Targeted Nanoparticle Thermometry: A Method to Measure Local Temperature at the Nanoscale Point Where Water Vapor Nucleation Occurs

An optical nanothermometer technique based on laser trapping, moving and targeted attaching an erbium oxide nanoparticle cluster is developed to measure the local temperature. The authors apply this new nanoscale temperature measuring technique (limited by the size of the nanoparticles) to measure the temperature of vapor nucleation in water. Vapor nucleation is observed after superheating water above the boiling point for degassed and nondegassed water. The average nucleation temperature for water without gas is 560 K but this temperature is lowered by 100 K when gas is introduced into the water. The authors are able to measure the temperature inside the bubble during bubble formation and find that the temperature inside the bubble spikes to over 1000 K because the heat source (optically‐heated nanorods) is no longer connected to liquid water and heat dissipation is greatly reduced.     

Temperature‐Dependent Exciton and Trap‐Related Photoluminescence of CdTe Quantum Dots Embedded in a NaCl Matrix: Implication in Thermometry

Temperature‐dependent optical studies of semiconductor quantum dots (QDs) are fundamentally important for a variety of sensing and imaging applications. The steady‐state and time‐resolved photoluminescence properties of CdTe QDs in the size range from 2.3 to 3.1 nm embedded into a protective matrix of NaCl are studied as a function of temperature from 80 to 360 K. The temperature coefficient is found to be strongly dependent on QD size, with the highest sensitivity obtained for the smallest size of QDs. The emission from solid‐state CdTe QD‐based powders is maintained with high color purity over a wide range of temperatures. Photoluminescence lifetime data suggest that temperature dependence of the intrinsic radiative lifetime in CdTe QDs is rather weak, and it is mostly the temperature‐dependent nonradiative decay of CdTe QDs which is responsible for the thermal quenching of photoluminescence intensity. By virtue of the temperature‐dependent photoluminescence behavior, high color purity, photostability, and high photoluminescence quantum yield (26%–37% in the solid state), CdTe QDs embedded in NaCl matrices are useful solid‐state probes for thermal imaging and sensing over a wide range of temperatures within a number of detection schemes and outstanding sensitivity, such as luminescence thermochromic imaging, ratiometric luminescence, and luminescence lifetime thermal sensing.     

PbS/CdS/ZnS Quantum Dots: A Multifunctional Platform for In Vivo Near‐Infrared Low‐Dose Fluorescence Imaging

Over the past decade, near‐infrared (NIR)‐emitting nanoparticles have increasingly been investigated in biomedical research for use as fluorescent imaging probes. Here, high‐quality water‐dispersible core/shell/shell PbS/CdS/ZnS quantum dots (hereafter QDs) as NIR imaging probes fabricated through a rapid, cost‐effective microwave‐assisted cation exchange procedure are reported. These QDs have proven to be water dispersible, stable, and are expected to be nontoxic, resulting from the growth of an outer ZnS shell and the simultaneous surface functionalization with mercaptopropionic acid ligands. Care is taken to design the emission wavelength of the QDs probe lying within the second biological window (1000–1350 nm), which leads to higher penetration depths because of the low extinction coefficient of biological tissues in this spectral range. Furthermore, their intense fluorescence emission enables to follow the real‐time evolution of QD biodistribution among different organs of living mice, after low‐dose intravenous administration. In this paper, QD platform has proven to be capable (ex vivo and in vitro) of high‐resolution thermal sensing in the physiological temperature range. The investigation, together with the lack of noticeable toxicity from these PbS/CdS/ZnS QDs after preliminary studies, paves the way for their use as outstanding multifunctional probes both for in vitro and in vivo applications in biomedicine.     

