Upconversion Luminescence through Cooperative and Energy-Transfer Mechanisms in Yb3+ -Metal-Organic Frameworks.

Lanthanide-doped metal-organic frameworks (Ln-MOFs) have versatile luminescence properties, however it is challenging to achieve lanthanide-based upconversion luminescence in these materials. Here, 1,3,5-benzenetricarboxylic acid (BTC) and trivalent Yb3+ ions were used to generate crystalline Yb-BTC MOF 1D-microrods with upconversion luminescence under near infrared excitation via cooperative luminescence. Subsequently, the Yb-BTC MOFs were doped with a variety of different lanthanides to evaluate the potential for Yb3+ -based upconversion and energy transfer. Yb-BTC MOFs doped with Er3+ , Ho3+ , Tb3+ , and Eu3+ ions exhibit both the cooperative luminescence from Yb3+ and the characteristic emission bands of these ions under 980 nm irradiation. In contrast, only the 497 nm upconversion emission band from Yb3+ is observed in the MOFs doped with Tm3+ , Pr3+ , Sm3+ , and Dy3+ . The effects of different dopants on the efficiency of cooperative luminescence were established and will provide guidance for the exploitation of Ln-MOFs exhibiting upconversion.

Cooperative Sensitization Upconversion in Solution Dispersions of Co-Crystal Assemblies of Mononuclear Yb3+ and Eu3+ Complexes.

Lanthanide upconversion luminescence in nanoparticles has prompted continuous breakthroughs in information storage, temperature sensing, and biomedical applications, among others. Achieving upconversion luminescence at the molecular scale is still a critical challenge in modern chemistry. In this work, we explored the upconversion luminescence of solution dispersions of co-crystals composed of discrete mononuclear Yb(DBM)3 Bpy and Eu(DBM)3 Bpy complexes (DBM: dibenzoylmethane, Bpy: 2,2'-bipyridine). The 613 nm emission of Eu3+ was observed under excitation of Yb3+ at 980 nm. From the series of molecular assemblies studied, the most intense luminescence was obtained for a 1 : 1 molar ratio of Yb3+ : Eu3+ , resulting in a high quantum yield of 0.67 % at 2.1 W cm-2 . The structure and energy transfer mechanism of the assemblies were fully characterized. This is the first example of an Eu3+ -based upconverting system composed of two discrete mononuclear lanthanide complexes present as co-crystals in non-deuterated solution.

Energy Migration Control of Multimodal Emissions in an Er3+ -Doped Nanostructure for Information Encryption and Deep-Learning Decoding.

Modulating the emission wavelengths of materials has always been a primary focus of fluorescence technology. Nanocrystals (NCs) doped with lanthanide ions with rich energy levels can produce a variety of emissions at different excitation wavelengths. However, the control of multimodal emissions of these ions has remained a challenge. Herein, we present a new composition of Er3+ -based lanthanide NCs with color-switchable output under irradiation with 980, 808, or 1535 nm light for information security. The variation of excitation wavelengths changes the intensity ratio of visible (Vis)/near-infrared (NIR-II) emissions. Taking advantage of the Vis/NIR-II multimodal emissions of NCs and deep learning, we successfully demonstrated the storage and decoding of visible light information in pork tissue.

Intrinsic Time-Tunable Emissions in Core-Shell Upconverting Nanoparticle Systems.

Color-tunable luminescence has been extensively investigated in upconverting nanoparticles for diverse applications, each exploiting emissions in different spectral regions. Manipulation of the emission wavelength is accomplished by varying the composition of the luminescent material or the characteristics of the excitation source. Herein, we propose core-shell ß-NaGdF4 : Tm3+ , Yb3+ /ß-NaGdF4 : Tb3+ nanoparticles as intrinsic time-tunable luminescent materials. The time dependency of the emission wavelength only depends on the different decay time of the two emitters, without additional variation of the dopant concentration or pumping source. The time-tunable emission was recorded with a commercially available camera. The dynamics of the emissions is thoroughly investigated, and we established that the energy transfer from the 1 D2 excited state of Tm3+ ions to the higher energy excited states of Tb3+ ions to be the principal mechanism to the population of the 5 D4 level for the Tb3+ ions.

Absolute upconversion quantum yields of blue-emitting LiYF4:Yb3+,Tm3+ upconverting nanoparticles.

