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In November 2007, OECD’s Working Party on Manufactured Nanomaterials (WPMN) launched the Sponsorship Programme for the Testing of Manufactured Nanomaterials (hereafter the Testing Programme). The objective was to conduct specific tests, relevant to human health and environmental safety endpoints, on a variety of manufactured nanomaterials (MN). The outcomes of the Testing Programme were intended to assess the applicability of the existing test guidelines1 to nanomaterials, as well as to provide useful information on any intrinsic properties of MNs, which are different from the same bulk material with greater external dimensions. Understanding the properties of NMs is crucial to choose appropriate strategies for hazard identification, risk assessment or risk management measures. The Testing Programme involved delegations from OECD member countries, some non-member economies and other stakeholders. The broad international representation, from a range of delegations enabled the programme to pool expertise and resources without which this programme would not have been possible.
The characterization of the optical properties of photoluminescent systems, that scatter, like dispersions of nanoparticles with sizes exceeding about 25 nm or solid nanophosphors is of increasing importance for many applications in the life and material sciences. Examples present nanoscale optical reporters and dye-doped microparticles for bioimaging, fluorescence assays or DNA sequencing as well as nanocrystalline emitters like semiconductor quantum dots and rods or lanthanide-based nanophosphors embedded into solid matrices for solid state lighting, display technologies, or barcoding/security applications. The assessment and comparison of material performance as well as the development of rational design strategies for improved systems require spectroscopic tools, which enable the determination of the signal-relevant optical properties like photoluminescence quantum yields and brightness values.
This encouraged us to built up an integrating sphere setup enabling absolute measurements of photoluminescence spectra and quantum yields of transparent and scattering photoluminescent dispersions and solid samples in different measurement geometries, i.e., direct and indirect illumination and the combination of both geometries and perform first measurements with selected emitters. Here, the design of this setup is presented and first recommendations concerning suitable measurement geometries are given.
Nanocrystalline fluorophores like semiconductor quantum dots and rods and recently also lanthanide-based upconversion phosphors with emission in the visible (vis), near-infrared (NIR), and IR (infrared) region are increasingly being used in bioimaging studies and fluorescence assays as well as in photovoltaics and solid state lighting. The assessment and comparison of material performance as well as the development of rational design strategies for improved systems require spectroscopic tools, which enable the determination of the signal-relevant optical properties like photoluminescence quantum yields and brightness values. In the case of nonlinear fluorescence as shown by upconversion materials, such measurements must be also performed as function of excitation power density. In this work, we report on methods for the absolute determination of the photoluminescence quantum yield and brightness of fluorescent particles in dispersion and as powders based on integrating sphere spectroscopy and underline the importance of such measurements for the understanding of the photophysics of such nanocrystals.
Lanthanide-doped up-converting nanoparticles (UCNPs), are promising reporters for bioanalysis and theranostics, which are excitable in the near infrared (NIR) by multiphoton absorption processes, and show multiple narrow emission bands in the visible (vis) and NIR, excellent photostability, and long luminescence lifetimes in the µs range. The rational design of brighter UCNP requires an improved understanding of the radiationless deactivation pathways in UCNP, that are affected by size, surface chemistry, and microenvironment. In this respect, we discuss the experimental requirements on absolute measurements of the upconversion quantum yield and its excitation radiant power density dependence and present the design and characterization of unique integrating sphere setup for such measurements in the vis to IR spectral region including its calibration, the influence of the excitation beam profile and solutions to perform such measurements in aqueous media.
The mechanism of nanotriangle formation in multivesicular vesicles (MMV) is investigated by using time-dependent SAXS measurements in combination with UV−vis spectroscopy, light, and transmission electron microscopy. In the first time period 6.5 nm sized spherical gold nanoparticles are formed inside of the vesicles, which build up soft nanoparticle aggregates. In situ SAXS experiments show a linear increase of the volume and molar mass of nanotriangles in the second time period. The volume growth rate of the triangles is 16.1 nm3/min, and the growth rate in the vertical direction is only 0.02 nm/min. Therefore, flat nanotriangles with a thickness of 7 nm and a diameter of 23 nm are formed. This process can be described by a diffusionlimited Ostwald ripening growth mechanism. TEM micrographs visualize soft coral-like structures with thin nanoplatelets at the periphery of the aggregates, which disaggregate in the third time period into nanotriangles and spherical particles. The 16 times faster growth of nanotriangles in the lateral than that in the vertical direction is related to the adsorption of symmetry breaking components, i.e., AOT and the polyampholyte PalPhBisCarb, on the {111} facets of the gold nanoplatelets in combination with confinement effects of the vesicular template phase.
Even although quite a number of studies have been performed so far to demonstrate nanoparticle-specific effects of substances in living systems, clear evidence of these effects is still under debate. The present study was designed as a comparative proteomic analysis of human intestinal cells exposed to a commercial silver nanoparticle reference material and ions from AgNO3. A two-dimensional gel electrophoresis/MALDI mass spectrometry (MS)-based proteomic analysis was conducted after 24-h incubation of differentiated Caco-2 cells with non-cytotoxic and low cytotoxic silver concentrations (2.5 and 25 µg ml−1 nanosilver, 0.5 and 5 µg ml−1 AgNO3). Out of an overall number of 316 protein spots differentially expressed at a fold change of ≥ 1.4 or ≤ −1.4 in all treatments, 169 proteins could be identified. In total, 231 spots were specifically deregulated in particle-treated groups compared with 41 spots, which were limited to AgNO3-treatments. Forty-four spots (14 %) were commonly deregulated by both types of treatment. A considerable fraction of the proteins differentially expressed after treatment with nanoparticles is related to protein folding, synthesis or modification of proteins as well as cellular assembly and organization. Overlays of networks obtained for particulate and ionic treatments showed matches, indicating common mechanisms of combined particle and ionic silver exposure and exclusive ionic silver treatment. However, proteomic responses of Caco-2 cells treated with higher concentrations of silver species also showed some differences, for example regarding proteins related to fatty acid and energy metabolism, suggesting an induction of also some different molecular mechanisms for particle exposure and ionic treatment.
Recent developments in Förster resonance energy transfer (FRET) diagnostics using quantum dots
(2016)
The exceptional photophysical properties and the nanometric dimensions of colloidal semiconductor quantum dots (QD) have strongly attracted the bioanalytical community over the last approximately 20 y. In particular, the integration of QDs in the analysis of biological components and interactions, and the related diagnostics using Förster resonance energy transfer (FRET), have allowed researchers to significantly improve and diversify fluorescence-based biosensing. In this TRENDS article, we review some recent developments in QD-FRET biosensing that have implemented this technology in electronic consumer products, multiplexed analysis, and detection without light excitation for diagnostic applications. In selected examples of smartphone-based imaging, single- and multistep FRET, steady-state and time-resolved spectroscopy, and bio/chemiluminescence detection of QDs used as both FRET donors and acceptors, we highlight the advantages of QD-based FRET biosensing for multiplexed and sensitive diagnostics.
Characterization of silver nanoparticles in cell culture medium containing fetal bovine serum
(2016)
Nanoparticles are being increasingly used in consumer products worldwide, and their toxicological effects are currently being intensely debated. In vitro tests play a significant role in nanoparticle risk assessment, but reliable particle characterization in the cell culture medium with added fetal bovine serum (CCM) used in these tests is not available. As a step toward filling this gap, we report on silver ion release by silver nanoparticles, and changes in the particle radii and in their protein corona when incubated in CCM. Particles of a certified reference material (CRM), p1, and particles of a commercial silver nanoparticle material, p2, were investigated. The colloidal stability of p1 is provided by the surfactants polyethylene glycole-25 glyceryl trioleate and polyethylene glycole-20 sorbitan monolaurate, whereas p2 is stabilized by polyvinylpyrrolidone (PVP). Dialysis of p1 and p2 reveal that their silver ion release rates in CCM are much larger than in water. Particle characterization was performed with asymmetrical flow field-flow fractionation (FFF), small-angle X-ray scattering (SAXS), dynamic light scattering (DLS) and electron microscopy. p1 and p2 have similar hydrodynamic radii of 15 nm and 16 nm, respectively. The silver core radii are 9.2 and 10.2 nm. Gel electrophoresis and subsequent peptide identification reveal that albumin is the main corona component of p1 and p2 after incubation in CCM, which consists of Dulbeccos Modified Eagle Medium with 10% fetal bovine serum added.
The surface chemistry / functionalization of nanomaterials and microparticles largely controls the stability of these materials as well as their solubility and subsequent biofunctionalization and their interactions with biological systems. Moreover, in the case of some nanomaterials like semiconductor quantum dots or lanthanide-based upconversion nanocrystals, the ligand shell strongly affects their optical properties, e.g., via passivation of surface states and traps that favor luminescence quenching or the protection of surface atoms from quenching water molecules. This renders analytical methods for the quantification of surface groups like functionalities very important. Targets of broad interest are here amino, carboxyl, alkine and maleimide groups used for common bioconjugation reactions and typical ligands like thiols and polyethylene glycol (PEG) molecules of varying length, used for the tuning of material hydrophilicity and biocompatibility, minimization of unspecific interactions, prevention of biofouling, and enhancement of blood circulation times as well as surface-bound biomolecules like streptavidin or other biomolecules relevant e.g., for diagnostic assays. Here, we focus on simple optical methods relying on standard laboratory instrumentation, validated by method comparison and/or mass balances and present examples for their use for the characterization of different types of nanomaterials and microparticles.
Luminescence-based detection methods, ranging from fluorescence spectroscopy for photophysical and mechanistic studies over sensing applications, chromatographic separation techniques and the microarray technology with fluorescence detection to fluorescence microscopy, flow cytometry, single molecule spectroscopy, and molecular imaging to integrating sphere spectroscopy, are among the most widely used methods in the life and material sciences. This is due to e.g., their unique sensitivity enabling the detection of single molecules, potential for multiplexing, ease of combination with spatial resolution, and suitability for remote sensing. Many of these advantages are closely linked to the choice of suitable molecular and nanoscale fluorescent reporters, typically required for signal generation. This includes organic dyes without and with sensor function, fluorophore-encoded polymeric and silica nanoparticles as well as nanocrystalline systems like semiconductor quantum dots and upconversion phosphors, emitting in the visible (vis), near-infrared (NIR), and IR (infrared). Current challenges present the environment sensitivity of most fluorophores, rendering fluorescence spectra, measured intensities/fluorescence quantum yields, and fluorescence decay kinetics matrix-dependent, and instrument-specific distortions of measured fluorescence signals that need to be considered for quantification and comparability of data, particularly fluorescence spectra.
Here, current applications of luminescence-based methods and different types of reporters will be presented. In this context, suitable spectroscopic tools for the characteri-zation of the optical properties of fluorescent reporters and fluorophore-encoded microparticles, analytical tools for the determination of the surface chemistry of different types of particles, and different multiplexing strategies will be discussed.
Due to their unique physical properties, particularly their electronic and luminescent properties, graphene quantum dots (GQDs) are expected to be suitable for a wide range of applications in bioimaging, electro-optical and photonic materials or energy harvesting among others.1 Tuning the surface chemistry provides an efficient approach to modulate the fluorescence and distinct electronic properties of GQDs.2 Nevertheless, the role of surface chemistry on the electronic structure of GQDs remains poorly understood. In this presentation, we will compare systematically the electronic and chemical structures of GQDs functionalized with carboxylic and aminated groups to those of non-functionalized GQDs, combining theoretical and experimental approaches, here various photon-based spectroscopies. First, the electronic structure of GQDs was characterized by soft X-ray absorption (XA) and X-ray emission (XE) spectroscopies, probing unoccupied and occupied electronic states, respectively, at the carbon K edge for the first time. The interpretation of the XA/XE spectra was done based on theoretical calculations. Then, the chemical structure of the GQDs was characterized in situ by ATR-FTIR in water, thereby accounting for the importance of the interface between GQDs and water believed to play a central role in the chemical reactivity and the optical properties. We previously demonstrated that monitoring the OH vibrations of water molecules during exposure to humid air was a powerful method to probe H-bonding environment around carbon nanomaterials.3 For GQDs, clear surface-dependent water adsorption profiles are observed and discussed. Finally, UV/Vis absorption and photoluminescence measurements were done to characterize the optical properties of these GQDs. Our results suggest that the surface chemistry of the GQDs affects significantly their electronic structure and optical properties. These findings will contribute to an improved understanding of the structure–activity relationship of GQDs and other carbon nanomaterials with surface modifications.
