Lanthanide-based nanomaterials for temperature sensing in the near-infrared spectral region: illuminating progress and challenges.

Being first proposed as a method to overcome limitations associated with conventional contact thermometers, luminescence thermometry has been extensively studied over the past two decades as a sensitive and fast approach to remote and minimally invasive thermal sensing. Herein, lanthanide (Ln)-doped nanoparticles (Ln-NPs) have been identified as particularly promising candidates, given their outstanding optical properties. Known primarily for their upconversion emission, Ln-NPs have also been recognized for their ability to be excited with and emit in the near-infrared (NIR) regions matching the NIR transparency windows. This sparked the emergence of the development of NIR-NIR Ln-NPs for a wide range of temperature-sensing applications. The shift to longer excitation and emission wavelengths resulted in increased efforts being put into developing nanothermometers for biomedical applications, however most research is still preclinical. This mini-review outlines and addresses the challenges that limit the reliability and implementation of luminescent nanothermometers to real-life applications. Through a critical look into the recent developments from the past 4 years, we highlight attempts to overcome some of the limitations associated with excitation wavelength, thermal sensitivity, calibration, as well as light-matter interactions. Strategies range from use of longer excitation wavelengths, brighter emitters through strategic core/multi-shell architectures, exploitation of host phonons, and a shift from double- to single-band ratiometric as well as lifetime-based approaches to innovative methods based on computation and machine learning. To conclude, we offer a perspective on remaining gaps and where efforts should be focused towards more robust nanothermometers allowing a shift to real-life, e.g., in vivo, applications.

Confining single Er3+ ions in sub-3 nm NaYF4 nanoparticles to induce slow relaxation of the magnetisation.

Molecular systems known as single-molecule magnets (SMMs) exhibit magnet-like behaviour of slow relaxation of the magnetisation and magnetic hysteresis and have potential application in high-density memory storage or quantum computing. Often, their intrinsic magnetic properties are plagued by low-energy molecular vibrations that lead to phonon-induced relaxation processes, however, there is no straightforward synthetic approach for molecular systems that would lead to a small amount of low-energy vibrations and low phonon density of states at the spin-resonance energies. In this work, we apply knowledge accumulated over the last decade in molecular magnetism to nanoparticles, incorporating Er3+ ions in an ultrasmall sub-3 nm diamagnetic NaYF4 nanoparticle (NP) and probing the slow relaxation dynamics intrinsic to the Er3+ ion. Furthermore, by increasing the doping concentration, we also investigate the role of intraparticle interactions within the NP. The knowledge gained from this study is anticipated to enable better design of magnetically high-performance molecular and bulk magnets for a wide variety of applications, such as molecular electronics.

Introduction to fundamental processes in optical nanomaterials.

An introduction to the joint Nanoscale and Chemical Communications (ChemComm) themed collection focused on fundamental processes in optical nanomaterials that features a series of articles describing the properties of this versatile class of materials while highlighting some of their potential applications.

Core-multi-shell design: unlocking multimodal capabilities in lanthanide-based nanoparticles as upconverting, T2-weighted MRI and CT probes.

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. Lanthanide-based nanoparticles are promising candidates for multimodal imaging because of their optical, magnetic and X-ray attenuation properties. We prepared a set of hexagonal-phase (ß)-NaGdF4:Yb,Er/NaGdF4/NaDyF4 core/shell/shell nanoparticles (Dy-CSS NPs) and demonstrated their 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 (UC) emission due to Dy3+ poisoning. Particular attention was paid to controlled nanoparticle architectures with tuned inner shell thicknesses separating Dy3+ and Er3+/Yb3+ to shed light on the distance-dependent loss of UC due to Yb3+ → Dy3+ energy transfer. Based on the Er3+ UC spectra and the excited state lifetime of Yb3+, a 4 nm thick NaGdF4 inner shell did not only restore but enhanced the UC emission. We further investigated the effect of the outer NaDyF4 shell thickness on the particles' magnetic and CT performance. MRI T2 relaxivity measurements in vitro at a magnetic field of 7 T performed on citrate-capped Dy-CSS NPs revealed that NPs with the thickest outer shell thickness (4 nm) exhibited the highest r2 value, with a superior T2 contrast effect compared to commercial iron oxide and other Dy-based T2 contrast agents. In addition, the citrate-capped Dy-CSS NPs were demonstrated suitable for CT in in vitro imaging phantoms at X-ray energies of 110 keV, rendering them interesting alternatives to clinically used iodine-based agents that operate at lower energies.

