Luminescence Thermometry with Nanoparticles: A Review.

Luminescence thermometry has emerged as a very versatile optical technique for remote temperature measurements, exhibiting a wide range of applicability spanning from cryogenic temperatures to 2000 K. This technology has found extensive utilization across many disciplines. In the last thirty years, there has been significant growth in the field of luminous thermometry. This growth has been accompanied by the development of temperature read-out procedures, the creation of luminescent materials for very sensitive temperature probes, and advancements in theoretical understanding. This review article primarily centers on luminescent nanoparticles employed in the field of luminescence thermometry. In this paper, we provide a comprehensive survey of the recent literature pertaining to the utilization of lanthanide and transition metal nanophosphors, semiconductor quantum dots, polymer nanoparticles, carbon dots, and nanodiamonds for luminescence thermometry. In addition, we engage in a discussion regarding the benefits and limitations of nanoparticles in comparison with conventional, microsized probes for their application in luminescent thermometry.

The Upconversion Luminescence of Ca3Sc2Si3O12:Yb3+,Er3+ and Its Application in Thermometry.

To develop novel luminescent materials for optical temperature measurement, a series of Yb3+- and Er3+-doped Ca3Sc2Si3O12 (CSS) upconversion (UC) phosphors were synthesized by the sol-gel combustion method. The crystal structure, phase purity, and element distribution of the samples were characterized by powder X-ray diffraction and a transmission electron microscope (TEM). The detailed study of the photoluminescence emission spectra of the samples shows that the addition of Yb3+ can greatly enhance the emission of Er3+ by effective energy transfer. The prepared Yb3+ and Er3+ co-doped CSS phosphors exhibit green emission bands near 522 and 555 nm and red emission bands near 658 nm, which correspond to the 2H11/2→4I15/2, 4S3/2→4I15/2, and 4F9/2→4I15/2 transitions of Er3+, respectively. The temperature-dependent behavior of the CSS:0.2Yb3+,0.02Er3+ sample was carefully studied by the fluorescence intensity ratio (FIR) technique. The results indicate the excellent sensitivity of the sample, with a maximum absolute sensitivity of 0.67% K-1 at 500 K and a relative sensitivity of 1.34% K-1 at 300 K. We demonstrate here that the temperature measurement performance of FIR technology using the CSS:Yb3+,Er3+ phosphor is not inferior to that of infrared thermal imaging thermometers. Therefore, CSS:Yb3+,Er3+ phosphors have great potential applications in the field of optical thermometry.

Comparison of Performance between Single- and Multiparameter Luminescence Thermometry Methods Based on the Mn5+ Near-Infrared Emission.

Herein, we investigate the performance of single- and multiparametric luminescence thermometry founded on the temperature-dependent spectral features of Ca6BaP4O17:Mn5+ near-infrared emission. The material was prepared by a conventional steady-state synthesis, and its photoluminescence emission was measured from 7500 to 10,000 cm-1 over the 293-373 K temperature range in 5 K increments. The spectra are composed of the emissions from 1E → 3A2 and 3T2 → 3A2 electronic transitions and Stokes and anti-Stokes vibronic sidebands at 320 cm-1 and 800 cm-1 from the maximum of 1E → 3A2 emission. Upon temperature increase, the 3T2 and Stokes bands gained in intensity while the maximum of 1E emission band is redshifted. We introduced the procedure for the linearization and feature scaling of input variables for linear multiparametric regression. Then, we experimentally determined accuracies and precisions of the luminescence thermometry based on luminescence intensity ratios between emissions from the 1E and 3T2 states, between Stokes and anti-Stokes emission sidebands, and at the 1E energy maximum. The multiparametric luminescence thermometry involving the same spectral features showed similar performance, comparable to the best single-parameter thermometry.

Barium hexaferrite nanoplatelets with polyphenol coatings for versatile applications as a stable, magnetic, and antimicrobial colloid.

