Near-infrared Excitation Research Articles

Elucidation of the Effect of Solar Light on the Near-Infrared Excitation Raman Spectroscopy-Based Analysis of Fabric Dyes

Elucidation of the Effect of Solar Light on the Near-Infrared Excitation Raman Spectroscopy-Based Analysis of Fabric Dyes

Fluence-Dependent Photoinduced Charge Transfer Dynamics in Polymer-Wrapped Semiconducting Single-Walled Carbon Nanotubes.

Because an individual single-walled carbon nanotube (SWNT) can absorb multiple photons, the exciton density within a single tube depends upon excitation conditions. In SWNT-based energy conversion systems, interactions between excitons and charges make it possible for multiple types of charge transfer reactions. We exploit a SWNT-molecular donor-acceptor hybrid system (R-PBN(b)-Ph6-PDI-[(6,5) SWNT]) that fixes spatial organization and stoichiometry of perylene diimide (PDI) electron acceptors on the nanotube surface, to elucidate how excitation fluence affects ultrafast charge separation (CS) and the nature of charge recombination (CR) dynamics triggered upon SWNT near-infrared excitation. Pump-probe data characterizing these photoinduced CS and thermal CR reactions were acquired over excitation fluences that produce ∼5-125 excitons per 700 nm long nanotube. These experiments show that optical excitation gives rise to CS states in which PDI radical anions (PDI-•) and SWNT hole polarons (SWNT•+) have geminate and nongeminate spatial relationships. Under low excitation fluences, the observed dynamics reflect CR reactions of these geminate and nongeminate CS states. As excitation fluence increases, persistent excitons, which have not undergone CS, undergo reaction with ([SWNT(•+)n]-(PDI-•)n) CS states to produce lower-energy CS states that are characterized by hole (SWNT•+) and electron (SWNT•-) polarons. When nongeminate SWNT•+ and SWNT•- charge carriers are generated, CR dynamics depend on the time scale required for these oppositely charged solvated SWNT polarons to encounter each other. Because SWNT excitons have substantial excited-state reduction (1E-/*) and excited-state oxidation (1E*/+) potentials, they can drive additional charge transfer reactions involving initially prepared CS states under experimental conditions where excess excitons are present.

Plasmon-enhanced two photon excited emission from edges of one-dimensional plasmonic hotspots with continuous-wave laser excitation.

One-dimensional junctions between parallelly and closely arranged multiple silver nanowires (NWs) exhibit a large electromagnetic (EM) enhancement factor (FR) owing to both localized and surface plasmon resonances. Such junctions are referred to as one-dimensional (1D) hotspots (HSs). This study found that two-photon excited emissions, such as hyper-Rayleigh, hyper-Raman, and two-photon fluorescence of dye molecules, are generated at the edge of 1D HSs of NW dimers with continuous-wave near-infrared (NIR) laser excitation and propagated through 1D HSs; however, they were not generated from the centers of 1D HSs. Numerical EM calculations showed that FR of the NIR region for the edges of 1D HSs was larger than that for the centers by ∼102 times, resulting in the observation of two-photon excited emissions only from the edge of 1D HSs. The analysis of the NW dimer gap distance dependence of FR revealed that the lowest surface plasmon (SP) mode, compressed and localized at the edges of 1D HSs, was the origin of the large FR in the NIR region. The propagation of two-photon-excited emissions was supported by the higher-order coupled SP mode.

Molecular Engineering of a Tumor-Targeting Thione-Derived Diketopyrrolopyrrole Photosensitizer to Attain NIR Excitation Over 850 nm for Efficient Dual Phototherapy.

Photosensitizers with near-infrared (NIR) excitation, especially above 800 nm which is highly desired for phototherapy, remain rare due to the fast nonradiative relaxation process induced by exciton-vibration coupling. Here, a diketopyrrolopyrrole-derived photosensitizer (DTPA-S) is developed via thionation of carbonyl groups within the diketopyrrolopyrrole skeleton, which results in a large bathochromic shift of 81 nm, endowing the photosensitizer with strong NIR absorption at 712 nm. DTPA-S is then introduced with a functional biomolecule (N3-PEG2000-RGD) via click reaction for the construction of integrin αvβ3 receptor-targeted nano-micelles (NanoDTPA-S/RGD), which endows the photosensitizer with a further superlarge absorption redshift of 138 nm, thus extending the absorption maxima to ≈850 nm. Remarkably, thiocarbonyl substitution increases the nonbonding characters in frontier molecular orbitals, which can effectively suppress the nonradiative vibrational relaxation process via reducing the reorganization energy, enabling efficient reactive oxygen species (ROS) generation under 880 nm excitation. Screened by in vitro and in vivo assays, NanoDTPA-S/RGD with high water solubility, excellent tumor-targeting ability, and photodynamic/photothermal therapy synergistic effect exhibits satisfactory phototherapeutic performance. Overall, this study demonstrates a new design of efficient NIR-triggered diketopyrrolopyrrole photosensitizer with facile installation of functional biomolecules for potential clinical applications.

