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Harnessing the synergy between upconverting nanoparticles and lanthanide complexes in a multi-wavelength responsive hybrid system
摘要： We prepared a hybrid system composed of a continuous film of dinuclear lanthanide complex [Ln2bpm(tfaa)6] (Ln = Tb or Eu) and upconverting nanoparticles (UCNPs) using a straightforward drop-cast methodology. The system displayed visible emission under near-infrared (NIR) excitation, simultaneously stemming from sub-10-nm UCNPs and [Ln2] complexes, the latter species being otherwise directly excitable only using UV-blue radiation. In light of the results of steady-state – including power-dependent – and time-resolved optical measurements, we identified the radiative, primarily ligand-mediated nature of the energy transfer from Tm3+ ions in the UCNPs-to-Ln3+ ions in the complexes. Hyperspectral mapping and electron microscopy observations of the surface of the hybrid system confirmed the continuous and concomitant distribution of UCNPs and lanthanide complexes over the extensive composite films. Key features of the hybrid system are the simultaneous UV-blue and NIR light harvesting capabilities and their ease of preparation. These traits render the presented hybrid system a formidable candidate for the development of photoactivated devices capable to operate under multiple excitation wavelength and to transduce the absorbed light into narrow, well-defined spectral regions.
关键词： hybrid system,complex,energy transfer,lanthanide,films,upconverting nanoparticles,hyperspectral imaging
更新于2025-09-23 15:23:52
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Apparent self-heating of individual upconverting nanoparticle thermometers
摘要： Individual luminescent nanoparticles enable thermometry with sub-diffraction limited spatial resolution, but potential self-heating effects from high single-particle excitation intensities remain largely uninvestigated because thermal models predict negligible self-heating. Here, we report that the common “ratiometric” thermometry signal of individual NaYF4:Yb3+,Er3+ nanoparticles unexpectedly increases with excitation intensity, implying a temperature rise over 50 K if interpreted as thermal. Luminescence lifetime thermometry, which we demonstrate for the first time using individual NaYF4:Yb3+,Er3+ nanoparticles, indicates a similar temperature rise. To resolve this apparent contradiction between model and experiment, we systematically vary the nanoparticle’s thermal environment: the substrate thermal conductivity, nanoparticle-substrate contact resistance, and nanoparticle size. The apparent self-heating remains unchanged, demonstrating that this effect is an artifact, not a real temperature rise. Using rate equation modeling, we show that this artifact results from increased radiative and non-radiative relaxation from higher-lying Er3+ energy levels. This study has important implications for single-particle thermometry.
关键词： upconverting nanoparticles,NaYF4:Yb3+,Er3+,thermometry,luminescence,self-heating
更新于2025-09-23 15:21:21
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Near-Infrared-Detached Adhesion Enabled by Upconverting Nanoparticles
摘要： Achieving efficient and biocompatible detachment between adhered wet materials (i.e., tissues and hydrogels) is a major challenge. Recently, photodetachable topological adhesion has shown great promise as a strategy for conquering this hurdle. However, this photodetachment was triggered by UV light with poor biocompatibility and penetration capacity. This study describes near-infrared (NIR) light-detached topological adhesion based on polyacrylic acid coated upconverting nanoparticles (UCNP@PAA) and a photodetachable adhesive (termed Cell-Fe). Cell-Fe is a coordinated topological adhesive consisting of carboxymethylcellulose and Fe3+ that can be photodecomposed by UV light. To prepare a substrate for NIR-detached topological adhesion, UCNP@PAA and Cell-Fe were mixed and brushed on the surface of the model adherent. The UCNP@PAA can harvest NIR light and convert it into UV light, triggering the decomposition of the Cell-Fe and inducing the detachment. This NIR-detached topological adhesion is also feasible in deep tissue because of the ability of NIR light to penetrate tissue.
