Near-Infrared Dual-Modal Sensing of Force and Temperature in Total Knee Replacement Using Mechanoluminescent Phosphor of Sr3Sn2O7: Nd, Yb.

Knee replacement surgery confronts challenges including patient dissatisfaction and the necessity for secondary procedures. A key requirement lies in dual-modal measurement of force and temperature of artificial joints during postoperative monitoring. Here, a novel non-toxic near-infrared (NIR) phosphor Sr3Sn2O7:Nd, Yb, is designed to realize the dual-modal measurement. The strategy is to entail phonon-assisted upconversion luminescence (UCL) and trap-controlled mechanoluminescence (ML) in a single phosphor well within the NIR biological transmission window. The phosphor is embedded in medical bone cement forming a smart joint in total knee replacements illustrated as a proof-of-concept. The sensing device can be charged in vitro by a commercial X-ray source with a safe dose rate for ML, and excited by a low power 980 nm laser for UCL. It attains impressive force and temperature sensing capabilities, exhibiting a force resolution of 0.5% per 10 N, force detection threshold of 15 N, and a relative temperature sensitive of up to 1.3% K-1 at 309 K. The stability against humidity and thermal shock together with the robustness of the device are attested. This work introduces a novel methodological paradigm, paving the way for innovative research to enhance the functionality of artificial tissues and joints in living organisms.

In vivo biological safety investigation of Yb-CALGO femtosecond laser dental surgery.

While lasers have found their successful applications in various clinical specialties, in clinical dental practice, traditional mechanical drills are still predominantly utilized. Although erbium-doped lasers have been demonstrated for dental therapy, their clinical performance is still not satisfactory due to the long pulse width, low peak power, and small repetition rate. To attain a smaller thermal diffusion thus better biological safety and surgical precision, as well as more rapid ablation, the advancement of femtosecond laser techniques has opened another route of dental surgery; however, no biological safety investigation has been reported. Here, we present a systematic study of dental ablation by a Yb:CaAlGdO4 regenerative amplifier with a central wavelength of 1040 nm and pulse width of 160 fs. The in vivo experiment of dental surgery investigating the inflammatory response has been reported, for the first time to the best of our knowledge. It is demonstrated that dental surgery by Yb:CaAlGdO4 femtosecond laser ablation has better biological safety compared to the turbine drilling, thanks to its non-contact and ultrafast heat dissipation nature.

Brachytherapy at the nanoscale with protein functionalized and intrinsically radiolabeled [169Yb]Yb2O3 nanoseeds.

PURPOSE: Classical brachytherapy of solid malignant tumors is an invasive procedure which often results in an uneven dose distribution, while requiring surgical removal of sealed radioactive seed sources after a certain period of time. To circumvent these issues, we report the synthesis of intrinsically radiolabeled and gum Arabic glycoprotein functionalized [169Yb]Yb2O3 nanoseeds as a novel nanoscale brachytherapy agent, which could directly be administered via intratumoral injection for tumor therapy. METHODS: 169Yb (T½ = 32 days) was produced by neutron irradiation of enriched (15.2% in 168Yb) Yb2O3 target in a nuclear reactor, radiochemically converted to [169Yb]YbCl3 and used for nanoparticle (NP) synthesis. Intrinsically radiolabeled NP were synthesized by controlled hydrolysis of Yb3+ ions in gum Arabic glycoprotein medium. In vivo SPECT/CT imaging, autoradiography, and biodistribution studies were performed after intratumoral injection of radiolabeled NP in B16F10 tumor bearing C57BL/6 mice. Systematic tumor regression studies and histopathological analyses were performed to demonstrate therapeutic efficacy in the same mice model. RESULTS: The nanoformulation was a clear solution having high colloidal and radiochemical stability. Uniform distribution and retention of the radiolabeled nanoformulation in the tumor mass were observed via SPECT/CT imaging and autoradiography studies. In a tumor regression study, tumor growth was significantly arrested with different doses of radiolabeled NP compared to the control and the best treatment effect was observed with ~ 27.8 MBq dose. In histopathological analysis, loss of mitotic cells was apparent in tumor tissue of treated groups, whereas no significant damage in kidney, lungs, and liver tissue morphology was observed. CONCLUSIONS: These results hold promise for nanoscale brachytherapy to become a clinically practical treatment modality for unresectable solid cancers.

On-chip erbium-ytterbium-co-doped lithium niobate microdisk laser with an ultralow threshold.

