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Tailor-made nanoparticles are of increasing interest in e.g. catalysis, as sensor materials, analytical assays, or can have superior photophysical properties. A major issue concerning the preparation of high-quality and functional nanoparticles is a good control of particle size, shape, polydispersity, and composition.
Small Angle X-ray Scattering (SAXS) is a non-destructive method for the analysis of nanostructures in a wide variety of materials. This method allows determining averaged structural parameters on a length scale from just above atomic sizes up to several 100 nanometers such as sizes, size distributions, volume fractions, and inner surface sizes. Moreover, anomalous Small Angle X-ray Scattering (ASAXS) exploits the anomalous dispersion of the scattering amplitudes near the X-ray absorption edges of the elements contained in the sample. These element sensitive contrast variations can be used to analyse average composition fluctuations on the nm scale. Two kinds of nanoparticles are chosen here to elaborate the advantages of ASAXS in the analysis of complex materials.
A facile and efficient methodology is developed for the thermal synthesis of size-tunable, stable, and uniform bimetallic NiCu core–shell nanoparticles (NPs) for various application in catalysis. Their diameter can be tuned in a range from 6 nm to 30 nm and the Ni:Cu ratio is adjustable in a wide range from 1:1 to 30:1. The NPs are structurally characterized by a method combination of transmission electron microscopy, anomalous small-angle X-ray scattering (ASAXS), X-ray absorption fine structure, and X-ray photoelectron spectroscopy. Here, we focus on the ASAXS method and its ability to analyses nanostructure parts and their compositions at once. As a result, a NiCu alloyed core surrounded by a Ni enriched shell and an outer NiO shell was found.
Semiconductor nanocrystals (quantum dots, QDs) are well known for their superior photophysical properties and enabled advancements in several key technologies of the 21st century and numerous technological applications like in photovoltaics, LED displays, photocatalysis, and biosensing. To achieve high photoluminescence quantum yields (PLQY) and enhanced photostability the QD core needs to be passivated by a second semiconductor, which possess a larger band gap to confine the charges within the QD core. An important parameter is thereby the lattice mismatch between the core and shell. To avoid strong lattice strain, which would alter the photophysical properties, an intermediary shell can be used as a lattice adapter between the core and the outer shell leading to core/shell/shell systems. These systems have shown to possess high PLQYs combined with a strong long-term stability and can be found in modern QLED displays. ASAXS was used here to better understand the core/shell/shell structure of InP/ZnSe/ZnS QDs to enable a correlation between their structural and photophysical properties.
Inorganic nanocrystals with linear and nonlinear luminescence in the ultraviolet, visible, near infrared and shortwave infrared like semiconductor quantum dots and spectrally shifting lanthanide-based nanophosphors have meanwhile found applications in the life and material sciences ranging from optical reporters for bioimaging and sensing over security barcodes to solid state lighting and photovoltaics. These nanomaterials commonly have increasingly sophisticated core/shell particle architectures with shells of different chemical composition and thickness to minimize radiationless deactivation at the particle surface that is usually the main energy loss mechanism [1]. For lanthanide-based spectral shifters, particularly for very small nanoparticles, also surface coatings are needed which protect near-surface lanthanide ions from luminescence quenching by high energy vibrators like O-H groups and prevent the disintegration of these nanoparticles under high dilution conditions. [2,3,4]. The identification of optimum particle structures requires quantitative spectroscopic studies focusing on the key performance parameter photoluminescence quantum yield [5,6], ideally flanked by single particle studies to assess spectroscopic inhomogeneities on a particle-to-particle level for typical preparation methods [7], Moreover, in the case of upconversion nanoparticles with a multi-photonic and hence, excitation power density (P)-dependent luminescence, quantitative luminescence studies over a broad P range are required to identify particle architectures that are best suited for applications in fluorescence assays up to fluorescence microscopy. Here, we present methods to quantify the photoluminescence of these different types of emitters in the vis/NIR/SWIR and as function of Pand demonstrate the importance of such measurements for a profound mechanistic understanding of the nonradiative deactivation pathways in semiconductor and upconversion nanocrystals of different size and particle architecture in different environments.
