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Photon upconversion upon 1550 nm excitation is of high relevance for applications in the third biological excitation window, for photovoltaics beyond current limitations, and enables appealing options in the field of glass Fiber telecommunications. Trivalent doped erbium ions (Er3+) are the material of choice for 1550 nm excited upconversion, however, they suffer from a low absorption cross-section and a low brightness. Therefore, the ability of Silicon metasurfaces to provide greatly enhanced electrical near-fields is employed to enable efficient photon upconversion even at low external Illumination conditions. Hexagonally shaped β-NaYF4:Er3+ nanoparticles are placed on large-area silicon metasurfaces designed to convert near-infrared (1550 nm) to visible light. More than 2400-fold enhanced photon upconversion luminescence is achieved by using this metasurface instead of a planar substrate.
With the aid of optical simulations based on the finite-element method, this result is attributed to the coupling of the excitation source with metasurface resonances at appropriate incident angles. Analysis of the excitation power density dependence of upconversion luminescence and red-to-green-emission ratios enables the estimation of nanoscale near-field enhancement on the metasurface. The findings permit the significant reduction of required external excitation intensities for photon upconversion of 1550 nm light, opening perspectives in biophotonics, telecommunication, and photovoltaics.
We demonstrate the potential of time-resolved luminescence spectroscopy for the straightforward assessment and in situ monitoring of the stability of upconversion nanocrystals (UCNPs). Therefore, we prepared hexagonal NaYF4:Yb3+,Er3+ UCNPs with various coatings with a focus on phosphonate ligands of different valency, using different ligand exchange procedures, and studied their dissolution behaviour in phosphate-buffered saline (PBS) dispersions at 20 °C and 37 °C with various analytical methods. The amount of the released UCNPs constituting fluoride ions was quantified by potentiometry using a Fluoride ion-sensitive electrode and particle disintegration was confirmed by transmission electron microscopy studies of the differently aged UCNPs. In parallel, the luminescence features of the UCNPs were measured with special emphasis on the lifetime of the sensitizer emission to demonstrate its suitability as Screening parameter for UCNP stability and changes in particle composition. The excellent correlation between the changes in luminescence lifetime and fluoride concentration highlights the potential of our luminescence lifetime method for UCNP stability screening and thereby indirect monitoring of the release of potentially hazardous fluoride ions during uptake and dissolution in biological systems. Additionally, the developed in situ optical method was used to distinguish the dissolution dynamics of differently sized and differently coated UCNPs.
Imaging in the shortwave-infrared region (SWIR, λ = 1000–2500 nm) has the potential to enable deep tissue imaging with high resolution. Critical to the development of these Methods is the identification of low molecular weight, biologically compatible fluorescent probes that emit beyond 1000 nm.
Exchanging the bridging oxygen atom on the xanthene scaffold (C10’ position) with electron withdrawing groups has been shown to lead to significant redshifts in absorbance and emission. Guided by quantum chemistry computational modeling studies, we investigated the installation of a Ketone bridge at the C10’ position. This simple modification extends the absorbance maxima to 860 nm and the emission beyond 1000 nm, albeit with reduced photon output. Overall, These studies demonstrate that broadly applied xanthene dyes can be extended into the SWIR range.
Scattering luminescent materials dispersed in liquid and solid matrices and luminescent powders are increasingly relevant for fundamental research and industry. Examples are luminescent nano- and microparticles and phosphors of different compositions in various matrices or incorporated into ceramics with applications in energy conversion, solid-state lighting, medical diagnostics, and security barcoding. The key parameter to characterize the performance of these materials is the photoluminescence/fluorescence quantum yield (Φf), i.e., the number of emitted photons per number of absorbed photons. To identify and quantify the sources of uncertainty of absolute measurements of Φf of scattering samples, the first interlaboratory comparison (ILC) of three laboratories from academia and industry was performed by following identical measurement protocols. Thereby, two types ofcommercial stand-alone integrating sphere setups with different illumination and detection geometries were utilized for measuring the Φf of transparent and scattering dye solutions and solid phosphors, namely, YAG:Ce optoceramics of varying surface roughness, used as converter materials for blue light emitting diodes. Special emphasis was dedicated to the influence of the measurement geometry, the optical properties of the blank utilized to determine the number of photons of the incident excitation light absorbed by the sample, and the sample-specific surface roughness. While the Φf values of the liquid samples matched between instruments, Φf measurements of the optoceramics with different blanks revealed substantial differences. The ILC results underline the importance of the measurement geometry, sample position, and blank for reliable Φf data of scattering the YAG:Ce optoceramics, with the blank’s optical properties accounting for uncertainties exceeding 20%.