Erbium-ion-doped lithium niobate (LN) microcavity lasers working in the communication band have attracted extensive attention recently. However, their conversion efficiencies and laser thresholds still have significant room to improve. Here, we prepared microdisk cavities based on erbium-ytterbium-co-doped LN thin film by using ultraviolet lithography, argon ion etching, and a chemical-mechanical polishing process. Benefiting from the erbium-ytterbium co-doping-induced gain coefficient improvement, laser emission with an ultralow threshold (∼1 µW) and high conversion efficiency (1.8 × 10-3%) was observed in the fabricated microdisks under a 980-nm-band optical pump. This study provides an effective reference for improving the performance of LN thin-film lasers.

Ultralow-quantum-defect single-frequency fiber laser.

A single-frequency distributed-Bragg-reflector fiber laser at 980 nm with a quantum defect of less than 0.6% was developed with a 1.5-cm 12 wt% ytterbium-doped phosphate fiber pumped by a 974.5-nm laser diode. Linearly polarized single-longitude-mode laser with a polarization extinction ratio (PER) of nearly 30 dB and spectral linewidth of less than 1.8 kHz was obtained. A maximum output power of 275 mW was measured at a launched pump power of 620 mW. The performance of the single-frequency fiber laser pumped at 909 nm and 976 nm was also characterized. This research demonstrated an approach to high-power single-frequency fiber laser oscillators with mitigated thermal effects.

Domino synthesis of 5-aminoimidazoles from Strecker multicomponent adducts via ytterbium-promoted isocyanide insertion/5-exo-dig cyclization.

A new Lewis acid promoted domino isocyanide insertion/5-exo-dig cyclization of readily available Strecker 3-component adducts to 4-substituted 5-aminoimidazole derivatives is herein reported. Despite their potential as relevant heterocyclic scaffolds in medicinal chemistry programs, this class of compounds is still underrepresented, with current synthetic strategies poorly efficient in terms of timing and yields. To this end, we show how the exploitation of unconventional reactivities of isocyanides, promoted by ytterbium-triflate, could represent a key resource to enable a fast and easy access to such an unexplored area of the chemical space.

A Linearly Polarized Wavelength-Tunable Q-Switched Fiber Laser with a Narrow Spectral Bandwidth of 112 MHz.

A tunable and narrow-bandwidth Q-switched ytterbium-doped fiber (YDF) laser is investigated in this paper. The non-pumped YDF acts as a saturable absorber and, together with a Sagnac loop mirror, provides a dynamic spectral-filtering grating to achieve a narrow-linewidth Q-switched output. By adjusting an etalon-based tunable fiber filter, a tunable wavelength from 1027 nm to 1033 nm is obtained. When the pump power is 1.75 W, the Q-switched laser pulses with a pulse energy of 10.45 nJ, and a repetition frequency of 11.98 kHz and spectral linewidth of 112 MHz are obtained. This work paves the way for the generation narrow-linewidth Q-switched lasers with tunable wavelengths in conventional ytterbium, erbium, and thulium fiber bands to address critical applications such as coherent detection, biomedicine, and nonlinear frequency conversion.

A Novel Near-Infrared Ytterbium Complex [Yb(DPPDA)2](DIPEA) with Φ = 0.46% and τobs = 105 µs.

The luminescent performances of near-infrared (NIR) lanthanide (Ln) complexes were restricted greatly by vibration quenching of X-H (X = C, N, O) oscillators, which are usually contained in ligands and solvents. Encapsulating Ln3+ into a cavity of coordination atoms is a feasible method of alleviating this quenching effect. In this work, a novel ytterbium complex [Yb(DPPDA)2](DIPEA) coordinated with 4,7-diphenyl-1,10-phenanthroline-2,9-dicarboxylic acid (DPPDA) was synthesized and characterized by FT-IR, ESI-MS and elemental analysis. Under the excitation of 335 nm light, [Yb(DPPDA)2](DIPEA) showed two emission peaks at 975 and 1011 nm, respectively, which were assigned to the characteristic 2F5/2 → 2F7/2 transition of Yb3+. Meanwhile, this ytterbium complex exhibited a plausible absolute quantum yield of 0.46% and a luminescent lifetime of 105 µs in CD3OD solution. In particular, its intrinsic quantum yield was calculated to be 12.5%, and this considerably high value was attributed to the near-zero solvent molecules bound to Yb3+ and the absence of X-H oscillators in the first coordination sphere. Based on experimental results, we further proposed that the sensitized luminescence of [Yb(DPPDA)2](DIPEA) occurred via an internal redox mechanism instead of an energy transfer process.

Upconversion in a d-f [RuYb3] Supramolecular Assembly.