The upconversion quantum yield (ΦUC) is an essential parameter for the characterization of the optical performance of lanthanoid-doped upconverting nanoparticles (UCNPs). Despite its nonlinear dependence on excitation power density (Pexc), it is typically reported only as a single number. Here, we present the first measurement of absolute upconversion quantum yields of the individual emission bands of blue light-emitting LiYF4:Yb3+,Tm3+ UCNPs in toluene. Reporting the quantum yields for the individual emission bands is required for assessing the usability of UCNPs in various applications that require upconverted light of different wavelengths, such as bioimaging, photocatalysis and phototherapy. Here, the reliability of the ΦUC measurements is demonstrated by studying the same batch of UCNPs in three different research groups. The results show that whereas the total upconversion quantum yield of these UCNPs is quite high-typically 0.02 at a power density of 5 W cm-2-most of the upconverted photon flux is emitted in the 794 nm upconversion band, while the blue emission band at 480 nm is very weak, with a much lower quantum yield of ∼6 × 10-5 at 5 W cm-2. Overall, although the total upconversion quantum yield of LiYF4:Yb3+,Tm3+ UCNPs seems satisfying, notably for NIR bioimaging, blue-light demanding phototherapy applications will require better-performing UCNPs with higher blue light upconversion quantum yields.

Upconverting nanoparticles: assessing the toxicity.

Lanthanide doped nanoparticles (Ln:NPs) hold promise as novel luminescent probes for numerous applications in nanobiophotonics. Despite excellent photostability, narrowband photoluminescence, efficient anti-Stokes emission and long luminescence lifetimes, which are needed to meet the requirements of multiplexed and background free detection at prolonged observation times, concern about their toxicity is still an issue for both in vivo and in vitro applications. Similar to other chemicals or pharmaceuticals, the very same properties that are desirable and potentially useful from a biomedical perspective can also give rise to unexpected and hazardous toxicities. In engineered bionanomaterials, the potentially harmful effects may originate not only from their chemical composition but also from their small size. The latter property enables the nanoparticles to bypass the biological barriers, thus allowing deep tissue penetration and the accumulation of the nanoparticles in a number of organs. In addition, nanoparticles are known to possess high surface chemical reactivity as well as a large surface-to-volume ratio, which may seriously affect their biocompatibility. Herein we survey the underlying mechanisms of nanotoxicity and provide an overview on the nanotoxicity of lanthanides and of upconverting nanoparticles.

Intense NIR emissions at 0.8 µm, 1.47 µm, and 1.53 µm from colloidal LiYbF4:Ln(3+) (Ln = Tm(3+) and Er(3+)) nanocrystals.

We report on the synthesis of diamond shaped Ln(3+)-doped LiYbF4 (Ln = Tm and Er) nanocrystals with flat edges via the thermal decomposition method. Strong near-infrared emissions at 0.8 µm, 1.47 µm and 1.53 µm are observed from colloidal dispersions of Tm(3+)-doped and Er(3+)-doped LiYbF4 nanocrystals, respectively, under 0.98 µm diode laser excitation. The NIR emission intensities for Tm(3+)-doped and Er(3+)-doped LiYbF4 nanocrystals are comparable with those of the sodium counterpart NaYbF4, suggesting that LiYbF4 is also an excellent host matrix for lanthanide ions to obtain strong NIR emissions in colloidal solutions of LiYbF4 (Tm(3+) or Er(3+)) nanocrystals.

Silica-coated LiYF4:Yb3+, Tm3+ upconverting nanoparticles are non-toxic and activate minor stress responses in mammalian cells.

Lanthanide-doped upconverting nanoparticles (UCNPs) are ideal candidates for use in biomedicine. The interaction of nanomaterials with biological systems determines whether they are suitable for use in living cells. In-depth knowledge of the nano-bio interactions is therefore a pre-requisite for the development of biomedical applications. The current study evaluates fundamental aspects of the NP-cell interface for square bipyramidal UCNPs containing a LiYF4:Yb3+, Tm3+ core and two different silica surface coatings. Given their importance for mammalian physiology, fibroblast and renal proximal tubule epithelial cells were selected as cellular model systems. We have assessed the toxicity of the UCNPs and measured their impact on the homeostasis of living non-malignant cells. Rigorous analyses were conducted to identify possible toxic and sub-lethal effects of the UCNPs. To this end, we examined biomarkers that reveal if UCNPs induce cell killing or stress. Quantitative measurements demonstrate that short-term exposure to the UCNPs had no profound effects on cell viability, cell size or morphology. Indicators of oxidative, endoplasmic reticulum, or nucleolar stress, and the production of molecular chaperones varied with the surface modification of the UCNPs and the cell type analyzed. These differences emphasize the importance of evaluating cells of diverse origin that are relevant to the intended use of the nanomaterials. Taken together, we established that short-term, our square bipyramidal UCNPs are not toxic to non-malignant fibroblast and proximal renal epithelial cells. Compared with established inducers of cellular stress, these UCNPs have minor effects on cellular homeostasis. Our results build the foundation to explore square bipyramidal UCNPs for future in vivo applications.