Colloidal stabilization of magnetic nanoparticles is one of the most important steps in the preparation of magnetic nanoparticles for potential biomedical applications. A special kind of magnetic nanoparticle are barium hexaferrite nanoplatelets (BSHF NPLs) with a hexagonal shape and a permanent magnetic moment. One strategy for the stabilization of BHF in aqueous media is to use coatings. In our research, we used an eco-friendly tannic acid, as a coating on BSHF NPLs. As-prepared BSHF NPLs coated with tannic acid were examined with transmission electron microscopy, infrared and UV-Vis spectroscopy, electro-kinetic measurements, and their room-temperature magnetic properties were measured. Stable colloids were tested in two biological complex media and antimicrobial properties of the material were examined. To enhance the antimicrobial properties of our material, we used tannic acid as a platform for the in-situ production of silver on BSHF NPLs. New hybrid material with silver also possesses magnetic properties and excellent antimicrobial activity against Escherichia coli and Staphylococcus aureus.

Testing and Analysis of Uniaxial Mechanical Fatigue, Charpy Impact Fracture Energy and Microhardness of Two Low-Carbon Steels.

The paper presents and analyzes the results of experimental tests performed on two non-alloy low carbon steels (1.1141 and 1.0122) in cases of their exposure to impact fracture energy and uniaxial high cyclic mechanical stress-controlled fatigue. The experimental results provide insight into the changes in the Charpy impact fracture energy of the V-notched test specimen that occur as a result of temperature changes. The experimental results also provide insight into the mechanical response of the tested materials to mechanical uniaxial high-cycle fatigue at room temperature in an air atmosphere and at different applied stress ratios. Material fatigue tests refer to symmetric (R = -1), asymmetric (R = -0.5) and pulsating tensile (R = 0) cycles. The test results are shown in the S-N diagrams and refer to the highest applied stresses in relation to the number of failures at a given stress ratio. Using the modified staircase method, the fatigue limit (endurance limit) was calculated for both tested materials at each prescribed stress ratio. For both tested steel alloys, and at prescribed stress ratios, the fatigue limit levels (σ_f) are shown as follows: for steel C15E+C (1.1141)→σf[250.8R=-1; 345.4R=-0.5; 527R=0](MPa); and for steel S235JRC+C (1.0122)→σf[202R=-1; 310R=-0.5; 462R=0](MPa). All uniaxial fatigue tests were performed on unnotched, smooth, highly-polished specimens. The microhardness of both materials was also tested.

Exploiting High-Energy Emissions of YAlO3:Dy3+ for Sensitivity Improvement of Ratiometric Luminescence Thermometry.

The sensitivity of luminescence thermometry is enhanced at high temperatures when using a three-level luminescence intensity ratio approach with Dy3+- activated yttrium aluminum perovskite. This material was synthesized via the Pechini method, and the structure was verified using X-ray diffraction analysis. The average crystallite size was calculated to be around 46 nm. The morphology was examined using scanning electron microscopy, which showed agglomerates composed of densely packed, elongated spherical particles, the majority of which were 80-100 nm in size. The temperature-dependent photoluminescence emission spectra (ex = 353 nm, 300-850 K) included Dy3+ emissions in blue (458 nm), blue (483 nm), and violet (430 nm, T 600 K). Luminescence intensity ratio, the most utilized temperature readout method in luminescent thermometry, was used as the testing method: a) using the intensity ratio of Dy3+ ions and 4I15/2→6H15/2/4F9/2→6H15/2 transitions; and b) employing the third, higher energy 4G11/2 thermalized level, i.e., using the intensity ratio of 4G11/2→6H15/2/4F9/2→6H15/2 transitions, thereby showing the relative sensitivities of 0.41% K-1 and 0.86% K-1 at 600 K, respectively. This more than doubles the increase in sensitivity and therefore demonstrates the method's usability at high temperatures, although the major limitation of the method is the chemical stability of the host material and the temperature at which the temperature quenching commences. Lastly, it must be noted that at 850 K, the emission intensities from the energetically higher levels were still increasing in YAP: Dy3+.

Mn5+-activated Ca6Ba(PO4)4O near-infrared phosphor and its application in luminescence thermometry.

