Making Nd3+ a Sensitive Luminescent Thermometer for Physiological Temperatures—An Account of Pitfalls in Boltzmann Thermometry
Аутори
Suta, MarkusAntić, Željka
Đorđević, Vesna R.
Kuzman, Sanja
Dramićanin, Miroslav
Meijerink, Andries
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
Ratiometric luminescence thermometry employing luminescence within the biological transparency windows provides high potential for biothermal imaging. Nd3+ is a promising candidate for that purpose due to its intense radiative transitions within biological windows (BWs) I and II and the simultaneous efficient excitability within BW I. This makes Nd3+ almost unique among all lanthanides. Typically, emission from the two 4F3/2 crystal field levels is used for thermometry but the small ~100 cm−1 energy separation limits the sensitivity. A higher sensitivity for physiological temperatures is possible using the luminescence intensity ratio (LIR) of the emissive transitions from the 4F5/2 and 4F3/2 excited spin-orbit levels. Herein, we demonstrate and discuss various pitfalls that can occur in Boltzmann thermometry if this particular LIR is used for physiological temperature sensing. Both microcrystalline, dilute (0.1%) Nd3+-doped LaPO4 and LaPO4: x% Nd3+ (x = 2, 5, 10, 25, 100) nanocrystals... serve as an illustrative example. Besides structural and optical characterization of those luminescent thermometers, the impact and consequences of the Nd3+ concentration on their luminescence and performance as Boltzmann-based thermometers are analyzed. For low Nd3+ concentrations, Boltzmann equilibrium starts just around 300 K. At higher Nd3+ concentrations, cross-relaxation processes enhance the decay rates of the 4F3/2 and 4F5/2 levels making the decay faster than the equilibration rates between the levels. It is shown that the onset of the useful temperature sensing range shifts to higher temperatures, even above ~ 450 K for Nd concentrations over 5%. A microscopic explanation for pitfalls in Boltzmann thermometry with Nd3+ is finally given and guidelines for the usability of this lanthanide ion in the field of physiological temperature sensing are elaborated. Insight in competition between thermal coupling through non-radiative transitions and population decay through cross-relaxation of the 4F5/2 and 4F3/2 spin-orbit levels of Nd3+ makes it possible to tailor the thermometric performance of Nd3+ to enable physiological temperature sensing.
Кључне речи:
Nd3+ / luminescence thermometry / in vivo imaging / Boltzmann equilibrium / time-resolved spectroscopyИзвор:
Nanomaterials, 2020, 10, 3, 543-Финансирање / пројекти:
DOI: 10.3390/nano10030543
ISSN: 2079-4991
PubMed: 32197319
WoS: 000526090400143
Scopus: 2-s2.0-85082190409
Колекције
Институција/група
VinčaTY - JOUR AU - Suta, Markus AU - Antić, Željka AU - Đorđević, Vesna R. AU - Kuzman, Sanja AU - Dramićanin, Miroslav AU - Meijerink, Andries PY - 2020 UR - https://vinar.vin.bg.ac.rs/handle/123456789/8909 AB - Ratiometric luminescence thermometry employing luminescence within the biological transparency windows provides high potential for biothermal imaging. Nd3+ is a promising candidate for that purpose due to its intense radiative transitions within biological windows (BWs) I and II and the simultaneous efficient excitability within BW I. This makes Nd3+ almost unique among all lanthanides. Typically, emission from the two 4F3/2 crystal field levels is used for thermometry but the small ~100 cm−1 energy separation limits the sensitivity. A higher sensitivity for physiological temperatures is possible using the luminescence intensity ratio (LIR) of the emissive transitions from the 4F5/2 and 4F3/2 excited spin-orbit levels. Herein, we demonstrate and discuss various pitfalls that can occur in Boltzmann thermometry if this particular LIR is used for physiological temperature sensing. Both microcrystalline, dilute (0.1%) Nd3+-doped LaPO4 and LaPO4: x% Nd3+ (x = 2, 5, 10, 25, 100) nanocrystals serve as an illustrative example. Besides structural and optical characterization of those luminescent thermometers, the impact and consequences of the Nd3+ concentration on their luminescence and performance as Boltzmann-based thermometers are analyzed. For low Nd3+ concentrations, Boltzmann equilibrium starts just around 300 K. At higher Nd3+ concentrations, cross-relaxation processes enhance the decay