Adding More Shape to Nanoscale Reference Materials─LiYF:Yb,Tm Bipyramids as Standards for Sizing Methods and Particle Number Concentration.

The increasing industrial use of nanomaterials calls for the reliable characterization of their physicochemical key properties like size, size distribution, shape, and surface chemistry, and test and reference materials (RMs) with sizes and shapes, closely matching real-world nonspheric nano-objects. An efficient strategy to minimize efforts in producing nanoscale RMs (nanoRMs) for establishing, validating, and standardizing methods for characterizing nanomaterials are multimethod nanoRMs. Ideal candidates are lanthanide-based, multicolor luminescent, and chemically inert nanoparticles (NPs) like upconversion nanoparticles (UCNPs), which can be prepared in different sizes, shapes, and chemical composition with various surface coatings.

A Strategy for Quantitative Imaging of Lanthanide Tags in A549 Cells Using the Ratio of Internal Standard Elements.

One remaining handicap for spatially resolved elemental quantification in biological samples is the lack of a suitable internal standard (IS) that can be reliably measured across both calibration standards and samples. In this work, multielement quantitative intracellular imaging of cells tagged with lanthanide nanoparticles containing key lanthanides, e.g.

Aggregation/Crystallization-Induced Emission in Naphthyridine-Based Carbazolyl-Modified Donor-Acceptor Boron Dyes Tunable by Fluorine Atoms.

Four donor-acceptor boron difluoride complexes based on the carbazole electron donor and the [1,3,5,2]oxadiazaborinino[3,4-a][1,8]naphthyridine acceptor were designed, synthesized, and systematically spectroscopically investigated in solutions, in dye-doped polymer films, and in the solid states. The dyes exhibit an intense blue to red solid-state emission with photoluminescence quantum yields of up to 59 % in pure dye samples and 86 % in poly(methyl methacrylate) films. All boron complexes show aggregation-induced emission and reversible mechanofluorochromism.

Frequency-Domain Method for Characterization of Upconversion Luminescence Kinetics.

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.

Assessing the reproducibility and up-scaling of the synthesis of Er,Yb-doped NaYF-based upconverting nanoparticles and control of size, morphology, and optical properties.

Lanthanide-based, spectrally shifting, and multi-color luminescent upconverting nanoparticles (UCNPs) have received much attention in the last decades because of their applicability as reporter for bioimaging, super-resolution microscopy, and sensing as well as barcoding and anti-counterfeiting tags. A prerequisite for the broad application of UCNPs in areas such as sensing and encoding are simple, robust, and easily upscalable synthesis protocols that yield large quantities of UCNPs with sizes of 20 nm or more with precisely controlled and tunable physicochemical properties from low-cost reagents with a high reproducibility. In this context, we studied the reproducibility, robustness, and upscalability of the synthesis of β-NaYF:Yb, Er UCNPs via thermal decomposition.

The potential of bioprinting for preparation of nanoparticle-based calibration standards for LA-ICP-ToF-MS quantitative imaging.

This paper discusses the feasibility of a novel strategy based on the combination of bioprinting nano-doping technology and laser ablation-inductively coupled plasma time-of-flight mass spectrometry analysis for the preparation and characterization of gelatin-based multi-element calibration standards suitable for quantitative imaging. To achieve this, lanthanide up-conversion nanoparticles were added to a gelatin matrix to produce the bioprinted calibration standards. The features of this bioprinting approach were compared with manual cryosectioning standard preparation, in terms of throughput, between batch repeatability and elemental signal homogeneity at 5 μm spatial resolution.

Quantification of the Activator and Sensitizer Ion Distributions in NaYF :Yb , Er Upconverting Nanoparticles Via Depth-Profiling with Tender X-Ray Photoemission.

The spatial distribution and concentration of lanthanide activator and sensitizer dopant ions are of key importance for the luminescence color and efficiency of upconverting nanoparticles (UCNPs). Quantifying dopant ion distributions and intermixing, and correlating them with synthesis methods require suitable analytical techniques. Here, X-ray photoelectron spectroscopy depth-profiling with tender X-rays (2000-6000 eV), providing probe depths ideally matched to UCNP sizes, is used to measure the depth-dependent concentration ratios of Er to Yb , [Er ]/[Yb ], in three types of UCNPs prepared using different reagents and synthesis methods.

Composition, thickness, and homogeneity of the coating of core-shell nanoparticles-possibilities, limits, and challenges of X-ray photoelectron spectroscopy.

Core-shell nanoparticles have attracted much attention in recent years due to their unique properties and their increasing importance in many technological and consumer products. However, the chemistry of nanoparticles is still rarely investigated in comparison to their size and morphology. In this review, the possibilities, limits, and challenges of X-ray photoelectron spectroscopy (XPS) for obtaining more insights into the composition, thickness, and homogeneity of nanoparticle coatings are discussed with four examples: CdSe/CdS quantum dots with a thick coating and a small core; NaYF-based upconverting nanoparticles with a large Yb-doped core and a thin Er-doped coating; and two types of polymer nanoparticles with a poly(tetrafluoroethylene) core with either a poly(methyl methacrylate) or polystyrene coating.

Stability, dissolution, and cytotoxicity of NaYF-upconversion nanoparticles with different coatings.

Upconversion nanoparticles (UCNPs) have attracted considerable attention owing to their unique photophysical properties. Their utilization in biomedical applications depends on the understanding of their transformations under physiological conditions and their potential toxicity. In this study, NaYF:Yb,Er UCNPs, widely used for luminescence and photophysical studies, were modified with a set of four different coordinatively bound surface ligands, i.

Time-resolved luminescence spectroscopy for monitoring the stability and dissolution behaviour of upconverting nanocrystals with different surface coatings.

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.

Simple Self-Referenced Luminescent pH Sensors Based on Upconversion Nanocrystals and pH-Sensitive Fluorescent BODIPY Dyes.

We present the design and fabrication of pH responsive ratiometric dual component sensor systems based on multicolor emissive upconversion nanoparticles (UCNP) and pH sensitive BODIPY dyes with tunable p K values embedded into a polymeric hydrogel matrix. The use of NIR excitable NaYF:Yb,Tm UCNPs enables background free read-out. Furthermore, the spectrally matching optical properties of the UCNPs and the dyes allow the UCNPs to serve as excitation light source for the analyte-responsive BODIPY as well as intrinsic reference.

Surface Modifications for Photon-Upconversion-Based Energy-Transfer Nanoprobes.

An emerging class of inorganic optical reporters are near-infrared (NIR) excitable lanthanide-based upconversion nanoparticles (UCNPs) with multicolor emission and long luminescence lifetimes in the range of several hundred microseconds. For the design of chemical sensors and optical probes that reveal analyte-specific changes in their spectroscopic properties, these nanomaterials must be combined with sensitive indicator dyes that change their absorption and/or fluorescence properties selectively upon interaction with their target analyte, utilizing either resonance energy transfer (RET) processes or reabsorption-related inner filter effects. The rational development of UCNP-based nanoprobes for chemical sensing and imaging in a biological environment requires reliable methods for the surface functionalization of UCNPs, the analysis and quantification of surface groups, a high colloidal stability of UCNPs in aqueous media as well as the chemically stable attachment of the indicator molecules, and suitable instrumentation for the spectroscopic characterization of the energy-transfer systems and the derived nanosensors.