In this review we present new concepts and recent progress in the application of semiconductur quantum dots (QD) as labels in two important areas of biology, bioimaging and biosensing. We analyze the biologically relevant properties of QDs focusing on the following topics: QD surface treatment and stability labeling of cellular structures and receptors with QDs, incorporation of QDs in living cells, cytotoxicity of QDs and influence of the biolocical environment on the biological and optical properties of QDs. Initially, we consider utilization of QDs as agants in high-resolution bioimaging techniques that can provide information at the molecular levels. The deverse range of modern live-cell QD-based imaging techniques with resolution far beyond the diffraction limit of light is examined. In each technique, we discuss the pros and cons of QD use and deliberate how QDs can be further engineered to facilitate their application in the respective imaging techniques and to produce significant improvements in resolution. Then we review QD-based point-of-care bioassays, bioprobes, and biosensors designed in different formats ranging from analytic biochemistry assays and ELISA, to novel point-of-care smartphone integrated QD-based biotests. Here, a wide range of QD-based fluorescence bioassays with optical transduction, electrochemiluminescence and photoelectrochemical assays are discussedc. Finally, this review provides an analysis of the prospects of application of QDs in selected important Areas of biology.
Aluminum has gathered toxicological Attention based on relevant human exposure and its suspected hazardous potential. Nanoparticles from food supplements or Food contact materials may reach the human gastrointestinal tract.
Here, we monitored the physicochemical fate of aluminum containing nanoparticles and aluminum ions when passaging an in vitro model of the human gastrointestinal tract. Smallangle X-ray scattering (SAXS), transmission electron microscopy (TEM), ion beam microscopy (IBM), secondary ion beam mass spectrometry (TOF-SIMS), and inductively coupled plasma mass spectrometry (ICP-MS) in the singleparticle mode were employed to characterize two aluminumcontaining nanomaterials with different particle core materials (Al0, γAl2O3) and soluble AlCl3. Particle size and shape remained unchanged in saliva, whereas strong Agglomeration of both aluminum nanoparticle species was observed at low pH in gastric fluid together with an increased ion release. The levels of free aluminum ions decreased in intestinal fluid and the particles deagglomerated, thus liberating primary particles again. Dissolution of nanoparticles was limited and substantial changes of their shape and size were not detected. The amounts of particle-associated phosphorus, chlorine, potassium, and calcium increased in intestinal fluid, as compared to nanoparticles in standard dispersion.
Interestingly, nanoparticles were found in the intestinal fluid after addition of ionic aluminum. We provide a comprehensive characterization of the fate of aluminum nanoparticles in simulated gastrointestinal fluids, demonstrating that orally ingested nanoparticles probably reach the intestinal epithelium. The balance between dissolution and de novo complex formation should be considered when evaluating nanotoxicological experiments.
There is an increasing interest in optical reporters like semiconductor and lanthanide-based nanocrystals with emission > 800 nm and recently also > 1000 nm for bioanalysis, medical diagnostics, and safety barcodes. Mandatory for the comparison of different emitter classes and the rational design of the next generation of reporters for the short wavelength infrared (SWIR) region are reliable and quantitative photoluminescence measurements in this challenging wavelength region. This is of special relevance for nanocrystalline emitters like semiconductor quantum dots and rods as well as for upconversion and downconversion nanocrystals, where surface states and the accessibility of emissive states by quenchers largely control accomplishable quantum yields and hence, signal sizes and detection sensitivities from the reporter side. Such measurements are currently hampered by the lack of suitable methods and standards for instrument calibration and validation as well as by the lack of quantum yield standards with emission > 800 nm and especially > 1000 nm.
In this respect, we present the design of integrating sphere setups for absolute and excitation power densitydependent measurements of emission spectra and quantum yields in the wavelength region of 650 to 1650 nm
including calibration strategies and first candidates for potential fluorescence standards. Subsequently, the photoluminescence properties of different types of nanocrystals are presented and discussed including absolute photoluminescence measurements of upconversion and down conversion emission in different solvents.
There is an increasing interest in molecular and nanoscale with emission > 800 nm and recently also > 1000 nm for bioanalysis, medical diagnostics, bioimaging, and safety barcodes. Mandatory for the comparison of different emitter classes and the rational design of the next generation of reporters for the short wavelength infrared (SWIR) Region are reliable and quantitative photoluminescence measurements in this challenging wavelength region. This is of special relevance for nanocrystalline emitters like semiconductor quantum dots and rods as well as lanthanide-based upconversion and downconversion nanocrystals, where surface states and the accessibility of emissive states by quenchers largely control accomplishable photoluminescence quantum yields and hence, signal sizes and detection sensitivities from the reporter side. Such measurements are currently hampered by the lack of suitable methods and standards for instrument calibration and validation and quantum yield standards with emission > 800 nm and especially > 1000 nm.
In this respect, we present the design of integrating sphere setups for absolute and excitation power density-dependent measurements of emission spectra and photoluminescence quantum yields in the wavelength Region of 650 to 1650 nm including calibration strategies and first candidates for potential fluorescence standards.
Subsequently, the photoluminescence properties of different types of nanocrystals are presented including the upconversion and downconversion emission of differently sized and surface functionalized lanthanide-doped nanoparticles and photoluminescence quenching effects are quantified.
Upconversion nanoparticles (UCNPs) offer new strategies for luminescence-based sensing and imaging. One of the best studied materials are ..-NaYF4 UCNPs doped with 20 % Yb3+ and 2 % Er3+, which efficiently convert 976 nm light to photons emitted at 540 nm, 655 nm, and 845 nm, respectively, reveal long luminescence lifetimes (> 100 µs), are photostable and chemically inert. Their upconversion (UC) luminescence (UCL) properties are, however, strongly influenced by particle size, surface chemistry, and microenvironment. In addition, the multiphotonic absorption processes responsible for UCL render UCL excitation power density (..) dependent. This makes quantitative UCL measurements as well as the determination of UC quantum yields (.UC) very challenging.
The rational design of brighter UCNPs particle architectures and the interest in identifying optimum particle architectures for FRET-based sensing and imaging schemes, which often rely on core-only UCNPs to minimize donor-acceptor distances, encouraged us to assess the influence of particle size and P on UCL. Here, we present the photophysical properties of a series of hexagonal NaYF4 UCNPs with sizes from 10 to 43 nm with different surface ligands dispersed in organic solvents and water studied by steady state and time-resolved fluorometry as well as quantitatively by integrating sphere spectrometry with P varied over about three orders of magnitude. Our results underline the need for really quantitative luminescence studies for mechanistic insights and the potential of high P to compensate for UCL quenching due to high energy phonons and surface effects.
The rational design of functional nanomaterials for optical applications in the material and life sciences requires optical-spectroscopic methods for the quantitative characterization of their signal-relevant optical properties. Additionally, methods for the simple and quantitative analysis of the surface chemistry are desired as the chemical nature and number of the surface groups and ligands can affect the optical features and controls the interaction of these nanomaterials with their environment. Here, we present quantitative photoluminescenvce studies of different types of vis/NIR-emissive nanomaterials like semiconductor quantum dots and upconversion nanocrystals will be presented and their relevance for the mechanistic understanding of nonradiative decay channels and the rational design of new nanomaterials will be underpinned. In this respect, also validation concepts for such measurements and absolute fluorometry will be introduced. In addition, the potential of optical spectroscopy for surface group and ligand analysis surface chemistry will be demonstrated exemplarily for semiconductor quantum dots
Lanthanide-doped photon-upconversion nanoparticles (UCNPs) have been in the focus of many research activities in the material and life sciences over the last 15 years because of their potential to convert light between different spectral regions and their unique photophysical properties. In order to fully exploit the application potential of these fascinating nanomaterials, a number of challenges has to be overcome such as the low brightness particularly of small UCNPs and the reliable quantification of the excitation power density (P)-dependent upconversion luminescence (UCL). Here, the need and requirements on the characterization of the optical properties of UCNPs are discussed with special focus on the reliabiliy and comparability of relative and quantitative luminescence measurements and prerequisites for their standardization.
Lanthanide-doped photon-upconversion nanoparticles (UCNPs) have been the Focus of many Research activities in materials and life sciences in the last 15 years because of their potential to convert light between different spectral regions and their unique photophysical properties. To fully exploit the application potential of These facinating nanomaterials, a number of challenges have to be overcome, such as the low brightness, particularly of small UCNPs, and the reliable quantification of the excitation-power-density-dependent upconversion luminescence. In this series of critical Reviews, recent developments in the design, Synthesis, optical-spectroscopic characterization, and application of UCNPs are presented with Special Focus on bioanalysis and the life sciences. Here we guide the reader from the Synthesis of UCNPs to different concepts to enhance their luminescence, including the required optical-spectroscopic assessment to quantify material Performance; surface modification strategies and bioanalytical applications as well as selected examples of the use of UCNPs as reporters in different Assay formats are addressed in part II. Future Trends and challenges in the field of upconversion are discussed with Special emphasis on UCNP Synthesis and material characterization, particularly quantitative luminescence studies.
Photoluminescence techniques are amongst the most widely used Tools in the life sciences, with new and exciting applications in medical diagnostics and molecular Imaging continuously emerging. Advantages include their comparative ease of use, unique sensitivity, non-invasive character, and potential for Multiplexing, remote sensing, and miniaturization. General drawbacks are, however, signals, that contain unwanted wavelength- and polarization contributions from Instrument-dependent effects, which are also time-dependent due to aging of Instrument-components, and difficulties to measure absolute flourescence entensities. Moreover, scattering Systems require Special measurement geometries and the interest in new optical Reporters with Emission > 1000 nm strategies for reliable measurements in the second diagnostic for the comparison of material Performance and the rational designg of new flourophores with improved properties.
Here, we present strategies to versatile method-adaptable liquid and solid flourescence Standards for different flourescence paramters including traceable Instrument calibration procedures and the design of integrating spere setups for the absolute measurements of emission spectra and Quantum yields in the wavelength Region of 350 to 1600 nm. Examples are multi-Emitter glasses, spectral flourescence Standards, and quantum yield Standards for the UV/vis/NIR.
Semiconductor nanocrystals with a spherical (QDs) core and a spherical or a rod-shaped Shell, u.a., so-called Quantum dot-Quantum rods (QDQRs) are increasingly used as fluorescent Reporters or optically active components in the life and material science, e.g., in solid state lightening including Plasma Displays. (1,2) Morever, there is an increasing interest in materials with emission >800 nm for bioanalysis, medical diagnostics, and safety barcodes. Prerequisites for the mechanistic understanding of nonradiativ decay channels needed for the rational design of improved nanomaterials and the comparison of material Performance are reliable fluorescence measurements and validated methods for the assessment of their surface chemistry. (3,4) The latter is of particular importance for nanocrystalline Emitters, where surface states and the accessibility of emissive states by quenchers largely control photoluminescence properties. (5) Here, we present results from systematic spectroscopic studies including absolutely measured photolumunescence Quantum yields of different vissible and NIR emisisve QD and QDQRs Systems of varying particle architecture size and surface chemistries in Dispersion and embedded in salt crystals. (6,7)
The quantum yield is a critically important parameter in the development of lanthanide-based upconverting nanoparticles (UCNPs) for use as novel contrast agents in biological imaging and optical reporters in assays. The present work focuses on the influence of the beam Profile in measuring the quantum yield (f) of nonscattering dispersions of nonlinear upconverting probes, by establishing a relation between f and excitation light power density from a rate equation analysis. A resulting 60% correction in the measured f due to the beam profile utilized for excitation underlines the significance of the beam profile in such measurements, and its impact when comparing results from different Setups and groups across the world.
