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AbstractGallium fluoride phosphate glasses feature low refractive index, high energy radiation resistance, wide transmission range, and favorable emission characteristics of rare‐earth dopants. For the development of optimized glass compositions, a fundamental understanding of these properties in terms of glass structure is sought. We report nuclear magnetic resonance (NMR) structural studies of glasses in the system xGa(PO3)3–(40 − x)GaF3–20BaF2–20ZnF2–20SrF2 (x = 5, 10, 15, 20, and 25 mol%). 31P NMR results with 71Ga recoupling show that the network structure is dominated by P–O–Ga linkages, and no P–O–P linkages exist. 71Ga NMR results show that Ga is mainly six‐coordinated featuring a mixed fluoride/phosphate coordination. Quantitative estimates of this ligand distribution around gallium were obtained by 71Ga{31P} spin echo double resonance (REDOR) measurements. Photophysical properties suggest changes in the Eu(III) ligand distribution toward a fluoride‐dominated environment at low P/F ratio while the glass network is largely sustained by bridging oxygen atoms via P–O–Ga linkages.
Oxide glasses are intrinsically brittle, lacking sufficient atomic-scale mechanisms that can relax mechanical stresses in the vicinity of a propagating crack. As a result, fracture is typically well-captured by considering local bond rupture at the crack tip. Here we demonstrate that barrier energies related to the low-temperature 𝛾-relaxation mode in alkali-aluminosilicate glasses are inversely related to the fracture toughness measured via standardized three-point bending fracture experiments. This holds true for both a series with varying cations (Li, Na, K) and one with varying Li concentration. The structural rationale for this finding is gained via Raman spectroscopy. The findings suggest that a fundamental structural relaxation mode measured on bulk specimens can serve as an effective guideline for fracture toughness of oxide glasses. Data for additional silicate glasses support this conclusion.
Infectious bacterial diseases, intensified by antibiotic resistance, cause millions of deaths annually and pose risks beyond human health, including water and food contamination. Current diagnostics are often slow, require complex equipment, and lack specificity, highlighting the need for rapid and reliable detection methods. To address this, we developed a luminescent sensor based on NaYF4 upconverting nanoparticles (UCNPs) doped with Er3+ or Tm3+, coated with COOH-PEG4-COOH, and functionalized with vancomycin (Van) or polymyxin-B (Poly) to selectively target Gram-positive and Gram-negative bacteria, respectively. Gold nanoparticles (AuNPs) served as quenchers, enabling a ratiometric “turn-on” mechanism: upon bacterial binding, the UCNP emission, initially quenched by AuNPs, was partially restored. This allowed Differentiation through changes in the green/red (G/R) ratio for Er-UCNP@PEG4-Van and the blue/red (B/R) ratio for Tm-UCNP@PEG4-Poly. The sensor distinguished between Gram-positive and Gram-negative bacteria over a wide concentration range (0.05 to 5 × 105 CFU/mL) and showed high correlation with actual bacterial counts (r = 0.99 for S. aureus, r = 0.91 for E. coli). This platform is a potential fast, selective, and reliable tool for bacterial detection in clinical and environmental settings.
Development of efficient portable sensors for accurately detecting biomarkers is crucial for early disease diagnosis, yet remains a significant challenge. To address this need, we introduce the enhanced luminescence lateral-flow assay, which leverages highly luminescent upconverting nanoparticles (UCNPs) alongside a portable reader and a smartphone app. The sensor’s efficiency and versatility were shown for kidney health monitoring as a proof of concept. We engineered Er3+- and Tm3+-doped UCNPs coated with multiple layers, including an undoped
inert matrix shell, a mesoporous silica shell, and an outer layer of
gold (UCNP@mSiO2@Au). These coatings synergistically enhance emission by over 40-fold and facilitate biomolecule conjugation, rendering UCNP@mSiO2@Au easy to use and suitable for a broad range of bioapplications. Employing these optimized nanoparticles in lateral-flow assays, we successfully detected two acute kidney injury-related biomarkers-kidney injury molecule-1 (KIM-1) and neutrophil gelatinase-associated lipocalin (NGAL)-in urine samples. Using our sensor platform, KIM-1 and NGAL can be accurately detected and quantified
within the range of 0.1 to 20 ng/mL, boasting impressively low limits of detection at 0.28 and 0.23 ng/mL, respectively. Validating our approach, we analyzed clinical urine samples, achieving biomarker concentrations that closely correlated with results obtained via ELISA. Importantly, our system enables biomarker quantification in less than 15 min, underscoring the performance of our novel UCNP-based approach and its potential as reliable, rapid, and user-friendly diagnostics.
