Search Results (15)

Poly(2-oxazoline) (POx), a typical thermoresponsive polymer with good biocompatibility, was conjugated with environment-sensitive tetraphenylenethene (TPE) and hydroxyphenylbenzoxazole (HBO) to achieve unique thermometer readings. Through phase transition induced by temperature, the thermometers can measure temperature in biologic range with ratiometric fluorescence response, ultrahigh sensitivity and good reversibility. Moreover, the thermometer can be used to measure the change in temperature with large fluorescence difference in living cells. Full article

A Near-Infrared (NIR) ratiometric luminescence thermometer with the composition of Yb₁Gd₂Al_1.98Cr_0.02Ga₃O₁₂ was prepared and studied. When excited by 660 nm in the first biological transparent window (BTW), the sample shows a peak structure of around 1000 nm due to the ²F_5/2 → ²F_7/2 transitions of Yb³⁺ via the energy transfer process from Cr³⁺. Due to the Boltzmann distribution, the Yb³⁺ PL intensities in the shorter wavelength side (i.e., 1st BTW) and longer wavelength side (i.e., 2nd BTW) exhibit opposite temperature dependencies. The luminescence intensity ratio (LIR) of Yb³⁺ in shorter and longer wavelength ranges works as a luminescence thermometer with a relative sensitivity of 0.55% K⁻¹ at 310 K. In addition, YbGd₂Al_1.98Cr_0.02Ga₃O₁₂ can also be employed for temperature sensing based on the LIR of Cr³⁺ (²E → ⁴A₂) at around 700 nm and Yb³⁺ (²F_5/2 → ²F_7/2) at around 1000 nm, achieving a remarkable relative sensitivity of 2.69% at 100 K. This study confirms that the YbGd₂Al_1.98Cr_0.02Ga₃O₁₂ thermometer fulfills the requirements for biological temperature measurements. Full article

Gold nanoparticles are widely used as local heaters under optical excitation. Hybrid molecular-plasmon nanostructures based on gold nanoparticles and water-soluble porphyrin have been developed. A colloidal solution of gold nanoparticles was obtained by laser ablation of metallic gold in water, ensuring its highest chemical purity. The hybrid nanostructures formation was performed due to the Coulomb interaction of cationic porphyrin and gold nanoparticles. The revealed functional properties of hybrid nanostructures make them promising for controllable nano-heater applications (for example, photothermal therapy). Gold nanoparticles act as heaters, whereas porphyrin serves as a fluorescent thermometer with a single optical excitation. Full article

In this paper we describe the results of the influence of temperature in the range of 280–340 K on the luminescence of bimetallic Eu/Tb complexes with N-heterocyclic ligand L based on 2,2′-bipyridyldicarboxylic acid in acetonitrile. The experiments were carried out for systems with various Eu/Tb ratios. The stability of the complexes of the ligand L with metal M (Eu or Tb) was determined using spectrophotometric titration in acetonitrile solutions. The LM complexes’ stability constants were found to be typical for these systems; however, the stability of Eu complex is slightly higher than that for Tb. Along with rising temperature, we observed a decrease in Tb emission intensity and, at the same time, an enhancement in Eu luminescence. An explanation of Eu luminescence enhancement involves the appearance of charge transfer states, bands of which can be observed in the Eu luminescence excitation spectra as difference spectra measured with two close temperatures. The unusual Eu luminescence enhancement upon heating was observed for the first time for the complex with tetradentate O,N-type heterocyclic diamide ligand L, while an inverse phenomenon was observed with the Tb luminescence. The Eu luminescence enhancement was found earlier for various carboxylate complex salts, but not for heterocyclic coordination complexes. This allows the construction of a ratiometric luminescent thermometer in the range of 280–340 K using the ratio of luminescence intensities for Eu and Tb. The stability constants for the individual Eu and Tb complexes help us to understand the equilibrium in L:Tb:Eu complex system and shed light on plausible speciation in solution. Full article