Janus Micromotors for Photophoretic Motion and Photon Upconversion Applications Using a Single Near-Infrared Wavelength.

External stimuli can trigger changes in temperature, concentration, and momentum between micromotors and the medium, causing their propulsion and enabling them to perform different tasks with improved kinetic efficiencies. Light-activated micromotors are attractive systems that achieve improved motion and have the potential for high spatiotemporal control. Photophoretic swarming motion represents an attractive means to induce micromotor movement through the generation of temperature gradients in the medium, enabling the micromotors to move from cold to hot regions. The micromotors studied herein are assembled with Fe3O4 nanoparticles, and NaGdF4:Yb3+,Er3+/NaGdF4:Yb3+ and LiYF4:Yb3+,Tm3+ upconverting nanoparticles. The Fe3O4 nanoparticles were localized to one hemisphere to produce a Janus architecture that facilitates improved upconversion luminescence with the upconverting nanoparticles distributed throughout. Under 976 nm excitation, Fe3O4 nanoparticles generate the temperature gradient, while the upconverting nanoparticles produce visible light that is used for micromotor motion tracking and triggering of reactive oxygen species generation. As such, the motion and application of the micromotors are achieved using a single excitation wavelength. To demonstrate the practicality of this system, curcumin was adsorbed to the micromotor surface and degradation of Rhodamine B was achieved with kinetic rates that were over twice as fast as the static micromotors. The upconversion luminescence was also used to track the motion of the micromotors from a single image frame, providing a convenient means to understand the trajectory of these systems. Together, this system provides a versatile approach to achieving light-driven motion while taking advantage of the potential applications of upconversion luminescence such as tracking and detection, sensing, nanothermometry, particle velocimetry, photodynamic therapy, and pollutant degradation.

Achieving photostability in dye-sensitized upconverting nanoparticles and their use in Fenton type photocatalysis.

Dye sensitization is a promising approach to enhance the luminescence of lanthanide-doped upconverting nanoparticles. However, the poor photostability of near-infrared dyes hampers their use in practical applications. To address this, commercial IR820 was modified for improved photostability and covalently bonded to amine-functionalized silica-coated LnUCNPs. Two methods of covalent linking were investigated: linking the dye to the surface of the silica shell, and embedding the dye within the silica shell. The photostability of the dyes when embedded in the silica shell exhibited upconversion emissions from NaGdF4:Er3+,Yb3+/NaGdF4:Yb3+ nanoparticles for over four hours of continuous excitation with no change in intensity. To highlight this improvement, the photostable dye-embedded system was successfully utilized for Fenton-type photocatalysis, emphasizing its potential for practical applications. Overall, this study presents a facile strategy to circumvent the overlooked limitations associated with photodegradation, opening up new possibilities for the use of dye-sensitized lanthanide-doped upconverting nanoparticles in a range of fields.

Biomolecules incorporated in halide perovskite nanocrystals: synthesis, optical properties, and applications.

Halide perovskite nanocrystals (HPNCs) have emerged at the forefront of nanomaterials research over the past two decades. The physicochemical and optoelectronic properties of these inorganic semiconductor nanoparticles can be modulated through the introduction of various ligands. The use of biomolecules as ligands has been demonstrated to improve the stability, luminescence, conductivity and biocompatibility of HPNCs. The rapid advancement of this field relies on a strong understanding of how the structure and properties of biomolecules influences their interactions with HPNCs, as well as their potential to extend applications of HPNCs towards biological applications. This review addresses the role of several classes of biomolecules (amino acids, proteins, carbohydrates, nucleotides, etc.) that have shown promise for improving the performance of HPNCs and their potential applications. Specifically, we have reviewed the recent advances on incorporating biomolecules with HP nanomaterials on the formation, physicochemical properties, and stability of HP compounds. We have also shed light on the potential for using HPs in biological and environmental applications by compiling some recent of proof-of-concept demonstrations. Overall, this review aims to guide the field towards incorporating biomolecules into the next-generation of high-performance HPNCs for biological and environmental applications.

The role of lanthanide luminescence in advancing technology.