In summary, we report a highly modular solid TTA-UC system comprising of a crystalline, thermally stable PCN222(Pd) MOF with CA-coated MOF channels and with a DPA annihilator embedded in a solution-like environment in the MOF channels. This solid material displays blue upconverted delayed emission with a luminescence lifetime of 373 us, a threshold value of 329 mW*cm-2 and a triplet–triplet energy transfer efficiency of 82%. This optical application adds another facet to the versatile chemistry of PCN-222 MOFs. The design concept is also applicable to other TTA-UC pairs and enables tuning of the UCL color, for example, by replacing DPA with other dyes as exemplarily shown for 2,5,8,11-tetra-tert-butyl-perylene, that yields UCL at 450 nm. Current work aims to reduce the oxygen sensitivity and to increase the retention of the trapped annihilators in organic environments, for example, by tuning the chain length of the carboxylic acid and by coating the MOF surface. In addition, the TTA-UC efficiency will be further enhanced by reducing the reabsorption of the UC emission caused by Pd(TCPP) and by optimizing the sensitizer/annihilator interface.
Lanthanide-doped upconversion nanoparticles (UCNPs) are of great interest for biomedical applications. Currently, the applicability of UCNP bionanotechnology is hampered by the generally low luminescence intensity of UCNPs and inefficient energy Transfer from UCNPs to surface-bound chromophores used e.g. for photodynamic therapy or analyte sensing. In this work, we address the low-Efficiency issue by developing versatile core-Shell nanostructures, where high-concentration sensitizers and activators are confined in the core and Shell Region of representative hexagonal NaYF2:Yb,Er UCNPs. After Doping concentration optimization, the sensitizer-rich core is able to harvest/accumulate more excitation energy and generate almost one order of Magnitude higher luminescence intesity than conventional homogeneously doped nanostructures. At the same time, the activator Ions located in the Shell enable a ~6 times more efficient resonant energy Transfer from UCNPs to surface-bound acceptor dye molecules due to the short distance between donor-acceptor pairs. Our work provides new insights into the rational design of UCNPs and will greatly encrease the General applicability of upconversion nanotechnologies.
To demonstrate the potential of time-resolved flow cytometry (FCM) for bioanalysis, clinical diagnostics, and optically encoded bead-based assays, we performed a proof-of-principle study to detect biomolecular interactions utilizing fluorescence lifetime (LT)-encoded micron-sized polymer beads bearing target-specific bioligands and a recently developed prototype lifetime flow cytometer (LT-FCM setup). This instrument is equipped with a single excitation light source and different fluorescence detectors, one operated in the photon-counting mode for time-resolved measurements of fluorescence decays and three detectors for conventional intensity measurements in different spectral windows. First, discrimination of bead-bound biomolecules was demonstrated in the time domain exemplarily for two targets, Streptavidin (SAv) and the tumor marker human chorionic gonadotropin (HCG). In a second step, the determination of biomolecule concentration levels was addressed representatively for the inflammation-related biomarker tumor necrosis factor (TNF-α) utilizing fluorescence intensity measurements in a second channel of the LT-FCM instrument. Our results underline the applicability of LT-FCM in the time domain for measurements of biomolecular interactions in suspension assays. In the future, the combination of spectral and LT encoding and multiplexing and the expansion of the time scale from the lower nanosecond range to the longer nanosecond and the microsecond region is expected to provide many distinguishable codes. This enables an increasing degree of multiplexing which could be attractive for high throughput screening applications.
Risk assessment of nanomaterials requires not only standardized toxicity studies but also validated methods for nanomaterial surface characterization with known uncertainties. In this context, a first bilateral interlaboratory comparison on Surface group quantification of nanomaterials is presented that assesses different reporter-free and labeling methods for the quantification of the total and accessible number of amine functionalities on commercially available silica nanoparticles that are widely used in the life sciences. The overall goal of this comparison is the identification of optimum methods as well as achievable measurement uncertainties and the comparability of the results across laboratories. We also examined the robustness and ease of implementation of the applied analytical methods and discussed method-inherent limitations. In summary, this comparison presents a first step toward the eventually required standardization of methods for surface group quantification.
The frequency-domain (FD) method provides an alternative to the commonly used time-domain (TD) approach in characterizing the luminescence kinetics of luminophores, with its own strengths, e.g., the capability to decouple multiple lifetime components with higher reliability and accuracy. While extensively explored for characterizing luminophores with down-shifted emission, this method has not been investigated for studying nonlinear luminescent materials such as lanthanide-doped upconversion nanoparticles (UCNPs), featuring more complicated kinetics. In this work, employing a simplified rate-equation model representing a standard two-photon energy-transfer upconversion process, we thoroughly analyzed the response of the luminescence of UCNPs in the FD method. We found that the FD method can potentially obtain from a single experiment the effective decay rates of three critical energy states of the sensitizer/activator ions involved in the upconversion process. The validity of the FD method is demonstrated by experimental data, agreeing reasonably well with the results obtained by TD methods.
Introduction. Comparing different emitter classes and rationally designing the next generation of molecular and nanoscale probes for bioimaging applications require accurate and quantitative methods for the measurement of the key parameter photoluminescence quantum yield f.1 f equals the number of emitted per number of absorbed photons. This is particularly relevant for increasingly used fluorescence imaging in the short wave-infrared region (SWIR) ≥ 900 nm providing deeper penetration depths, a better image resolution, and an improved signal-to-noise or tumor-to-background ratio.2, 3 However, spectroscopic measurements in the SWIR are more challenging and require specific calibrations and standards.