The near-infrared luminescence of Ca6Ba(PO4)4O:Mn5+ is demonstrated and explained. When excited into the broad and strong absorption band that spans the 500-1000 nm spectral range, this phosphor provides an ultranarrow (FWHM = 5 nm) emission centered at 1140 nm that originates from a spin-forbidden 1E → 3A2 transition with a 37.5% internal quantum efficiency and an excited-state lifetime of about 350 µs. We derived the crystal field and Racah parameters and calculated the appropriate Tanabe-Sugano diagram for this phosphor. We found that 1E emission quenches due to the thermally-assisted cross-over with the 3T2 state and that the relatively high Debye temperature of 783 K of Ca6Ba(PO4)4O facilitates efficient emission. Since Ca6Ba(PO4)4O also provides efficient yellow emission of the Eu2+ dopant, we calculated and explained its electronic band structure, the partial and total density of states, effective Mulliken charges of all ions, elastic constants, Debye temperature, and vibrational spectra. Finally, we demonstrated the application of phosphor in a luminescence intensity ratio thermometry and obtained a relative sensitivity of 1.92%K-1 and a temperature resolution of 0.2 K in the range of physiological temperatures.

Self-referenced method for the Judd-Ofelt parametrisation of the Eu3+ excitation spectrum.

Judd-Ofelt theory is a cornerstone of lanthanides' spectroscopy given that it describes 4fn emissions and absorptions of lanthanide ions using only three intensity parameters. A self-referenced technique for computing Judd-Ofelt intensity parameters from the excitation spectra of Eu3+-activated luminescent materials is presented in this study along with an explanation of the parametrisation procedure and free user-friendly web application. It uses the integrated intensities of the 7F0 → 5D2, 7F0 → 5D4, and 7F0 → 5L6 transitions in the excitation spectrum for estimation and the integrated intensity of the 7F0 → 5D1 magnetic dipole transition for calibration. This approach facilitates an effortless derivation of the Ω6 intensity parameter, which is challenging to compute precisely by Krupke's parametrisation of the emission spectrum and, therefore, often omitted in published research papers. Compared to the parametrisation of absorption spectra, the described method is more accurate, can be applied to any material form, and requires a single excitation spectrum.

Organic solvent-assisted co-precipitation synthesis of red-emitting K2TiF6:Mn phosphors with improved quantum efficiency and optimized morphology.

We report an organic solvent-assisted (OSA) co-precipitation strategy for the production of Mn4+-activated K2TiF6 phosphor. The phosphor particle size was controlled through the selection of organic solvents with an alcohol functional group and different carbon chain lengths used in the synthesis. The synergistic effect of the organic solvent and hydrofluoric acid results in large smoothed hexagonal-shaped crystal sheets of particles that become larger as the carbon chain length of the organic solvent increases. The photoluminescence (PL) properties of K2TiF6:Mn powders strongly depend on the size and thickness of the particles. The addition of n-butanol during the synthesis increases the emission intensity of K2TiF6:Mn by 208%. The PL quantum efficiency of phosphors prepared using the n-butanol-assisted strategy is much higher (98.2%) than that of conventionally prepared phosphors (89.9%). Our findings demonstrate a way to prepare the K2TiF6:Mn phosphor with targeted morphology and very high quantum efficiency and also provide the route for the optimization of all Mn4+-activated fluoride phosphors used in white light-emitting diodes.

Hydrothermal Synthesis and Properties of Yb3+/Tm3+ Doped Sr2LaF7 Upconversion Nanoparticles.

We report the procedure for hydrothermal synthesis of ultrasmall Yb3+/Tm3+ co-doped Sr2LaF7 (SLF) upconversion phosphors. These phosphors were synthesized by varying the concentrations of Yb3+ (x = 10, 15, 20, and 25 mol%) and Tm3+ (y = 0.75, 1, 2, and 3 mol%) with the aim to analyze their emissions in the near IR spectral range. According to the detailed structural analysis, Yb3+ and Tm3+ occupy the La3+ sites in the SLF host. The addition of Yb3+/Tm3+ ions has a huge impact on the lattice constant, particle size, and PL emission properties of the synthesized SLF nanophosphor. The results show that the optimal dopant concentrations for upconversion luminescence of Yb3+/Tm3+ co-doped SLF are 20 mol% Yb3+ and 1 mol% Tm3+ with EDTA as the chelating agent. Under 980 nm light excitation, a strong upconversion emission of Tm3+ ions around 800 nm was achieved. In addition, the experimental photoluminescence lifetime of Tm3+ emission in the SLF host is reported. This study discovered that efficient near IR emission from ultrasmall Yb3+/Tm3+ co-doped SLF phosphors may have potential applications in the fields of fluorescent labels in bioimaging and security applications.

