Advancements in Biomedical Applications of Calcium Phosphate Glass and Glass-Based Devices-A Review.

Calcium phosphate (CaP) glass has recently gained popularity as a promising material for a wide range of biomedical applications. Recent developments have seen CaP glasses moving from a passive implant material to an active degradable material, particularly as a major constituent of bioresorbable photonic devices. This holds great promise in advanced biomedical applications, since the main constituents of CaP glasses are present in the human body. In this review, the progressive advancements in the biomedical applications of calcium phosphate glass-based devices over the past 50 years are discussed. An overview of their role as reinforcing agents and the studies on doping their matrices for ion releasing and drug and gene delivery are reviewed. Recent applications of CaP glass and fibers in soft-tissue engineering and their potential for optical quality bioresorbable devices are then discussed along with the current challenges and potential future directions, emphasizing the promising role of CaP glass in the next generation of biomaterials. Considering their progress and potential in performing several biomedical functionalities over time, CaP glass-based devices hold promise for becoming enabling tools as an implantable, bioresorbable, multifunctional class of devices in future biomedicine.

Fiber Optic Sensors for Harsh and High Radiation Environments in Aerospace Applications.

In the upcoming space revolutions aiming at the implementation of automated, smart, and self-aware crewless vehicles and reusable spacecraft, sensors play a significant role in the control systems. In particular, fiber optic sensors, with their small footprint and electromagnetic immunity, represent a great opportunity in aerospace. The radiation environment and the harsh conditions in which these sensors will operate represent a challenge for the potential user in the aerospace vehicle design and the fiber optic sensor specialist. We present a review that aims to be a primer in the field of fiber optic sensors in radiation environments for aerospace. We review the main aerospace requirements and their relationship with fiber optics. We also present a brief overview of fiber optics and sensors based on them. Finally, we present different examples of applications in radiation environments for aerospace applications.

Ion-exchanged glass microrods as hybrid SERS/fluorescence substrates for molecular beacon-based DNA detection.

Ion-exchange in molten nitrate salts containing metal ions (i.e. silver, copper, etc.) represents a well-established technique able to modify the chemical-physical properties of glass materials. It is widely used not only in the field of integrated optics (IO) but also, more recently, in plasmonics due to the possibility to induce the formation of metal nanoparticles in the glass matrix by an ad hoc thermal post-process. In this work, the application of this technology for the realisation of low-cost and stable surface-enhanced Raman scattering (SERS) active substrates, based on soda-lime glass microrods, is reported. The microrods, with a radius of a few tens of microns, were obtained by cutting the end of an ion-exchanged soda-lime fibre for a length less than 1 cm. As ion source, silver nitrate was selected due to the outstanding SERS properties of silver. The ion-exchange and thermal annealing post-process parameters were tuned to expose the embedded silver nanoparticles on the surface of the glass microrods, avoiding the use of any further chemical etching step. In order to test the combined SERS/fluorescence response of these substrates, labelled molecular beacons (MBs) were immobilised on their surface for deoxyribonucleic acid (DNA) detection. Our experiments confirm that target DNA is attached on the silver nanoparticles and its presence is revealed by both SERS and fluorescence measurements. These results pave the way towards the development of low-cost and stable hybrid fibres, in which SERS and fluorescence interrogation techniques are combined in the same optical device.

Characterization of sub-nanosecond pulsed laser amplification with Er:Yb co-doped phosphate glass fibers.

We present an experimental characterization of the amplification of sub-nanosecond duration laser pulses at a wavelength of 1538 nm in short custom-made Er:Yb phosphate glass fibers with different core diameters. The fibers vary in their diameter from 100 µm (highly multi-mode) down to 12 µm (single-mode). The peak power, energy per pulse, and spectral shape of the amplified signal are presented. With our input pulses, the measurements show that the large core diameter fibers do not increase the amplification of the 1538 nm signal. We believe this is due to the high re-absorption of the Er3+ ions in the phosphate fiber. The optimal fiber geometry was found to have a core diameter of 20 µm with a length of 14 cm. The maximum peak power is 8.25 kW, corresponding to a net gain of 10.9 dB, with a pulse duration of 0.7 ns and a repetition rate of 40 kHz.

Impact of ZnO Addition on Er3+ Near-Infrared Emission, the Formation of Ag Nanoparticles, and the Crystallization of Sodium Fluorophosphate Glass.

