Superparamagnetic and highly bioactive SPIONS/bioactive glass nanocomposite and its potential application in magnetic hyperthermia.

Magnetic bioactive glass-ceramics are biomaterials applied for magnetic hyperthermia in bone cancer treatment, thereby treating the bone tumor besides regenerating the damaged bone. However, combining high bioactivity and high saturation magnetization remains a challenge since the thermal treatment step employed to grow magnetic phases is also related to loss of bioactivity. Here, we propose a new nanocomposite made of superparamagnetic iron oxide nanoparticles (SPIONs) dispersed in a sol-gel-derived bioactive glass matrix, which does not need any thermal treatment for crystallization of magnetic phases. The scanning and transmission electron microscopies, X-ray diffraction, and dynamic light scattering results confirm that the SPIONs are actually embedded in a nanosized glass matrix, thus forming a nanocomposite. Magnetic and calorimetric characterizations evidence their proper behavior for hyperthermia applications, besides evidencing inter-magnetic nanoparticle interactions within the nanocomposite. Bioactivity and in vitro characterizations show that such nanocomposites exhibit apatite-forming properties similar to the highly bioactive parent glass, besides being osteoinductive. This methodology is a new alternative to produce magnetic bioactive materials to which the magnetic properties only rely on the quality of the SPIONs used in the synthesis. Thereby, these nanocomposites can be recognized as a new class of bioactive materials for applications in bone cancer treatment by hyperthermia.

Synthesis, characterization, and incorporation of upconverting nanoparticles into a dental adhesive.

The purpose of this study was to describe the synthesis, characterization, and functionalization of b-NaYF4:30%Yb/0.5%Tm upconverting nanocrystals for use as nanofillers in a dental adhesive and microscopically evaluate the interface between the particles and a commercial adhesive. The upconverting nanoparticles were synthesized and purified by thermal decomposition, and their chemical composition determined by energy dispersive X-Ray spectroscopy. The crystalline structure was characterized using X-Ray diffraction and morphology and size were observed with scanning and transmission electron microscopy. Upconverting emission was evaluated by spectrophotometry irradiating the particles with a 975 nm diode laser. Particles were functionalized with polyacrylic acid and the success was confirmed by measurement of Zeta Potential and transmission electron microscopy. The results of X-ray diffraction found a pure hexagonal phase crystalline pattern. Scanning electron microscopy showed uniform dispersion of hexagonal-shaped particles of approximately 150 nm. Upconversion emission was observed in 344 nm, 361 nm, 450 nm, 474nm, 646 nm, 803 nm. Functionalization success was confirmed by formation of a stable aqueous colloid with a Zeta potential of -29.5mV and the absence of voids in the particle-adhesive interface on the transmission electron microscopy images. The reported synthesis and functionalization process produced upconverting nanoparticles emitting photons within the blue spectral region (450 nm and 474 nm).

Controlling the thermal switching in upconverting nanoparticles through surface chemistry.

Photon upconversion taking place in small rare-earth-doped nanoparticles has been recently observed to be thermally modulated in an anomalous manner, showing thermal enhancement of the emission intensity. This effect was proved to be linked to the role of adsorbed water molecules as surface quenchers. The surface capping of the particles has a direct influence on the thermal dynamics of water adsorption and desorption, and therefore on the optical properties. Here, we show that the upconversion intensity of small-size (<25 nm) nanoparticles co-doped with Yb3+ and Er3+ ions, and functionalized with different capping molecules, presents clear irreversibility patterns upon thermal cycling that strongly depend on the chemical nature of the nanoparticle surface. By performing temperature-controlled luminescence measurements we observed the formation of a thermal hysteresis loop, resembling an optical switching phenomenon, whose shape and trajectory depend on the hydrophilicity of the surface. Additionally, an intensity overshoot takes place immediately after turning off the heating source, affecting each radiative transition differently. We performed numerical modelling to understand this effect considering non-radiative energy transfer from the surface defect states to the Er3+ ions. These findings are relevant for the comprehension of nanoparticle-based luminescence and the interplay between the surface and volume effects, and more generally, for applications involving UCNPs such as nanothermometry and bioimaging, and the development of optical encoding systems.