Optomagnetic Nanoplatforms for In Situ Controlled Hyperthermia

Magnetic nanoparticles (M:NPs) are unique agents for in vivo thermal therapies due to their multimodal capacity for efficient heat generation under optical and/or magnetic excitation. Nevertheless, their transfer from laboratory to the clinic is hampered by the absence of thermal feedback and by the influence that external conditions (e.g., agglomeration and biological matrix interactions) have on their heating efficiency. Overcoming these limitations requires, first, the implementation of strategies providing thermal sensing to M:NPs in order to obtain in situ thermal feedback during thermal therapies. At the same time, M:NPs should be modified so that their heating efficiency will be maintained independently of the environment and the added capability for thermometry. In this work, optomagnetic hybrid nanostructures (OMHSs) that simultaneously satisfy these two conditions are presented. Polymeric encapsulation of M:NPs with neodymium‐doped nanoparticles results in a hybrid structure capable of subtissue thermal feedback while making the heating efficiency of M:NPs independent of the medium. The potential application of the OMHSs herein developed for fully controlled thermal therapies is demonstrated by an ex vivo endoscope‐assisted controlled intracoronary heating experiment.     

Decoupling Theranostics with Rare Earth Doped Nanoparticles

Theranostic nanoagents targeted for personalized medicine provide a unified platform for therapeutics and diagnostics. To be able to discretely control each individually, allows for safer, more precise, and truly multifunctional theranostics. Rare earth doped nanoparticles can be rationally tailored to best match this condition with the aid of core/shell engineering. In such nanoparticles, the light‐mediated theranostic approach is functionally decoupled—therapeutics or diagnostics are prompted on‐demand, by wavelength‐specific excitation. These decoupled rare earth nanoparticles (dNPs) operate entirely under near‐infrared (NIR) excitation, for minimized light interference with the target and extended tissue depth action. Under heating‐free 806 nm irradiation, dNPs behave solely as high‐contrast NIR‐to‐NIR optical markers and nanothermometers, visualizing and probing the area of interest without prompting the therapeutic effect beforehand. On the contrary, 980 nm NIR irradiation is upconverted by the dNPs to UV/visible light, which triggers secondary photochemical processes, e.g., generation of reactive oxygen species by photosensitizers coupled to the dNPs, causing damage to cancer cells. Additionally, integration of NIR nanothermometry helps to control the temperature in the vicinity of the dNPs avoiding possible overheating and quenching of upconversion (UC) emission, harnessed for photodynamic therapy. Overall, a new direction is outlined in the development of state‐of‐the‐art rare earth based theranostic nanoplatforms.     

Ag/Ag2S Nanocrystals for High Sensitivity Near‐Infrared Luminescence Nanothermometry

Temperature sensing in biological media (cells, tissues, and living organisms) has become essential in the development of the last generation of diagnostics and therapeutic strategies. Thermometry can be used for early detection of different diseases, such as cancer, stroke, or inflammation processes, one of whose incipient symptoms is the appearance of localized temperature singularities. Luminescence nanothermometry, as a tool to accurately provide temperature sensing in biological media, requires the rational design and development of nanothermometers operating in the second biological window. In this work, this is achieved using Ag/Ag₂S nanocrystals as multiparametric thermal sensing probes. Temperature sensing with remarkably high sensitivity (4% °C^?1) is possible through intensity‐based measurements, as their infrared emission is strongly quenched by small temperature variations within the biological range (15–50 °C). Heating also results in a remarkable redshift of the emission band, which allows for concentration‐independent temperature sensing based on infrared ratiometric measurements, with thermal sensitivity close to 2% °C^?1. These results make Ag/Ag₂S nanocrystals the most sensitive among all noncomposite nanothermometers operating in the second biological window reported so far, allowing for deep‐tissue temperature measurements with low uncertainty (0.2 °C).     

Quantum Dot‐Based Thermal Spectroscopy and Imaging of Optically Trapped Microspheres and Single Cells

Laser‐induced thermal effects in optically trapped microspheres and single cells are investigated by quantum dot luminescence thermometry. Thermal spectroscopy has revealed a non‐localized temperature distribution around the trap that extends over tens of micrometers, in agreement with previous theoretical models besides identifying water absorption as the most important heating source. The experimental results of thermal loading at a variety of wavelengths reveal that an optimum trapping wavelength exists for biological applications close to 820 nm. This is corroborated by a simultaneous analysis of the spectral dependence of cellular heating and damage in human lymphocytes during optical trapping. This quantum dot luminescence thermometry demonstrates that optical trapping with 820 nm laser radiation produces minimum intracellular heating, well below the cytotoxic level (43 °C), thus, avoiding cell damage.