Mechanoluminescence and Photoluminescence Heterojunction for Superior Multimode Sensing Platform of Friction, Force, Pressure, and Temperature in Fibers and 3D-Printed Polymers.

Endowing a single material with various types of luminescence, that is, exhibiting a simultaneous optical response to different stimuli, is vital in various fields. A photoluminescence (PL)- and mechanoluminescence (ML)-based multifunctional sensing platform is built by combining heterojunctioned ZnS/CaZnOS:Mn2+ mechano-photonic materials using a 3D-printing technique and fiber spinning. ML-active particles are embedded in micrometer-sized cellulose fibers for flexible optical devices capable of emitting light driven by mechanical force. Individually modified 3D-printed hard units that exhibit intense ML in response to mechanical deformation, such as impact and friction, are also fabricated. Importantly, they also allow low-pressure sensing up to ≈100 bar, a range previously inaccessible by any other optical sensing technique. Moreover, the developed optical manometer based on the PL of the materials demonstrates a superior high-pressure sensitivity of ≈6.20 nm GPa-1 . Using this sensing platform, four modes of temperature detection can be achieved: excitation-band spectral shifts, emission-band spectral shifts, bandwidth broadening, and lifetime shortening. This work supports the possibility of mass production of ML-active mechanical and optoelectronic parts integrated with scientific and industrial tools and apparatus.

Ratiometric Upconversion Temperature Sensor Based on Cellulose Fibers Modified with Yttrium Fluoride Nanoparticles.

In this study, an optical thermometer based on regenerated cellulose fibers modified with YF3: 20% Yb3+, 2% Er3+ nanoparticles was developed. The presented sensor was fabricated by introducing YF3 nanoparticles into cellulose fibers during their formation by the so-called Lyocell process using N-methylmorpholine N-oxide as a direct solvent of cellulose. Under near-infrared excitation, the applied nanoparticles exhibited thermosensitive upconversion emission, which originated from the thermally coupled levels of Er3+ ions. The combination of cellulose fibers with upconversion nanoparticles resulted in a flexible thermometer that is resistant to environmental and electromagnetic interferences and allows precise and repeatable temperature measurements in the range of 298-362 K. The obtained fibers were used to produce a fabric that was successfully applied to determine human skin temperature, demonstrating its application potential in the field of wearable health monitoring devices and providing a promising alternative to thermometers based on conductive materials that are sensitive to electromagnetic fields.

Optically active plasmonic cellulose fibers based on Au nanorods for SERS applications.

Cellulose might be a promising material for surface-enhanced Raman scattering (SERS) substrates due to its wide availability, low cost, ease of fabrication, high flexibility and low optical activity. This work shows, for the first time development of the cellulose-based substrate, that owes its SERS activity to the presence of gold nanorods in its internal structure, and not only on the surface, as it is shown elsewhere, thus ensuring superior stability of the obtained material. This flexible cellulose-based substrate exhibiting plasmonic activity, provide easy and reproducible detection of different analytes via SERS technique. The substrate was prepared by introduction of gold nanorods into the cellulose fibers matrix using an eco-friendly process based on N-Methylmorpholine-N-Oxide. Au-modified cellulose fibers were used for the detection of p-Mercaptobenzoic acid and Bovine Serum Albumin by the SERS method. The obtained results show that this substrate offers large signal enhancement of 6-orders of magnitude, and high signal reproducibility with a relative standard deviation of 8.3%. Additionally, washing tests (90 °C, 20 h) showed superior stability of the as prepared plasmonic fibers, thus proving the good reusability of the substrates and the long shelf life.

Improving performance of luminescent nanothermometers based on non-thermally and thermally coupled levels of lanthanides by modulating laser power.

This work sheds light on the pump power impact on the performance of luminescent thermometers, which is often underestimated by researchers. An up-converting, inorganic nanoluminophore, YVO4:Yb3+,Er3+ (nanothermometer) was synthesized using the hydrothermal method and a subsequent calcination. This nanomaterial appears as a white powder composed of small nanoparticles (≈20 nm), exhibiting a very intense, green upconverted luminescence (λex = 975 nm), visible to the naked eye. Its emission spectrum consists of four Er3+ bands (500-850 nm) and one Yb3+ band (>900 nm). The obtained compound exhibits temperature-dependent luminescence properties, hence it is used as an optical nanosensor of temperature. The determined band intensity ratios of the non-thermally coupled levels (non-TCLs) of Yb3+/Er3+ and thermally coupled levels (TCLs) of Er3+ are correlated with temperature, and they are used for ratiometric sensing of temperature. The effects of the pump (NIR laser) power on the luminescence properties of the material, including band intensity ratios, absolute and relative sensitivities and temperature resolution are analysed. It was pointed out that the applied laser power has a huge impact on the values of the aforementioned thermometric parameters, and manipulating the laser power can significantly improve the performance of optical nanothermometers.