Entrapped Molecule-Like Europium-Oxide Clusters in Zinc Oxide with Nearly Unaffected Host Structure.

Nanocrystalline ZnO sponges doped with 5 mol% EuO1.5 are obtained by heating metal-salt complex based precursor pastes at 200-900 °C for 3 min. X-ray diffraction, transmission electron microscopy, and extended X-ray absorption fine structure (EXAFS) show that phase separation into ZnO:Eu and c-Eu2 O3 takes place upon heating at 700 °C or higher. The unit cell of the clean oxide made at 600 °C shows only ≈0.4% volume increase versus undoped ZnO, and EXAFS shows a ZnO local structure that is little affected by the Eu-doping and an average Eu3+ ion coordination number of ≈5.2. Comparisons of 23 density functional theory-generated structures having differently sized Eu-oxide clusters embedded in ZnO identify three structures with four or eight Eu atoms as the most energetically favorable. These clusters exhibit the smallest volume increase compared to undoped ZnO and Eu coordination numbers of 5.2-5.5, all in excellent agreement with experimental data. ZnO defect states are crucial for efficient Eu3+ excitation, while c-Eu2 O3 phase separation results in loss of the characteristic Eu3+ photoluminescence. The formation of molecule-like Eu-oxide clusters, entrapped in ZnO, proposed here, may help in understanding the nature of the unexpected high doping levels of lanthanide ions in ZnO that occur virtually without significant change in ZnO unit cell dimensions.

Phytoglycogen Encapsulation of Lanthanide-Based Nanoparticles as an Optical Imaging Platform with Therapeutic Potential.

Lanthanide-based upconverting nanoparticles (UCNPs) are largely sought-after for biomedical applications ranging from bioimaging to therapy. A straightforward strategy is proposed here using the naturally sourced polymer phytoglycogen to coencapsulate UCNPs with hydrophobic photosensitizers as an optical imaging platform and light-induced therapeutic agents. The resulting multifunctional sub-micrometer-sized luminescent beads are shown to be cytocompatible as carrier materials, which encourages the assessment of their potential in biomedical applications. The loading of UCNPs of various elemental compositions enables multicolor hyperspectral imaging of the UCNP-loaded beads, endowing these materials with the potential to serve as luminescent tags for multiplexed imaging or simultaneous detection of different moieties under near-infrared (NIR) excitation. Coencapsulation of UCNPs and Rose Bengal opens the door for potential application of these microcarriers for collagen crosslinking. Alternatively, coloading UCNPs with Chlorin e6 enables NIR-light triggered generation of reactive oxygen species. Overall, the developed encapsulation methodology offers a straightforward and noncytotoxic strategy yielding water-dispersible UCNPs while preserving their bright and color-tunable upconversion emission that would allow them to fulfill their potential as multifunctional platforms for biomedical applications.

Metabolic Consequences of Developmental Exposure to Polystyrene Nanoplastics, the Flame Retardant BDE-47 and Their Combination in Zebrafish.