The development of new glasses is often hampered by inefficient trial‐and‐error approaches. The traditional glass manufacturing process is not only time‐consuming, but also difficult to reproduce with inevitable variations in process parameters. These challenges are addressed by implementing an ontology‐based digital infrastructure coupled with a robotic melting system. This system facilitates high‐throughput glass synthesis and ensures the collection of consistent process data. In addition, the digital infrastructure includes machine learning models for predicting glass properties and a tool for extracting patent information. Current glass databases have significant gaps in the relationships between compositions, process parameters, and properties due to inconsistent studies and nonconforming units. In addition, process parameters are often omitted, and even original literature references provide limited information. By continuously expanding the database with consistent, high‐quality data, it is aimed to fill these gaps and accelerate the glass development process.
Ratiometric optical sensors, which provide real-time measurements by comparing the intensities of two spectrally separated emission bands, are highly effective for monitoring oxygen levels. By combining oxygen-independent and oxygensensitive emission characteristics, they offer accurate quantification, distinguishing them from other sensor types. In this work, we designed a ratiometric optical sensor concept based on a biscyclometalated platinum(II) complex coupled with an organic naphthalonitrile-based fluorophore and incorporated it into mesoporous silica nanoparticles. This encapsulation strategy significantly improved the stability and water-dispersibility of the otherwise hydrophobic coordination compound while preventing aggregation and enhancing its photophysical properties. Both the free molecule and its nanoparticle-encapsulated form were characterized, revealing high sensitivity to oxygen variations with the unique feature of self-referenced ratiometric readout. The sensor’s response was effectively measured at the single-particle level using photoluminescence microscopy, providing temporally and spatially resolved oxygen readouts. The versatility of the system was demonstrated across different experimental setups, including suspensions, solids, and agarose-embedded forms, highlighting is adaptability to a wide range of applications. This system holds significant promise for advanced oxygen monitoring, offering a reliable tool for high-resolution detection in complex environments with multiple orthogonal readouts.
Gallium fluoride–phosphate glasses are promising materials with wide optical transmission window, high volumetric density, and the ability to accommodate high concentrations of rare earth dopant ions within a tailored fluoride-rich coordination environment, resulting in high emission cross sections. In this work, the compositional system 25Ga(PO3)3–20ZnF2–30BaF2–(25–x–y)SrF2–xAgNO3–yNdF3 (x = 0–10 mol%, y = 0 or 1 mol%) was studied to understand how silver species affect the near-infrared (NIR) emission of Nd3+ ions, when the glasses are subjected to controlled heat treatment and to femtosecond direct laser writing (DLW). The glasses were obtained via the melt-quenching technique and characterized by DSC, XRD, UV-Vis-NIR absorption, and PL spectroscopy. The as-prepared glasses show broad UV-Vis excitation and emission bands arising from the coexistence of Ag+ ions and ionic Ag pairs. In samples with 10 mol% Ag+, brownish coloration and modified emission profiles indicated Ag nanoparticle formation at the surface. Heat treatment promoted the conversion of isolated Ag+ into ionic pairs, producing broadband emissions tunable by excitation wavelength and Ag+ concentration. In co-doped samples, Nd3+ introduced absorption dips in the Ag-related UV-Vis bands, consistent with energy transfer, which was further confirmed by shortened Ag excited-state lifetimes and increased Nd3+ NIR emission under UVVis excitation. In order to control the spatial distribution and size of Ag aggregates (nanoclusters, NCs) and to increase the energy transfer efficiency to Nd3+, femtosecond direct laser writing (DLW) was employed to co-doped glasses with 3 and 5 mol% Ag+. This approach enabled three-dimensional localized growth of Ag NCs with sub-micron spatial control. In the laser processed regions, the NIR emissions of Nd3+ at 900 and 1060 nm were significantly enhanced, clearly evidencing enhanced energy transfer from the localized laserinduced Ag-NCs to the Nd3+ ions. These findings suggest the possibility of tailoring high optical contrast near-IR emissions in glasses, enabling progress in advanced photonic applications.
We introduce a novel technique for coherent control that employs resonant internally generated fields in CdTe quantum dot (QD) thin films at the L-point. The bulk band gap of CdTe at the L-point amounts to 3.6 eV, with the transition marked by strong Coulomb coupling. Third harmonic generation (λ3 = 343 nm, hν = 3.61 eV) for a fundamental wavelength of λ 1 = 1,030 nm is used to control quantum interference of three-photon resonant paths between the valence and conduction bands. Different thicknesses of the CdTe QDs are used to manipulate the phase relationship between the external fundamental and the internally generated third harmonic, resulting in either suppression or strong enhancement of the resonant third harmonic, while the nonresonant components remain nearly constant. This development could pave the way for new quantum interference–based applications in ultrafast switching of nanophotonic devices.