We have prepared a hetero-tetrametallic assembly consisting of three ytterbium ions coordinated to a central [Ru(bpm)3]2+ (bpm = 2,2'-bipyrimidine) motif. Irradiation into the absorption band of the peripheral ytterbium ions at 980 nm engenders emission of the 3MLCT state of the central [Ru(bpm)3]2+ core at 636 nm, which represents the first example of f → d molecular upconversion (UC). Time-resolved measurements reveal a slow rise of the UC emission, which was modeled with a mathematical treatment of the observed kinetics according to a cooperative photosensitization mechanism using a virtual Yb centered doubly excited state followed by energy transfer to the Ru centered 1MLCT state.

Strong Circularly Polarized Luminescence at 1550 nm from Enantiopure Molecular Erbium Complexes.

Circularly polarized luminescence (CPL) in two subregions of the near-infrared (NIR) has been achieved. By leveraging the rigidity and diminishing detrimental vibrations of the heterobimetallic binolate complexes of erbium [(Binol)3ErNa3], species exhibiting an exceptionally high dissymmetry factor (|glum |) of 0.47 at 1550 nm were obtained. These erbium complexes are the first reported examples of CPL observed beyond 1200 nm. Analogous complexes of ytterbium and neodymium also exhibited strong CPL (|glum| = 0.17, 0.05, respectively) in a higher energy NIR window (800-1200 nm). All complexes exhibit high quantum yields (Er: 0.58%, Yb: 17%, Nd: 9.3%) and high BCPL values (Er: 57 M-1 cm-1, Yb: 379 M-1 cm-1, Nd: 29 M-1 cm-1). Because of their strong CPL emission in the telecom band (1550 nm), biologically relevant NIR emission window (800-1100 nm), and synthetic versatility, the complexes reported here could permit further promising developments in quantum communication technologies and biologically relevant sensors.

Determination of the Isotopic Composition of Ytterbium by MC-ICP-MS Using an Optimized Regression Model.

In this study, we measure the absolute isotope ratios of ytterbium (Yb) by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) using an optimized regression model for mass bias correction. A rhenium (Re) reference material (NIST SRM 3143), which has been characterized previously, is selected as a primary calibrator to calibrate the absolute Yb isotope ratios for three Yb materials (GSB, Alfa Yb, and GBW). The three-isotope plot for all collected data indicates that the results of Yb isotope ratios obtained are not affected by any polyatomic interferences and the mass-independent isotopic fractionation. Furthermore, the recalibrated Hf historical isotope ratios by using the absolute Yb isotopic composition obtained in this study for the isobaric interference correction on Hf isotopes are in agreement with the original historical values. This work has further demonstrated the applicability of the regression model for the calibrated measurements of absolute isotope ratios using MC-ICP-MS. The three mono-elemental Yb standard solutions are thus proposed as the reference materials for Yb isotope ratio measurements in environmental and geoscience applications.

Quantification of the Activator and Sensitizer Ion Distributions in NaYF4 :Yb3+ , Er3+ Upconverting Nanoparticles Via Depth-Profiling with Tender X-Ray Photoemission.

The spatial distribution and concentration of lanthanide activator and sensitizer dopant ions are of key importance for the luminescence color and efficiency of upconverting nanoparticles (UCNPs). Quantifying dopant ion distributions and intermixing, and correlating them with synthesis methods require suitable analytical techniques. Here, X-ray photoelectron spectroscopy depth-profiling with tender X-rays (2000-6000 eV), providing probe depths ideally matched to UCNP sizes, is used to measure the depth-dependent concentration ratios of Er3+ to Yb3+ , [Er3+ ]/[Yb3+ ], in three types of UCNPs prepared using different reagents and synthesis methods. This is combined with data simulations and inductively coupled plasma-optical emission spectroscopy (ICP-OES) measurements of the lanthanide ion concentrations to construct models of the UCNPs' dopant ion distributions. The UCNP sizes and architectures are chosen to demonstrate the potential of this approach. Core-only UCNPs synthesized with XCl3 ·6H2 O precursors (ß-phase) exhibit a homogeneous distribution of lanthanide ions, but a slightly surface-enhanced [Er3+ ]/[Yb3+ ] is observed for UCNPs prepared with trifluroacetate precursors (α-phase). Examination of Yb-core@Er-shell UCNPs reveals a co-doped, intermixed region between the single-doped core and shell. The impact of these different dopant ion distributions on the UCNP's optical properties is discussed to highlight their importance for UCNP functionality and the design of efficient UCNPs.

Fingerprint multiplex CARS at high speed based on supercontinuum generation in bulk media and deep learning spectral denoising.