All near-infrared multiparametric luminescence thermometry using Er3+, Yb3+-doped YAG nanoparticles.

This paper presents four new temperature readout approaches to luminescence nanothermometry in spectral regions of biological transparency demonstrated on Yb3+/Er3+-doped yttrium aluminum garnet nanoparticles. Under the 10 638 cm-1 excitation, down-shifting near infrared emissions (>10 000 cm-1) are identified as those originating from Yb3+ ions' 2F5/2 → 2F7/2 (∼9709 cm-1) and Er3+ ions' 4I13/2 → 4I15/2 (∼6494 cm-1) electronic transitions and used for 4 conceptually different luminescence thermometry approaches. Observed variations in luminescence parameters with temperature offered an exceptional base for studying multiparametric temperature readouts. These include the temperature-dependence of: (i) intensity ratio between emissions from Stark components of Er3+ 4I13/2 level; (ii) intensity ratio between emissions of Yb3+ (2F5/2 → 2F7/2 transition) and Er3+ (4I13/2 → 4I15/2 transition); (iii) band shift and bandwidth and (iv) lifetime of the Yb3+ emission (2F5/2 → 2F7/2 transition) with maximal sensitivities of 1% K-1, 0.8% K-1, 0.09 cm-1 K-1, 0.46% K-1 and 0.86% K-1, respectively. The multimodal temperature readout provided by this material enables its application in different luminescence thermometry setups as well as improved the reliability of the temperature sensing by the cross-validation between measurements.

Influence of Metallic Oxide Nanoparticles on the Mechanical Properties of an A-TIG Welded 304L Austenitic Stainless Steel.

Austenitic stainless steels represent a significant aerospace material, being used for various castings, structural components, landing gear components, afterburners, exhaust components, engine parts, and fuel tanks. The most common joining process is tungsten inert gas (TIG) welding, which possesses many advantages such as suitability to weld a wide range of ferrous and non-ferrous metals and alloys, providing high quality welds with good mechanical properties. Its major disadvantage is low productivity due to low penetration and welding speed. This can be overcome by introducing an activating flux before welding. The activating flux reverses the material flow of the weld pool, significantly increasing penetration. Therefore, shielding gas consumption is reduced and welding without a consumable is enabled. However, the consumable in conventional TIG also enables the conditioning of the mechanical properties of welds. In this study, Si and Ti metallic oxide nanoparticles were used to increase the weld penetration depth, while bend testing, tensile, and impact toughness were determined to evaluate the mechanical properties of welds. Furthermore, optical emission spectroscopy, light, and scanning electron microscope were used to determine the chemical compositions and microstructures of the welds. Chemical compositions and weld mechanical properties were similar in all specimens. The highest tensile and impact properties were obtained with the specimen welded with the flux containing 20% TiO2 and 80% SiO2 nanoparticles. Although lower than those of the base metal, they were well within the nominal base metal mechanical properties.

Surface Plasmon Enhancement of Eu3+ Emission Intensity in LaPO4/Ag Nanoparticles.

A promising way to improve the performance of luminescent materials is to combine them with noble metal nanoparticles. Herein, a set of silver/europium-doped lanthanum orthophosphate (Ag/La0.95Eu0.05PO4) nanostructures with different concentrations of silver nanoparticles were prepared and investigated. The presented overlap between the strongest europium (Eu3+) excitation line and the broad silver nanoparticle surface plasmon resonance makes the combination prospective for coupling. X-ray powder diffraction confirmed the monoclinic monazite structure. The transmission electron microscopy revealed particles with a rod-like shape and ~4 aspect ratio. Photoluminescence spectra show characteristic Eu3+ ion red emission. One of the requirements for an enhanced luminescence effect is the precise control of the distance between the noble metal nanoparticles and the emitter ion. The distance is indirectly varied throughout the change of Ag nanoparticle concentration in the La0.95Eu0.05PO4 host. The emission intensity increases with the increase in Ag nanoparticles up to 0.6 mol %, after which the luminescence decreases due to the nanoparticles' close packing and aggregation leading to the displacement of La0.95Eu0.05PO4 from the vicinity of the metal particles and reabsorption of the emitted light. The emission intensity of La0.95Eu0.05PO4 increases more than three times when the Eu3+ excitation is supported by the localized surface plasmon resonance in the Ag/La0.95Eu0.05PO4 nanostructures.

