Critical Aspects on the Chemical Stability of NaYF4-Based Upconverting Nanoparticles for Biomedical Applications.

This review summarizes essential information about the chemical stability of NaYF4-based upconverting nanoparticles (UCNPs) in aqueous solutions, a crucial aspect for achieving high quality standards for biomedical materials. We present an in-depth analysis of the major experimental evidence and proposed mechanisms that provide a theoretical framework for understanding UCNPs degradation, destabilization, and dissolution under different conditions such as media composition, temperature, particle size, and the synthetic methods employed. The ion release and disintegration of the UCNP crystal structure may trigger cytotoxic events within living organisms and impact on their optical properties, precluding their safe use in biological environments. Also, we present a summary of the characterization techniques' toolbox employed for monitoring and detecting these degradation processes. Closing the existing "information gap" that links UCNP physicochemical properties, such as solubility and chemical stability, with the biological response of living organisms or tissues, is vital for using these nanoparticles as biological tracer probes, theranostic vehicles, or for clinical purposes. The understanding of chemical phenomena at the nanoparticle solid-liquid interface is mandatory to complete the molecular picture of nanosized objects, orienting in a rational manner the efforts of research and development in the early stages of these functional materials.

Kinetic study of the thermoluminescence of KMgF3:LaF3 compounds employing the general one trap model.

The parameters characterising the trap centres involved in the thermoluminescence of KMgF3:LaF3 compounds have been found by deconvolving the glow curve with the General One Trap model (GOT). For the fitting procedure the Levenberg-Marquardt method has been employed. Tm-T(stop) measurements along with initial rise measurements were performed in order to estimate the number of peaks the glow curve is made up of, and the corresponding activation energies. Instead of the Runge-Kutta method, a novel algorithm has been employed to integrate the differential equation of the GOT model, which reduces the computational time nearly 30 times with respect to the former when the glow curve is recorded with a lineal heating rate profile. The strong computational time reduction makes feasible a large number of runs with different guess values. An interesting result is that the concentration of disconnected deep traps is much less than the concentration of trap centres.

Response of LiF:Mg,Ti to low energy carbon and oxygen ions.

The extended track interaction model (ETIM) has been formulated to explain the TL-fluence response for peak 5 to heavy ions using radial dose distributions produced by the ions in LiF and their luminescent centre occupation probability distributions. In this work, an experimental study of the TLD-100 fluence response to carbon and oxygen ions and its interpretation in terms of a Monte Carlo simulation of ETIM applied to peak 5 are presented. Irradiations were performed with 7.34 and 10.3 MeV 12C and 8.34 MeV 16O ions in the fluence interval between 2 x 10(7) and 2 x 10(11) cm(-2). Individual glow curve responses show the expected increase of supralinearity as the peak temperature increases. Data for peak 5 show a weak dependence with energy. These latter results are difficult to understand when one considers the differences in the expected radial occupancies for different ion energies.

Measurements of the optical density and the thermoluminescent response of LiF:Mg,Ti exposed to high doses of 60Co gamma rays.

The absorption spectra and glow curves of LiF:Mg,Ti exposed to high doses of 60Co gamma rays as well as the optical density curves and thermoluminescent (TL) response as a function of dose were measured. Absorption peaks around 442 nm (2.8 eV), 307 nm (4.0 eV) and 248 nm (5.0 eV) were observed. The optical density is a linear function of dose up to 2500 Gy and then sublinear for the 5.0 eV band, and for the 4.0 eV band it is sublinear with a filling constant of 2.1 x 10(-4) and 6.2 x 10(-4) Gy(-1). The dose response of the 2.8 eV band is linear from 2500 Gy to 10 kGy with a slope of 1.0 x 10(-5) Gy(-1). Once the absorption spectra were obtained, the glow curves and the TL response were obtained. In the dose range, 290-10,000 Gy, the TL response of peaks 5 and 7 was supralinear-sublinear.

Performance of different thermoluminescence dosimeters in 90SR+90Y radiation fields.

The dosimetry of beta radiation is a difficult process especially because of the low penetration of beta particles in matter. The dosemeter utilised for this kind of procedure needs to approximate an ideal point-like detector: it should be as thin as possible, and its area should be small. The thermoluminescence dosemeters (TLDs) meet with these requirement properties. The aim of this work was to study the dosimetric characteristics of different TLDs to verify the possibility of their use for the calibration of 90Sr+90Y plane applicators. The response reproducibility, calibration curves, TL response as a function of the source-detector distance, the transmission factors and the linearity of the sample response were obtained for several types of dosimetric pellets.

On the quasi-equilibrium problem in thermally stimulated luminescence and conductivity.