In the present study, we applied a regularized inversion method to extract the particle size, magnetic moment and relaxation-time distribution of magnetic nanoparticles from small-angle x-ray scattering (SAXS), DC magnetization (DCM) and AC susceptibility (ACS) measurements. For the measurements the particles were colloidally dispersed in water. At first approximation the particles could be assumed to be spherically shaped and homogeneously magnetized single-domain particles. As model functions for the inversion, we used the particle form factor of a sphere (SAXS), the Langevin function (DCM) and the Debye model (ACS). The extracted distributions exhibited features/peaks that could be distinctly attributed to the individually dispersed and non-interacting nanoparticles. Further analysis of these peaks enabled, in combination with a prior characterization of the particle ensemble by electron microscopy and dynamic light scattering, a detailed structural and magnetic characterization of the particles. Additionally, all three extracted distributions featured peaks, which indicated deviations of the scattering (SAXS), magnetization (DCM) or relaxation (ACS) behavior from the one expected for individually dispersed, homogeneously magnetized nanoparticles. These deviations could be mainly attributed to partial agglomeration (SAXS, DCM, ACS), uncorrelated surface spins (DCM) and/or intra-well relaxation processes (ACS). The main advantage of the numerical inversion method is that no ad hoc assumptions regarding the line shape of the extracted distribution functions are required, which enabled the detection of these contributions. We highlighted this by comparing the results with the results obtained by standard model fits, where the functional form of the distributions was a priori assumed to be log-normal shaped.
The implementation of fluorescent methods is of outstanding importance in the field of optical chemical sensor Technology and biosciences. Their bioanalytical applications are manifold including fluorescence microscopy, fluorescence in situ hybridization, DNA sequencing, fluorescence-activated cell sorting, immunoassays, analysis of DNA and Protein microarrays, and quantitative PCR, just to name a few examples. Particularly, fluorescence microscopy is a valuable method in the versatile field of biomedical imaging methods which nowadays utilizes different fluorescence Parameters like emission wavelength/Color and lifetime for the discrimination between different targets. Sectional Images are available with confocal microscopes. Tissue, cells or single cellular compartments can be stained and visualized with fluorescent dyes and biomolecules can be selectively labeled with fluorescent dyes to Monitor biomolecular interactions inside cells or at Membrane bound receptors.
On the other hand , fluorophores can act as indicator (or "molecular probe") to visualize intrinsically colorless and non-fluorescent ionic and neutral analytes such as pH, Oxygen (pO2), metal ions, anions, hydrogen peroxide or bioactive small organic molecules such as Sugars or nucleotides. Thereby, their photoluminescent properties (fluorescence or phoporescence intensity, exitation and/or Emission wavelength, emission lifetime or anisotropy) respond to the presence of these species in their immediate Environment. In general, the use of luminescent probes has the advantage that they can be delivered directly into the sample, and detected in a contactless remote mode. By now, these probes are often encapsulated in different types of nanoparticles (NPs) made from (biodegradable) organic polymers, biopolymers or inorganic materials like silica or bound to their surface.
At the core of luminescence color and lifetime Tuning of rare earth doped upconverting nanoparticles (UCNPs), is the understanding of the Impact of the particle architecture for commonly used sensitizer (S) and activator (A) Ions. In this respect, a series of core@Shell NaYF4 UCNPs doped with Yb3+ and Ho3+ ions are presented here, where the same dopant concentrations are distributed in different particle architectures following the scheme: YbHo core and YbHo@..., ...@YbHo, Yb@Ho, Ho@Yb, YbHo@Yb, and Yb@YbHo core-Shell NPs. As refealed by quantitative steady-state and time-resolved luminescence studies, the relative spatial Distribution of the A and S ions in the UCNPs and their protection from surface quenching has a critical Impact on ther luminescence characteristics. Although the increased amount of Yb3+ Ions boosts UCNP Performance by amplifying the Absorption, the Yb3+ ions can also efficiently dissipate the energy stored in the material through energy Migration to the surface, thereby reducing the Overall energy Transfer Efficiency to the activator ions. The results provide yet another proof that UC Phosphor chemistry combined with materials Engineering through intentional core@shell structures may help to fine-tune the luminescence Features of UCNPs for their specific future applications in biosensing, bioimaging, photovoltaics, and Display technologies.
Quantum dot (QD) based nanomaterials are very promising materials for the fabrication of optoelectronic devices like solar cells, light emitting diodes (LEDs), and photodetectors as well as as reporters for chemo- and biosensing and bioimaging. Many of These applications involve the monitoring of changes in photoluminescence intensity and energy transfer processes which can strongly depend on excitation wavelength or energy. In this work, we analyzed the excitation energy dependence (EED) of the photoluminescence quantum yields (PL QYs) and decay kinetics and the circular dichroism (CD) spectra of CdSe/CdS core/shell QDs with different thicknesses of the surface passivation shell. Our results demonstrate a strong correlation between the spectral position of local maxima observed in the EED of PL QY and the zero-crossing points of the CD profiles. Theoretical analysis of the energy band structure of the QDs with effective mass approximation suggests that these structures could correspond to exciton energy levels. This underlines the potential of CD spectroscopy for the study of electronic energy structure of chiroptically active nanocrystals which reveal quantum confinement effects.
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.
A facile method to probe the vascular permeability of nanoparticles in nanomedicine applications
(2017)
The effectiveness of nanoparticles (NP) in nanomedicine depends on their ability to extravasate from vasculature towards the target tissue. This is determined by their permeability across the endothelial barrier. Unfortunately, a quantitative study of the diffusion permeability coefficients (Pd) of NPs is difficult with in vivo models. Here, we utilize a relevant model of vascular-tissue interface with tunable endothelial permeability in vitro based on microfluidics. Human umbilical vein endothelial cells (HUVECs) grown in microfluidic devices were treated with Angiopoietin 1 and cyclic adenosine monophosphate (cAMP) to vary the Pd of the HUVECs monolayer towards fluorescent polystyrene NPs (pNPs) of different sizes, which was determined from image analysis of their fluorescence intensity when diffusing across the monolayer. Using 70 kDa dextran as a probe, untreated HUVECs yielded a Pd that approximated tumor vasculature while HUVECs treated with 25 μg/mL cAMP had Pd that approximated healthy vasculature in vivo. As the size of pNPs increased, its Pd decreased in tumor vasculature, but remained largely unchanged in healthy vasculature, demonstrating a trend similar to tumor selectivity for smaller NPs. This microfluidic model of vascular-tissue interface can be used in any laboratory to perform quantitative assessment of the tumor selectivity of nanomedicine-based systems.
Size and shape are crucial parameters which have impact on the potential of nanoparticles to penetrate cell membranes and epithelial barriers. Current research in nanotoxicology additionally focuses on particle coating. To distinguish between core- and coating-related effects in nanoparticle uptake and translocation, two nanoparticles equal in size, coating and charge but different in core material were investigated.
Silver and iron oxide nanoparticles coated with poly(acrylic acid) were chosen and extensively characterized by small-angle x-ray scattering, nanoparticle tracing analysis and transmission electron microscopy (TEM). Uptake and transport were studied in the intestinal Caco-2 model in a Transwell System with subsequent elemental analysis. TEM and ion beam microscopy were conducted for particle visualization.
Although equal in size, charge and coating, the behavior of the two particles in Caco-2 cells was different: while the internalized amount was comparable, only iron oxide nanoparticles additionally passed the epithelium. Our findings suggest that the coating material influenced only the uptake of the nanoparticles whereas the translocation was determined by the core material.
Knowledge about the different roles of the particle coating and core materials in crossing biological barriers will facilitate toxicological risk assessment of nanoparticles and contribute to the optimization of pharmacokinetic properties of nano-scaled pharmaceuticals.
Functional Nanomaterials with VIS/NIR Emission-Spectroscopic Properties And Surface Group Analysis
(2017)
Optical-spectroscopic methods for the quantitative characterization of the optical properties of different types of vis/NIR-emissive nanomaterials like semiconductor quantum dots and upconversion nanocrystals will be presented and their relevance for the mechanistic understanding of nonradiative decay channels and the rational design of new nanomaterials will be underpinned. In this respect, also validation concepts for such measurements and absolute fluorometry will be introduced. In addition, the potential of optical spectroscopy for surface group and ligand analysis surface chemistry will be demonstrated exemplarily for semiconductor quantum dots.
At the core of luminescence color and lifetime tuning of rare earth doped upconverting nanoparticles (UCNPs) is the understanding of the impact of the particle architecture for commonly used sensitizer (S) and activator (A) ions. In this respect, we present here a series of core@shell NaYF4 UCNPs doped with Yb3+ and Ho3+ ions, where the same dopant concentrations were distributed in different particle architectures following the scheme: YbHo core and YbHo@..., …@YbHo, Yb@Ho, Ho@Yb, YbHo@Yb, and Yb@YbHo core-shell NPs. As revealed by quantitative steady state and time-resolved luminescence studies, the relative spatial distribution of the A and S ions in the UCNPs and their protection from surface quenching has critical impact on their luminescent characteristics. Interestingly, although the increased amount of Yb3+ ions boosts UCNP performance by increasing the absorption, the Yb3+ ions can also dissipate the energy stored in the material through energy migration to surface, thereby reducing the overall energy transfer efficiency to the activator ions.
Lanthanide doped photon upconverting nanophosphors (UCNPs) have the unique capability to produce narrow band, multi-color emission in the UV/vis/NIR upon multiphotonic absorption of infrared light, which makes them promising reporters for diagnostic, bioanalytical, and biological applications. This minimizes background signals, which normally occur due to autofluorescence from auxochromes, in biological matrices and enables deep penetration depths in biological applications. Moreover, UCNPs show long luminescence lifetimes in the μs range favorable for time gated emission in conjunction with a high photostability and chemical inertness and they do not blink. One of the most efficient upconversion (UC) phosphors for conversion of 976 nm to 655 nm and 545 nm light presents the hexagonal NaYF4-host crystal doped with 20 % Yb3+ used as sensitizer to absorb infrared light and 2 % Er3+ acting as activator mainly responsible for light emission. The high transparency in the relevant spectral windows of this host together with its low phonon frequencies ensure relatively high luminescence efficiencies.
Although UCNPs are ideal candidates for many chemical and biological sensing and imaging applications, compared to other well-known chromophores like organic dyes or QDs, they suffer from a comparatively low brightness due to the low absorption cross sections of the parity forbidden f-f-transitions and low photoluminescence quantum yields (QYUC) particularly in the case of small nanoparticles with sizes of < 50 nm. The rational design of more efficient UCNPs requires an improved understanding of the nonradiative decay pathways in these materials that are influenced by particle architecture including dopant ion concentration and homogeneity of dopant distribution within UCNPs, size/surface-to-volume ratio, surface chemistry, and microenvironment. A promising approach to overcome the low efficiency of UCNPs is to use plasmonic interactions between a noble metal (Ag or Au) structure in the proximity of UCNPs and the incident light. This interaction leads to a modification of the spectroscopic properties due
to local field enhancements and can involve an increase of the photoluminescence. In this respect, we study the interactions of UCNPs with metal structures (clusters and shells) by varying shape and size. Here, first results derived from integrating sphere spectroscopy and time-resolved fluorescence measurements are presented.
Ternary semiconductors Quantum Dots (t-QDs) like AgInS (AIS) QDs are interesting alternatives to Cd-based QDs for applications as optical active materials in light-emitting diodes (LEDs), solar concentrators and solar cells as well as as biodiagnostic tools, respectively.
AIS QDs exhibit broad photoluminescence (PL) spectra in the visible and near infrared, which are tunable by size and chemical composition (ratio of components or doping).