We introduce a broadband coherent anti-Stokes Raman scattering (CARS) microscope based on a 2-MHz repetition rate ytterbium laser generating 1035-nm high-energy (≈µJ level) femtosecond pulses. These features of the driving laser allow producing broadband red-shifted Stokes pulses, covering the whole fingerprint region (400-1800 cm-1), employing supercontinuum generation in a bulk crystal. Our system reaches state-of-the-art acquisition speed (<1 ms/pixel) and unprecedented sensitivity of ≈14.1 mmol/L when detecting dimethyl sulfoxide in water. To further improve the performance of the system and to enhance the signal-to-noise ratio of the CARS spectra, we designed a convolutional neural network for spectral denoising, coupled with a post-processing pipeline to distinguish different chemical species of biological tissues.

Standoff CARS spectroscopy and imaging using an ytterbium-based laser system.

A laser system for standoff coherent anti-Stokes Raman scattering (CARS) spectroscopy of various materials under ambient light conditions is presented. The system is based on an ytterbium laser and an ultrafast optical parametric amplifier for the generation of a broadband pump tunable from 880 to 930 nm, a Stokes at 1025 nm, and a narrowband probe at 512.5 nm. High-resolution Raman spectra encompassing the fingerprint region (400-1800 cm-1) are obtained in 5 ms for toluene, and 100 ms for two types of sugars, glucose and fructose, at a distance of 1 m. As a demonstration of the potential of the setup, hyperspectral images of a 2×2-cm2 target area are collected for a toluene cuvette and a glucose/fructose pressed disk. Our approach is suitable for implementation of a portable system for standoff CARS imaging of chemical and biological materials.

Enhancement of the NIR Emission of Cr3+-Yb3+ Co-doped La3GaGe5O16 Phosphors by Doping Nd3+ Ions via Efficient Energy Transfer for NIR Spectroscopy Regulation.

The efficient energy transfer in La3GaGe5O16:Cr3+, Yb3+/Nd3+ and La3GaGe5O16:Cr3+, Yb3+, Nd3+ was investigated in detail. In this phosphor, Cr3+ acts as the energy absorber (250-700 nm) to sensitize Yb3+/Nd3+ in La3GaGe5O16. Under excitation at 418 nm, La3GaGe5O16:Cr3+, Yb3+ phosphors exhibited a broad emission band in the near-infrared (NIR) region located at 976 nm (La3GaGe5O16:Cr3+, Nd3+ at 1056 nm), which was attributed to the 2F5/2-2F7/2 transition of the Yb3+ ions (2F3/2 → 4I11/2 transition of Nd3+). Moreover, a Nd3+ ion was introduced into La3GaGe5O16:Cr3+, Yb3+. The analysis of excitation spectra and decay time proves that Nd3+ acts as a bridging ion in the system. This can be used as a new strategy to enhance the energy transfer in Cr3+, Yb3+ co-doped phosphors, and these phosphors have potential applications in NIR spectroscopy regulation.

Manipulating Upconversion Emission and Thermochromic Properties of Ho3+/Yb3+-Codoped Al2Mo3O12 Microparticles by Negative Lattice Expansion for Multimode Visual Optical Thermometry.

To ameliorate the inherent thermal quenching behaviors of upconverting materials, a series of Ho3+/Yb3+-codoped Al2Mo3O12 (i.e., Al2Mo3O12:Ho3+/2xYb3+) microparticles were developed. Upon excitation at 980 nm, intense upconversion (i.e., UC) emissions arising from Ho3+ are observed, and their optimal states occur at x = 0.09. Besides, the UC mechanisms of these generated emissions from 5F4/5S2 and 5F5 levels all pertain to a two-photon absorption process. Furthermore, modified thermal quenching performances are realized in the resultant microparticles, in which the intensities of the UC emissions arising from 5F4/5S2 levels decrease as the temperature increases, while that of the UC emission from the 5F5 level increases and then decreases with the increase of temperature. The coexistence of nonradiative transition promoted crossrelaxation, and energy transfer routes can be responsible for the above phenomenon. By studying the diverse UC emission characteristics at high temperatures, we revealed the thermometric properties of Al2Mo3O12:Ho3+/2xYb3+ microparticles, where their sensitivities can be regulated by selecting the spectral mode and dopant contents. According to the intensity ratio of the UC emissions originating from 5F5 → 5I8 to (5F4,5S2) → 5I7 transitions at different temperatures, one obtains that the relative and absolute sensitivities of the developed compounds reach up to 0.464% and 0.1739 K-1, respectively. Additionally, by the analysis of the thermochromic performances of final products, their thermometric characteristics were also investigated. Note that the environmental temperature is able to be facilely read out by distinguishing the emitting color. These results verify that the Al2Mo3O12:Ho3+/2xYb3+ microparticles are promising luminescent materials for multimode visual optical thermometry.