Single-use plastic production is higher now than ever before. Much of this plastic is released into aquatic environments, where it is eventually weathered into smaller nanoscale plastics. In addition to potential direct biological effects, nanoplastics may also modulate the biological effects of hydrophobic persistent organic legacy contaminants (POPs) that absorb to their surfaces. In this study, we test the hypothesis that developmental exposure (0-7 dpf) of zebrafish to the emerging contaminant polystyrene (PS) nanoplastics (⌀100 nm; 2.5 or 25 ppb), or to environmental levels of the legacy contaminant and flame retardant 2,2',4,4'-Tetrabromodiphenyl ether (BDE-47; 10 ppt), disrupt organismal energy metabolism. We also test the hypothesis that co-exposure leads to increased metabolic disruption. The uptake of nanoplastics in developing zebrafish was validated using fluorescence microscopy. To address metabolic consequences at the organismal and molecular level, metabolic phenotyping assays and metabolic gene expression analysis were used. Both PS and BDE-47 affected organismal metabolism alone and in combination. Individually, PS and BDE-47 exposure increased feeding and oxygen consumption rates. PS exposure also elicited complex effects on locomotor behaviour with increased long-distance and decreased short-distance movements. Co-exposure of PS and BDE-47 significantly increased feeding and oxygen consumption rates compared to control and individual compounds alone, suggesting additive or synergistic effects on energy balance, which was further supported by reduced neutral lipid reserves. Conversely, molecular gene expression data pointed to a negative interaction, as co-exposure of high PS generally abolished the induction of gene expression in response to BDE-47. Our results demonstrate that co-exposure to emerging nanoplastic contaminants and legacy contaminants results in cumulative metabolic disruption in early development in a fish model relevant to eco- and human toxicology.

Trends in hyperspectral imaging: from environmental and health sensing to structure-property and nano-bio interaction studies.

Hyperspectral imaging (HSI) is a technique that allows for the simultaneous acquisition of both spatial and spectral information. While HSI has been known for years in the field of remote sensing, for instance in geology, cultural heritage, or food industries, it recently emerged in the fields of nano- and micromaterials as well as bioimaging and -sensing. Herein, the attractiveness of HSI arises from the suitability for generating knowledge about environment-specific optical properties, such as photoluminescence of optical probes in a biological sample or at a single-crystal/particle level, to be leveraged into better understanding of structure-property relationships and nano-bio interactions, respectively. Moreover, given its excellent spectral resolution, HSI is highly suitable for optical multiplexing in multiple dimensions, as sought after for, e.g., high throughput biological imaging by simultaneous tracking of multiple targets. Overall, HSI is an emerging technique that has the potential to transform analytical approaches from biomedicine to advanced materials research. This Trends Article provides insight into the potential of HSI, highlighting selected examples from well-established fields including environmental monitoring and food quality control to set the stage for the discussion of emerging opportunities at the micro- and nanoscale. Herein, special focus is set on photoluminescent micro- and nanoprobes for health and spectral conversion applications.

Cubic versus hexagonal - phase, size and morphology effects on the photoluminescence quantum yield of NaGdF4:Er3+/Yb3+ upconverting nanoparticles.

Upconverting nanoparticles (UCNPs) are well-known for their capacity to convert near-infrared light into UV/visible light, benefitting various applications where light triggering is required. At the nanoscale, loss of luminescence intensity is observed and thus, a decrease in photoluminescence quantum yield (PLQY), usually ascribed to surface quenching. We evaluate this by measuring the PLQY of NaGdF4:Er3+,Yb3+ UCNPs as a function of size (ca. 15 to 100 nm) and shape (spheres, cubes, hexagons). Our results show that the PLQY of α-phase NaGdF4 Er3+,Yb3+ surpasses that of ß-NaGdF4 for sizes below 20 nm, an observation related to distortion of the crystal lattice when the UCNPs become smaller. The present study also underlines that particle shape must not be neglected as a relevant parameter for PLQY. In fact, based on a mathematical nucleus/hull volumetric model, shape was found to be particularly relevant in the 20 to 60 nm size range of the investigated UCNPs.

Microwave-assisted synthesis of NaMnF3 particles with tuneable morphologies.

Here, the synthesis of sub-micron MMnF3 (M = Na or K) particles by a rapid microwave-assisted approach is reported. Adjustment of the Na+-to-Mn2+ ratio in the reaction mixture yielded tuneable morphologies, i.e., rods, ribbons, and plates. Relaxometric results indicated that poly(acrylic acid)-capped MMnF3 particles exhibited characteristic magnetic properties, which endows them with potential T1-weighted contrast agent capabilities.

Effect of light scattering on upconversion photoluminescence quantum yield in microscale-to-nanoscale materials.