In order to enhance the PL quantum yield (PL QY or Fpl) and prevent material deterioration and oxidation, these QDs are covered by ZnS shell. Here we show a spectroscopic study of differently colored AIS QDs synthesized in water, evaluating their PL properties, their PL QY and their PL decay.
The simple aqueous synthesis that avoids further ligand exchange steps for bioanalytical applications, the tunable emission color, the high PL QY, the high absorption coefficients and the long lifetime make these t-QDs promising Cd-free materials as biodiagnostic tools or optical active materials.
"The optical properties of semiconductor nanocrystals (SCNC) are controlled by constituent material, particle size, and surface chemistry, specifically the number of dangling bonds favoring nonradiative deactivation. This can lead to a distribution of photoluminescence Quantum yields (PL QY) amongst the SCNC particles, i.e., mixtures of “bright” and “grey” or “dark” SCNCs.
Particularly the number of absorbing, yet not emitting particles can have a significant effect on the PL quantum yield obtained in ensemble measurements, leading to ist underestimation. The “dark fraction” is not assessable in common ensemble measurements; it can be probed only on a single particle level using a confocal laser scanning microscope coupled with an AFM. Such a setup was used to study core‐shell CdSe SCNCs with different shells and surface chemistries. Special emphasis was dedicated to correlate brightness, blinking, dark fraction, and decay kinetics of the single SCNCs with the ensemble PL QY and the PL decay kinetics. The results of this study can help to identify new synthetic routes and surface modifications to colloidally and photochemically stable SCNCs with a PL QY of close to unity."
Core-shell nanoparticles are widespread in nature, industrial applications and nanotechnology research. Facile ways of modern synthesis will be discussed and possibilities to reveal their structures with small-angle X-ray scattering (SAXS). A recent review on using block copolymer templates as one of the most reliable routes for tuning size and shape of nanoparticles is provided by Li et al.1 Ferritin and apoferritin are archetypical examples for protein-based core-shell nanoparticles. Their structures are easily accessed by synchrotron SAXS2 but also with commercial instruments and allow fast performance tests.3 SASfit4 is a suitable program tool based on classical curve fitting and McSAS5 is a complementary program based on a Monte Carlo technique. Detailed refinements of SAXS data evaluation are on the way for better data analysis.6 A sub nanometer resolution is state-of-the-art for quantification of the size distribution of polyacrylic acid stabilized silver nanoparticles.3 Such particles are useful in catalysis.7 It was observed that the catalytic activity can be tuned easily by varying the shell material of the particles.
tNegatively charged ultrathin gold nanotriangles (AuNTs) were synthesized in a vesicular dioctyl sodiumsulfosuccinate (AOT)/phospholipid-based template phase. These “naked” AuNTs with localized surfaceplasmon resonances in the NIR region at about 1300 nm and special photothermal properties are ofparticular interest for imaging and hyperthermia of cancerous tissues. For these kinds of applicationsthe toxicity and the cellular uptake of the AuNTs is of outstanding importance. Therefore, this studyfocuses on the toxicity of “naked” AOT-stabilized AuNTs compared to polymer-coated AuNTs. Poly-meric coating consisted of non-modified hyperbranched poly(ethyleneimine) (PEI), maltose-modifiedpoly(ethyleneimine) (PEI-Mal) and heparin. The toxicological experiments were carried out with twodifferent cell lines (embryonic kidney carcinoma cell line HEK293T and NK-cell leukemia cell line YTS).This study revealed that the heparin-coating of AuNTs improved biocompatibility by a factor of 50 whencompared to naked AuNTs. Of note, the highest nontoxic concentration of the AuNTs coated with PEI andPEI-Mal is drastically decreased. Overall, this is mainly triggered by the different surface charges of poly-meric coatings. Therefore, AuNTs coated with heparin were selected to carry out uptake studies. Theirpromising high biocompatibility and cellular uptake may open future studies in the field of biomedicalapplications.
Fate of fluorescence labels - Their adsorption and desorption kinetics to silver nanoparticles
(2018)
Silver nanoparticles are among the most widely used and produced nanoparticles. Because of their frequent application in consumer products, the assessment of their toxicological potential has seen a renewed importance. A Major difficulty is the traceability of nanoparticles in in vitro and in vivo experiments. Even if the particles are labeled, for example, by a fluorescent marker, the dynamic exchange of ligands often prohibits their spatial localization. Our study provides an insight into the adsorption and desorption kinetics of two different fluorescent labels on silver nanoparticles with a core radius of 3 nm by dynamic light scattering, small-angle X-ray scattering, and fluorescence spectroscopy. We used BSA-FITC and tyrosine as examples for common fluorescent ligands. It is shown that the adsorption of BSA-FITC takes at least 3 days, whereas tyrosine adsorbs immediately. The quantitative amount of stabilizer on the particle surface was determined by fluorescence spectroscopy and revealed that the particles are stabilized by a monolayer of BSA-FITC (corresponding to 20 ± 9 molecules), whereas tyrosine forms a multilayered structure consisting of 15900 ± 200 molecules. Desorption experiments show that the BSA-FITC-stabilized particles are ideally suited for application in in vitro and in vivo experiments because the ligand desorption takes several days. Depending on the BSA concentration in the particles surroundings, the rate constant is k = 0.2 per day or lower when applying first order kinetics, that is, 50% of the BSAFITC molecules are released from the particle’s surface within 3.4 days. For illustration, we provide a first application of the fluorescence-labeled particles in an uptake study with two different commonly used cell lines, the human liver cell model HepG2 and the human intestinal cell model of differentiated Caco-2 cells.
Lanthanide-based upconversion nanoparticles (UCNPs) offer new strategies for luminescence-based sensing and imaging. One of the best studied materials are hexagonal ß-NaYF4 UCNPs doped with 20% Yb3+ and 2% Er3+, which efficiently convert 976 nm light to photons emitted at 540 nm, 655 nm, and 845 nm, respectively, reveal Long luminescence lifetimes (> 100 µs), and are very photostable and chemically inters.[1,2] The properties of their upconversion (UC) luminescence (UCL) are, however, strongly influenced by particle size, concentration and spatial arrangement of dopant Ions, surface chemistry, and microenvironment.[3,4] In addition, the multiphotonic absorption processes responsible for UCL render UCL dependent on excitation power density (P).
The rational design of brighter UCNPs particle architectures encouraged us to assess systematically the influence of these parameters on UCL for differently doped UCNPs relying on the commonly used ß-NaYf4 matrix using steady state and time resolved fluorometry as well as integrating sphere spectroscopy for P varied over almost three orders of magnitude. This includes comprehensive studies of the influence of size and shell, Yb3+ and Er3+ dopand concentrations, and energy Transfer processes from UCNPs to surface-bound organic dyes or vice versa [5]. Our results underline the need for really quantitative luminescence studies for mechanistic insights, the potential of high p to compensate for UCL surface quenching, and the matrix- and P-dependence of the optimum dopand concentration.
We synthesized and characterized a set of ultrasmall hexagonal-phase NaGdF4: 20% Yb3+, 2% Er3+ upconversion nanoparticles with core diameters of 3.7 ± 0.5 nm. In order to assess passivation effects and the influence of possible core−shell intermixing and to identify optimum particle structures for combined imaging in the visible and near-infrared (vis−NIR: 410−850 nm) and short-wave infrared (SWIR: 1520 nm), NaYF4 shells of varying thicknesses (monolayer to 10 nm) were introduced and the influence of this parameter on the upconversion and downshifting photoluminescence of these particles was studied at different excitation power densities. This included excitation power-dependent emission spectra, slope factors, quantum yields, and excited state decay kinetics. These measurements revealed enhancement factors of the upconversion quantum yield of >10 000 in the low power region and an excitation power density-independent quantum yield of the downshifted emission at 1520 nm between 0.1 and 14%. The optimized shell thickness for combined vis and SWIR imaging was identified as 5 nm. Moreover, lifetimes and quantum yields can be continuously tuned by shell thickness which can be exploited for lifetime multiplexing and encoding. The fact that we did not observe a saturation of the upconversion quantum yield or the excited state decay kinetics with increasing shell thickness is ascribed to a strong intermixing of the active core with the inert shell during the shelling procedure. This indicates the potential of spectroscopic tools to detect cation intermixing.
The increasing interest in molecular and nanoscale emitters with photoluminescence > 800 nm and recently also > 1000 nm for bioanalysis, medical diagnostics, bioimaging, and safety Barcodes requires quantitative spectroscopic studies, which are, however still challenging in this long wavelength region. This is of special relevance for nanocrystalline emitters like semiconductor quantum dots and rods as well as lanthanide-based upconversion and downconversion nanocrystals, where surface states and the accessibility of emissive states by quenchers largely control accomplishable photoluminescence quantum yields and hence, signal sizes and detection sensitivities from the reporter side. Moreover, nonlinear emitters like lanthanide-based upconversion nanocrystals require also power density-dependent studies of their luminescence spectra, quantum yields, and decay kinetics. Here, we present suitable absolute methods and underline the impact of such measurements on a profound mechanistic understanding of the nonradiative deactivation pathways in semiconductor and upconversion nanocrystals of different chemical composition and particle architecture.
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.
Optical spectroscopy – Techniques, instrumentation, and typical molecular and nanoscale reporters
(2018)
Different types of optical spectroscopies are introduced with special emphasis on method-inherent limitations and reliable instrument calibration and performance validation. In addition, different classes of molecular and nanocrystalline emitters are presented and the underlying photophysical processes are briefly described.
The overall interest in nanotoxicity, triggered by the increasing use of nanomaterials in the material and life sciences, and the synthesis of an ever increasing number of new functional nanoparticles calls for standardized test procedures1,2 and for efficient approaches to screen the potential genotoxicity of these materials. Aiming at the development of fast and easy to use, automated 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 detection of DNA double strand breaks as a sign for genotoxicity3. Here, we provide 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 and different cell lines like Hep-2 and 8E11 cells, which reveal a dependence of the genotoxicity on the chemical composition as well as the surface chemistry of these nanomaterials. 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.
A systematic study of the luminescence properties of monodisperse β-NaYF4: 20% Yb3+, 2% Er3+ upconversion nanoparticles (UCNPs) with sizes ranging from 12–43 nm is presented utilizing steady-state and time-resolved fluorometry.
Special emphasis was dedicated to the absolute quantification of size- and environment-induced quenching of upconversion luminescence (UCL) by highenergy O–H and C–H vibrations from solvent and ligand molecules at different excitation power densities (P). In this context, the still-debated Population pathways of the 4F9/2 energy level of Er3+ were examined. Our results Highlight the potential of particle size and P value for color tuning based on the pronounced near-infrared emission of 12 nm UCNPs, which outweighs the red Er3+ emission under “strongly quenched” conditions and accounts for over 50% of total UCL in water. Because current rate equation models do not include such emissions, the suitability of these models for accurately simulating all (de)population pathways of small UCNPs must be critically assessed. Furthermore, we postulate population pathways for the 4F9/2 energy level of Er3+, which correlate with the size-, environment-, and P-dependent quenching states of the higher Er3+ energy levels.
Upconversion core/shell nanocrystals with different mean sizes ranging from 15 to 45 nm were prepared via a modified synthesis procedure based on anhydrous rare‐earth acetates. All particles consist of a core of NaYF4:Yb,Er, doped with 18 % Yb3+ and 2 % Er3+, and an inert shell of NaYF4, with the shell thickness being equal to the radius of the core particle. Absolute measurements of the photoluminescence quantum yield at a series of different excitation power densities show that the quantum yield of 45 nm core/shell particles is already very close to the quantum yield of microcrystalline upconversion phosphor powder. Smaller core/shell particles prepared by the same method show only a moderate decrease in quantum yield. The quantum yield of 15 nm core/shell particles, for instance, is reduced by a factor of three compared to the bulk upconversion phosphor at high power densities (100 W cm−2) and by approximately a factor of 10 at low power densities (1 W cm−2).
Polymeric core-shell particles were synthesized in a semi-batch emulsion polymerization process. The shell of the particles consist of PVDF with a high amount of beta-phase. Small-angle X-ray scattering (SAXS) was used to quantify the size of the cores of the particles and the thickness of the shell.