Upconverting Lanthanide Fluoride Core@Shell Nanorods for Luminescent Thermometry in the First and Second Biological Windows: ß-NaYF4:Yb3+- Er3+@SiO2 Temperature Sensor.

Upconverting core@shell type ß-NaYF4:Yb3+-Er3+@SiO2 nanorods have been obtained by a two-step synthesis process, which encompasses hydrothermal and microemulsion routes. The synthesized nanomaterial forms stable aqueous colloids and exhibits a bright dual-center emission (λex = 975 nm), i.e., upconversion luminescence of Er3+ and down-shifting emission of Yb3+, located in the first (I-BW) and the second (II-BW) biological windows of the spectral range, respectively. The intensity ratios of the emission bands of Er3+ and Yb3+ observed in the vis-near-infrared (NIR) range monotonously change with temperature, i.e., the thermalized Er3+ levels (2H11/2 → 4I15/2/4S3/2 → 4I15/2) and the nonthermally coupled Yb3+/Er3+ levels (2F5/2 → 2F7/2/4I9/2 → 4I15/2 or 4F9/2 → 4I15/2). Hence, their thermal evolutions have been correlated with temperature using the Boltzmann type distribution and second-order polynomial fits for temperature-sensing purposes, i.e., Er3+ 525/545 nm (max Sr = 1.31% K-1) and Yb3+/Er3+ 1010/810 nm (1.64% K-1) or 1010/660 nm (0.96% K-1). Additionally, a fresh chicken breast was used as a tissue imitation in the performed ex vivo experiment, showing the advantage of the use of NIR Yb3+/Er3+ bands, vs. the typically used Er3+ 525/545 nm band ratio, i.e., better penetration of the luminescence signal through the tissue in the I-BW and II-BW. Such nanomaterials can be utilized as accurate and effective, broad-range vis-NIR optical, contactless sensors of temperature.

Modification of cellulose fibers with inorganic luminescent nanoparticles based on lanthanide(III) ions.

This article presents synthesis and properties of the fibers modified with luminescent, inorganic nanoparticles doped with lanthanide(III) ions, i.e. LaF3:Ce3+, Gd3+, Eu3+; CeF3:Tb3+ and CePO4:Tb3+. The fibers with luminescent properties were prepared via so called Lyocell process. This method involves dissolving cellulose in aqueous solution of N-methylmorpholine-N-oxide (NMMO) and a subsequent spinning of the fibers, using a dry-wet method. Thanks to the successful incorporation of the modifier nanoparticles (NPs) into the cellulose matrices, the fibers exhibited bright, multicolor emission upon UV irradiation and good mechanical properties, which allowed further textile processing. This type of fibers, as well as the as-prepared textiles/fabric can be used as an anti-counterfeiting agent for clothes and documents protection.

Luminescent-Magnetic Cellulose Fibers, Modified with Lanthanide-Doped Core/Shell Nanostructures.

Novel luminescent-magnetic cellulose microfibers were prepared by a dry-wet spinning method with the use of N-methylmorpholine-N-oxide. The synthesized luminescent-magnetic core/shell type nanostructures, based on the lanthanide-doped fluorides and magnetite nanoparticles (NPs)-Fe3O4/SiO2/NH2/PAA/LnF3, were used as nanomodifiers of the fibers. Thanks to the successful incorporation of the bifunctional nanomodifiers into the cellulose structure, the functionalized fibers exhibited superior properties, that is, bright multicolor emission under UV light and strong magnetic response. By the use of the as-prepared fibers, the luminescent-magnetic thread was fabricated and used to sew and make a unique pattern in the glove material, as a proof of concept for advanced, multimodal cloths'/materials' protection against counterfeiting. The presence and uniform distribution of the modifier NPs in the polymer matrix were confirmed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray analysis (EDX). The concentration of the modifier NPs in the fibers was determined by inductively coupled plasma mass spectrometry, EDX, and magnetic measurements. The luminescence characteristics of the materials were examined by photoluminescence spectroscopy, and their magnetic field-responsive behavior was investigated by a superconducting quantum interference device.