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348 Handbook on the Physics and Chemistry of Rare Earths eg, poly(N-isopropylacrylamide) (PNIPAM) (Gota et al., 2009; Graham et al., 2010), or an organic–inorganic hybrid host (Carlos et al., 2007). Since organic dyes were patented in 1941 as “temperature indicator” (Jennings, 1941), many advances have been made. Molecular thermome- ters based on light-absorbing aromatic compounds (de Silva et al., 1997), rhodamine 101 (Clark et al., 1998), rhodamine B (RhB) (Ross et al., 2001), rhodamine 101 Rh B (Glawdel et al., 2009), fluorescein isothiocyanates (Guan et al., 2007), and cyanine dyes (Mikkelsen and Wallach, 1977) have become very popular in luminescence temperature determination, essentially in a biological context (Okabe et al., 2012). For a comprehensive review of the subject see, for instance, the works of Hoogenboom and collaborators (de la Rosa et al., 2016; Pietsch et al., 2011). Although the most available and used thermal probes are based on organic dyes, QDs and Ln3+-based materials have been gaining relevance due to their higher photostability and relatively high emission quantum yields. QDs have been proposed for submicron thermometry, since they present temperature-dependent luminescence (intensity changes or emission peak shifts) (Haro-Gonzalez et al., 2013; Li et al., 2007). Nanomedicine stands out as the most appealing area, since bioconjugation of QDs make them target selective. However, QDs are often composed of highly cytotoxic elements (eg, Cd), which make difficult their future use in clinical trials (Cho et al., 2007; Gnach et al., 2015). For a comprehensive review of the application of QDs in micro and nanothermometry, see, for instance, the works of Jaque and collaborators (Maestro et al., 2010a, 2013). Ln3+-based materials are versatile, stable, and narrow band emitters with, in general, high emission quantum yields (>50%) (B€unzli, 2010, 2015; B€unzli and Eliseeva, 2013; Comby and B€unzli, 2007). In fact, different emitting centers can cover the entire electromagnetic spectrum, ranging from UV (eg, Gd3+) to IR (eg, Er3+, Yb3+, Nd3+); thus, it is virtually possible to design on-demand luminescent probes for a large variety of applications (Binnemans, 2009; B€unzli, 2010; Carlos et al., 2009; Chen et al., 2013; Feng and Zhang, 2013). A large number of Ln3+-based molecular thermometers cover- ing temperatures from the cryogenic (T < 100 K) to the physiological (298–323 K) ranges have been reported, essentially in the last couple of years, involving chelate complexes (Brites et al., 2010; Peng et al., 2010a; Uchiyama et al., 2006), metal-organic frameworks (MOFs) (Cadiau et al., 2013; Cui et al., 2015b; Wang et al., 2015c), upconverting NPs (UCNPs) (Lojpur et al., 2014; Savchuk et al., 2014; Vetrone et al., 2010b), and downshifting nanomaterials (Balabhadra et al., 2015; Benayas et al., 2015; Rocha et al., 2014b). For a comprehensive review, see the works on high-temperature ther- mographic phosphors (Heyes, 2009; Rabhiou et al., 2011), on temperature- sensitive paints (the Ln3+ probe is incorporated into a polymer binder and the resulting paint sprayed onto a surface to map temperature distribution)PDF Image | HANDBOOK ON THE PHYSICS AND CHEMISTRY OF RARE EARTHS
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