Surface functionalization of 2D- and 3D-supports and nanomaterials are nowadays at the core of many applications of functional materials in the life and material sciences. Examples range from membranes and microarrays over bead-based assays, immunoseparation, and next generation sequencing to nanometer-sized optical reporters, nanosensors, and magnetic and optical contrast agents. Typically performed functionalization procedures include silanization and grafting reactions with reactive monomers to introduce functional groups like amino or carboxylic acid groups and the attachment of ligands like polyethylene glycol (PEG) molecules and biomolecules such as peptides, proteins, and DNA.[1-3]
We present here a versatile concept to quantify the number of bioanalytically relevant functional groups like carboxyl, amino, and aldehyde moieties through the specific binding and subsequent release of small reporter molecules such as fluorescent dyes and non-fluorescent chromophores utilizing cleavable linkers or the formation of cleavable bonds as a reversible covalent labeling strategy. This is representatively demonstrated for different types of nano- and microparticles with different labeling densities of carboxyl, amino, and aldehyde groups. This strategy enables to separate the signal-generating molecule from the bead surface, thereby circumventing uncertainties associated with light scattering, binding-induced changes in reporter fluorescence, and fluorescence quenching dye-dye interactions on crowded material surfaces.[1-3] Moreover, the reporters are chosen to be detectable with different analytical methods as prerequisite for straightforward validation via method compari-sons and mass balances. Applications of these assays and multimodal cleavable probes range from a quantitative comparison of bead batches and process control to a qualitative prediction of the coupling efficiencies in bioconjugation reactions.
Different types of optical spectroscopies are introduced with special emphasis on method-inherent limitations and reliable instrument calibration and performance validation. In addition, procedures for the determination of spectroscopic key parameters like the photoluminescence quantum yield are presented including required instrument calibrations and material-specific effects related to certain emitters.
Dose enhancement by gold nanoparticles (AuNP) was shown to increase the biological effectiveness of radiation damage in biomolecules and tissue. Most of the current studies focus on external beam therapy on combination with AuNP. Here we present a Monte-Carlo study (Geant4) to characterise radioactive AuNP. Radioactive 198 Au emits beta and gamma rays and is considered for applications with solid tumours. To effectively apply 198 AuNP their energy deposit characteristics have to be determined in terms of intrinsic and extrinsic properties e.g. AuNP diameter, AuNP density, and their clustering behaviour. After each decay process, the energy deposit, inelastic scattering events, kinetic energy spectrum of secondary particles within the AuNP themselves and in a spherical target volume of water up to 1 μm radius were determined. Simulations were performed for AuNP radii ranging from 2.5 nm to 20 nm radius, different cluster sizes and densities. The results show an increase of the energy deposit in the vicinity of the AuNP up to 150 nm. This effect nearly vanishes for distances up to one micron. For the case of AuNP clusters and the same activity, the enhancement of the energy deposit increases with the relative gold mass percentage and therefore can be adjusted by changing AuNP radius or clustering behaviour.
Simulational tools are applied to investigate the physical properties of nanoparticles.
For the description of radioactive gold nanoparticles, particles scattering simulations are performed with the Geant4 monte carlo simulation toolkit.
The temperature dependent behaviour of the magnetization dynamics of different magnetic nanoparticles are simulated with the object oriented micormagnetic framework (OOMMF).
Yb,Nd,Er-doped upconversion nanoparticles (UCNPs) have attracted considerable interest as luminescent reporters for bioimaging, sensing, energy conversion/shaping, and anticounterfeiting due to their capability to convert multiple near-infrared (NIR) photons into shorter wavelength ultraviolet, visible or NIR luminescence by successive absorption of two or more NIR photons. This enables optical measurements in complex media with very little background and high penetration depths for bioimaging. The use of Nd3+ as substitute for the commonly employed sensitizer Yb3+ or in combination with Yb3+ shifts the excitation wavelength from about 980 nm, where the absorption of water can weaken upconversion luminescence, to about 800 nm, and laser-induced local overheating effects in cells, tissue, and live animal studies can be minimized. To systematically investigate the potential of Nd3+ doping, we assessed the performance of a set of similarly sized Yb3+,Nd3+,Er3+-doped core- and core–shell UCNPs of different particle architecture in water at broadly varied excitation power densities (P) with steady state and time-resolved fluorometry for excitation at 980 nm and 808 nm. As a measure for UCNPs performance, the P-dependent upconversion quantum yield (Φ) and its saturation behavior were used as well as particle brightness (B). Based upon spectroscopic measurements at both excitation wavelengths in water and in a lipid phantom and B-based calculations of signal size at different penetration depths, conditions under which excitation at 808 nm is advantageous are derived and parameters for the further optimization of triple-doped UCNPs are given.
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.
In contrast to microplastics, little is known about nanoplastics (1 to 100 nm). In order to make the dectecability of nanoplasics more reliable, we started to develop nanoplastic reference materials. This project also aims to anser the question of how the single chain conformation of bio(polymers) changes in contact with nanoplastics. Small-angle X-ray and neutron scattering methods are suitable methods for studing this topic. Recently the soft and hard interactions between polystyrene nanoplasics and human serum albumin corona was investigated with small-angle neutron scattering. Here we concentrate on small-angle X-ray scattering as our favorite method to study how (bio)polymers change their conformation in contact with nanoplastics. The scattering of bovine serum albumin in its native state can be detected easily. The scattering pattern of this biopolymer changes dramatically when its globular stucture changes to a coil structure. Modeling of chain conformations and the calculation of the scattering pattern is relatively easy to perform. Numerous model calculations will be provided to predict the changes of conformation of single bio(polymer) chains when in conatact with nanoplastics. These predictions will be compared with recent experimenal results from in situ measurments of bio(polymers) in contact with nanoplastics. The impact of temperature, polymer concentration and salt on the single-chain conformation changes will be discussed.
Dose enhancement by gold nanoparticles (AuNP) was shown to increase the biological effectiveness of radiation damage in biomolecules and tissue. Most of the current studies focus on external beam therapy on combination with AuNP. Here we present a Monte-Carlo study (Geant4) to characterise radioactive AuNP. Radioactive ¹⁹⁸Au emits beta and gamma rays and is considered for applications with solid tumours. To effectively apply ¹⁹⁸AuNP their energy deposit characteristics have to be determined in terms of intrinsic and extrinsic properties e.g. AuNP diameter, AuNP density, and their clustering behaviour. After each decay process, the energy deposit, inelastic scattering events, kinetic energy spectrum of secondary particles within the AuNP themselves and in a spherical target volume of water up to 1 μm radius were determined. Simulations were performed for AuNP radii ranging from 2.5 nm to 20 nm radius, different cluster sizes and densities. The results show an increase of the energy deposit in the vicinity of the AuNP up to 150 nm. This effect nearly vanishes for distances up to one micron. For the case of AuNP clusters and the same activity, the enhancement of the energy deposit increases with the relative gold mass percentage and therefore can be adjusted by changing AuNP radius or clustering behaviour.
Relative and Absolute Methods for Measuring Photoluminescence Quantum Yields of UV/vis/NIR Emitters
(2019)
One of the key spectroscopic performance parameters of molecular and particulate emitters is the photoluminescence quantum yield (PL QY) that provides a direct measure for the number of emitted per absorbed photons. This triggered the interest in methods suitable for measuring this property for emitters in various environments in the UV/vis/NIR and above 1000 nm as well as on the ensemble and single emitter level. Moreover, for nonlinear emitters like lanthanide-based upconversion nanocrystals methods including instrumentation for power density-dependent PL QY studies are required.
An overview of the research activities in Division Biophotonics of BAM is given and suitable relative and absolute methods for the deter-mination of PL QY of organic dyes and different types of application-relevant nanomaterials in dispersion and in the solid state are presen-ted. This covers also the design and calibration of integrating sphere setups, achievable uncertainties, and candidates for PL QY reference materials.
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.
We report the synthesis and characterization of carbon nanodots (CDs) with high quantum yield (>50%) and tailored optical absorption as well as emission properties. A well-described protocol with polyethyleneimine (PEI) as amine precursor is used as a reference to a new CD system which is stabilized by aromatic 2,3-diaminopyridine (DAP) molecules instead. The DAP stabilizer is installed in order to red-shift the absorption peak of the n-π* electron transition allowing efficient radiative recombination and light emission. Size, shape, and chemical composition of the samples are determined by (HR)TEM, EDX and FTIR-spectroscopy. Optical parameters are investigated using UV-VIS, PL and QY measurements. Several parameters such as concentration, excitation wavelength and pH are studied. Zeta-potential analysis indicate that pH-induced (de-)protonation processes of functional moieties directly affect the n-π* energy bands. This results in unique pH-dependent absorption and emission characteristics which are discussed on the specific chemical composition of each CD system.
Non-linear optical emitters are promising materials for energy applications and biotechnologies. Solid-state multi-band emitters like lanthanide doped up-conversion nanoparticles (UCNPs) show excellent photostability, are excitable in the near infrared (NIR), and show emission bands from the UV to SWIR spectral regions. The optical properties of these materials strongly depend on the excitation power density, i.e., the number of photons absorbed per time interval. The upconversion (ΦUC) and downshifting quantum efficiencies (ΦDS) of these materials, the excitation power dependent population, and the deactivation dynamics are influenced by nanoparticle architecture, doping concentration, and the microenvironment. We studied the fundamental changes of the luminescence properties of ß-NaYF4 UCNPs doped with Yb3+ and Er3+ depending on size, different surroundings such as aqueous and organic media, and different surface chemistries. We obtained further insights into shelling procedures, FRET optimization, influence of doping concentration, and advantages of different sensitizer ions.
Merocyanine–triarylamine bichromophores are readily synthesized by sequentially Pd-catalyzed insertion alkynylation–Michael–Suzuki four-component reactions. White-light emissive systems form upon aggregation in 1 : 99 and 0.1 : 99.9 vol% CH2Cl2–cyclohexane mixtures, ascribed to aggregation-induced dual emission (AIDE) in combination with partial energy transfer between both chromophore units as supported by spectroscopic studies.
These files contain cell models for TOPAS/Geant4 and the inclusion of nano particles in particle scattering simulations. A simple spherical cell with nanoparticles can be generated in a fast manner. The user has the option to include the following organelles: nucleus, mitochondria, cell membrane. Additionally nanoparticles can be included in the cytosol and at the surface of the nucleus and/or the mitochondria.
The C++ classes in this repository extend the functionality of the TOPAS (http://www.topasmc.org/) Monte-Carlo program, which is itself a wrapper of the Geant4 MCS Toolkit (http://geant4.org). The sourcecode together with examples and scorers are provided.
"If you use this extension please cite the following literature:
Hahn, M.B., Zutta Villate, J.M. "Combined cell and nanoparticle models for TOPAS to study radiation dose enhancement in cell organelles." Sci Rep 11, 6721 (2021).
https://doi.org/10.1038/s41598-021-85964-2 "
Amphiphilic polymer nanogels (NGs) are promising drug delivery vehicles that extend the application of conventional hydrophilic NGs to hydrophobic cargoes. By randomly introducing hydrophobic groups into a hydrophilic polymer network, loading and release profiles as well as surface characteristics of these colloids can be tuned. However, very little is known about the underlying internal structure of such complex colloidal architectures. Of special interest is the question how the amphiphilic network composition influences the internal morphology and the “fuzzy” surface structure. To shine light into the influence of varying network amphiphilicity on these structural features, we investigated a small library of water-swollen amphiphilic NGs using small-angle X-ray scattering (SAXS). It was found that overall hydrophilic NGs, consisting of pure poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA), display a disordered internal structure as indicated by the absence of a SAXS peak. In contrast, a SAXS peak is present for amphiphilic NGs with various amounts of incorporated hydrophobic groups such as cholesteryl (CHOLA) or dodecyl (DODA). The internal composition of the NGs is considered structurally homologous to microgels. Application of the Teubner–Strey model reveals that hydrophilic PHPMA NGs have a disordered internal structure (positive amphiphilicity factor) while CHOLA and DODA samples have an ordered internal structure (negative amphiphilicity factor). From the SAXS data it can be derived that the internal structure of the amphiphilic NGs consists of regularly alternating hydrophilic and hydrophobic domains with repeat distances of 3.45–5.83 nm.
