J. R., Jaunky D. B., Piekny A., Naccache R.. Intracellular ratiometric temperature sensing using fluorescent carbon dots. Nanoscale Adv. 2019;1:105–113. doi: 10.1039/C8NA00255J. PubMed DOI PMC

Mi C., Zhou J., Wang F., Lin G., Jin D.. Ultrasensitive ratiometric nanothermometer with large dynamic range and photostability. Chem. Mater. 2019;31:9480–9487. doi: 10.1021/acs.chemmater.9b03466. DOI

Duan C., Liang L., Li L., Zhang R., Xu Z. P.. Recent progress in upconversion luminescence nanomaterials for biomedical applications. J. Mater. Chem. B. 2018;6:192–209. doi: 10.1039/C7TB02527K. PubMed DOI

Nam S. H., Bae Y. M., Park Y. I., Kim J. H., Kim H. M., Choi J. S., Lee K. T., Hyeon T., Suh Y. D.. Long-term real-time tracking of lanthanide ion doped upconverting nanoparticles in living cells. Angew. Chem., Int. Ed. 2011;50:6093–6097. doi: 10.1002/anie.201007979. PubMed DOI

Liang H., Yang K., Yang Y., Hong Z., Li S., Chen Q., Li J., Song X., Yang H.. A lanthanide upconversion nanothermometer for precise temperature mapping on immune cell membrane. Nano Lett. 2022;22:9045–9053. doi: 10.1021/acs.nanolett.2c03392. PubMed DOI

Li X., Gai S., Li Ch., Wang D., Niu N., He F., Yang P.. Monodisperse lanthanide fluoride nanocrystals: Synthesis and luminescent properties. Inorg. Chem. 2012;51:3963–3971. doi: 10.1021/ic200925v. PubMed DOI

Zhou J., Liu Z., Li F.. Upconversion nanophosphors for small-animal imaging. Chem. Soc. Rev. 2012;41:1323–1349. doi: 10.1039/C1CS15187H. PubMed DOI

Tao, K. ; Sun, K. . Chapter 6 - Upconversion nanoparticles: A toolbox for biomedical applications. In Photonanotechnology for Therapeutics and Imaging. Micro and Nano Technologies, Choi, S. K. , Ed.; Elsevier, 2020; 147–176.

Podhorodecki A., Krajnik B., Golacki L. W., Kostiv U., Pawlik G., Kaczmarek M., Horák D.. Percolation limited emission intensity from upconverting NaYF4:Yb3+, Er3+ nanocrystals-a single nanocrystal optical study. Nanoscale. 2018;10:21186–21196. doi: 10.1039/C8NR05961F. PubMed DOI

Kembuan C., Saleh M., Rühle B., Resch-Genger U., Graf Ch.. Coating of upconversion nanoparticles with silica nanoshells of 5–250 nm thickness. Beilstein J. Nanotechnol. 2019;10:2410–2421. doi: 10.3762/bjnano.10.231. PubMed DOI PMC

Chu H., Cao T., Dai G., Liu B., Duan H., Kong Ch., Tian N., Hou D., Sun Z.. Recent advances in functionalized upconversion nanoparticles for light-activated tumor therapy. RSC Adv. 2021;11:35472–35488. doi: 10.1039/D1RA05638G. PubMed DOI PMC

Chen G., Qiu H., Prasad P. N., Chen X.. Upconversion nanoparticles: Design, nanochemistry, and applications in Theranostics. Chem. Rev. 2014;114:5161–5214. doi: 10.1021/cr400425h. PubMed DOI PMC

Zhou J., Yao L., Li Ch., Li F.. A versatile fabrication of upconversion nanophosphors with functional-surface tunable ligands. J. Mater. Chem. 2010;20:8078–8085. doi: 10.1039/c0jm01041c. DOI

Wang M., Abbineni G., Clevenger A., Mao Ch., Xu S.. Upconversion nanoparticles: Synthesis, surface modification and biological applications. Nanomed.: Nanotechnol. Biol. Med. 2011;7:710–729. doi: 10.1016/j.nano.2011.02.013. PubMed DOI PMC

Zhang X., Guo Z., Zhang X., Gong L., Dong X., Fu Y., Wang Q., Gu Z.. Mass production of poly­(ethylene glycol) monooleate-modified core-shell structured upconversion nanoparticles for bio-imaging and photodynamic therapy. Sci. Rep. 2019;9:5212. doi: 10.1038/s41598-019-41482-w. PubMed DOI PMC

Gu B., Zhang Q.. Recent advances on functionalized upconversion nanoparticles for detection of small molecules and ions in biosystems. Adv. Sci. 2018;5:1700609. doi: 10.1002/advs.201700609. PubMed DOI PMC

Bose A., Burman D. R., Sikdar B., Patra P.. Nanomicelles: Types, properties and applications in drug delivery. IET Nanobiotechnol. 2021;15:19–27. doi: 10.1049/nbt2.12018. PubMed DOI PMC