Owing to its high reliability and accuracy, the ratiometric luminescent thermometer can provide non-contact and fast temperature measurements. In particular, the nanomaterials doped with lanthanide ions can achieve multi-mode luminescence and temperature measurement by modifying the type of doped ions and excitation light source. The better penetration of the near-infrared (NIR) photons can assist bio-imaging and replace thermal vision cameras for photothermal imaging. In this work, we prepared core–shell cubic phase nanomaterials doped with lanthanide ions, with Ba₂LuF₇ doped with Er³⁺/Yb³⁺/Nd³⁺ as the core and Ba₂LaF₇ as the coating shell. The nanoparticles were designed according to the passivation layer to reduce the surface energy loss and enhance the emission intensity. Green upconversion luminescence can be observed under both 980 nm and 808 nm excitation. A single and strong emission band can be obtained under 980 nm excitation, while abundant and weak emission bands appear under 808 nm excitation. Meanwhile, multi-mode ratiometric optical thermometers were achieved by selecting different emission peaks in the NIR window under 808 nm excitation for non-contact temperature measurement at different tissue depths. The results suggest that our core–shell NIR nanoparticles can be used to assist bio-imaging and record temperature for biomedicine. Full article

The development and utilization of 3p-block based MOFs as fluorescent materials has attracted significant attention in recent years. Herein, we have successfully constructed a versatile luminescent Ga-MOF (SNNU-63) with a 3d¹⁰ configuration and a large ligand twist configuration. Interestingly, the as-synthesized Ga-MOF exhibits excellent luminescence property and a good material for blue light-emitting diode (LED). At 80 K, this Ga-MOF shows multi-emission centers at 381, 462, and 494 nm. As a ratiometric thermometer, this Ga-MOF exhibits an excellent temperature sensing property with high relative sensitivity (S_m = 2.60 % K⁻¹ at 110 K). The fluorescence intensity ratio I₃₈₁/I₄₉₄ shows a very good fit for the Boltzmann results (80–240 K). Moreover, the luminescent Ga-MOF exhibits an excellent selective detection of Fe³⁺ over other metal ions in aqueous an medium, and the limit of detection (LOD) towards Fe³⁺ ions is calculated to be 1.227 × 10⁻⁴ M. This work presents a versatile luminescent Ga-MOF material as a blue LED and fluorescent probe for low-temperature and selective Fe³⁺ sensing. Full article

The synthesis and characterization of novel luminescent amorphous POSS-based polysilsesquioxanes (PSQs) with Tb³⁺ and Eu³⁺ ions directly integrated in the polysilsesquioxane matrix is presented. Two different Tb³⁺/Eu³⁺ molar ratios were applied, with the aim of disclosing the relationships between the nature and loading of the ions and the luminescence properties. Particular attention was given to the investigation of site geometry and hydration state of the metal centers in the inorganic framework, and of the effect of the Tb³⁺ → Eu³⁺ energy transfer on the overall optical properties of the co-doped materials. The obtained materials were characterized by high photostability and colors of the emitted light ranging from orange to deep red, as a function of both the Tb³⁺/Eu³⁺ molar ratio and the chosen excitation wavelength. A good energy transfer was observed, with higher efficiency displayed when donor/sensitizer concentration was lower than the acceptor/activator concentration. The easiness of preparation and the possibility to finely tune the photoluminescence properties make these materials valid candidates for several applications, including bioimaging, sensors, ratiometric luminescence-based thermometers, and optical components in inorganic or hybrid light-emitting devices. Full article

Multi-emissive compounds have attracted significant attention from the research community owing to the wide array of potential application areas. However, to move towards application, such systems should be readily immobilized by solution-based methods to form soft materials such as gels and films. Herein we report the use of Langmuir–Blodgett (LB) deposition to easily immobilize luminescent lanthanide-based amphiphilic solids into multi-emissive ultrathin LB films, by multilayering different luminescent amphiphiles. Utilizing this technique, we have reliably fabricated dual- and triple-emissive films where the overall emission from the film is tuned. Furthermore, we have demonstrated that these multi-emissive films are temperature-dependent, with emission profiles significantly altering from 294 to 340 K, resulting in colour changes and potential application as ultrathin, contactless ratiometric thermometer coatings. Full article