Synthesis and luminescent properties of multi-mode core-shell-shell LaPO4:RE (RE³⁺ = Er³⁺, Eu³⁺) microspheres for anti-counterfeiting ink applications

To meet the demands for product and consumer protection, we developed biocompatible multi-mode emitting core-shell-shell rare earth phosphates for anti-counterfeiting inks. These core-shell-shell structures feature SiO2 microspheres as the core, with LaPO4 nanocrystals doped with erbium (Er) and europium (Eu) as the interlayer, and an outer SiO2 shell. The SiO2@LaPO4:Er0.1,Eux@SiO2 (x = 0.01, 0.02, 0.03, 0.04, 0.05) microspheres display dual emissions when excited by 254 nm and 365 nm UV light, offering a novel anti-counterfeiting approach. Another core-shell-shell structure was created with LaPO4:Er3+ and LaPO4:Eu3+ separately coated on SiO2 cores, mixed, and then covered with a SiO2 shell. Under 980 nm near-infrared laser excitation, these structures emit bright upconverted green light, while 254/365 nm UV light induces red/yellow down-conversion luminescence. This design minimizes up-conversion luminescence quenching of Er3+ ions from cross-relaxation with Eu3+ ions. The SiO2 core minimizes energy loss, regulates particle size, and enhances luminescence. A certain thickness of the silicon shell layer also protects against luminescence quenching. The inks exhibit high dispersibility, non-reproducibility, and excellent luminescence, making them effective for anti-counterfeiting.

Ratiometric optical temperature sensing properties based on up-conversion luminescence of novel NaLaTi2O6:Yb3+,Er3+/Ho3+ phosphors

To satisfy the increasing necessity of contactless optical thermometry, utilizing both thermally coupled (TCLs) or non-thermally-coupled (NTCLs) energy levels of rare earth ions in novel phosphors has significant potential for devising the optical thermometers with high temperature sensitivity. Herein, a sequence of novel Yb3+,Er3+/Ho3+ doped NaLaTi2O6 (NLTO) phosphors were sintered using a high-temperature solid-state reaction approach. Structure, phase component and luminescence performance were identified in detail. Upon 980 nm near-infrared (NIR) excitation, the obtained materials presented typical Er3+/Ho3+ characteristic emission wavelengths in visible region, which include two green emission bands around 522 and 543 nm, as well as a weaker red band around 661 nm for Er3+ doped NLTO, a green emission band around 545 nm and a red band around 657 nm for Ho3+ doped NLTO. Besides, a unusual emission band around 757 nm of Ho3+ in visible edge region was also clearly found. The temperature sensing properties of representative NLTO:Yb3+,Er3+/Ho3+ samples were assessed based on the fluorescence intensity ratio (FIR) technique of TCLs or NTCLs energy levels. The maximal absolute sensitivity (Sa) and relative sensitivity (Sr) were determined to be 0.0374 K-1 (293 K) and 0.970% K-1 (293 K) by taking the FIR of NTCLs 2H11/2→4I15/2 and 4F9/2→4I15/2 transitions in NLTO:Yb3+,Er3+. Simultaneously, the maximal Sa and Sr were 0.0306 K-1 (573 K) and 0.776% K-1 (373 K) using the FIR of NTCLs 5F5→5I8 and 5F4,5S2→5I7 transitions in NLTO:Yb3+,Ho3+. Consequently, the temperature sensitivities above can be compared to reported results, which indicate that as-prepared materials have a promising application in optical temperature sensors field.

Dual-Mechanism Design Strategy for High-Efficiency and Long-Lived Organic Afterglow Materials.