Scattering affects excitation power density, penetration depth and upconversion emission self-absorption, resulting in particle size -dependent modifications of the external photoluminescence quantum yield (ePLQY) and net emission. Micron-size NaYF4:Yb3+, Er3+ encapsulated phosphors (∼4.2 µm) showed ePLQY enhancements of >402%, with particle-media refractive index disparity (Δn): 0.4969, and net emission increases of >70%. In sub-micron phosphor encapsulants (∼406 nm), self-absorption limited ePLQY and emission as particle concentration increases, while appearing negligible in nanoparticle dispersions (∼31.8 nm). These dependencies are important for standardising PLQY measurements and optimising UC devices, since the encapsulant can drastically enhance UC emission.

Fast, Low-Cost Synthesis of ZnO:Eu Nanosponges and the Nature of Ln Doping in ZnO.

A low-cost template-free solution chemical route to highly porous nanocrystalline sponges of ZnO-EuO1.5 with 0-5 mol % Eu is presented. The process uses Zn- and Eu-acetate-nitrate and triethanolamine as precursors in methanol. After evaporation of the solvent and heating at 200 °C for 3 min, crystalline ZnO:Eu sponges with minor amounts of organic residues were obtained. Heating to 400 °C replaced the organics with carbonate, which in its turn was decomposed at temperatures below 600 °C, forming ZnO:Eu sponges. Samples heated to 200-1000 °C for 3 min were studied with XRD, SEM, TEM, TG, XPS, and IR spectroscopy. The ZnO:Eu crystallite sizes could be tuned from below 10 nm for sponges prepared at 200-500 °C, to over 100 nm range at 900 °C, without sintering of the overall microstructure. XRD showed the presence of hexagonal ZnO:Eu (or at 700-1000 °C, ZnO:Eu and cubic Eu2O3) as the only phases present. The ZnO:Eu had slightly larger unit cell dimensions than the literature value of ZnO for samples obtained at 200-600 °C, while the unit cells of samples obtained at higher temperatures were quite close to the value of undoped ZnO. XPS showed that Eu was mainly in its 3+ state and well-distributed within the sponges but segregated at the ZnO sponge surface upon heating at 700-1000 °C, in accordance with XRD studies showing Eu2O3 formation.

Hyperspectral Imaging as a Tool to Study Optical Anisotropy in Lanthanide-Based Molecular Single Crystals.

In this work, we describe a protocol for a novel application of hyperspectral imaging (HSI) in the analysis of luminescent lanthanide (Ln3+)-based molecular single crystals. As representative example, we chose a single crystal of the heterodinuclear Ln-based complex [TbEu(bpm)(tfaa)6] (bpm=2,2'-bipyrimidine, tfaa- =1,1,1-trifluoroacetylacetonate) exhibiting bright visible emission under UV excitation. HSI is an emerging technique that combines 2-dimensional spatial imaging of a luminescent structure with spectral information from each pixel of the obtained image. Specifically, HSI on single crystals of the [Tb-Eu] complex provided local spectral information unveiling variation of the luminescence intensity at different points along the studied crystals. These changes were attributed to the optical anisotropy present in the crystal, which results from the different molecular packing of Ln3+ ions in each one of the directions of the crystal structure. The HSI herein described is an example of the suitability of such technique for spectro-spatial investigations of molecular materials. Yet, importantly, this protocol can be easily extended for other types of luminescent materials (such as micron-sized molecular crystals, inorganic microparticles, nanoparticles in biological tissues, or labelled cells, among others), opening many possibilities for deeper investigation of structure-property relationships. Ultimately, such investigations will provide knowledge to be leveraged into the engineering of advanced materials for a wide range of applications from bioimaging to technological applications, such as waveguides or optoelectronic devices.

Water dispersible ligand-free rare earth fluoride nanoparticles: water transfer versus NaREF4-to-REF3 phase transformation.