Mohajeri E., Noudeh G. D.. Effect of temperature on the critical micelle concentration and micellization thermodynamic of nonionic surfactants: Polyoxyethylene sorbitan fatty acid esters. E-J. Chem. 2012;9:2268–2274. doi: 10.1155/2012/961739. DOI

Riter R. E., Willard D. M., Levinger N. E.. Water immobilization at surfactant interfaces in reverse micelles. J. Phys. Chem. B. 1998;102:2705–2714. doi: 10.1021/jp973330n. DOI

Ying G.-G., Williams B., Kookana R.. Environmental fate of alkylphenols and alkylphenol ethoxylates-a review. Environ. Int. 2002;28:215–226. doi: 10.1016/S0160-4120(02)00017-X. PubMed DOI

Chen L.-J., Lin S.-Y., Huang Ch-Ch., Chen E.-M.. Temperature dependence of critical micelle concentration of polyoxyethylenated non-ionic surfactants. Coll. Surf. A: Physicochem. Eng. Asp. 1998;135:175–181. doi: 10.1016/S0927-7757(97)00238-0. DOI

Kostiv U., Engstová H., Krajnik B., Šlouf M., Proks V., Podhorodecki A., Ježek P., Horák D.. Monodisperse Core-Shell NaYF4:Yb3+/Er3+@NaYF4:Nd3+-PEG-GGGRGDSGGGY-NH2 Nanoparticles Excitable at 808 and 980 nm: Design, Surface Engineering, and Application in Life Sciences. Front. Chem. 2020;8:497. doi: 10.3389/fchem.2020.00497. PubMed DOI PMC

van der Loop T. H., Panman M. R., Lotze S., Zhang J., Vad T., Bakker H. J., Sager W. F. C., Woutersen S.. Structure and dynamics of water in nonionic reverse micelles: a combined time-resolved infrared and small angle x-ray scattering study. J. Chem. Phys. 2012;137:044503. doi: 10.1063/1.4736562. PubMed DOI

Krajnik, B. ; Hołodnik-Małecka, K. ; Rybarczyk, N. ; Święs, M. ; Horák, D. ; Podhorodecki, A. . Temperature mapping using single NaYF

Yi G. S., Chow G. M.. Water-Soluble NaYF4:Yb, Er­(Tm)/NaYF4/Polymer Core/Shell/Shell Nanoparticles with Significant Enhancement of Upconversion Fluorescence. Chem. Mater. 2007;19:341–343. doi: 10.1021/cm062447y. DOI

Yi G. S., Chow G. M.. Synthesis of Hexagonal-Phase NaYF4:Yb, Er and NaYF4:Yb, Tm Nanocrystals with Efficient Up-Conversion Fluorescence. Adv. Funct. Mater. 2006;16:2324–2329. doi: 10.1002/adfm.200600053. DOI

Saïdi E., Samson B., Aigouy L., Volz S., Löw P., Bergaud Ch., Mortier M.. Scanning thermal imaging by near-field fluorescence spectroscopy. Nanotechnology. 2009;20:115703. doi: 10.1088/0957-4484/20/11/115703. PubMed DOI

Rabouw F. T., Prins P. T., Villanueva-Delgado P., Castelijns M., Geitenbeek R. G., Meijerink A.. Quenching Pathways in NaYF4:Er3+, Yb3+ Upconversion Nanocrystals. ACS Nano. 2018;12:4812–4823. doi: 10.1021/acsnano.8b01545. PubMed DOI PMC

Fischer S., Bronstein N. D., Swabeck J. K., Chan E. M., Alivisatos A. P.. Precise Tuning of Surface Quenching for Luminescence Enhancement in Core-Shell Lanthanide-Doped Nanocrystals. Nano Lett. 2016;16:7241–7247. doi: 10.1021/acs.nanolett.6b03683. PubMed DOI

Banerjee S., Sutanto S., Kleijn J. M., Cohen Stuart M. A.. Towards detergency in liquid CO2 - A surfactant formulation for particle release in an apolar medium. Colloids Surf. A: Physicochem. Eng. Asp. 2012;415:1–9. doi: 10.1016/j.colsurfa.2012.10.004. DOI

Kahlweit M., Strey M., Busse G.. Microemulsions: A qualitative thermodynamic approach. J. Phys. Chem. 1990;94:3881–3894. doi: 10.1021/j100373a006. DOI

Kahlweit M., Strey R., Firman P., Haase D., Jen J., Schomäcker R.. General patterns of the phase behavior of mixtures of H20, nonpolar solvents, amphiphiles, and electrolytes. 1. Langmuir. 1988;4:499–511. doi: 10.1021/la00081a002. DOI

Sanchez-Dominguez, M. ; Aubery, C. ; Solans, C. . Chapter 9 - New trends on the synthesis of inorganic nanoparticles using microemulsions as confined reaction media. In Small Nanoparticles Technology. Hashim, A. A. , Ed.; Intech Open, 2012; 195–220.