Organic room-temperature phosphorescence (RTP) and afterglow materials hold great potential for various applications, but there remain inherent trade-offs between the afterglow efficiency and the lifetime. Here, we propose a dual-mechanism design strategy, leveraging the RTP or thermally activated delayed fluorescence (TADF) mechanism for a high afterglow efficiency and the organic long-persistent luminescence (OLPL) mechanism for a prolonged afterglow duration. The intramolecular charge transfer (ICT)-type difluoroboron β-diketonate molecules with a large S1 dipole moment are doped as the luminescent component into the organic matrix with a large dipole moment, and a series of TADF-type afterglow materials can be achieved with an afterglow efficiency of up to 88.7% and an afterglow lifetime of 200 ms. To prolong the afterglow duration, an electron donor is introduced as the third component to generate traps and facilitate charge separation. The obtained materials exhibit a dual afterglow mechanism, first exhibiting a TADF/RTP afterglow with an afterglow efficiency of up to 50.9%, followed by an hours-long OLPL afterglow emission with an afterglow efficiency of up to 13.1%. Further investigations reveal that an appropriate heavy-atom effect can facilitate the intersystem crossing process, which can promote the charge separation process and thus improve the OLPL afterglow performance. Additionally, rare-earth upconversion materials are introduced into OLPL materials to enable their near-infrared excitation properties, showcasing their potential applications in bioimaging.

Reversible pH-switchable NIR-II nano-photosensitizer for precise imaging and photodynamic therapy of tumors

Photodynamic therapy (PDT) has attracted widespread attention from researchers as an emerging cancer treatment method. There have been many reports on various types of NIR-II photosensitizers for imaging and treatment of tumor sites. However, there are few reports on the development of NIR-II organic small molecule photosensitizers that have intelligent response to the tumor microenvironment, precise imaging, real-time treatment, and high biocompatibility. In this work, we developed a series of NIR-II photosensitizers (RBTs) with near-infrared excitation, good photostability, and large Stokes shift. Among them, RBT-Br exhibited higher reactive oxygen species (ROS) generation efficiency due to the introduction of halogen heavy atoms to enhance intersystem crossing (ISC). It is noteworthy that RBT-Br can generate singlet oxygen (1O2) and superoxide anion radicals (•O2−) simultaneously under 730 nm laser. Subsequently, we used molecular engineering technology to construct three pH-responsive NIR-II photosensitizers (RBT-pHs) by utilizing the closure of the lactam ring, among which RBT-pH-1 (pKa = 6.78) is able to be directionally activated under the stimulation of tumor micro-acid environment, with its fluorescence emission window reaching 933 nm. Subsequently, RBT-pH-1 NPs encapsulated in DSPE-mPEG5k were applied for PDT treatment of mouse tumors. The results showed that RBT-pH-1 NPs were activated by the acidic tumor microenvironment and generated ROS under laser excitation, exhibiting precise tumor imaging and significant tumor growth inhibition. We look forward to these multifunctional NIR-II organic small molecule photosensitizers providing a more efficient approach for clinical treatment of tumors. Statement of significanceA reversible pH-switchable NIR-II nano-photosensitizer RBT-pH-1 NPs (pKa = 6.76) is developed for precise imaging and PDT therapy of mouse tumors, which can be effectively used for targeted enrichment and activation of tumor micro-acid environments. The results show that this NIR-II photosensitizer generates ROS through tumor micro-acid environment stimulation and laser triggering, showing precise tumor imaging guidance and significant tumor growth inhibition.

Fluorine Doping Mediated Epitaxial Growth of NaREF4 on TiO2 for Boosting NIR Light Utilization in Bioimaging and Photodynamic Therapy.

By integrating TiO2 with rare earth upconversion nanocrystals (NaREF4), efficient energy transfer can be achieved between the two subunits under near-infrared (NIR) excitation, which hold tremendous potential in the fields of photocatalysis, photodynamic therapy (PDT), etc. However, in the previous studies, the combination of TiO2 with NaREF4 is a non-epitaxial random blending mode, resulting in a diminished energy transfer efficiency between the NaREF4 and TiO2. Herein, we present a fluorine doping-mediated epitaxial growth strategy for the synthesis of TiO2-NaREF4 heteronanocrystals (HNCs). Due to the epitaxial growth connection, NaREF4 can transfer energy through phonon-assisted pathway to TiO2, which is more efficient than the traditional indirect secondary photon excitation. Additionally, F doping brings oxygen vacancies in the TiO2 subunit, which further introduces new impurity energy levels in the intrinsic band gap of TiO2 subunit, and facilitates the energy transfer through phonon-assisted method from NaREF4 to TiO2. As a proof of concept, TiO2-NaGdF4 : Yb,Tm@NaYF4@NaGdF4 : Nd@NaYF4 HNCs were rationally constructed. Taking advantage of the dual-model up- and downconversion luminescence of the delicately designed multi-shell structured NaREF4 subunit, highly efficient photo-response capability of the F-doped TiO2 subunit and the efficient phonon-assisted energy transfer between them, the prepared HNCs provide a distinctive nanoplatform for bioimaging-guided NIR-triggered PDT.