New sol-gel-derived magnetic bioactive glass-ceramics containing superparamagnetic hematite nanocrystals for hyperthermia application.

Although the three main phases of iron oxide - hematite, maghemite, and magnetite - exhibit superparamagnetic properties at the nanoscale, only maghemite and magnetite phases have been explored in magnetic bioactive glass-ceramics aimed at applications in cancer treatment by hyperthermia. In this work, it is reported for the first time the superparamagnetic properties of hematite nanocrystals grown in a 58S bioactive glass matrix derived from sol-gel synthesis. The glass-ceramics are based on the (100-x)(58SiO2-33CaO-9P2O5)-xFe2O3 system (x = 10, 20 and 30 wt%). A thermal treatment leads to the growth of hematite (α-Fe2O3) nanocrystals, conferring superparamagnetic properties to the glass-ceramics, which is enough to produce heat under an external alternating magnetic field. Besides, the crystallization does not inhibit materials bioactivity, evidenced by the formation of calcium phosphate onto the glass-ceramic surface upon soaking in simulated body fluid. Moreover, their cytotoxicity is similar to other magnetic bioactive glass-ceramics reported in the literature. Finally, these results suggest that hematite nanocrystals' superparamagnetic properties may be explored in multifunctional glass-ceramics applied in bone cancer treatment by hyperthermia allied to bone regeneration.

Synthesis, characterization, and incorporation of upconverting nanoparticles into a dental adhesive

Abstract: The purpose of this study was to describe the synthesis, characterization, and functionalization of b-NaYF4:30%Yb/0.5%Tm upconverting nanocrystals for use as nanofillers in a dental adhesive and microscopically evaluate the interface between the particles and a commercial adhesive. The upconverting nanoparticles were synthesized and purified by thermal decomposition, and their chemical composition determined by energy dispersive X-Ray spectroscopy. The crystalline structure was characterized using X-Ray diffraction and morphology and size were observed with scanning and transmission electron microscopy. Upconverting emission was evaluated by spectrophotometry irradiating the particles with a 975 nm diode laser. Particles were functionalized with polyacrylic acid and the success was confirmed by measurement of Zeta Potential and transmission electron microscopy. The results of X-ray diffraction found a pure hexagonal phase crystalline pattern. Scanning electron microscopy showed uniform dispersion of hexagonal-shaped particles of approximately 150 nm. Upconversion emission was observed in 344 nm, 361 nm, 450 nm, 474nm, 646 nm, 803 nm. Functionalization success was confirmed by formation of a stable aqueous colloid with a Zeta potential of −29.5mV and the absence of voids in the particle-adhesive interface on the transmission electron microscopy images. The reported synthesis and functionalization process produced upconverting nanoparticles emitting photons within the blue spectral region (450 nm and 474 nm).

Self-Calibrated Double Luminescent Thermometers Through Upconverting Nanoparticles.

Luminescent nanothermometry uses the light emission from nanostructures for temperature measuring. Non-contact temperature readout opens new possibilities of tracking thermal flows at the sub-micrometer spatial scale, that are altering our understanding of heat-transfer phenomena occurring at living cells, micro electromagnetic machines or integrated electronic circuits, bringing also challenges of calibrating the luminescent nanoparticles for covering diverse temperature ranges. In this work, we report self-calibrated double luminescent thermometers, embedding in a poly(methyl methacrylate) film Er3+- and Tm3+-doped upconverting nanoparticles. The Er3+-based primary thermometer uses the ratio between the integrated intensities of the 2 H 11 / 2 → 4 I15/2 and 4 S 3 / 2 → 4 I15/2 transitions (that follows the Boltzmann equation) to determine the temperature. It is used to calibrate the Tm3+/Er3+ secondary thermometer, which is based on the ratio between the integrated intensities of the 1 G 4 → 3 H6 (Tm3+) and the 4 S 3 / 2 → 4 I15/2 (Er3+) transitions, displaying a maximum relative sensitivity of 2.96% K-1 and a minimum temperature uncertainty of 0.07 K. As the Tm3+/Er3+ ratio is calibrated trough the primary thermometer it avoids recurrent calibration procedures whenever the system operates in new experimental conditions.