The chemical stability of oleate-capped sub-10 nm α- and ß-NaREF4 NPs (RE = Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu for α- and RE = Pr, Nd, Sm, Eu, Gd, Tb, Dy for ß-phase NPs) was evaluated under the acidic conditions used for ligand removal towards water dispersibility. It was found that for such small NPs, a pH lower than 3 was necessary for the water transfer to be efficient and to yield well-dispersed ligand-free NPs. In stark contrast to the generally considered good chemical stability of NaREF4, these conditions were observed to pose a risk to phase transformation of the NaREF4 NPs into much larger, hexagonal- or orthorhombic-phase REF3, depending on the NP composition. A correlation between the thermodynamic stability of the α/ß-NaREF4 and the hexagonal/orthorhombic REF3 phases - dictated by the RE ion choice - and the chemical stability of the NPs was found. For instance, ß-NaGdF4 NPs remained stable, while α-NaGdF4 NPs underwent phase transformation into hexagonal GdF3. More general, NaREF4 NPs based on lighter RE ions were more prone towards phase transformation, while those based on heavier RE ions exhibited stability. Herein, within the RE series, the borderline for phase transformation was identified as Tb/Dy for α-NaREF4 NPs and Sm/Eu for ß-NaREF4 NPs, respectively. Also, given the large interest in luminescent NPs for, e.g. biomedical applications, optically active Ln3+ ions (Ln = Nd, Eu, Tb, Er/Yb) were doped into α/ß-NaGdF4 host NPs, and the dopant influence on the chemical stability was evaluated. Steady state and time-resolved spectroscopy unveiled spectral features characteristic for Ln3+ f-f transitions, i.e. downshifting and upconversion, before and after ligand removal. Overall, the results herein described emphasise the importance of minding the chemical procedure used for ligand removal of NaREF4 NPs of different crystalline phases and RE compositions.

Exploring the dual functionality of an ytterbium complex for luminescence thermometry and slow magnetic relaxation.

We present a comprehensive investigation of the magnetic and optical properties of an ytterbium complex, which combines two desirable and practical features into a single molecular system. Based upon YbIII ions that promote near-infrared optical activity and a chemical backbone that is ideal for an in-depth understanding of the magnetic behaviour, we have designed a multifunctional opto-magnetic species that operates as a luminescent thermometer and as a single-molecule magnet (SMM). Our magnetic investigations, in conjunction with ab initio calculations, reveal one of the highest energy barriers reported for an YbIII-based complex. Moreover, we correlate this anisotropic barrier with the emission spectrum of the compound, wherein we provide a complete assignment of the energetic profile of the complex. Such studies lay the foundation for the design of exciting multi-faceted materials that are able to retain information at the single-molecule level and possess built-in thermal self-monitoring capabilities.

A Luminescent Thermometer Exhibiting Slow Relaxation of the Magnetization: Toward Self-Monitored Building Blocks for Next-Generation Optomagnetic Devices.

The development and integration of Single-Molecule Magnets (SMMs) into molecular electronic devices continue to be an exciting challenge. In such potential devices, heat generation due to the electric current is a critical issue that has to be considered upon device fabrication. To read out accurately the temperature at the submicrometer spatial range, new multifunctional SMMs need to be developed. Herein, we present the first self-calibrated molecular thermometer with SMM properties, which provides an elegant avenue to address these issues. The employment of 2,2'-bipyrimidine and 1,1,1-trifluoroacetylacetonate ligands results in a dinuclear compound, [Dy2(bpm)(tfaa)6], which exhibits slow relaxation of the magnetization along with remarkable photoluminescent properties. This combination allows the gaining of fundamental insight in the electronic properties of the compound and investigation of optomagnetic cross-effects (Zeeman effect). Importantly, spectral variations stemming from two distinct thermal-dependent mechanisms taking place at the molecular level are used to perform luminescence thermometry over the 5-398 K temperature range. Overall, these properties make the proposed system a unique molecular luminescent thermometer bearing SMM properties, which preserves its temperature self-monitoring capability even under applied magnetic fields.

Triplet-State Position and Crystal-Field Tuning in Opto-Magnetic Lanthanide Complexes: Two Sides of the Same Coin.