Facile synthesis, multimode and tunable luminescence, and multifunctional applications of rare earth ions activated lead-free double perovskite crystals

Lead-free double perovskites have gained recognition as top luminescent materials due to their environmental friendliness, high chemical stability, structural adjustability, and excellent photoelectric properties. However, the poor modulation of emission restricts their applications, and it is highly desirable to explore stable and efficient double perovskites with multimode luminescence and adjustable spectra for multifunctional photoelectric applications. Herein, the rare earth ions Ln3+ (Er3+ and Ho3+) doped Cs2NaYCl6:Sb3+ crystals were synthesized by a simple solvothermal route. The X-ray diffraction pattern (XRD), energy-dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and elemental mapping images demonstrate that the Sb3+, Er3+, and Ho3+ ions have been homogeneously incorporated into the Cs2NaYCl6 crystals. As anticipated, the emission spectra of Cs2NaYCl6:Sb3+/Ln3+ are composed of two bands. One broad blue band derives from self-trapped exciton (STE) in [SbCl6]3− octahedra while another group of emission peaks stems from the f-f transitions of Ln3+ ions. The emission colors of Cs2NaYCl6:Sb3+/Ln3+ phosphors can be tuned in a wide range by modulating the doping concentrations of Ln3+ ions. The efficient energy transfer from STE to Ln3+ is the key point to achieving the efficient and tunable emissions Cs2NaYCl6:Sb3+/Ln3+ samples. Interestingly, Cs2NaYCl6:Sb3+/Ln3+ can also exhibit characteristic up-conversion luminescence of Ln3+ under near-infrared (NIR) excitation besides the down-conversion luminescence, revealing that the materials may have potential applicability in multimode anti-counterfeiting and information encryption applications. Furthermore, the light emitting diodes (LEDs) assembled by Cs2NaYCl6:Sb3+ and Cs2NaYCl6:Sb3+/Ln3+ phosphors display dazzling blue, green, and red emissions under a forward bias current, which indicates that the as-obtained double perovskites materials may have great potential in solid-state lighting and optoelectronic devices.

Shortwave Infrared Imaging of a Quantum Dot-Based Magnetic Guidewire Toward Non-Fluoroscopic Peripheral Vascular Interventions.

Peripheral vascular interventions (PVIs) offer several benefits to patients with lower extremity arterial diseases, including reduced pain, simpler anesthesia, and shorter recovery time, compared to open surgery. However, to monitor the endovascular tools inside the body, PVIs are conducted under X-ray fluoroscopy, which poses serious long-term health risks to physicians and patients. Shortwave infrared (SWIR) imaging of quantum dots (QDs) has shown great potential in bioimaging due to the non-ionizing penetration of SWIR light through tissues. In this paper, a QD-based magnetic guidewire and its system is introduced that allows X-ray-free detection under SWIR imaging and precise steering via magnetic manipulation. The QD magnetic guidewire contains a flexible silicone tube encapsulating a QD polydimethylsiloxane (PDMS) composite, where HgCdSe/HgS/CdS/CdZnS/ZnS/SiO2 core/multi-shell QDs are dispersed in the PDMS matrix for SWIR imaging upon near-infrared excitation, as well as a permanent magnet for magnetic steering. The SWIR penetration of the QD magnetic guidewire is investigated within an artificial tissue model (1% Intralipid) and explore the potential for non-fluoroscopic PVIs within a vascular phantom model. The QD magnetic guidewire is biocompatible in its entirety, with excellent resistance to photobleaching and chemical alteration, which is a promising sign for its future clinical implementation.

