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.

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.

New ZnO-Based Glass Ceramic Sensor for H2 and NO2 Detection.

In this study, a glass ceramic with a nominal composition 58ZnO:4Bi2O3:4WO3:33.3B2O3 was synthesized by melt quenching technique. A gas sensor was then manufactured using a ZnO sol-gel phase as a permanent binder of the glass-ceramic to an alumina substrate having interdigitated electrodes. The film sensitivity towards humidity, NH3, H2 and NO2 was studied at different temperatures. X-ray diffraction technique (XRD), field emission- scanning electron microscopy (FE-SEM) and differential thermal analysis (DTA) were used to characterize the prepared material. Though the response in the sub-ppm NO2 concentration range was not explored, the observed results are comparable with the latest found in the literature.

Formation Mechanism of Elemental Te Produced in Tellurite Glass Systems by Femtosecond Laser Irradiation.

The formation of elemental trigonal tellurium (t-Te) on tellurite glass surfaces exposed to femtosecond laser pulses is discussed. Specifically, the underlying elemental crystallization phenomenon is investigated by altering laser parameters in common tellurite glass compositions under various ambient conditions. Elemental crystallization of t-Te by a single femtosecond laser pulse is unveiled by high-resolution imaging and analysis. The thermal diffusion model reveals the absence of lattice melting upon a single laser pulse, highlighting the complexity of the phase transformation. The typical cross-section displays three different crystal configurations over its depth, in which the overall thickness increases with each subsequent pulse. The effect of various controlled atmospheres shows the suppressing nature of the elemental crystallization, whereas the substrate temperature shows no significant impact on the nucleation of t-Te nanocrystals. This research gives new insight into the elemental crystallization of glass upon femtosecond laser irradiation and shows the potential to fabricate functional transparent electronic micro/nanodevices.

Effect of Low Copper Doping on the Optical, Cytocompatible, Antibacterial, and SARS-CoV-2 Trapping Properties of Calcium Phosphate Glasses.

Calcium phosphate glasses (CPGs) are acquiring great importance in the biomedical field because of their thermomechanical and bioresorbable properties. In this study, optically transparent copper (1 mol %)-doped calcium phosphate glasses (CPGs_Cu) were prepared through the melt-quenching method, and their biocompatibility and antibacterial and antiviral properties were evaluated and compared with undoped CPGs. Biocompatibility was evaluated on murine fibroblast NIH-3T3 cells as a preliminary study of cytocompatibility. The in vitro tests were performed through indirect and direct cytotoxicity analyses by MTT and Alamar Blue assays and supported by electron microscopy observations. Microbiological analyses were performed against the most common Gram-negative and Gram-positive pathogens that cause nosocomial infections: Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae, Staphylococcus aureus, and the methicillin-resistant Staphylococcus aureus strain. In addition, the bioglass samples were exposed to SARS-CoV-2 to assess their effects on viral survival. The obtained results assessed the biocompatibility of both bioglass types and their ability to reduce the viral load and trap the virus. In addition, Cu2+-doped bioglass was found to be antibacterial despite its low content (1 mol %) of copper, making this a promising candidate material for biomedical applications, e.g., surgery probes, drug delivery, and photodynamic therapy.

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.

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.

"Re-engineering of a food oven for thermal sanitization of Personal Protective Equipment against Sars-CoV-2 virus".

One of the main issues addressed by the recent COVID-19 pandemic which affected the whole world is the availability of Personal Protective Equipment (PPE) (e.g., face masks, white coats, or disposable gloves). This issue impacts on sustainability from different perspectives, such as more generated waste or environmental pollution, both for manufacturing and disposal, or more inequalities deriving from who can afford and access PPE and who cannot, since many shortages were recorded during the pandemic as well as fluctuating unit prices. Moreover, quite often PPE intended for single use are improperly used more times, thus generating a biological risk of infection. In an attempt to propose an innovative solution to face this problem, in this paper the re-design of an oven originally intended for food purposes is presented, with the aim of operating a thermal sanitization of PPE. The machinery and its components are detailed, together with physical and microbiological tests performed on non-woven PPE to assess the effect of treatment on mechanical properties and viral load. The pilot machinery turned out to be effective in destroying a bovine coronavirus at 95 °C and thus reducing contaminating risk in one hour without compromising the main properties of PPE, opening perspectives for the commercialization of the solution in the near future.

