Non-invasive precise thermometers working at the nanoscale with high spatial resolution, where the conventional methods are ineffective, have emerged over the last couple of years as a very active field of research. This has been strongly stimulated by the numerous challenging requests arising from nanotechnology and biomedicine. This critical review offers a general overview of recent examples of luminescent and non-luminescent thermometers working at nanometric scale. Luminescent thermometers encompass organic dyes, QDs and Ln 3+ ions as thermal probes, as well as more complex thermometric systems formed by polymer and organic-inorganic hybrid matrices encapsulating these emitting centres. Non-luminescent thermometers comprise of scanning thermal microscopy, nanolithography thermometry, carbon nanotube thermometry and biomaterials thermometry. Emphasis has been put on ratiometric examples reporting spatial resolution lower than 1 micron, as, for instance, intracellular thermometers based on organic dyes, thermoresponsive polymers, mesoporous silica NPs, QDs, and Ln 3+ -based up-converting NPs and b-diketonate complexes. Finally, we discuss the challenges and opportunities in the development for highly sensitive ratiometric thermometers operating at the physiological temperature range with submicron spatial resolution.
Present technological demands in disparate areas, such as microfluidics and nanofluidics, microelectronics and nanoelectronics, photonics and biomedicine, among others, have reached to a development such that conventional contact thermal probes are not accomplished anymore to perform accurate measurements with submicrometric spatial resolution. The development of novel noncontact thermal probes is, then, mandatory, contributing to an expansionary epoch of luminescence thermometry. Luminescence thermometry based on trivalent lanthanide ions has become very popular since 2010 due to the unique versatility, stability, and narrow emission band profiles of the ions that cover the entire electromagnetic spectrum with relatively high emission quantum yields. Here, a perspective overview on the field is given from the beginnings in the 1950s until the most recent cutting‐edge examples. The current movement toward usage of the technique as a new tool for thermal imaging, early tumor detection, and as a tool for unveiling the properties of the thermometers themselves or of their local neighborhoods is also summarized.
Metal-organic frameworks (MOFs) are excellent platforms for engineering luminescence properties as their building blocks, metal ions, linkers, and guest ions or molecules, are all potential sources of light emission. Temperature is one of the most important physical properties affecting the dynamics and viability of natural and engineered systems. Because the luminescence of certain lanthanide-bearing MOFs changes considerably with temperature, in the last few years, these materials have been explored as optical thermometers, especially in temperature sensing based on the intensity ratios of two separate electronic transitions. This review discusses the main concepts and ideas assisting the design of such ratiometric thermometers, and identifies the main challenges presented to this nascent field: develop nanothermometers for bio-applications and nanomedicine; understand the energy transfer mechanisms determining the thermal sensitivity; achieve effective primary thermometers; realize multifunctional nanothermometers; integrate Ln -based thermometers in commercial products.
A unique Eu3+/Tb3+ luminescent self‐referencing nanothermometer allowing absolute measurements in the 10–350 K temperature range and sub‐micrometer spatial resolution is reported (see Figure). It has up to 4.9%·K−1 temperature sensitivity and high photostability for long‐term use. The combination of molecular thermometry, superparamagnetism and luminescence in a nanometric host matrix provides multifunctionality opening the way for new exciting applications.
Brownian motion is one of the most fascinating phenomena in nature. Its conceptual implications have a profound impact in almost every field of science and even economics, from dissipative processes in thermodynamic systems, gene therapy in biomedical research, artificial motors and galaxy formation to the behaviour of stock prices. However, despite extensive experimental investigations, the basic microscopic knowledge of prototypical systems such as colloidal particles in a fluid is still far from being complete. This is particularly the case for the measurement of the particles' instantaneous velocities, elusive due to the rapid random movements on extremely short timescales. Here, we report the measurement of the instantaneous ballistic velocity of Brownian nanocrystals suspended in both aqueous and organic solvents. To achieve this, we develop a technique based on upconversion nanothermometry. We find that the population of excited electronic states in NaYF:Yb/Er nanocrystals at thermal equilibrium can be used for temperature mapping of the nanofluid with great thermal sensitivity (1.15% K at 296 K) and a high spatial resolution (<1 μm). A distinct correlation between the heat flux in the nanofluid and the temporal evolution of Er emission allows us to measure the instantaneous velocity of nanocrystals with different sizes and shapes.
Luminescent thermometers working at the nanoscale with high spatial resolution, where the conventional methods are ineffective, have emerged over the last couple of years as a very active field of research. Lanthanide-based materials are among the most versatile thermal probes used in luminescent nanothermometers. Here, nanorods of metal organic framework Tb0.99Eu0.01(BDC)1.5(H2O)2 (BDC = 1-4-benzendicarboxylate) have been prepared by the reverse microemulsion technique and characterized and their photoluminescence properties studied from room temperature to 318 K. Aqueous suspensions of these nanoparticles display an excellent performance as ratiometric luminescent nanothermometers in the physiological temperature (300-320 K) range.
The recent development of core/shell engineering of rare earth doped luminescent nanoparticles has ushered a new era in fluorescence thermal biosensing, allowing for the performance of minimally invasive experiments, not only in living cells but also in more challenging small animal models. Here, the potential use of active-core/active-shell Nd(3+)- and Yb(3+)-doped nanoparticles as subcutaneous thermal probes has been evaluated. These temperature nanoprobes operate in the infrared transparency window of biological tissues, enabling deep temperature sensing into animal bodies thanks to the temperature dependence of their emission spectra that leads to a ratiometric temperature readout. The ability of active-core/active-shell Nd(3+)- and Yb(3+)-doped nanoparticles for unveiling fundamental tissue properties in in vivo conditions was demonstrated by subcutaneous thermal relaxation monitoring through the injected core/shell nanoparticles. The reported results evidence the potential of infrared luminescence nanothermometry as a diagnosis tool at the small animal level.
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