Impact of high sensitizer doping on the transient multiband upconversion luminescence in β-NaYF4:Yb/Ho microcrystals

Under intense near-infrared light excitation, upconversion luminescence (UCL) nanomaterials exhibit multiband emission and high sensitizer quenching concentration, indicating the potential to enhance upconversion (UC) quantum efficiency. In comparison to other common activator ions (e.g. Er3+, Tm3+, Ho3+), Ho3+ possesses abundant energy levels. However, previous studies mostly focused on the red (Ho3+:5F5 → 5I8) and green (Ho3+:5F4,5S2 → 5I8) emissions. In this paper, we have examined the transient UCL characteristics of β-NaYF4:Yb/Ho microcrystals (MCs) excited by a high-power 976 nm ns pulsed laser (∼0.32 GW/cm2). The energy transfer (ET) pathways with varying Yb3+ doping (20–98 mol%) are determined by the time evolution spectra. In high Yb3+ doping system (98 mol%), the electron population of Ho3+ accelerates, and the multiband UC rise is shortened by 6 times (from ∼3 μs to ∼500 ns). We identified a new pathway for electron populating with higher Yb3+ doping ( ≥ 40 mol%), which is Yb3+:2F5/2 + Ho3+:3L9 → Yb3+:2F7/2 + Ho3+:3M9. As Yb3+ concentration increases, the varying lifetime and intensity distribution of UCL leads to variations in the luminescence color evolution. Our result shows that altering the Yb3+ doping concentration provides a way to control the energy flow between energy levels of Ho3+, which can modulate the rise time and color evolution of Yb–Ho co-doped UC MCs. This study is expected to promote the advancement of fast-respond optoelectronic devices, UC displays, and micro-nano lasers. Kewordsmultiband upconversion luminescence; high-power excitation; upconversion luminescence dynamics; high sensitizer concentration; upconversion pathways.

Hot Electron Cooling in n-Doped Colloidal Nanoplatelets Following Near-Infrared Intersubband Excitation.

Intersubband transition was recently discovered in colloidal nanoplatelets, but the associated intersubband carrier relaxation dynamics remains poorly understood. In particular, it is crucial to selectively excite the intersubband transition and to follow the hot electron dynamics in the absence of valence-band holes. This is achieved herein by exciting the predoped electrons in CdSe/ZnS nanoplatelets using near-infrared femtosecond pulses and monitoring nonequilibrium electron dynamics using broad-band visible pulses. We find that the n = 2 electrons relax to the n = 1 subband and establish a Fermi-Dirac distribution within 200 fs, and finally reach an equilibrium with the lattice within a few ps. The cooling dynamics depend mainly on the excitation fluence but weakly on the doping density and the lattice temperature. These characteristics are well captured by our numerical simulation that explicitly accounts for the state occupation effect and optical phonon scattering.

Near-infrared excitation Raman spectroscopy of colored fabric contaminated with body fluids

Confirmatory identification of dyes in the physical pieces of evidence, such as hair and fabric, is critically important in forensics. This information can be used to demonstrate the link between a person of interest and a crime scene. High performance liquid chromatography is broadly used for dye analysis. However, this technique is destructive and laborious. This problem can be overcome by near-Infrared excitation Raman spectroscopy (NIeRS), non-invasive and non-destructive technique that can be used to determine chemical structure of highly fluorescent dyes. Analyzed fabric materials often possess body fluid stains, which may obscure the accuracy of NIeRS-based identification of dyes. In this study, we investigate the extent to which fabric contamination with body fluids can alter the accuracy of NIeRS. Our results showed that NIeRS coupled with partial-least squared discriminant analysis (PLS-DA) enabled on average 97.6% accurate identification of dyes on fabric contaminated with dry blood, urine and semen. We also found that NIeRS could be used to identify blood, urine and semen on such fabric with 99.4% accuracy. Furthermore, NIeRS could be used to differentiate between wet and dry blood, as well as reveal the presence of blood on washed fabric. These results indicate that NIeRS coupled with PLS-DA could be used as a robust and reliable analytical approach in forensic analysis of fabric.