The impact of the progressive addition of ZnO up to 5 mol% on the thermal, structural, and optical properties of Er3+-doped phosphate glasses within the system NaPO3-NaF-ZnO-Ag2O is discussed. The glass network was found to depolymerize upon the addition of ZnO. This promotes a slight increase in the intensity of the emission at 1.5 µm as well as enhances the silver ions clustering ability under the heat treating. The Ag-nanoparticles formed after moderate heat-treatment can further enhance the emission at 1.5 µm, whereas an excessive amount of the clusters leads to the opposite effect. The addition of ZnO helps to slightly increase the glass ability of the system. The crystallization behavior study revealed that surface crystallization is observed for all the glasses. It is found that even a small ZnO addition changes the crystalline phases formed after devitrification. Moreover, the addition of ZnO decreases the crystallization tendency of the glass.

In vivo testing of a bioresorbable phosphate-based optical fiber.

Optical fibers have recently attracted a noticeable interest for biomedical applications because they provide a minimally invasive method for in vivo sensing, imaging techniques, deep-tissue photodynamic therapy or optogenetics. The silica optical fibers are the most commonly used because they offer excellent optical properties, and they are readily available at a reasonable price. The fused silica is a biocompatible material, but it is not bioresorbable so it does not decompose in the body and the fibers must be ex-planted after in vivo use and their fragments can present a considerable risk to the patient when the fiber breaks. In contrast, optical fibers made of phosphate glasses can bring many benefits because such glasses exhibit good transparency in ultraviolet-visible and near-infrared regions, and their solubility in water can be tailored by changing the chemical composition. The bioresorbability and toxicity of phosphate glass-based optical fibers were tested in vivo on male laboratory rats for the first time. The fiber was spliced together with a standard graded-index multi-mode fiber pigtail and an optical probe for in vitro pH measurement was prepared by the immobilization of a fluorescent dye on the fiber tip by a sol-gel method to demonstrate applicability and compatibility of the fiber with common fiber optics.

Spectroscopic Properties of Er3+-Doped Particles-Containing Phosphate Glasses Fabricated Using the Direct Doping Method.

The effect of the incorporation of Er2O3-doped particles on the structural and luminescence properties of phosphate glasses was investigated. A series of different Er2O3-doped TiO2, ZnO, and ZrO2 microparticles was synthesized using soft chemistry and then added into various phosphate glasses after the melting at a lower temperature than the melting temperature. The compositional, morphological, and structural analyses of the particles-containing glasses were performed using elemental mapping by field emission-scanning electron microscopy (FE-SEM) with energy dispersive x-ray spectrometry (EDS) and x-ray diffraction (XRD). Additionally, the luminescence spectra and the lifetime values were measured to study the influence of the particles incorporation on the spectroscopic properties of the glasses. From the spectroscopic properties of the glasses with the composition 50P2O5-40SrO-10Na2O, a large amount of the Er2O3-doped particles is thought to dissolve during the glass melting. Conversely, the particles were found to survive in glasses with a composition 90NaPO3-(10 - x)Na2O-xNaF (with x = 0 and 10 mol %) due to their lower processing temperature, thus clearly showing that the direct doping method is a promising technique for the development of new active glasses.

Bioresorbable optical fiber Bragg gratings.

We demonstrate, for the first time, an inscription and wet dissolution study of Bragg gratings in a bioresorbable calcium-phosphate glass optical fiber. Bragg gratings, with average refractive index changes of 5.8×10-4, were inscribed using 193 nm excimer laser radiation. Results on the dissolution of the irradiated fiber in simulated physiological conditions are presented after immersing a tilted Bragg grating in a phosphate buffered saline solution for 56 h; selective chemical etching effects are also reported. The investigations performed pave the way toward the use of such phosphate glass fiber Bragg gratings for the development of soluble photonic sensing probes for the efficient in vivo monitoring of vital mechanical or chemical parameters.

Design, Synthesis, and Structure-Property Relationships of Er3+-Doped TiO2 Luminescent Particles Synthesized by Sol-Gel.

Titania particles doped with various concentrations of Erbium were synthesized by the sol-gel method followed by different heat treatments. The shape and the grain growth of the particles were noticeably affected by the concentration of Erbium and the heat treatment conditions. An infrared emission at 1530 nm, as well as green and red up-conversion emissions at 550 and 670 nm, were observed under excitation at 976 nm from all of the synthesized particles. The emission spectra and lifetime values appeared to be strongly influenced by the presence of the different crystalline phases. This work presents important guidelines for the synthesis of functional Er3+-doped titania particles with controlled and tailored spectroscopic properties for photonic applications.

Towards the use of bioresorbable fibers in time-domain diffuse optics.