Comparison of Three Ratiometric Temperature Readings from the Er3+ Upconversion Emission.

The emission of Er3+ provides three combinations of emission bands suitable for ratiometric luminescence thermometry. Two combinations utilize ratios of visible emissions (2H11/2→4I15/2 at 523 nm/ 4S3/2→4I15/2 at 542 nm and 4F7/2→4I15/2 at 485 nm/ 4S3/2→4I15/2 at 545 nm), while emissions from the third combination are located in near-infrared, e.g., in the first biological window (2H11/2→4I13/2 at 793 nm/ 4S3/2→4I13/2 at 840 nm). Herein, we aimed to compare thermometric performances of these three different ratiometric readouts on account of their relative sensitivities, resolutions, and repeatability of measurements. For this aim, we prepared Yb3+,Er3+:YF3 nanopowders by oxide fluorination. The structure of the materials was confirmed by X-ray diffraction analysis and particle morphology was evaluated from FE-SEM measurements. Upconversion emission spectra were measured over the 293-473 K range upon excitation by 980 nm radiation. The obtained relative sensitivities on temperature for 523/542, 485/542, and 793/840 emission intensity ratios were 1.06 ± 0.02, 2.03 ± 0.23, and 0.98 ± 0.10%K-1 with temperature resolutions of 0.3, 0.7, and 1.8 K, respectively. The study showed that the higher relative temperature sensitivity does not necessarily lead to the more precise temperature measurement and better resolution, since it may be compromised by a larger uncertainty in measurement of low-intensity emission bands.

Making Nd3+ a Sensitive Luminescent Thermometer for Physiological Temperatures-An Account of Pitfalls in Boltzmann Thermometry.

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.

Ratiometric temperature measurement using negative thermal quenching of intrinsic BiFeO3 semiconductor nanoparticles.

A strategy for optical nanothermometry using the negative thermal quenching behavior of intrinsic BiFeO3 semiconductor nanoparticles has been reported here. X-ray diffraction measurement shows polycrystalline BiFeO3 nanoparticles with a rhombohedral distorted perovskite structure. Transmission electron microscopy shows agglomerated crystalline nanoparticles around 20 nm in size. Photoluminescence measurements show that intensity of the defect level emission increases significantly with temperature, while the intensity of near band emission and other defect levels emissions show an opposite trend. The most important figures of merit for luminescence nanothermometry: the absolute (S a) and the relative sensor sensitivity (S r) and the temperature resolution (ΔT m) were effectively resolved and calculated. The relative sensitivity and temperature resolution values are found to be 2.5% K-1 and 0.2 K, respectively which are among the highest reported values observed so far for semiconductors.

The Parallel Factor Analysis of Beer Fluorescence.

Fluorescence excitation-emission matrices were measured for 111 samples of different types of beer and studied by the parallel factor analysis (PARAFAC). The 5-component PARAFAC model was found to suitably describes the beer fluorescence, accounting for 99.4% of the fluorescence variance in the measured set of samples, and providing the completely resolved excitation and emission spectra of each component. The model was chosen based on a model's core consistency and split-half analysis. It is shown that beer fluorescence is the sum of fluorescence of aromatic amino acids (tryptophan, tyrosine, and phenylalanine), different forms of vitamin B, and phenolic compounds. Obtained PARAFAC model of beer fluorescence demonstrated the potential for the quantification and quality analysis of beer fluorophores and classification of different beer types.

Efficient Luminescence Enhancement of Mg2TiO4:Mn4+ Red Phosphor by Incorporating Plasmonic Ag@SiO2 Nanoparticles.