In the blossoming field of Cd-free semiconductor quantum dots (QDs), ternary I–III–VI QDs have received increasing attention due to the ease of the environmentally friendly synthesis of high-quality materials in water, their high photoluminescence (PL) Quantum yields (QYs) in the red and near infrared (NIR) region, and their inherently low toxicity. Moreover, their oxygen-insensitive long PL lifetimes of up to several hundreds of nanoseconds close a gap for applications exploiting the compound-specific parameter PL lifetime. To overcome the lack of reproducible synthetic methodologies and to enable a design-based control of their PL properties, we assessed and modelled the synthesis of high-quality MPA-capped AgInS2/ZnS (AIS/ZnS) QDs. Systematically refined Parameters included reaction time, temperature, Ag:In ratio, S:In ratio, Zn:In ratio, MPA:In ratio, and pH using a design-of-experiment approach.
Guidance for the optimization was provided by mathematical models developed for the application-relevant PL parameters, maximum PL wavelength, QY, and PL lifetime as well as the elemental composition in terms of Ag:In:Zn ratio. With these experimental data-based models, MPA:In and Ag:In ratios and pH values were identified as the most important synthesis parameters for PL Control and an insight into the connection of these parameters could be gained. Subsequently, the experimental conditions to synthetize QDs with tunable emission and high QY were predicted. The excellent agreement between the predicted and experimentally found PL features confirmed the reliability of our methodology for the rational design of high quality AIS/ZnS QDs with defined PL features.
This approach can be straightforwardly extended to other ternary and quaternary QDs and to doped QDs.
Two sets of polystyrene nanoparticles (PSNPs) with comparable core sizes but different carboxyl group densities were made and separated using asymmetric flow field flow fractionation (AF4), capillary electrophoresis (CE), and the off-line hyphenation of both methods. Our results revealed the significant potential of two-dimensional off-line AF4-CE hyphenation to improve the separation and demonstrated for the first time, the applicability of CE to determine the functional group density of nanoparticles (NPs). Compared to the result acquired with conductometric titration, the result obtained with synthesized 100 nm sized PSNPs revealed only a slight deviation of 1.7%. Commercial 100 nm sized PSNPs yielded a deviation of 4.6 %. For 60 nm sized PSNPs, a larger deviation of 10.6 % between both methods was observed, which is attributed to the lower separation resolution.
N-Benzyl aroyl-S,N-ketene acetals can be readily synthesized by condensation of aroyl chlorides and N-Benzyl 2-methyl benzothiazolium salts in good to excellent yields, yielding a library of 35 chromophores with bright solid-state emission and aggregation-induced emission characteristics.
Varying the substituent from electron-donating to electronwithdrawing enables the tuning of the solid-state emission Color from deep blue to red.
We present a comparative study of the spectroscopic properties of the donor–acceptor–donor substituted dyes triphenylamine-allylidenemalononitrile-julolidine (TMJ) and triphenylamine-allylidenemalononitriletriphenylamine (TMT), bearing one and two propeller-like triphenylamine donor moieties, in solvents of varying polarity and viscosity and in the aggregated and solid state. Our results reveal control of the aggregation-induced spectroscopic changes and the packing motifs of the dye molecules in the solid state by the chemical nature and structure of the second nitrogen-containing donor, i.e., a planar and a rigid julolidine or a twisted triphenyl group. Assuming that the TMT and TMJ aggregates show a comparable arrangement of the molecules to the respective crystals, these different molecular interactions in the solid state are responsible for aggregation induced emission (AIE) in the case of TMT and its absence for TMJ. Moreover, a versatile strategy for the fluorescence enhancement of only weakly emissive AIE dyes is shown, turning these dyes into bright nanoscale fluorescent reporters by using them as stains for preformed polymer particles.
Iron oxides used as food colorants are listed in the European Union with the number E172. However, there are no specifications concerning the fraction of nanoparticles in these pigments.
Here, seven E172 products were thoroughly characterized. Samples of all colors were analyzed with a Broad spectrum of methods to assess their physico-chemical properties. Small-Angle X-ray Scattering (SAXS), Dynamic Light Scattering (DLS), Transmission Electron Microscopy (TEM), zeta-potential, Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), X-ray diffraction (XRD), Brunauer-Emmett-Teller analysis (BET), Asymmetric Flow Field-Flow Fractionation (AF4) and in vitro cell viability measurements were used.
Nanoparticles were detected in all E172 samples by TEM or SAXS measurements. Quantitative results from both methods were comparable. Five pigments were evaluated by TEM, of which four had a size median below 100 nm, while SAXS showed a size median below 100 nm for six evaluated pigments. Therefore, consumers May be exposed to iron oxide nanoparticles through the consumption of food pigments.
We synthesized a generation of water-soluble, atomically precise gold nanoclusters (Au NCs) with anisotropic Surface containing a short dithiol pegylated chain (AuMHA/TDT). The AuMHA/TDT exhibit a high brightness (QY ∼ 6%) in the shortwave infrared (SWIR) spectrum with a detection above 1250 nm.
Furthermore, they show an extended half-life in blood (t1/2ß = 19.54 ± 0.05 h) and a very weak accumulation in organs. We also developed a non-invasive, whole-body vascular imaging system in the SWIR window with high-resolution, benefiting from a series of Monte Carlo image processing. The imaging process enabled to improve contrast by 1 order of magnitude and enhance the spatial Resolution by 59%. After systemic administration of these nanoprobes in mice, we can quantify vessel complexity in depth (>4 mm), allowing to detect very subtle vascular disorders non-invasively in bone morphogenetic protein 9 (Bmp9)-deficient mice. The combination of these anisotropic surface charged Au NCs plus an improved SWIR imaging device allows a precise mapping at high-resolution and an in depth understanding of the organization of the vascular network in live animals.
Aluminum (Al) can be taken up from food, packaging, or the environment and thus reaches the human gastrointestinal tract. Its toxic potential after oral uptake is still discussed. The fate of different solid and ionic Al species during the passage through the digestive tract is the focus of this research, as well as the cellular effects caused by these different Al species. The present study combines the physicochemical processing of three recently studied Al species (metallic Al0, mineral Al2O3, and soluble AlCl3) in artificial digestion fluids with in vitro cell systems for the human intestinal barrier. Inductively coupled plasma mass spectrometry (ICP-MS) and small-angle X-ray scattering (SAXS) methods were used to characterize the Al species in the artificial digestion fluids and in cell culture medium for proliferating and differentiated intestinal Caco-2 cells. Cytotoxicity testing and cellular impedance measurements were applied to address the effects of digested Al species on cell viability and cell proliferation. Microarray-based transcriptome analyses and quantitative real-time PCR were conducted to obtain a deeper insight into cellular mechanisms of action and generated indications for cellular oxidative stress and an influence on xenobiotic metabolism, connected with alterations in associated signaling pathways. These cellular responses, which were predominantly caused by formerly ionic Al species and only at very high concentrations, were not impacted by artificial digestion. A two-directional conversion of Al between ionic species and solid particles occurred throughout all segments of the gastrointestinal tract, as evidenced by the presence of nanoscaled particles. Nevertheless, this presence did not increase the toxicity of the respective Al species.
Since nanoscience has a tremendous impact on the development of electrochemistry, Wiley‐VCH paid attention to that by publishing thisbook as volume 17 within the series “Advances in Electrochemical Science and Engineering”.
This collection of “nanoaspects”on electrodes provides a helpful overview on principles and current findings to readers interested in such applications. It fulfills its intention of being “a valuable resource for researchers working in such fields as electrochemistry, materials science, spectroscopy, analytical and medicinal chemistry”.
By adding hyaluronic acid (HA) to dioctyl sodium sulfosuccinate (AOT)‐stabilized gold nanotriangles (AuNTs) with an average thickness of 7.5±1 nm and an edge length of about 175±17 nm, the AOT bilayer is replaced by a polymeric HA‐layer leading to biocompatible nanoplatelets. The subsequent reduction process of tetrachloroauric acid in the HA‐shell surrounding the AuNTs leads to the formation of spherical gold nanoparticles on the platelet surface. With increasing tetrachloroauric acid concentration, the decoration with gold nanoparticles can be tuned. SAXS measurements reveal an increase of the platelet thickness up to around 14.5 nm, twice the initial value of bare AuNTs. HRTEM micrographs show welding phenomena between densely packed particles on the platelet surface, leading to a crumble formation while preserving the original crystal structure. Crumbles crystallized on top of the platelets enhance the Raman signal by a factor of around 20, and intensify the plasmon‐driven dimerization of 4‐nitrothiophenol (4‐NTP) to 4,4′‐dimercaptoazobenzene in a yield of up to 50 %. The resulting crumbled nanotriangles, with a biopolymer shell and the absorption maximum in the second window for in vivo imaging, are promising candidates for biomedical sensing.
Nanoparticle suspensions were microprinted onto TEM grids for subsequent analysis by SEM/TSEM and evaluation of particle numbers using Image J software. Various nanoparticle types, concentrations and printing conditions (temperature, rel. humidity) were evaluated in order to determine the optimal conditions for producing a uniform distribution of particles on the substrate and eliminating the coffee ring effect.
Comprehensive Characterization of APTES Surface Modifications of Hydrous Boehmite Nanoparticles
(2020)
Hydrous boehmite (γ-AlOOH) nanoparticles (BNP) show great potential as nanoscale filler for the fabrication of fiber reinforced nanocomposite materials. Notably, the particle−matrix interaction has been demonstrated to be decisive for improving the matrix-dominant mechanical properties in the past years. Tailoring the surface properties of the nanofiller enables to selectively design the interaction and thus to exploit the benefits of the nanocomposite in an optimal way. Here, an extensive study is presented on the binding of (3-aminopropyl)triethoxysilane (APTES), a common silane surface modifier, on BNP in correlation to different process parameters (concentration, time, temperature, and pH). Furthermore, a comprehensive characterization of the modified BNP was performed by using elemental analysis (EA), thermogravimetric analysis (TGA) coupled with mass spectrometry (TGA-MS), and Kaiser’s test (KT). The results show an increasing monolayer formation up to a complete surface coverage with rising APTES concentration, time, and temperature, resulting in a maximal grafting density of 1.3 molecules/nm². Unspecific multilayer formation was solely observed under acidic conditions. Comparison of TGA-MS results with data recorded from EA, TGA, and KT verified that TGA-MS is a convenient and highly suitable method to elucidate the ligand binding in detail.
The hexapeptide hIAPP22–27 (NFGAIL) is known as a crucial amyloid core sequence of the human islet amyloid polypeptide (hIAPP) whose aggregates can be used to better understand the wild‐type hIAPP′s toxicity to β‐cell death. In amyloid research, the role of hydrophobic and aromatic‐aromatic interactions as potential driving forces during the aggregation process is controversially discussed not only in case of NFGAIL, but also for amyloidogenic peptides in general. We have used halogenation of the aromatic residue as a strategy to modulate hydrophobic and aromatic‐aromatic interactions and prepared a library of NFGAIL variants containing fluorinated and iodinated phenylalanine analogues. We used thioflavin T staining, transmission electron microscopy (TEM) and small‐angle X‐ray scattering (SAXS) to study the impact of side‐chain halogenation on NFGAIL amyloid formation kinetics. Our data revealed a synergy between aggregation behavior and hydrophobicity of the phenylalanine residue. This study introduces systematic fluorination as a toolbox to further investigate the nature of the amyloid self‐assembly process.