Multiplexed encoding schemes of nano- and micrometer sized particles with fluorescent dyes or quantum dots (QDs) and their optical detection, are of increasing interest for applications in the life sciences, for example in flow cytometry. Almost all strategies utilizing fluorescence focus on spectrally distinguishable emission bands or colors and different intensity levels as fluorescence codes. The fluorescence parameter lifetime has been, however, barely exploited. In this work the goal is to perform multiplexing with encoding fluorophores with different fluorescence lifetimes (LTs). In comparison to the spectral multiplexing strategies this has the advantage, that the different fluorescence LT codes can be measured with the excitation and emission wavelength, thus reducing instrument costs. Moreover, LTs should not depend on emitter concentration. Unlike organic dyes, the LTs of which are typically < 10 ns, the fluorescence LTs of ternary semiconductor QDs that represent a “green” alternative to conventional Cd-containing QDs are in the range of several hundred ns, independent of oxygen concentration, and can be tuned to a certain extent by chemical composition and surface chemistry. This present a time region that can be barely covered by other emitters that have either much shorter or longer lifetimes. In this project, different encoding strategies will be assessed and the encoded particles will be then used for fluorescence assays for the analysis of several targets in parallel. Therefor the encoded particles will be functionalized with different target-specific bioligands and read out with a specifically designed flow cytometer enabling time-resolved fluorescence detection. With this instrument, the particles will be discriminated by their fluorescence LTs In one detection channel while the analytes will be quantified by fluorescence labels in a second channel in the intensity domain.
Multiplexed encoding schemes of nano- and micrometer sized polymer particles with fluorescent dyes or quantum dots (QDs) and their optical detection, are of increasing interest for applications in the life sciences, for example in flow cytometry. Almost all strategies utilizing fluorescence focus on spectrally distinguishable emission bands or colors and different intensity levels as fluorescence codes.
In this work the goal is to perform multiplexing with encoding fluorophores with different fluorescence lifetimes (LTs). In comparison to the spectral multiplexing strategies this has the advantage, that the different fluorescence LT codes can be measured with the same excitation and emission wavelength, thus reducing instrumental costs. Moreover, LTs should not depend on emitter concentration. Unlike organic dyes, the LTs of which are typically <10ns, the fluorescence LTs of ternary semiconductor QDs which represent a “green” alternative to conventional Cd-containing QDs are in the range of several hundred ns, independent of oxygen concentration, and can be tuned to a certain extent by chemical composition and surface chemistry. This presents a time region that can barely be covered by other emitters that have either much shorter or longer lifetimes. In this project, different encoding strategies will be assessed, and the encoded particles will then be used for fluorescence assays for the analysis of several targets in parallel. Therefore, the encoded particles will be functionalized with different target-specific bioligands and read out with a specifically designed flow cytometer enabling time-resolved fluorescence detection. With this instrument, the particles will be discriminated by their fluorescence LTs in one detection channel while the analytes will be quantified by fluorescence labels in a second channel in the intensity domain.
Spectral encoding of cells or particles and the discrimination of multiple spectral codes are a critical process in flow cytometry (FCM). Typical issues in spectral encoding are, e.g., the spectral overlap of codes, or the increasing complexity of instruments . The exploitation of the photoluminescence lifetime (LT) as an encoding parameter could be used to circumvent both of these issues, as it adds another dimension to the parameter space, or, when used as a stand-alone parameter, requiring only one excitation light source and one detector. While LT encoding was considered already decades ago it is still not implemented as a routine technique in FCM yet, mainly due to the challenge of very few photons being available within the limited transition time of a cell or particle through the laser spot.
Recently, we demonstrated LT-FCM based on luminophores with ns LTs in a compact and low-cost flow cytometer. Measurements on polymer microbeads containing luminophores with distinctly different excited state LTs enabled the complete discrimination of three LT codes and five codes in total could be identified.
Now, we have extended our approach towards considerably longer LTs by custom-made polymer microbeads loaded with different ratios of InP/ZnS and AgInS2 quantum dots. The use of these materials significantly expands the usable time range for LT encoding to up to several hundred ns. Our studies demonstrate the possibility to further increase the number of viable LT codes for multiplexing in LT-FCM without the need for extensive hardware modifications.