Sensing temperature in biological systems is of great importance, as it is constructive to understanding various physiological and pathological processes. However, the realization of highly sensitive temperature sensing with organic fluorescent nanothermometers remains challenging. In this study, we report a ratiometric fluorescent nanogel thermometer and study its application in the determination of bactericidal temperature. The nanogel is composed of a polarity-sensitive aggregation-induced emission luminogen with dual emissions, a thermoresponsive polymer with a phase transition function, and an ionic surface with net positive charges. During temperature-induced phase transition, the nanogel exhibits a reversible and sensitive spectral change between a red-emissive state and a blue-emissive state by responding to the hydrophilic-to-hydrophobic change in the local environment. The correlation between the emission intensity ratio of the two states and the external temperature is delicately established, and the maximum relative thermal sensitivities of the optimal nanogel are determined to be 128.42 and 68.39% °C⁻¹ in water and a simulated physiological environment, respectively. The nanogel is further applied to indicate the bactericidal temperature in both visual and ratiometric ways, holding great promise in the rapid prediction of photothermal antibacterial effects and other temperature-related biological events. Full article

Molecular vibrations in the solid-state, detectable in the terahertz (THz) region, are the subject of research to further develop THz technologies. To observe such vibrations in terahertz time-domain spectroscopy (THz-TDS) and low-frequency (LF) Raman spectroscopy, two supramolecular assemblies with the formula [Nd^III (phen)₃ (NCX)₃] 0.3EtOH (X = S, 1-S; Se, 1-Se) were designed and prepared. Both compounds show several THz-TDS and LF-Raman peaks in the sub-THz range, with the lowest frequencies of 0.65 and 0.59 THz for 1-S and 1-Se, and 0.75 and 0.61 THz for 1-S and 1-Se, respectively. The peak redshift was observed due to the substitution of SCN⁻ by SeCN⁻. Additionally, temperature-dependent TDS-THz studies showed a thermal blueshift phenomenon, as the peak position shifted to 0.68 THz for 1-S and 0.62 THz for 1-Se at 10 K. Based on ab initio calculations, sub-THz vibrations were ascribed to the swaying of the three thiocyanate/selenocyanate. Moreover, both samples exhibited near-infrared (NIR) emission from Nd (III), and very good thermometric properties in the 300–150 K range, comparable to neodymium (III) oxide-based thermometers and higher than previously reported complexes. Moreover, the temperature dependence of fluorescence and THz spectroscopy analysis showed that the reduction in anharmonic thermal vibrations leads to a significant increase in the intensity and a reduction in the width of the emission and LF absorption peaks. These studies provide the basis for developing new routes to adjust the LF vibrational absorption. Full article

Two homometallic Coordination Polymers (CPs) with composition [Ln(hfac)₃bipy]_n (Ln³⁺ = Eu³⁺, 1, and Tb³⁺, 2; hfac = hexafluoroacetylacetonato, bipy = 4,4′-bipyridine) were used to develop a family of ratiometric luminescent thermometers containing Eu³⁺ and Tb³⁺ as red and green emitters, respectively. The thermometric properties of pure CPs and of their mixtures having an Eu³⁺/Tb³⁺ molar ratio of 1:1, 1:3, 1:5, and 1:10 (samples: Eu1Tb1, Eu1Tb3, Eu1Tb5, and Eu1Tb10) were studied in the 83–383 K temperature range. Irrespective of the chemical composition, we observed similar thermometric responses characterized by broad applicative temperature ranges (from 100 to 165 K wide), and high relative thermal sensitivity values (S_r), up to 2.40% K⁻¹, in the physiological temperature range (298–318 K). All samples showed emissions endowed with peculiar and continuous color variation from green (83 K) to red (383 K) that can be exploited to develop a colorimetric temperature indicator. At fixed temperature, the color of the emitted light can be tuned by varying composition and excitation wavelength. Full article