Lanthanide-complex-based luminescence thermometry and single-molecule magnetism are two effervescent fields of research, owing to the great promise they hold from an application standpoint. The high thermal sensitivity achievable, their contactless nature, along with sub-micrometric spatial resolution make these luminescent thermometers appealing for accurate temperature probing in miniaturised electronics. To that end, single-molecule magnets (SMMs) are expected to revolutionise the field of spintronics, thanks to the improvements made in terms of their working temperature-now surpassing that of liquid nitrogen-and manipulation of their spin state. Hence, the combination of such opto-magnetic properties in a single molecule is desirable in the aim of overcoming, among others, addressability issues. Yet, improvements must be made through design strategies for the realisation of the aforementioned goal. Moving forward from these considerations, we present a thorough investigation of the effect that changes in the ligand scaffold of a family of terbium complexes have on their performance as luminescent thermometers and SMMs. In particular, an increased number of electron-withdrawing groups yields modifications of the metal coordination environment and a lowering of the triplet state of the ligands. These effects are tightly intertwined, thus, resulting in concomitant variations of the SMM and the luminescence thermometry behaviour of the complexes. Supported by ab initio calculations, we can rationally interpret the observed trends and provide solid foundations for the development of opto-magnetic lanthanide complexes.

Cubic versus hexagonal - effect of host crystallinity on the T1 shortening behaviour of NaGdF4 nanoparticles.

Sodium gadolinium fluoride (NaGdF4) nanoparticles are promising candidates as T1 shortening magnetic resonance imaging (MRI) contrast agents due to the paramagnetic properties of the Gd3+ ion. Effects of size and surface modification of these nanoparticles on proton relaxation times have been widely studied. However, to date, there has been no report on how T1 relaxivity (r1) is affected by the different polymorphs in which NaGdF4 crystallizes: cubic (α) and hexagonal (ß). Here, a microwave-assisted thermal decomposition method was developed that grants selective access to NaGdF4 nanoparticles of either phase in the same size range, allowing the influence of host crystallinity on r1 to be investigated. It was found that at 3 T cubic NaGdF4 nanoparticles exhibit larger r1 values than their hexagonal analogues. This result was interpreted based on Solomon-Bloembergen-Morgan theory, suggesting that the inner sphere contribution to r1 is more pronounced for cubic NaGdF4 nanoparticles as compared to their hexagonal counterparts. This holds true irrespective of the chosen surface modification, i.e. small citrate groups or longer chain poly(acrylic acid). Key aspects were found to be a polymorph-induced larger hydrodynamic diameter and the higher magnetization possessed by cubic nanoparticles.

Microwave-Assisted Solvothermal Synthesis of Upconverting and Downshifting Rare-Earth-Doped LiYF4 Microparticles.

Growing attention toward optically active materials has prompted the development of novel synthesis methods for a more reliable and efficient access to these systems. In this regard, microwave-assisted approaches provide unique advantages over traditional solvothermal methods reliant on convectional heating: namely, significantly shorter reaction durations, more rigid reaction conditions, and thus a higher degree of reproducibility. Reported herein for the first time is a rapid synthesis of rare-earth (RE3+)-doped LiYF4 upconverting and downshifting microparticles with well-defined bipyramidal morphology and good size dispersion via a microwave-assisted solvothermal process. The suggested material growth mechanism identifies a suitable Li+ to RE3+ ion ratio, an abundance of pH-sensitive acetate surface-capping ligands, and an appropriate reaction temperature/time profile as crucial for enabling a phase transformation of an intermediary yttrium ammonium fluoride phase into LiYF4 and subsequent particle ripening. The versatility of the reported method is highlighted by its extension toward the synthesis of other state of the art M(RE)F4 (M = alkali metal) optical materials: RE3+-doped LiYbF4 microparticles and ß-NaGdF4 and α-NaYF4 nanoparticles. All of the obtained Yb3+/Er3+- and Yb3+/Tm3+-codoped M(RE)F4 materials exhibited characteristic upconversion emission, while downshifting capabilities were induced through Ce3+/Tb3+ codoping of LiYF4. Further attention was devoted to single-particle optical characterization via hyperspectral imaging of Yb3+/Er3+- and Yb3+/Tm3+-codoped LiYF4 microparticles to explore the spatial variability of upconversion emission within individual particles.