In this research project, a new OECD Test Guideline (TG) for the determination of “Particle Size and Particle Size Distributions of Nanomaterials” was developed as the existing OECD TG 110 is considered to be outdated in terms of applicable size range (not covering sizes <200 nm) and methods. By its scope with an applicable size range from 1 to 1000 nm the new Test Guideline (TG PSD) covers the whole nanoscale. The TG PSD is applicable for particulate and fibrous nanomaterials. The prescribed, pairwise measurement of fibre diameter and length in the TG PSD allows for the first time to differen-tiate fibres with regard to their size-dependent hazard properties. Measurement instructions for each included method were validated within two separated interlaboratory comparisons, as a distinction between near spherical particles and fibres when applying the methods has to be made.
Besides information on content and structure of the TG PSD, this final report outlines essential steps, considerations and organisational aspects during the development of the TG. Insights into the selec-tion, preparation and prevalidation of test materials used in the interlaboratory comparison are given. Finally, main results of the interlaboratory comparisons and their impacts on the TG PSD are pre-sented.
Final Draft of the OECD Test Guideline for Particle Size and Particle Size Distribution of Nanomaterials.
The OECD Working Party on Manufactured Nanomaterials (WPMN) has actively worked towards understanding possible safety issues for manufactured nanomaterials and has contributed significantly to resolving these by developing Test Guidelines, Guidance Documents, Test Reports and other publications with the aim of a safe use of manufactured nanomaterials. The OECD website (www.oecd.org/science/nanosafety) and the referenced publications contain more background information.
Among others, the OECD Test Guideline “Particle Size Distribution/Fibre Length and Diameter Distributions” (TG 110, adopted in 1981) was identified to require an update to address the specific needs of manufactured nanomaterials as the TG 110 is currently only valid for particles and fibres with sizes above 250 nm. The WPMN prioritised to either update TG 110 to be applicable also to particles at the nanoscale or draft a new nanomaterial specific Test Guideline (TG). Eventually, it was decided to develop a new TG for particle size and particle size distribution measurements of nanomaterials covering the size range from 1 nm to 1000 nm for further justification. This TG overlaps with TG 110 in the size range from 250 nm to 1000 nm. When measuring particulate or fibrous materials, the appropriate TG should be selected depending on the size range of particles tested. In line with TG 110, the new TG for nanomaterials includes separate parts for particles and fibres. For the part of this TG which addresses particles, several methods applicable to nanomaterials were reviewed and included to take into account developments since 1981 when the TG110 was adopted. This TG includes the following methods: Atomic Force Microscopy (AFM), Centrifugal Liquid Sedimentation (CLS)/Analytical Ultracentrifugation (AUC), Dynamic Light Scattering (DLS), Differential Mobility Analysis System (DMAS), (Nano)Particle Tracking Analysis (PTA/NTA), Small Angle X-Ray Scattering (SAXS), Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM).
For measuring the diameter and length of fibres, analysing images captured with electron microscopy is currently the only method available. This TG includes Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM).
To test the validity of this TG, an ILC was performed. Test materials were chosen to reflect a broad 68 range of nanomaterial classes, e.g. metals, metal oxides, polymers and carbon materials. Where possible, well-characterised test materials were used. Additionally, the test materials were chosen, so that they reflect a broad range of sizes representing the size range 1 nm to 1000 nm and finally,
for fibres only, aspect ratios from length/diameter of 3 to > 50.
Whilst a decisive role of the particle-matrix interphase on the mechanical properties of nanoparticle-filled polymers has been demonstrated in the last years, the arbitrary design of this interphase remains a very challenging goal. In principle, this could be realized via an appropriate surfacemodification of the nanofiller prior to its incorporation in the polymer. For most systems, such as for boehmite nanofillers, however, the interaction of organic modifiers with the particle surface has not been studied in detail, and only single studies are known rather than systematic investiga- tions on the effects of different chemical functions anchored on the particle surface. In this chapter, we present an extensive study on the binding of APTES, a common silane surface modifier, with boehmite, and show that thermogravimetric analysis (TGA) coupled with mass spectrometry (MS) is a convenient and highly suitable method to elucidate the ligand binding in detail. Furthermore, a two-step coupling strategy is presented, demonstrating that based on APTES anchored to the parti- cle surface, the condensation of various carboxylic acids can be utilized to enable highly diverse chemical properties of the nanofillers, which leads to very different particle-matrix interactions in the nanocomposites.
Surface self-assembly of spherical nanoparticles of sizes below 10 nm into hierarchical heterostructures is under arising development despite the inherent difficulties of obtaining complex ordering patterns on a larger scale. Due to template-mediated interactions between oil-dispersible superparamagnetic nanoparticles (MNPs) and polyethylenimine-stabilized gold nanoparticles (Au(PEI)NPs) at the water–oil interface of microemulsions, complex nanostructured films can be formed. Characterization of the reverse microemulsion phase by UV–vis absorption revealed the formation of heteroclusters from Winsor type II phases (WPII) using Aerosol-OT (AOT) as the surfactant. SAXS measurements verify the mechanism of initial nanoparticle clustering in defined dimensions. XPS suggested an influence of AOT at the MNP surface. Further, cryo-SEM and TEM visualization demonstrated the elongation of the reverse microemulsions into cylindrical, wormlike structures, which subsequently build up larger nanoparticle superstructure arrangements. Such WPII phases are thus proven to be a new form of soft template, mediating the self-assembly of different nanoparticles in hierarchical network-like filaments over a substrate during solvent evaporation.
The chapter gives a brief introduction to (nano)compositecomposite materials having the focus on polymer-based nanocomposites. The different dimensionalities of nanoparticles are introduced, along with their distribution in the matrix.
Different application fields of polymer-based nanocomposites, like flame retardancy, filled rubbers, nanofilled thermosets and thermoplastics, separation membranes and nanodielectrics, are considered in greater detail.
Solvent annealing is a versatile tool to adjust the shape and morphology of block copolymer (BCP) particles. During this process, polar solvents are often used for block-selective swelling. However, such water-miscible solvents can induce (partial) solubilization of one block in the surrounding aqueous medium, thus, causing complex structural variations and even particle disassembly. To reduce the complexity in morphology control, we focused on toluene as a nonpolar polystyrene-selective solvent for the annealing of striped polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) ellipsoids. The selective stretching of PS chains produces unique asymmetric lamellae structures, which translate to an increase in the particle aspect ratio after toluene evaporation. Complete reversibility is achieved by changing to chloroform as a nonselective solvent. Moreover, surfactants can be used to tune block-selective wetting of the particle surface during the annealing; for example, a PS shell can protect the internal lamellae structure from disassembly. Overall, this versatile postassembly process enables the tailoring of the structural features of striped colloidal ellipsoids by only using commercial BCPs and solvents.
Aluminum (Al) is highly abundant in the biosphere and can occur in different physico-chemical states. It is present in human food and undergoes transitions between dissolved and particulate species during the passage of the gastrointestinal tract. Moreover, in a complex matrix such as food different inorganic and organic counterions can affect the chemical behavior of Al following oral uptake.
In this work, the effects of different counterions, namely chloride, citrate, sulfate, lactate and acetylacetonate, on Al uptake and toxicity in the human intestine are studied. The respective Al salts showed different dissolution behavior in biological media and formed nanoscaled particles correlating in reverse with the amount of their dissolved fraction. The passage through the intestinal barrier was studied using a Caco-2 Transwell® system, showing counterion-dependent variance in cellular uptake and transport. In addition, Al toxicity was investigated using Al species (Al3+, metallic Al0 and oxidic γAl2O3 nanoparticles) and counterions individually or in mixtures on Caco-2 and HepG2 cells. The strongest toxicity was observed using a combination of Al species, depending on solubility, and the lipophilic counterion acetylacetonate. Notably, only the combination of both led to toxicity, while both substances individually did not show toxic effects. A toxification of previously non-toxic Al-species by the presence of acetylacetonate is shown here for the first time. The dependency on the concentration of free Al ions was demonstrated using sodium hydrogen phosphate, which was able to counteract the toxic effects by complexing free Al ions.
These findings, using Al salts as an example for a common food contaminant, underline the importance of a consideration of the chemical properties of human nutrition, especially dissolution and hydrophobicity, which can significantly influence the cellular uptake and effects of xenobiotic substances.
Despite considerable advances in synthesizing high-quality core/shell upconversion (UC) nanocrystals (NC; UCNC) and UCNC photophysics, the application of near-infrared (NIR)-excitable lanthanide-doped UCNC in the life and material sciences is still hampered by the relatively low upconversion luminescence (UCL) of UCNC of small size or thin protecting shell. To obtain deeper insights into energy transfer and surface quenching processes involving Yb3+ and Er3+ ions, we examined energy loss processes in differently sized solid core NaYF4 nanocrystals doped with either Yb3+ (YbNC; 20% Yb3+) or Er3+ (ErNC; 2% Er3+) and co-doped with Yb3+ and Er3+ (YbErNC; 20% Yb3+ and 2% Er3+) without a surface protection shell and coated with a thin and a thick NaYF4 shell in comparison to single and co-doped bulk materials. Luminescence studies at 375 nm excitation demonstrate backenergy transfer (BET) from the 4G11/2 state of Er3+ to the 2F5/2 state of Yb3+, through which the red Er3+ 4F9/2 state is efficiently populated. Excitation power density (P)-dependent steady state and time-resolved photoluminescence measurements at different excitation and emission wavelengths enable to separate surface-related and volume-related effects for two-photonic and threephotonic processes involved in UCL and indicate a different influence of surface passivation on the green and red Er3+ emission.
The intensity and lifetime of the latter respond particularly to an increase in volume of the active UCNC core. We provide a threedimensional random walk model to describe these effects that can be used in the future to predict the UCL behavior of UCNC.
Post-assembly modifications are efficient tools to adjust colloidal features of block copolymer (BCP) particles. However, existing methods often address particle shape, morphology, and chemical functionality individually. For simultaneous control, we transferred the concept of seeded polymerization to phase separated BCP particles. Key to our approach is the regioselective polymerization of (functional) monomers inside specific BCP domains. This was demonstrated in striped PS-b-P2VP ellipsoids. Here, polymerization of styrene preferably occurs in PS domains and increases PS lamellar thickness up to 5-fold. The resulting asymmetric lamellar morphology also changes the particle shape, i.e., increases the aspect ratio. Using 4-vinylbenzyl azide as co-monomer, azides as chemical functionalities can be added selectively to the PS domains. Overall, our simple and versatile method gives access to various multifunctional BCP colloids from a single batch of pre-formed particles.
Current trends in materials and life sciences are flanked by the need to push detection limits to single molecules or single cells, enable the characterization of increasingly complex matrices or sophisticated nanostructures, speed up the time of analysis, reduce instrument complexity and costs, and improve the reliability of data. This requires suitable analytical tools such as spectroscopic, separation and imaging techniques, mass spectrometry, and hyphenated techniques as well as sensors and their adaptation to application-specific challenges in the environmental, food, consumer product, health sector, nanotechnology, and bioanalysis. Increasing concerns about health threatening known or emerging pollutants in drinking water, consumer products, and food and about the safety of nanomaterials led to a new awareness of the importance of analytical sciences. Another important driver in this direction is the increasing demand by legislation, particularly in view of the 17 sustainable development goals by the United Nations addressing clean energy, industry, and innovation, sustainable cities, clean water, and responsible consumption and production. In this respect, also the development of analytical methods that enable the characterization of material flows in production processes and support recycling concepts of precious raw materials becomes more and more relevant. In the future, this will provide the basis for greener production in the chemical industry utilizing recycled or sustainable starting materials.
This makes analytical chemistry an essential player in terms of the circular economy helping to increase the sustainability of production processes. In the life sciences sector, products based on proteins, such as therapeutic and diagnostic antibodies, increase in importance. These increasingly biotechnologically produced functional biomolecules pose a high level of complexity of matrix and structural features that can be met only by highly advanced methods for separation, characterization, and detection. In addition, metrological traceability and target definition are still significant challenges for the future, particularly in the life sciences.