Multimodal anti-counterfeiting and optical storage application based on luminescence reversible modification and color change of photochromic phosphor

Reversible upconversion luminescence (RUCL) modification based on photochromism has received considerable interest due to its potential applications in optical storage and invisible optical anti-counterfeiting. Herein, white β-Ba2ScAlO5: Yb3+, Er3+ (β-BSAO-YE) phosphor was irradiated with 254 nm light, which caused the phosphor to turn blue due to the increase of oxygen vacancy. The blue β-BSAO-YE phosphor returns to its original color upon stimulation with 808 nm laser light or 125 °C, exhibiting a double photo-induced reversible photochromic change. The green and red upconversion luminescence (UCL) of the β-BSAO-YE were reversibly modified according to their photochromic properties. The UCL modification changes the luminescence color of the pattern, indicating that β-BSAO-YE phosphor is an ideal compound anti-counterfeit agent. The light information recorded on the β-BSAO-YE binary photochromic dot matrix can be read under ultraviolet (UV) and near-infrared (NIR) excitation, demonstrating the potential application of β-BSAO-YE phosphors as optical data storage media. In addition, the cyclic experiment showed good photochromic and UCL modulation repeatability. The new luminescent β-BSAO-YE not only proposes a new way to exploring upconversion red light materials, but also provides new materials for optical storage, optical information and optical anti-counterfeiting.

(Invited) Near-Infrared Triggered Theranostics

In the last decade, the field of luminescent lanthanide doped nanoparticles has had a meteoric rise, progressing from the basic understanding of the photophysical properties governing their nanoscale luminescence, in particular upconversion, to their use in a plethora of applications, with considerable focus in biology and medicine. This interest stems primarily from the ability to stimulate these luminescent nanoparticles with near-infrared (NIR) light as well as their diverse emission wavelengths spanning the UV to the NIR. Therefore, with a single NIR excitation wavelength, it is possible to observe higher energy multiphoton luminescence, known as upconversion, or single photon NIR emission (known as down-shifted luminescence). The former upconversion process proceeds through the sequential absorption of multiple NIR photons through the long-lived 4f electronic energy states of the tri-positive lanthanide ions. As a result, upconversion is several of orders more efficient than conventional multiphoton absorption processes. This is especially interesting for applications in theranostics (therapy + diagnostics on the same platform) where the upconverted light can be used to trigger another light activated modality (therapy) while the NIR luminescence can be used for bioimaging and nanothermometry (diagnostics). Here, we present our work on the synthesis and development of various NIR excited (and emitting) core/shell lanthanide-doped nanostructures/nanoplatforms and demonstrate how their various emissions could be harnessed for applications in biology and nanomedicine.

Multiplex Bioimaging with Near-Infrared Fluorescent Graphene Quantum Dots

Due to high tissue penetration depth and low autofluorescence backgrounds, near-infrared (NIR) fluorescence imaging has recently become an advantageous diagnostic technique used in a variety of fields. However, most of the NIR fluorophores do not have therapeutic delivery capabilities, exhibit low photostabilities, and raise toxicity concerns. To address these issues, we developed and tested five types of biocompatible graphene quantum dots (GQDs) exhibiting spectrally separated fluorescence in the NIR range of 928 – 1053 nm with NIR excitation. Their optical properties in the NIR are attributed to either rare-earth metal dopants (Ho-NGQDs, Yb-NGQDs, Nd-NGQDs) or defect-states (NGQDs, RGQDs) as verified by Hartree-Fock calculations. Moderate up to 1.34 % quantum yields of these GQDs are well-compensated by their remarkable >4-hour photostability. At the biocompatible concentrations of up to 0.5 – 2 mg/mL GQDs successfully internalize into HEK-293 cells and enable in vitro imaging in the visible and NIR. Tested all together in HEK-293 cells five GQD types enable simultaneous multiplex imaging in the NIR-I and NIR-II shown for the first time in this work for GQD platforms. Substantial photostability, spectrally-separated NIR emission, and high biocompatibility of five GQD types developed here suggest their promising potential in multianalyte testing and multiwavelength bioimaging of combination therapies.

(Invited) Core-Multi-Shell Design: Unlocking Multimodal Capabilities in Lanthanide-Based Nanoparticles