rates of the 4F3/2 and 4F5/2 levels making the decay faster than the equilibration rates between the levels. It is shown that the onset of the useful temperature sensing range shifts to higher temperatures, even above ~ 450 K for Nd concentrations over 5%. A microscopic explanation for pitfalls in Boltzmann thermometry with Nd3+ is finally given and guidelines for the usability of this lanthanide ion in the field of physiological temperature sensing are elaborated. Insight in competition between thermal coupling through non-radiative transitions and population decay through cross-relaxation of the 4F5/2 and 4F3/2 spin-orbit levels of Nd3+ makes it possible to tailor the thermometric performance of Nd3+ to enable physiological temperature sensing. T2 - Nanomaterials T1 - Making Nd3+ a Sensitive Luminescent Thermometer for Physiological Temperatures—An Account of Pitfalls in Boltzmann Thermometry VL - 10 IS - 3 SP - 543 DO - 10.3390/nano10030543 ER -
@article{ author = "Suta, Markus and Antić, Željka and Đorđević, Vesna R. and Kuzman, Sanja and Dramićanin, Miroslav and Meijerink, Andries", year = "2020", abstract = "Ratiometric luminescence thermometry employing luminescence within the biological transparency windows provides high potential for biothermal imaging. Nd3+ is a promising candidate for that purpose due to its intense radiative transitions within biological windows (BWs) I and II and the simultaneous efficient excitability within BW I. This makes Nd3+ almost unique among all lanthanides. Typically, emission from the two 4F3/2 crystal field levels is used for thermometry but the small ~100 cm−1 energy separation limits the sensitivity. A higher sensitivity for physiological temperatures is possible using the luminescence intensity ratio (LIR) of the emissive transitions from the 4F5/2 and 4F3/2 excited spin-orbit levels. Herein, we demonstrate and discuss various pitfalls that can occur in Boltzmann thermometry if this particular LIR is used for physiological temperature sensing. Both microcrystalline, dilute (0.1%) Nd3+-doped LaPO4 and LaPO4: x% Nd3+ (x = 2, 5, 10, 25, 100) nanocrystals serve as an illustrative example. Besides structural and optical characterization of those luminescent thermometers, the impact and consequences of the Nd3+ concentration on their luminescence and performance as Boltzmann-based thermometers are analyzed. For low Nd3+ concentrations, Boltzmann equilibrium starts just around 300 K. At higher Nd3+ concentrations, cross-relaxation processes enhance the decay rates of the 4F3/2 and 4F5/2 levels making the decay faster than the equilibration rates between the levels. It is shown that the onset of the useful temperature sensing range shifts to higher temperatures, even above ~ 450 K for Nd concentrations over 5%. A microscopic explanation for pitfalls in Boltzmann thermometry with Nd3+ is finally given and guidelines for the usability of this lanthanide ion in the field of physiological temperature sensing are elaborated. Insight in competition between thermal coupling through non-radiative transitions and population decay through cross-relaxation of the 4F5/2 and 4F3/2 spin-orbit levels of Nd3+ makes it possible to tailor the thermometric performance of Nd3+ to enable physiological temperature sensing.", journal = "Nanomaterials", title = "Making Nd3+ a Sensitive Luminescent Thermometer for Physiological Temperatures—An Account of Pitfalls in Boltzmann Thermometry", volume = "10", number = "3", pages = "543", doi = "10.3390/nano10030543" }
Suta, M., Antić, Ž., Đorđević, V. R., Kuzman, S., Dramićanin, M.,& Meijerink, A.. (2020). Making Nd3+ a Sensitive Luminescent Thermometer for Physiological Temperatures—An Account of Pitfalls in Boltzmann Thermometry. in Nanomaterials, 10(3), 543. https://doi.org/10.3390/nano10030543
Suta M, Antić Ž, Đorđević VR, Kuzman S, Dramićanin M, Meijerink A. Making Nd3+ a Sensitive Luminescent Thermometer for Physiological Temperatures—An Account of Pitfalls in Boltzmann Thermometry. in Nanomaterials. 2020;10(3):543. doi:10.3390/nano10030543 .
Suta, Markus, Antić, Željka, Đorđević, Vesna R., Kuzman, Sanja, Dramićanin, Miroslav, Meijerink, Andries, "Making Nd3+ a Sensitive Luminescent Thermometer for Physiological Temperatures—An Account of Pitfalls in Boltzmann Thermometry" in Nanomaterials, 10, no. 3 (2020):543, https://doi.org/10.3390/nano10030543 . .