Our society is indebted to the numerous inventors and scientists who helped bring about the incredible technological advances in modern society that we all take for granted. The importance of knowing the history of these inventions is often underestimated, although our reliance on technology is escalating. Lanthanide luminescence has paved the way for many of these inventions, from lighting and displays to medical advancements and telecommunications. Given the significant role of these materials in our daily lives, knowingly or not, their past and present applications are reviewed. A majority of the discussion is devoted to pointing out the benefits of using lanthanides over other luminescent species. We aimed to give a short outlook outlines promising directions for the development of the considered field. This review aims to provide the reader enough content to further appreciate the benefits that these technologies have brought into our lives, with the perspective of travelling among the past and latest advances in lanthanide research, aiming for an even brighter future.

Combining Pr3+-Doped Nanoradiosensitizers and Endogenous Protoporphyrin IX for X-ray-Mediated Photodynamic Therapy of Glioblastoma Cells.

Glioblastoma multiforme is an aggressive type of brain cancer with high recurrence rates due to the presence of radioresistant cells remaining after tumor resection. Here, we report the development of an X-ray-mediated photodynamic therapy (X-PDT) system using NaLuF4:25% Pr3+ radioluminescent nanoparticles in conjunction with protoporphyrin IX (PPIX), an endogenous photosensitizer that accumulates selectively in cancer cells. Conveniently, 5-aminolevulinic acid (5-ALA), the prodrug that is administered for PDT, is the only drug approved for fluorescence-guided resection of glioblastoma, enabling dual detection and treatment of malignant cells. NaLuF4:Pr3+ nanoparticles were synthesized and spectroscopically evaluated at a range of Pr3+ concentrations. This generated radioluminescent nanoparticles with strong emissions from the 1S0 excited state of Pr3+, which overlaps with the Soret band of PPIX to perform photodynamic therapy. The spectral overlap between the nanoparticles and PPIX improved treatment outcomes for U251 cells, which were used as a model for the thin tumor margin. In addition to sensitizing PPIX to induce X-PDT, our nanoparticles exhibit strong radiosensitizing properties through a radiation dose-enhancement effect. We evaluate the effects of the nanoparticles alone and in combination with PPIX on viability, death, stress, senescence, and proliferation. Collectively, our results demonstrate this as a strong proof of concept for nanomedicine.

Lanthanide-doped Na(x)ScF(3+x) nanocrystals: crystal structure evolution and multicolor tuning.

Rare-earth-based nanomaterials have recently drawn considerable attention because of their unique energy upconversion (UC) capabilities. However, studies of Sc(3+)-based nanomaterials are still absent. Herein we report the synthesis and fine control of Na(x)ScF(3+x) nanocrystals by tuning of the ratio of oleic acid (OA, polar surfactant) to 1-octadecene (OD, nonpolar solvent). When the OA:OD ratio was increased from low (3:17) to high (3:7), the nanocrystals changed from pure monoclinic phase (Na(3)ScF(6)) to pure hexagonal phase (NaScF(4)) via a transition stage at an intermediate OA:OD ratio (3:9) where a mixture of nanocrystals in monoclinic and hexagonal phases was obtained and the coexistence of the two phases inside individual nanocrystals was also observed. More significantly, because of the small radius of Sc(3+), Na(x)ScF(3+x):Yb/Er nanocrystals show different UC emission from that of NaYF(4):Yb/Er nanocrystals, which broadens the applications of rare-earth-based nanomaterials ranging from optical communications to disease diagnosis.

Enhancing upconverted white light in Tm3+/Yb3+/Ho3+-doped GdVO4 nanocrystals via incorporation of Li+ ions.

The white light emission of Tm3+/Yb3+/Ho3+-doped GdVO4 nanocrystals, following excitation with near-infrared light (λexc = 980 nm), via a multiphoton upconversion process is presented. Upconverted blue emission from the Tm3+ ions as well as green/red emissions from the Ho3+ ions contributes to the observed white light. The calculated Commission internationale de l'éclairage (CIE) color coordinates were calculated to be x = 0.34; y = 0.32 and lie at the center of the white region. Furthermore, the intensity of the upconverted white light was enhanced by the incorporation of monovalent Li+ ions into the GdVO4 matrix. An explanation for this enhancement is proposed based on X-ray diffraction and fluorescence lifetime measurements.

Synthesis of ligand-free colloidally stable water dispersible brightly luminescent lanthanide-doped upconverting nanoparticles.