Construction of a Near-Infrared Luminescent 48-Metal Rectangular Zn(II)-Yb(III) Nanocluster with Carbonate Templates for the Dual-Emissive Detection of Rutin as a Medicinal Ingredient.

An interesting 48-metal Zn(II)-Yb(III) nanocluster (1) with a size of about 1.3 × 2.8 × 3.1 nm was constructed by carbonate templates from a Schiff base ligand. It exhibits ligand-centered emission and near-infrared (NIR) luminescence of Yb(III), which are used in the dual-emissive detection of rutin (Rut) with high sensitivity even in the presence of other interferences. The response behavior can be expressed by the second-order equation I980 nm/I510 nm = A*[Rut]2 + B*[Rut] + C, and the limits of detection to Rut for the emissions of 1 are 2.23 µM and 0.20 nM.

Ex vivo interaction study of NaYF4 :Yb,Er nanophosphors with isolated mitochondria.

Ex vivo interaction of NaYF4 :Yb,Er nanophosphors with isolated mitochondria has been investigated. The nanophosphors were synthesized using the hydrothermal method. The synthesized NaYF4 :Yb,Er nanophosphors were characterized for physicochemical properties. The NaYF4 :Yb,Er nanophosphors showed successful upconversion with excitation wavelength lying in the near-infrared region. The effect of synthesized NaYF4 :Yb,Er nanophosphors on mitochondria isolated from the chicken heart tissue was examined through ROS generation capacity, membrane fluidity, and complex II activity. The exposer of NaYF4 :Yb,Er nanophosphors to isolated mitochondria inhibits ROS generation activity as compared to control. The mitochondria membrane fluidity of the lipid bilayer and complex-II activity of mitochondria was observed to be unaltered after the interaction with NaYF4 :Yb,Er nanoparticles. The results confirm that synthesized NaYF4 :Yb,Er nanoparticles can be used as a safe contrast agent.

Divergence of the quadrupole-strain susceptibility of the electronic nematic system YbRu2Ge2.

Ferroquadrupole order associated with local [Formula: see text] atomic orbitals of rare-earth ions is a realization of electronic nematic order. However, there are relatively few examples of intermetallic materials which exhibit continuous ferroquadrupole phase transitions, motivating the search for additional materials that fall into this category. Furthermore, it is not clear a priori whether experimental approaches based on transport measurements which have been successfully used to probe the nematic susceptibility in materials such as the Fe-based superconductors will be as effective in the case of [Formula: see text] intermetallic materials, for which the important electronic degrees of freedom are local rather than itinerant and are consequently less strongly coupled to the charge-carrying quasiparticles near the Fermi energy. In the present work, we demonstrate that the intermetallic compound [Formula: see text] exhibits a tetragonal-to-orthorhombic phase transition consistent with ferroquadrupole order of the Yb ions and go on to show that elastoresistivity measurements can indeed provide a clear window on the diverging nematic susceptibility in this system. This material provides an arena in which to study the causes and consequences of electronic nematicity.

Toxicity of lanthanides on various fish cell lines.

The growing use of Lanthanides in new technologies has increased their anthropogenic releases into the aquatic environment over the last decades. However, knowledge on their ecotoxicological impacts is still incomplete, especially with regard to biological effects of Lanthanides mixtures and the possible regular variation in toxicity along the Lanthanides series. The present study evaluated the individual toxicity of all Lanthanides and the toxicity of mixtures of three of them, namely Neodymium (Nd3+), Gadolinium (Gd3+), and Ytterbium (Yb3+) on Danio rerio fibroblast-like cells (ZF4). Individual and mixtures toxicity of Neodymium (Nd3+) and Ytterbium (Yb3+) were also assessed on Danio rerio hepatic cells (ZFL) and Oncorhynchus mykiss epithelial cells (RTgill-W1). The measured Lanthanide concentrations were close to the nominal ones in the culture media of ZF4, ZFL, and RTgill-W1 cells (85-99%). A toxic impact was observed on the three fish cell lines exposed to all Lanthanides tested individually. RTgill-W1 appeared as the less sensitive cells, compared to the two others. Four Lanthanides, Erbium (Er3+), Thulium (Tm3+), Ytterbium (Yb3+) and Lutetium (Lu3+) showed a higher toxicity than the others on ZF4 cells but no correlation could be established between the toxicity of Lanthanides and the order of the elements within the Lanthanides series. Exposures to binary mixtures highlighted the presence of synergistic effects on cell viability for all cell lines.