In the last years bioresorbable materials are gaining increasing interest for building implantable optical components for medical devices. In this work we show the fabrication of bioresorbable optical fibers designed for diffuse optics applications, featuring large core diameter (up to 200 µm) and numerical aperture (0.17) to maximize the collection efficiency of diffused light. We demonstrate the suitability of bioresorbable fibers for time-domain diffuse optical spectroscopy firstly checking the intrinsic performances of the setup by acquiring the instrument response function. We then validate on phantoms the use of bioresorbable fibers by applying the MEDPHOT protocol to assess the performance of the system in measuring optical properties (namely, absorption and scattering coefficients) of homogeneous media. Further, we show an ex-vivo validation on a chicken breast by measuring the absorption and scattering spectra in the 500-1100 nm range using interstitially inserted bioresorbable fibers. This work represents a step toward a new way to look inside the body using optical fibers that can be implanted in patients. These fibers could be useful either for diagnostic (e. g. for monitoring the evolution after surgical interventions) or treatment (e. g. photodynamic therapy) purposes. Picture: Microscopy image of the 100 µm core bioresorbable fiber.

Effect of Partial Crystallization on the Structural and Luminescence Properties of Er3+-Doped Phosphate Glasses.

Er-doped phosphate glass ceramics were fabricated by melt-quenching technique followed by a heat treatment. The effect of the crystallization on the structural and luminescence properties of phosphate glasses containing Al2O3, TiO2, and ZnO was investigated. The morphological and structural properties of the glass ceramics were characterized by Field Emission-Scanning Electron Microscopy (FE-SEM), X-ray Diffraction (XRD), and micro-Raman spectroscopy. Additionally, the luminescence spectra and the lifetime values were measured in order to study the influence of the crystallization on the spectroscopic properties of the glasses. The volume ratio between the crystal and the glassy phases increased along with the duration of the heat treatment. The crystallization of the glass ceramics was confirmed by the presence of sharp peaks in the XRD patterns and different crystal phases were identified depending on the glass composition. Sr(PO3)2 crystals were found to precipitate in all the investigated glasses. As evidenced by the spectroscopic properties, the site of the Er3+ ions was not strongly affected by the heat treatment except for the fully crystallized glass ceramic which does not contain Al2O3, TiO2, and ZnO. An increase of the lifetime was also observed after the heat treatment of this glass. Therefore, we suspect that the Er3+ ions are incorporated in the precipitated crystals only in this glass ceramic.

Photonic bandgap confinement in an all-solid tellurite-glass photonic crystal fiber.

We report on the fabrication and optical assessment of an all-solid tellurite-glass photonic bandgap fiber. The manufacturing process via a preform drawing approach and the fiber characterization procedures are described and discussed. The fiber exhibits some minor morphological deformations that do not prevent the observation of optical confinement within the fiber by bandgap effects. The experimental fiber attenuation spectrum displays clear bandgap confinement regions whose positions are confirmed by modeling the guiding properties of the ideal geometry using a plane-wave expansion method. The model identifies the bound modes of the structure and provides confirmation of experimentally observed mode field profiles.

Analysis of Faraday effect in multimode tellurite glass optical fiber for magneto-optical sensing and monitoring applications.

The design and fabrication of a tellurite glass multimode optical fiber for magneto-optical applications are presented and discussed. The analysis of the polarization shows that an optical beam, linearly polarized at the fiber input, changes to elliptically polarized with an ellipticity of 1∶4.5 after propagating down the fiber. However, the elliptical distribution remains unchanged with or without an applied magnetic field, demonstrating that no circular dichroism occurs within the fiber. The Verdet constant of the tellurite glass in the fiber is measured to be 28±0.5 rad·(T·m)-1, diverging by less than 3% from the Verdet constant found on the same glass composition in bulk form. These results demonstrate the feasibility to develop reliable tellurite glass fibers by the preform drawing method for magneto-optical applications.

Multiple visible emissions by means of up-conversion process in a microstructured tellurite glass optical fiber.

We present a microstructured fiber whose 9 µm diameter core consists in three concentric rings made of three active glasses having different rare earth oxide dopants, Yb3+/Er3+, Yb3+/Tm3+ and Yb3+/Pr3+, respectively. Morphological and optical characterization of the optical fiber are presented. The photoluminescence spectrum is investigated for different pumping conditions using a commercial 980 nm laser diode. Tuning of the RGB (or white light) emission is demonstrated not only by adjusting the pump power but also by using an optical iris as spatial filter which, thanks to the microstructured core, also acts as a spectral filter.