The synthesis using the thermal decomposition of metal trifluoroacetates is being widely used to prepare oleate-capped lanthanide-doped upconverting NaYF(4):Er(3+)/Yb(3+) nanoparticles (Ln-UCNPs). These nanoparticles have no inherent aqueous dispersibility and inconvenient postsynthesis treatments are required to render them water dispersible. Here, we have developed a novel and facile approach to obtain water-dispersible, ligand-free, brightly upconverting Ln-UCNPs. We show that the upconversion luminescence is affected by the local environment of the lanthanide ions at the surface of the Ln-UCNPs. We observe a dramatic difference of the integrated upconverted red:green emission ratio for Ln-UCNPs dispersed in toluene compared to Ln-UCNPs dispersed in water. We can enhance or deactivate the upconversion luminescence by pH and H/D isotope vibronic control over the competitive radiative and nonradiative relaxation pathways for the red and green excited states. Direct biofunctionalization of the ligand-free, water-dispersible Ln-UCNPs will enable myriad new opportunities in targeting and drug delivery applications.

On the photostability and luminescence of dye-sensitized upconverting nanoparticles using modified IR820 dyes.

Dye sensitization is a promising route to enhance luminescence from lanthanide-doped upconverting nanoparticles (LnUCNPs) by improving the photon harvesting capability of LnUCNPs through the use of dye molecules, characterized by higher absorption coefficients. The literature does not fully address the poor photostability of NIR dyes, hindering solution-based applications. The improvements achieved by dye-sensitized LnUCNPs are usually obtained by comparison with non-dye sensitized LnUCNPs. This comparison results in exciting the LnUCNPs at different wavelengths with respect to the dye-sensitized LnUCNPs or at the same wavelengths, where, however, the non-dye sensitized LnUCNPs do not absorb. Both these comparisons are hardly conclusive for a quantification of the improvements achieved by dye-sensitization. Both shortcomings were addressed by studying the photodegradation via thorough spectroscopic evaluations of a 4-nitrothiophenol-modified and unmodified IR820-LnUCNP system. The modified IR820 dye system exhibits a 200% enhancement in the emission of NaGdF4:Er3+,Yb3+/NaGdF4:Yb3+ nanoparticles relative to the unmodified IR820-sensitized LnUCNPs and emits for over twice the duration, demonstrating a substantial improvement over previous dye-LnUCNP systems. Upconversion dynamics between the dyes and Er3+ establish the importance of back-transfer dynamics in modulating the dye-LnUCNP luminescence. Quantum yield measurements further illustrate the mechanism of sensitization and increased efficiency of this new nanosystem.

Cytotoxicity and Genotoxicity of Azobenzene-Based Polymeric Nanocarriers for Phototriggered Drug Release and Biomedical Applications.

Drug nanoencapsulation increases the availability, pharmacokinetics, and concentration efficiency for therapeutic regimes. Azobenzene light-responsive molecules experience a hydrophobicity change from a polar to an apolar tendency by trans-cis photoisomerization upon UV irradiation. Polymeric photoresponse nanoparticles (PPNPs) based on azobenzene compounds and biopolymers such as chitosan derivatives show prospects of photodelivering drugs into cells with accelerated kinetics, enhancing their therapeutic effect. PPNP biocompatibility studies detect the safe concentrations for their administration and reduce the chance of side effects, improving the effectiveness of a potential treatment. Here, we report on a PPNP biocompatibility evaluation of viability and the first genotoxicity study of azobenzene-based PPNPs. Cell line models from human ventricular cardiomyocytes (RL14), as well as mouse fibroblasts (NIH3T3) as proof of concept, were exposed to different concentrations of azobenzene-based PPNPs and their precursors to evaluate the consequences on mitochondrial metabolism (MTT assay), the number of viable cells (trypan blue exclusion test), and deoxyribonucleic acid (DNA) damage (comet assay). Lethal concentrations of 50 (LC50) of the PPNPs and their precursors were higher than the required drug release and synthesis concentrations. The PPNPs affected the cell membrane at concentrations higher than 2 mg/mL, and lower concentrations exhibited lesser damage to cellular genetic material. An azobenzene derivative functionalized with a biopolymer to assemble PPNPs demonstrated biocompatibility with the evaluated cell lines. The PPNPs encapsulated Nile red and dofetilide separately as model and antiarrhythmic drugs, respectively, and delivered upon UV irradiation, proving the phototriggered drug release concept. Biocompatible PPNPs are a promising technology for fast drug release with high cell interaction opening new opportunities for azobenzene biomedical applications.