Upconversion Nanocomposite Materials With Designed Thermal Response for Optoelectronic Devices.

Upconversion is a non-linear optical phenomenon by which low energy photons stimulate the emission of higher energy ones. Applications of upconversion materials are wide and cover diverse areas such as bio-imaging, solar cells, optical thermometry, displays, and anti-counterfeiting technologies, among others. When these materials are synthesized in the form of nanoparticles, the effect of temperature on the optical emissions depends critically on their size, creating new opportunities for innovation. However, it remains a challenge to achieve upconversion materials that can be easily processed for their direct application or for the manufacture of optoelectronic devices. In this work, we developed nanocomposite materials based on upconversion nanoparticles (UCNPs) dispersed in a polymer matrix of either polylactic acid or poly(methyl methacrylate). These materials can be processed from solution to form thin film multilayers, which can be patterned by applying soft-lithography techniques to produce the desired features in the micro-scale, and luminescent tracks when used as nanocomposite inks. The high homogeneity of the films, the uniform distribution of the UCNPs and the easygoing deposition process are the distinctive features of such an approach. Furthermore, the size-dependent thermal properties of UCNPs can be exploited by a proper formulation of the nanocomposites in order to develop materials with high thermal sensitivity and a thermochromic response. Here, we thus present different strategies for designing optical devices through patterning techniques, ink dispensing and multilayer stacking. By applying upconverting nanocomposites with unique thermal responses, local heating effects in designed nanostructures were observed.

Thermoplasmonic enhancement of upconversion in small-size doped NaGd(Y)F4 nanoparticles coupled to gold nanostars.

Plasmon enhancement of luminescence is a common strategy to boost the efficiency of both fluorescence and upconversion via the augmented local electromagnetic field. However, the local heating produced when exciting the plasmon resonance of metallic nanoparticles is often overlooked. As higher temperatures are usually detrimental for radiative processes, only the electromagnetic contribution is exploited for enhancement. We show here that for small size (<20 nm) rare-earth doped ß-NaGd(Y)F4 upconversion nanoparticles (UCNPs), the photothermal properties of gold nanostars (AuNSs) can be used to enhance the total emission intensity. On the contrary, for UCNPs of larger size, the thermoplasmonic effect is adverse for the emissivity. Therefore, we developed a novel strategy to enhance the emission intensity by combining the thermoplasmonic effect on AuNSs with the size-dependent thermal properties of UCNPs. Furthermore, by following the integrated intensity ratio between the emission lines of Er3+, 2H11/2 → 4I15/2 and 4S3/2 → 4I15/2, a direct correlation between the local temperature and the emission intensity could be established. Optical thermometry measurements show that the thermoplasmonic effect in AuNSs, with a plasmon absorption band close to the excitation wavelength, can produce an increment of the local temperature of more than 100 °C when exposed to 976 nm continuous-wave laser light at 50 W cm-2 of power density. The results provided here are relevant for the design and implementation of plasmon-enhanced luminescent devices, upconversion solar-cells, bioprobes and also for hyperthermia.

The nature and enhancement of magnetic surface contribution in model NiO nanoparticles.

We report an alternative synthesis method and novel magnetic properties of Ni-oxide nanoparticles (NPs). The NPs were prepared by thermal decomposition of nickel phosphine complexes in a high-boiling-point organic solvent. These particles exhibit an interesting morphology constituted by a crystalline core and a broad disordered superficial shell. Our results suggest that the magnetic behavior is mainly dominated by strong surface effects at low temperature, which become evident through the observation of shifted hysteresis loops (approximately 2.2 kOe), coercivity enhancement (approximately 10.2 kOe) and high field irreversibility (>or=50 kOe). Both an exchange bias and a vertical shift in magnetization can be observed in this system below 35 K after field cooling. Additionally, the exchange bias field shows a linear dependence on the magnetization shift values, which elucidate the role of pinned spins on the exchange fields. The experimental data are analyzed in terms of the interplay between the interface exchange coupling and the antiferromagnetically ordered structure of the core.