The comparison of different emitter classes and the rational design of the next generation of molecular and nanoscale reporters require accurate and quantitative photo-luminescence measurements. This is of special importance for all photoluminescence applications in the life and material sciences and nanobiophotonics. In the following, procedures for the determination of the spectroscopic key parameter photoluminescence quantum yield, i.e., the number of emitted per absorbed photons, in the UV/vis/NIR/SWIR are presented including pitfalls and achievable uncertainties and material-specific effects related to certain emitter classes are addressed.
Photoluminescence applications in the life and material sciences require bright molecular and nanocrystalline emitters, stimuli-responsive optical probes, signal enhancement, multiplexing, and barcoding strategies and traceable methods to quantify the signal-relevant optical properties of luminescent materials at the ensemble and single molecule/particle level. In this context, current research at Division Biophotonics of BAM is presented ranging from dye and nanocrystal photophysics, absolute measurements of photoluminescence quantum yields in the UV/vis/NIR/SWIR, lifetime multiplexing, and the development of different types of fluorescence standards for validating optical-spectroscopic measurements.
The rational synthesis and use of nanomaterials require the characterization of many different properties, ranging from particle size and size distribution over surface chemistry to more applicationrelevant features like optical, electrochemical, and magnetic properties. In the following, several methods for the characterization of functional groups on nanomaterials, like polymer and silica nanoparticles, semiconductor quantum dots, and lanthanide-based upconversion nanocrystals are presented. Additionally, procedures for the measurement of the key spectroscopic performance parameters of nanomaterials with linear and nonlinear photoluminescence, such as the photoluminescence quantum yield, are presented for the UV/vis/NIR/SWIR.
Nanomaterials are used in many different applications in the material and life sciences. Examples are optical reporters, barcodes, and nanosensors, magnetic and optical contrast agents, and catalysts. Due to their small size and large surface area, there are also concerns about their interaction with and uptake by biological systems. This has initiated an ever increasing number of cyctoxicity studies of nanomaterials of different chemical composition and surface chemistry, but until now, the toxicological results presented by different research groups often do not address or differ regarding a potential genotoxicity of these nanomaterials. This underlines the need for a standardized test procedure to detect genotoxicity.1,2
Aiming at the development of fast, easy to use, and automatable microscopic methods for the determination of the genotoxicity of different types of nanoparticles, we assess the potential of the fluorometric γH2AX assay for this purpose. This assay, which can be run on an automated microscopic detection system, relies on the determination of DNA double strand breaks as a sign for genotoxicity.3 Here, we present first results obtained with broadly used nanomaterials like CdSe/CdS and InP/ZnS quantum dots as well as iron oxide, gold, and polymer particles of different surface chemistry with previously tested colloidal stability. These studies will be also used to establish nanomaterials as positive and negative genotoxicity controls or standards for assay performance validation for users of this fluorometric genotoxicity assay. In the future, after proper validation, this microscopic platform technology will be expanded to other typical toxicity assays.
References. (1) Landsiedel, R.; Kapp, M. D.; Schulz, M.; Wiench, K.; Oesch, F., Reviews in Mutation Research 2009, 681, 241-258. (2) Henriksen-Lacey, M.; Carregal-Romero, S.; Liz-Marzán, L. M., Bioconjugate Chem. 2016, 28, 212-221. (3) Willitzki, A.; Lorenz, S.; Hiemann, R.; Guttek, K.; Goihl, A.; Hartig, R.; Conrad, K.; Feist, E.; Sack, U.; Schierack, P., Cytometry Part A 2013, 83, 1017-1026.
Correlating the photoluminescence (PL) properties of nanomaterials like semiconductor nanocrystals (QDs) and upconversion nanocrystals (UCNPs) assessed in ensemble studies and at the single particle level is increasingly relevant for applications of these nanomaterials in the life sciences like bioimaging studies or their use as reporters in microfluidic assays. Here we present a comparison of the spectroscopic properties of ensembles and single emitters for QDs like II/VI QDs and cadmium-free AIS/ZnS QDs as well as different UCNPs. The overall goal of this study was to derive particle architectures well suited for spectroscopic and microscopic applications.