The remarkable optomagnetic properties of the lanthanides (Ln) make Ln-based materials ideal for biomedical applications, including diagnostic (e.g., imaging, nanothermometry) and therapeutic (e.g., drug delivery, photodynamic therapy) approaches. This is due the unique electronic properties of the f-elements allowing for upconversion and near-infrared emission under near-infrared excitation as well as high magnetic moments. Yet, challenges remain, including low emission intensity and efficiency of small nanoparticles (NPs), and reliable, fast synthesis routes. As material chemists, we tackle these challenges with new designs of Ln-NPs by chemically controlled synthesis, application-oriented surface chemistry, and understanding of structure-property-relationships. We developed a straightforward and rapid microwave-assisted synthesis approach towards core-multi-shell Ln-NPs. Careful architecture design and choice of RE3+ dopant ions allow to tune the optical properties of the resultant nanoparticles, i.e., upconversion and near-infrared emission. This presentation will shed light on recent results with respect to microwave-assisted synthesis of Ln-NPs as well as structural and optomagnetic properties, seeking biomedical application.For instance, multimodal bioimaging probes merging optical imaging, magnetic resonance imaging (MRI), and X-ray computed tomography (CT) capabilities have attracted considerable attention due to their potential biomedical applications. This includes nanoparticles that combine upconverting Er3+/Yb3+ and magnetic NaDyF4 for optical/T2-weighted MRI/CT multimodal capabilities. A known drawback of multimodal probes that merge the upconverting Er3+/Yb3+ ion pair with magnetic Dy3+ ions for T2-weighted MRI is the loss of upconversion emission due to Dy3+ poisoning. The synthesis of controlled nanoparticle architectures with tuned inner NaGdF4 shell thicknesses separating Dy3+ and Er3+/Yb3+ allow to shed light on this distance-dependent loss of upconversion due to Yb3+ → Dy3+ energy transfer. As a result, the Ln-NP architecture was tuned to not only restore but enhanced the upconversion emission. In addition to multimodal imaging, Ln-NPs are promising candidates for application in nanothermometry due to the distinct, temperature-induced changes in their spectral features. We seek the development of novel Ln-NP nanothermometers for new opportunities in the near-infrared biological transparency windows (1000 to 2000 nm), by doping RE3+ ions, such as Er3+ and Tm3+ as well as unconventional Pr3+, into core-multi-shell lanthanide-based nanoparticles.

Broadband Near-Infrared Light Excitation Generates Long-Lived Near-Infrared Luminescence in Gallates.

Persistent luminescence describes the phenomenon whereby luminescence remains after the stoppage of excitation. Recently, upconversion persistent luminescence (UCPL) phosphors that can be directly charged by near-infrared (NIR) light have gained considerable attention due to their promising applications ranging from photonics to biomedicine. However, current lanthanide-based UCPL phosphors show small absorption cross sections and low upconversion charging efficiency. The development of UCPL phosphors faces challenges due to the lack of flexible upconversion charging pathways and poor design flexibility. Herein, we discovered a lattice defect-mediated broadband photon upconversion process and the accompanying NIR-to-NIR UCPL in Cr-doped zinc gallate nanoparticles. The zinc gallate nanoparticles can be directly activated by broadband NIR light in the 700-1000 nm range to produce persistent luminescence at about 700 nm, which is also readily enhanced by rationally tailoring the lattice defects in the phosphors. This proposed UCPL phosphor achieved a signal-to-background ratio of over 200 in bioimaging by efficiently avoiding interference from autofluorescence and light scattering. Our work reported a lattice defect-mediated photon upconversion phenomenon, which significantly expands the horizons for the flexible design of UCPL phosphors toward broad applications ranging from bioimaging to photocatalysis.

Varroa Mite Counting Based on Hyperspectral Imaging.

Varroa mite infestation poses a severe threat to honeybee colonies globally. This study investigates the feasibility of utilizing the HS-Cam and machine learning techniques for Varroa mite counting. The methodology involves image acquisition, dimensionality reduction through Principal Component Analysis (PCA), and machine learning-based segmentation and classification algorithms. Specifically, a k-Nearest Neighbors (kNNs) model distinguishes Varroa mites from other objects in the images, while a Support Vector Machine (SVM) classifier enhances shape detection. The final phase integrates a dedicated counting algorithm, leveraging outputs from the SVM classifier to quantify Varroa mite populations in hyperspectral images. The preliminary results demonstrate segmentation accuracy exceeding 99% and an average precision of 0.9983 and recall of 0.9947 across all the classes. The results obtained from our machine learning-based approach for Varroa mite counting were compared against ground-truth labels obtained through manual counting, demonstrating a high degree of agreement between the automated counting and manual ground truth. Despite working with a limited dataset, the HS-Cam showcases its potential for Varroa counting, delivering superior performance compared to traditional RGB images. Future research directions include validating the proposed hyperspectral imaging methodology with a more extensive and diverse dataset. Additionally, the effectiveness of using a near-infrared (NIR) excitation source for Varroa detection will be explored, along with assessing smartphone integration feasibility.