Upconversion rare Earths nanomaterials applied to photodynamic therapy and bioimaging.

Light-based therapies and diagnoses including photodynamic therapy (PDT) have been used in many fields of medicine, including the treatment of non-oncological diseases and many types of cancer. PDT require a light source and a light-sensitive compound, called photosensitizer (PS), to detect and destroy cancer cells. After absorption of the photon, PS molecule gets excited from its singlet ground state to a higher electronically excited state which, among several photophysical processes, can emit light (fluorescence) and/or generate reactive oxygen species (ROS). Moreover, the biological responses are activated only in specific areas of the tissue that have been submitted to exposure to light. The success of the PDT depends on many parameters, such as deep light penetration on tissue, higher PS uptake by undesired cells as well as its photophysical and photochemical characteristics. One of the challenges of PDT is the depth of penetration of light into biological tissues. Because photon absorption and scattering occur simultaneously, these processes depend directly on the light wavelength. Using PS that absorbs photons on "optical transparency windows" of biological tissues promises deeper penetration and less attenuation during the irradiation process. The traditional PS normally is excited by a higher energy photon (UV-Vis light) which has become the Achilles' heel in photodiagnosis and phototreatment of deep-seated tumors below the skin. Thus, the need to have an effective upconverter sensitizer agent is the property in which it absorbs light in the near-infrared (NIR) region and emits in the visible and NIR spectral regions. The red emission can contribute to the therapy and the green and NIR emission to obtain the image, for example. The absorption of NIR light by the material is very interesting because it allows greater penetration depth for in vivo bioimaging and can efficiently suppress autofluorescence and light scattering. Consequently, the penetration of NIR radiation is greater, activating the biophotoluminescent material within the cell. Thus, materials containing Rare Earth (RE) elements have a great advantage for these applications due to their attractive optical and physicochemical properties, such as several possibilities of excitation wavelengths - from UV to NIR, strong photoluminescence emissions, relatively long luminescence decay lifetimes (µs to ms), and high sensitivity and easy preparation. In resume, the relentless search for new systems continues. The contribution and understanding of the mechanisms of the various physicochemical properties presented by this system is critical to finding a suitable system for cancer treatment via PDT.

Refractive Indexes and Spectroscopic Properties to Design Er3+-Doped SiO2-Ta2O5 Films as Multifunctional Planar Waveguide Platforms for Optical Sensors and Amplifiers.

This paper reports on the news about refractive index measurements and spectroscopic features of thin films, which can be applied as optical planar waveguides, focusing on their manufacturing processes, designs, and possible applications as optical amplifiers and sensors. Er3+-doped SiO2-Ta2O5 planar waveguides, with Si/Ta ratios of 90:10, 80:20, 70:30, 60:40, and 50:50, were prepared by a soft sol-gel process. Multilayer films were deposited by the dip-coating technique onto 10 µm SiO2-Si (100) p-type silicon and Si (100) silicon easily and successfully. The mechanisms of the densification process, porosity, and hydroxy group or water molecule occurrence have been accompanied by m-line and vibrational spectroscopy analyses. The thickness and refractive index values were used to understand better the influence of temperature and annealing time on the densification of the bulk films and the reduction of the pore volume as the tantalum oxide concentration increases. The refractive index shows the density of the films, and by the atomic force microscopy (AFM) technique, the films showed low surface roughness, achieving relatively high light confinement within the waveguide structure, and negligible optical loss due to surface scattering. Nanoparticle crystallization of Ta2O5 with size distribution ranging from 2.0 to 15.0 nm embedded in SiO2 was observed with size depending on annealing time and tantalum concentration. Intense and broadband emission positioned at 1550 nm, which is attributed to the 4I13/2 → 4I15/2 transition of Er3+ ions, was observed for all planar waveguides under excitation at 271, 272, and 278 nm. Depending on the porosity degree, the adsorption of H2O molecules occurs, changing the refractive index and contributing to the deactivation of excited states of Er3+ ions, making them an optical platform for use as an optical sensor for different species. Besides, the densified waveguides containing 20 or 30 mol % Ta exhibit high potential for applications as broadband optical amplifiers for wavelength division multiplexing (WDM), optical sensing, or augmented reality.

Ligand induced switching of the band alignment in aqueous synthesized CdTe/CdS core/shell nanocrystals.

CdTe/CdS core/shell quantum dots (QDs) are formed in aqueous synthesis via the partial decomposition of hydrophilic thiols, used as surface ligands. In this work, we investigate the influence of the chemical nature (functional group and chain length) of the used surface ligands on the shell formation. Four different surface ligands are compared: 3-mercaptopropionic acid, MPA, thioglycolic acid, TGA, sodium 3-mercaptopropanesulfonate, MPS, and sodium 2-mercaptoethanesulfonate, MES. The QD growth rate increases when the ligand aliphatic chain length decreases due to steric reasons. At the same time, the QDs stabilized with carboxylate ligands grow faster and achieve higher photoluminescence quantum yields compared to those containing sulfonate ligands. The average PL lifetime of TGA and MPA capped QDs is similar (≈20 ns) while in the case of MPS shorter (≈15 ns) and for MES significantly longer (≈30 ns) values are measured. A detailed structural analysis combining powder X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) indicates the existence of two novel regimes of band alignment: in the case of the mercaptocarboxylate ligands the classic type I band alignment between the core and shell materials is predominant, while the mercaptosulfonate ligands induce a quasi-type II alignment (MES) or an inverted type I alignment (MPS). Finally, the effect of the pH value on the optical properties was evaluated: using a ligand excess in solution allows achieving better stability of the QDs while maintaining high photoluminescence intensity at low pH.