Strong doubts havc been expressed about the validity of the quasi-equilibrium (QE) assumption used in the derivation of the analytical expressions of thermoluminescence (TL). So far there is no established method available to check if QE actually prevails during the emission of an experimental TL signal. The present study shows that the level of QE changes with a change in the heating rate beta. The change in the level of QE in its turn gets reflected in a change in peak shape when the system turns to a non-QE condition. This property is used as the first ever experimental method to test whether or not the emission of a given glow peak occurs under the QE condition. An essential condition for holding the QE condition is found to be T(R)/taum> or = 10(-3) where T(R) and taum are the glow peak recording duration and the maximum value of the free carrier lifetime, respectively. This relation between T(R) and taum is useful in finding the approximate value of taum. The value of taum being a function of the concentration and cross section of the TL related centres, one may be able to assess these basic parameters from the study of TL glow curves. The theoretical results are discussed in the perspective of LiF (TLD-100).

On the correct measurement of relative heavy charged particles to gamma thermoluminescent efficiencies.

In order to better understand the most important experimental aspects for performing correct measurements of relative thermoluminescent (TL) efficiencies, an investigation has been carried out to quantify the effect of using different experimental procedures in the evaluation of 3 MeV proton-to-gamma relative efficiency (etap,gamma) of LiF:Mg,Ti. Variations in batch, presentation, annealing and reader have been studied. When the same protocol is used to measure proton and gamma TL response, efficiency values obtained range from 0.36 to 0.59 for peak 5 and from 0.44 to 0.79 for the total signal. The use of different annealings and different batches leads to 20% and 10% differences in etap,gamma respectively. Large differences (40%) are found between efficiency values measured with TLD-100 chips and those obtained using TLD-100 microcubes. When 'mixed' procedures are used to measure the proton and the gamma response, differences in etap,gamma may increase even more. The main conclusion of this work is to stress the importance of measuring an entire series of experiments in the same laboratory with a carefully defined protocol and using dosemeters from the same batch to obtain heavy charged particle TL response and gamma TL response with identical annealing and readout procedures.

The TL fluence response to heavy charged particles using the track interaction model and track structure information.

The extended track interaction model, ETIM, has recently being proposed to explain the TLD-100 fluence response of peak 5 to heavy ions. This model includes the track structure information through the use of the luminescent centre occupation probability obtained from radial dose distributions produced by the ions as they travel through the dosemeter. In this work an implementation of ETIM using Monte Carlo techniques is presented. The simulation was applied to calculate the response of peak 5 of both sensitised and normal TLD-100 crystals to 2.6 and 6.8 MeV 4He ions. The simulation shows that the TL-fluence response has a strong dependence on ion energy, in disagreement with experimental observations. In spite of this, good agreement between the simulated TL-fluence response calculated for the 6.8 MeV 4He radial distributions and the experimental data for the two energies was achieved.

Influence of fdelta(D) on modified track structure theory efficiency calculations.

Modified track structure theory (MTST) has been successfully applied to evaluate proton-to-gamma and helium-to-gamma relative TL efficiencies in LiF by using Monte Carlo radial dose distributions and the measured dose response function, fdelta(D), of 8.1 keV X rays. In this work, an investigation is performed to study the effect of the choice of fdelta(D) for the reference test radiation field, on the predicted MTST proton-to-gamma and helium-to-gamma efficiency values. Results from two sets of calculations are presented. Set 1 investigates five fdelta(D) functions with different shapes and its influence on the MTST efficiency values while set 2 applies MTST using several fdelta(D) functions selected with fdelta(D)max ranging from 2 to 4. Comparison of the predicted efficiency values with experimental data show that the choice of 8.1 keV X rays gives the best description of the data. Results from set 2 show that predicted efficiencies may vary by as much as 44% for peak 5 and as much as 70% for the total signal among different fdelta(D). This confirms the importance of using the adequate fdelta(D) from a test radiation which simulates as much as possible the energy spectra and irradiated volume produced by the secondary electrons arising from the heavy charged particle radiation under study.

Thermoluminescent response of LiF:Mg,Ti to 20 keV electrons.

The thermoluminescence response of LiF:Mg,Ti (TLD-100) to 20 keV electrons from a scanning electron microscope has been measured. Radiochromic dye films previously calibrated were used to determine the fluence incident on TLD-100 chips. The procedure for irradiation and glow curve deconvolution was adhered to the protocols previously determined in our laboratory for gamma rays and heavy charged particles. The response at electron fluences higher than 4 x 10(10) cm(-2) is supralinear, due to the increasingly relevant contribution of the high temperature peaks. The relative contribution of the high temperature peaks to the TL signal is abnormally small, about half that observed in gamma irradiation and four times smaller than what has been measured in low-energy X ray exposure.