Flexible PBAT-Based Composite Filaments for Tunable FDM 3D Printing.

Biobased composites with peculiar properties offer an attractive route for producing environmentally friendly materials. The reinforcement for poly(butylene adipate-co-terephthalate) (PBAT), based on zein-titanium dioxide (TiO2) complex (ZTC) microparticles, is presented and used to produce composite filaments, successfully 3-dimensionally (3D) printed by fused deposition modeling (FDM). The outcome of ZTC addition, ranging from 5 to 40 wt %, on the thermo-mechanical properties of composite materials was analyzed. Results reveal that storage modulus increased with increasing the ZTC content, leading to a slight increase in the glass transition temperature. The creep compliance varies with the ZTC concentration, denoting a better resistance to deformation under constant stress conditions for composites with higher complex content. Scanning electron microscopy was used to assess the quality of interphase adhesion between PBAT and ZTC, showing good dispersion and distribution of complex microparticles in the polymer matrix. Infrared spectroscopy confirmed the formation of a valid interface due to the formation of hydrogen bonds between filler and polymer matrix. Preliminary tests on the biocompatibility of these materials were also performed, showing no cytotoxic effects on cell viability. Finally, the 3D printability of biobased composites was demonstrated by realizing complex structures with a commercial FDM printer.

Novel approach towards cross-relaxation energy transfer calculation applied on highly thulium doped tellurite glasses.

In this paper we calculated, for the first time to the best of our knowledge, the cross relaxation parameter of Tm(3+) ions in tellurite glasses over a wide range of concentrations: from 0.36 mol% up to 10 mol%. A new measurement approach based on emission spectra monitoring is proposed. This method is very simple and allows to measure even very highly doped samples. The obtained values of cross-relaxation parameter show a linear dependence with respect to dopant concentration over the full investigated interval, suggesting a dipole-dipole interaction process. The measured slope is 1.81x10(-17) cm(3) s(-1) mol%(-1).

Temporal evolution and correlation between cooperative luminescence and photodarkening in ytterbium doped silica fibers.

The present work describes photodarkening from the viewpoint of cooperative luminescence. The temporal evolution of both effects was measured simultaneously by means of ytterbium doped aluminosilicate fibers for concentrations up to 1.8 wt% Yb3+. The quadratic dependence of photodarkening and cooperative luminescence versus dopant concentration was observed. The change in the photodarkening and cooperative luminescence mutual dynamics for highly and low doped fibers is ascribed to a different ion number which forms the cluster. Cooperative luminescence is proved to be a natural probe for photodarkening since it provides new pieces of information and contributes to the photodarkening mechanism description.

Concentration dependence and self-similarity of photodarkening losses induced in Yb-doped fibers by comparable excitation.

We report on an extensive investigation of photodarkening in Yb-doped silica fibers. A set of similar fibers, covering a large Yb concentration range, was made so as to compare the photodarkening induced losses. Careful measurements were made to ensure equal and uniform inversion for all the tested fibers. The results show that, with the specific set-up, the stretching parameter obtained through fitting has a very limited variation. This gives more meaning to the fitting parameters. Results tend to indicate a square law dependence of the concentration of excited ions on the final saturated loss. We also demonstrate self-similarity of loss evolution when experimental curves are simply normalized to fitting parameters. This evidence of self-similarity also supports the possibility of introducing a preliminary figure of merit for Yb-doped fiber. This will allow the impact of photodarkening on laser/amplifier devices to be evaluated.

Design and Manufacturing of a Nd-Doped Phosphate Glass-Based Jewel.

This paper reports the results of the designing, manufacturing and characterization of a jewel obtained by means of coupling the dogmas of industrial design to the analytical engineering approach. The key role in the design of the jewel was played by an in-house synthesized Neodymium (Nd)-doped phosphate glass, selected due to its easy handling and capability to change color according to the incident light wavelength. The glass core was covered by a metal alloy to mitigate its relatively high fragility and sensitivity to thermal shock and, at the same time, to highlight and preserve its beauty. The selection of the proper metal alloy, having thermo-mechanical properties compatible with those exhibited by the glass, was carried out by means of Ashby's maps, a powerful tool commonly adopted in the field of industrial design.

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.

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.

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.