In luminescence thermometry enabling temperature reading at a distance, an important challenge is to propose new solutions that open measuring and material possibilities. Responding to these needs, in the nanocrystalline phosphors of yttrium oxide Y₂O₃ and lutetium oxide Lu₂O₃, temperature-dependent emission of trivalent terbium Tb³⁺ dopant ions was recorded at the excitation wavelength 266 nm. The signal of intensity decreasing with temperature was monitored in the range corresponding to the ⁵D₄ → ⁷F₆ emission band. On the other hand, defect emission intensity obtained upon 543 nm excitation increases significantly at elevated temperatures. The opposite thermal monotonicity of these two signals in the same spectral range enabled development of the single band ratiometric luminescent thermometer of as high a relative sensitivity as 4.92%/°C and 2%/°C for Y₂O₃:Tb³⁺ and Lu₂O₃:Tb³⁺ nanocrystals, respectively. This study presents the first report on luminescent thermometry using defect emission in inorganic phosphors. Full article

Accurate temperature measurements with a high spatial resolution for application in the biomedical fields demand novel nanosized thermometers with new advanced properties. Here, a water dispersible ratiometric temperature sensor is fabricated by encapsulating in silica nanoparticles, organic capped PbS@CdS@CdS “giant” quantum dots (GQDs), characterized by dual emission in the visible and near infrared spectral range, already assessed as efficient fluorescent nanothermometers. The chemical stability, easy surface functionalization, limited toxicity and transparency of the silica coating represent advantageous features for the realization of a nanoscale heterostructure suitable for temperature sensing. However, the strong dependence of the optical properties on the morphology of the final core–shell nanoparticle requires an accurate control of the encapsulation process. We carried out a systematic investigation of the synthetic conditions to achieve, by the microemulsion method, uniform and single core silica coated GQD (GQD@SiO₂) nanoparticles and subsequently recorded temperature-dependent fluorescent spectra in the 281-313 K temperature range, suited for biological systems. The ratiometric response—the ratio between the two integrated PbS and CdS emission bands—is found to monotonically decrease with the temperature, showing a sensitivity comparable to bare GQDs, and thus confirming the effectiveness of the functionalization strategy and the potential of GQD@SiO₂ in future biomedical applications. Full article

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 ⁴F_3/2 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 ⁴F_5/2 and ⁴F_3/2 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 ⁴F_3/2 and ⁴F_5/2 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 ⁴F_5/2 and ⁴F_3/2 spin-orbit levels of Nd³⁺ makes it possible to tailor the thermometric performance of Nd³⁺ to enable physiological temperature sensing. Full article

Temperature is a significant parameter to regulate biological reactions and functions inside cells. Sensing the intracellular temperature with a competent method is necessary to understand life science. In this work, an energy-transfer polymeric thermometer was designed for temperature sensing. The thermometer was prepared from two thermo-responsive polymers with different lower critical solution temperatures (LCSTs) of 31.1 °C and 48.6 °C, coupling with blue and red fluorescent molecules, respectively, developed for ratiometric temperature sensing based on the Förster resonance energy transfer (FRET) mechanism. The polymers were synthesized from two monomers, N-isopropylacrylamide (NIPA) and N-isopropylmethacrylamide (NIPmA), which provided different temperature responses. The fluorescent intensity of each polymer (peaked at 436 and 628 nm, respectively) decreased upon the heating of the polymer aqueous solution. While these two polymer aqueous solutions were mixed, the fluorescent intensity decrease at 436 nm and substantial fluorescence enhancement at 628 nm was observed with the increasing temperature due to FRET effect. The cell imaging of HeLa cells by these thermo-responsive polymers was explored. The difference of LCSTs resulting in ratiometric fluorescence change would have a potential impact on the various biomedical applications. Full article