关键词： upconverting nanoparticles,NIR-detached adhesion,biocompatibility,deep tissue
更新于2025-09-23 15:19:57
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Energy Transfer Networks Within Upconverting Nanoparticles Are Complex Systems With Collective, Robust, and History-Dependent Dynamics
摘要： Applications of photon upconverting nanoparticles (UCNPs) in biological imaging and solar energy conversion demand that their anti-Stokes luminescence be both tunable and efficient. Rational design of more efficient UCNPs requires an understanding of energy transfer (ET) between their lanthanide dopants – dynamics that are typically characterized by measuring luminescence lifetimes. Existing knowledge, however, cannot explain basic observations in lifetime experiments such as their dependence on excitation power, significantly limiting the generality and reliability of lifetime measurements. Here, we elucidate the origins of the ET dynamics and luminescence lifetimes of Yb3+,Er3+-codoped NaYF4 UCNPs using time-resolved luminescence and novel applications of rate equations and stochastic simulations. Experiments and calculations consistently show that, at high concentrations of Er3+, the luminescence lifetimes of UCNPs decrease as much as 6-fold when excitation power densities are increased over six orders of magnitude. Since power-dependent lifetimes cannot be explained by intrinsic relaxation rates of individual transitions, we analyze lifetime data by treating each UCNP as a complex ET network. We find that UCNP ET networks exhibit four distinguishing characteristics of complex systems: collectivity, nonlinear feedback, robustness, and history dependence. We conclude that power-dependent lifetimes are the consequence of thousands of minor relaxation pathways that act collectively to depopulate and repopulate Er3+ emitting levels. These ET pathways are dependent on past excitation power because they originate from excited donors and excited acceptors; however, each transition has an unexpectedly small impact on lifetimes due to negative feedback in the network. This robustness is determined by systematically 'knocking out,' or disabling, ET transitions in kinetic models. Our classification of UCNP ET networks as complex systems explains why UCNP luminescence lifetimes do not match the intrinsic lifetimes of emitting states. In the future, UCNP networks may be engineered to rival the complexity of biological networks that pattern features with unmatched precision.
关键词： complex systems,energy transfer,upconverting nanoparticles,lanthanide dopants,power dependence,luminescence lifetimes
更新于2025-09-19 17:15:36
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Time-resolved universal temperature measurements using NaYF <sub/>4</sub> :Er <sup>3+</sup> ,Yb <sup>3+</sup> upconverting nanoparticles in an electrospray jet
摘要： Hexagonal upconverting nanoparticles (UCNPs) of NaYF4:Er3+,Yb3+ (ca. 300 nm) have been widely used to measure the temperature at the nanoscale using luminescence ratio thermometry. However, several factors limit their applications. For example, changes in the peak shape, mainly is the S-band emission, hinders their ability to be used as a universal temperature sensor. Herein, we introduce a universal calibration protocol for NaYF4:Er3+,Yb3+ upconverting nanoparticles that is robust to environmental changes and gives a precise temperature measurement. We used this new procedure to calculate the temperature profile inside a Taylor cone generated with an electrospray jet. Inside the Taylor cone the fluid velocity increases toward the tip of the cone. A constant acquisition length leads to a decrease in excitation and acquisition time. This decrease in excitation time causes a peak shape change that corrupts the temperature measurement if the entire peak shape is integrated in the calibration. Our universal calibration circumvents this problem and can be used for time-resolved applications. The temperature at the end of the Taylor cone increases due to the creation of a whispering gallery mode cavity with 980 nm excitation. We use time-resolved energy balance equations to support our optical temperature measurements inside the Taylor cone. We believe that the findings of this paper provide a foundation for time-resolved temperature measurements using NaYF4:Er3+,Yb3+ upconverting nanoparticles and can be used to understand temperature-dependent reactions such as protein unfolding inside microjet/microdroplets and microfluidic systems.
关键词： upconverting nanoparticles,microjet,nanothermometry,electrospray,temperature measurement,time-resolved measurement
更新于2025-09-10 09:29:36
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Spin–Lattice Relaxation and Diffusion Processes in Aqueous Solutions of Gadolinium-Based Upconverting Nanoparticles at Different Magnetic Fields
摘要： We investigated the influence of gadolinium (Gd)-based upconverting nanoparticles (UCNPs) on water spin–lattice relaxation (T1) and diffusion at different magnetic field strengths (0.4 T and 9.4 T). Our findings show that smaller NPs (12 nm compared to 19 nm) were more favourable for proton relaxivity. We also demonstrate that using simplified Solomon–Bloembergen–Morgan (SBM) model we can associate two measured diffusion coefficients with processes occurring near the surface of UCNPs and in bulk water. Using the relationship between relaxation and diffusion, we can estimate not only the total impact of NPs on relaxation of water molecules, but also the impact on relaxation of local water molecules, directly connected to paramagnetic Gd3+ ions in NPs. Different magnetic field strengths did not alter the spin–lattice relaxivity of NPs. This suggests that Gd-based UCNPs could be developed into high-performance multimodal magnetic resonance imaging contrast agents working over a broad range of imaging field strengths used in clinical routine.
关键词： Magnetic fields,MRI contrast agents,Gadolinium-based upconverting nanoparticles,Diffusion processes,Spin–lattice relaxation
更新于2025-09-04 15:30:14