One of prospective ways for boosting efficiency of luminescent materials is their combination with noble metal nanoparticles. Collective, so-called plasmon, oscillations of surface electrons in a nanoparticle can resonantly interact with incident or fluorescent light and cause an increase in the light absorption cross section or radiative rate for an adjacent emitter. Plasmonic inorganic phosphors require gentle host crystallization at which added noble nanoparticles will not suffer from aggregation or oxidation. The prospective plasmonic Mg2TiO4:Mn4+ phosphor containing core@shell Ag@SiO2 nanoparticles is prepared here by spare low-temperature annealing of a sol-gel host precursor. It is revealed that Mn4+ luminescence nonmonotonously depends on the size and concentration of 40 and 70 nm silver nanoparticles. It is demonstrated that luminescence of the Mg2TiO4:Mn4+ phosphor can be up to a 1.5 times increase when Mn4+ excitation is supported by localized surface plasmon resonance in Ag@SiO2 nanoparticles.

MgTiO3:Mn4+ a multi-reading temperature nanoprobe.

MgTiO3 nanoparticles doped with Mn4+, with homogeneous size ranging about 63.1 ± 9.8 nm, were synthesized by a molten salt assisted sol gel method. These nanoparticles have been investigated as optical thermal sensors. The luminescence of tetravalent manganese ion in octahedral environment within the perovskite host presents drastic variations with temperature. Three different thermometry approaches have been proposed and characterized. Two luminescence intensity ratios are studied. Firstly between the two R-lines of Mn4+ emission at low temperature (-250 °C and -90 °C) with a maximal sensitivity of 0.9% °C-1, but also secondly between 2E → 4A2 (R-line) and the 4T2 → 4A2 transitions. This allows studying the temperature variation within a larger temperature range (-200 °C to 50 °C) with a sensitivity between 0.6% °C-1 and 1.2% °C-1 over this range. The last proposed method is the study of the lifetime variation versus temperature. The effective lifetime value corresponds to a combination of transitions from two excited energy levels of the tetravalent manganese (2E and 4T2) in thermal equilibrium toward the fundamental 4A2 state. Since the more energetic transition (4T2 → 4A2) is spin-allowed, contrary to the 2E → 4A2 one, the lifetime drastically decreases with the increase in temperature leading to an impressive high sensitivity value of 4.1% °C-1 at 4 °C and an exceptional temperature resolution of 0.025 °C. According to their optical features, MgTiO3:Mn4+ nanoparticles are indeed suitable candidates for the luminescence temperature probes at the nanoscale over several temperature ranges.

Whitening-dependent changes of fluorescence of extracted human teeth.

OBJECTIVE: To evaluate in vitro the fluorescence properties of extracted human teeth whitened with 40% hydrogen peroxide. MATERIALS AND METHODS: A total of 28 extracted human teeth were pumiced for 1 minute using a low-speed dental handpiece and a disposable rubber cup. Pre-whitening fluorescence measurements (T0), maximum excitation (Exmax ), maximum emission (Emmax ), and maximum intensity (Imax 108 ), were performed using a spectrofluorometer. After T0 measurements, the teeth were whitened using the in-office method with 40% hydrogen peroxide, three times for 20 minutes. The fluorescence parameters were measured under the same conditions 7 and 14 days after bleaching (T1 and T2, respectively). RESULTS: Exmax exhibited a broader range 7 days after whitening and decreased after 14 days. The Emmax and Imax 108 displayed a narrower range after whitening. The mean Exmax differed significantly between the time points (F = 20.09. P < .001). The corresponding analysis for the mean Emmax differed significantly between the time points (F = 16.69, P < .001). The same was true for the mean Imax 108 (F = 9.69, P < .001). CONCLUSIONS: Within the limitations of this study, whitening provoked statistically significant changes in fluorescence of the intact teeth in vitro. CLINICAL SIGNIFICANCE: The appearance of human teeth and dental materials and their changes upon aging and exposure to different agents (staining, whitening) is a topic of great relevance to esthetic dentistry. While some appearance parameters, such as color, translucency, and gloss, have been thoroughly studied, fluorescence and its influence on overall tooth appearance is still not well understood, yet it has influenced the development of fluorescence emitting restorative materials.