However, innovative reference materials as required for the health and food sector and the characterization of advanced materials can only be developed when suitable analytical protocols are available. The so-called reproducibility crisis in sciences underlines the importance of improved measures of quality control for all kinds of measurements and material characterization. This calls for thorough method validation concepts, suitable reference materials, and regular interlaboratory comparisons of measurements as well as better training of scientists in analytical sciences.
The important contribution of analytical sciences to these developments is highlighted by a broad collection of research papers, trend articles, and critical reviews from these different application fields. Special emphasis is dedicated to often-overlooked quality assurance and reference materials.
The unique optoelectronic properties of semiconductor nanocrystals, also termed quantum dots (QDs), have led to many advances in optoelectronic devices, bioimaging, and biosensing. This strong potential in a wide range of applications sparked the interest for a better understanding of the QD formation mechanisms. Recent studies have shown that atomically defined, zero-dimensional magic-size clusters (MSCs) play a crucial role during the nucleation and growth of QDs. Thereby MSCs consist of discrete numbers of ions leading to narrow size distributions and thus narrow absorption peaks, which evolve in discrete steps from one stable size to the next. The formation of MSCs was found in the synthesis of II-VI and III-V QDs but only limited synthesis approaches are available for the synthesis of MSCs in single-ensemble form without coexistence of other-size QDs. These MSCs can further self-assemble into two- and three-dimensional hybrid structures using organic ligands like diamines, leading to enhanced photoluminescence properties and catalytic activities.
In this contribution, we present a synthesis strategy for the preparation of single-sized ZnSe MSCs. With a band gap of 2.7 eV and being an earth-abundant material, ZnSe QDs are interesting for light-emitting devices, blue-green lasers, photocatalysis, and fluorescence probes. In contrast to other studies, our approach is based on a one-pot heat-up synthesis and uses less toxic and dangerous zinc precursors (e.g. zinc stearate). Knowing that thiol-based ligands can alter the formation process of ZnSe QDs, we investigated the influence of 1-dodecanethiol on the ZnSe MSC formation using absorption spectroscopy, TEM, XPS, and XRD. By variation of the thiol ligand concentration and reaction temperature, we were able to synthesize two new ZnSe MSC sizes, the largest so far, by using easy-to-handle precursors.
Functionalized nanomaterials (NM) with their unique size-dependent properties are of increasing relevance for current and future developments in various fields such as medical and pharmaceutical industry, computing, electronics or food and consumer products. The performance and safety of NM are determined by the sum of their intrinsic physicochemical properties.1 Besides other key parameters, the particle surface chemistry, which is largely controlled by the chemical nature and density of functional groups and ligands, must be considered for a better performance, stability, and processibility of NM, as well as their interaction with the environment. Thus, particle standards with well-designed surfaces and methods for functional group quantification can foster the sustainable development of functional and safe(r) NM.2 Here we provide a brief overview of the ongoing research in division Biophotonics to design tailored amorphous silica reference particles with bioanalytically relevant functional groups and ligands, for the development of standardized and validated surface functional group quantification methods.
The OECD Working Party on Manufactured Nanomaterials (WPMN) has actively worked towards understanding possible safety issues for manufactured nanomaterials and has contributed significantly to resolving these by developing Test Guidelines, Guidance Documents, Test Reports and other publications with the aim of a safe use of manufactured nanomaterials. To address the specific needs of manufactured nanomaterials, the OECD Test Guideline No. 110 “Particle Size Distribution/Fibre Length and Diameter Distributions” was identified as one of the test guidelines (TGs) to require an update. The current TG 110 (adopted in 1981) is only valid for particles and fibres with sizes above 250 nm. The WPMN prioritised to either update TG 110 to be applicable also to particles at the nanoscale or draft a new nanomaterial specific (TG).
Eventually, it was decided to develop a new TG that covers the size range from 1 nm to 1000 nm, intended for particle size and particle size distribution measurements of nanomaterials. Paragraph 11 provides further justification on the need for such measurements for nanomaterials. This TG overlaps with TG 110 in the size range from 250 nm to 1000 nm. When measuring particulate or fibrous materials, the appropriate TG should be selected depending on the size range of particles tested. In line with TG 110, the new TG for nanomaterials includes separate parts for particles and fibres.
For the part of this TG which addresses particles, several methods applicable to nanomaterials were reviewed and included to take into account developments since 1981 when the TG 110 was adopted. This TG includes the following methods: Atomic Force Microscopy (AFM), Centrifugal Liquid Sedimentation (CLS)/Analytical Ultracentrifugation (AUC), Dynamic Light Scattering (DLS), Differential Mobility Analysis System (DMAS), (Nano)Particle Tracking Analysis (PTA/NTA), Small Angle X-Ray Scattering (SAXS), Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM). The method Single Particle Inductively Coupled Plasma Mass Spectrometry (sp-ICP-MS) could not be sufficiently validated within the interlaboratory comparison (ILC) carried out for the different methods in this TG (see also paragraph 6 for further details on the ILC). Applicability of sp-ICP-MS is strongly limited to nanomaterials with high mass values in combination with a sufficiently high particle size. However, the general method ICP-MS is widely used and the sp-mode for the size measurement of specific nanomaterials was successfully performed in ILCs elsewhere. The method is therefore included in the Appendix Part C of this TG, which further details the limitations of sp-ICP-MS.
For measuring the diameter and length of fibres, analysing images captured with electron microscopy is currently the only method available. This TG includes Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM).
To test the validity of this TG, an ILC was performed. Test materials were chosen to reflect a broad range of nanomaterial classes, e.g. metals, metal oxides, polymers and carbon materials. Where possible, well-characterised test materials were used.
Additionally, the test materials were chosen to reflect a broad range of sizes representing the size range 1 nm to 1000 nm. Specifically for fibres, a broad range of aspect ratios was included (length/diameter of 3 to > 50). Some of the test materials used are commercially available and further references are given in the validation report of the ILC. Sample preparation for physical chemical characterisation is critical for all listed methods. Due to the differences between individual nanomaterials and due to the wide range of individual material properties it is impossible to have a generic protocol to obtain the best possible sample preparation for every nanomaterial. Therefore, a generic protocol on sample preparation is not part of this TG. Information on sample preparation is given in the paragraphs 25-29, 33, 34 and 39 for particles and in paragraphs 159) for fibres. Further information on sample preparation of nanomaterials for physical chemical characterisation can be found in the OECD Guidance on Sample Preparation and Dosimetry for the Safety Testing of Manufactured Nanomaterials and elsewhere.
To enhance the biological effects of radiation damage in cancerous cells, we present an alternative approach to the use of gold nanoparticles (AuNP), focusing on the synthesis and characterization of highly monodisperse, spherical radioactive gold nanoparticles 198AuNP. The size of the AuNP size was optimized with the help of Geant4/TOPAS particle scattering simulations, and energy deposition per nm3 per decay for varying radii (2–10 nm) was evaluated. This work is the foundation for ongoing experimental work to evaluate cell death induced by 198AuNP which aims for the use of radioactive gold nanoparticles in cancer treatment.
High sensitizer and activator concentrations have been increasingly examined to improve the performance of multi-color emissive upconversion (UC) nanocrystals (UCNC) like NaYF4:Yb,Er and first strategies were reported to reduce concentration quenching in highly doped UCNC. UC luminescence (UCL) is, however, controlled not only by dopant concentration, yet by an interplay of different parameters including size, crystal and shell quality, and excitation power density (P). Thus, identifying optimum dopant concentrations requires systematic studies of UCNC designed to minimize additional quenching pathways and quantitative spectroscopy. Here, we quantify the dopant concentration dependence of the UCL quantum yield (ΦUC) of solid
NaYF4:Yb,Er/NaYF4:Lu upconversion core/shell nanocrystals of varying Yb3+ and Er3+ concentrations (Yb3+ series: 20%‒98% Yb3+; 2% Er3+; Er3+ series: 60% Yb3+; 2%‒40% Er3+). To circumvent other luminescence quenching processes, an elaborate synthesis yielding OH-free UCNC with record ΦUC of ~9% and ~25 nm core particles with a thick surface shell were used. High Yb3+ concentrations barely reduce ΦUC from ~9% (20% Yb3+) to ~7% (98% Yb3+) for an Er3+ concentration of 2%, thereby allowing to strongly increase the particle absorption cross section and UCNC brightness. Although an increased Er3+ concentration reduces ΦUC from ~7% (2% Er3+) to 1% (40%) for 60% Yb3+. Nevertheless, at very high P (> 1 MW/cm2) used for microscopic studies, highly Er3+-doped UCNC display a high brightness because of reduced saturation. These findings underline the importance of synthesis control and will pave the road to many fundamental studies of UC materials.
Current trends in materials and life sciences are flanked by the need to push detection limits to single molecules or single cells, enable the characterization of increasingly complex matrices or sophisticated nanostructures, speed up the time of analysis, reduce instrument complexity and costs, and improve the reliability of data. This requires suitable analytical tools such as spectroscopic, separation and imaging techniques, mass spectrometry, and hyphenated techniques as well as sensors and their adaptation to application-specific challenges in the environmental, food, consumer product, health sector, nanotechnology, and bioanalysis. Increasing concerns about health threatening known or emerging pollutants in drinking water, consumer products, and food and about the safety of nanomaterials led to a new awareness of the importance of analytical sciences. Another important driver in this direction is the increasing demand by legislation, particularly in view of the 17 sustainable development goals by the United Nations addressing clean energy, industry, and innovation, sustainable cities, clean water, and responsible consumption and production. In this respect, also the development of analytical methods that enable the characterization of material flows in production processes and support recycling concepts of precious raw materials becomes more and more relevant. In the future, this will provide the basis for greener production in the chemical industry utilizing recycled or sustainable starting materials.
This makes analytical chemistry an essential player in terms of the circular economy helping to increase the sustainability of production processes. In the life sciences sector, products based on proteins, such as therapeutic and diagnostic antibodies, increase in importance. These increasingly biotechnologically produced functional biomolecules pose a high level of complexity of matrix and structural features that can be met only by highly advanced methods for separation, characterization, and detection. In addition, metrological traceability and target definition are still significant challenges for the future, particularly in the life sciences.
However, innovative reference materials as required for the health and food sector and the characterization of advanced materials can only be developed when suitable analytical protocols are available. The so-called reproducibility crisis in sciences underlines the importance of improved measures of quality control for all kinds of measurements and material characterization. This calls for thorough method validation concepts, suitable reference materials, and regular interlaboratory comparisons of measurements as well as better training of scientists in analytical sciences.
The important contribution of analytical sciences to these developments is highlighted by a broad collection of research papers, trend articles, and critical reviews from these different application fields. Special emphasis is dedicated to often-overlooked quality assurance and reference materials.
Biofilms are ubiquitous in nature and in the man-made environment. Given their harmful effects on human health, an in-depth understanding of biofilms and the monitoring of their formation and growth are important. Particularly relevant for many metabolic processes and survival strategies of biofilms is their extracellular pH. However, most conventional techniques are not suited for minimally invasive pH measurements of living biofilms. Here, a fluorescent nanosensor is presented for ratiometric measurements of pH in biofilms in the range of pH 4.5–9.5 using confocal laser scanning microscopy. The nanosensor consists of biocompatible polystyrene nanoparticles loaded with pH-inert dye Nile Red and is surface functionalized with a pH-responsive fluorescein dye. Its performance was validated by fluorometrically monitoring the time-dependent changes in pH in E. coli biofilms after glucose inoculation at 37 °C and 4 °C. This revealed a temperature-dependent decrease in pH over a 4-h period caused by the acidifying glucose metabolism of E. coli. These studies demonstrate the applicability of this nanosensor to characterize the chemical microenvironment in biofilms with fluorescence methods.
The optical properties of these materials strongly depend on the excitation power density, i.e., the number of photons absorbed per time interval. The upconversion quantum efficiencies (ΦUC) of these materials, the excitation power dependent population i.e. the emission characteristics, and the deactivation dynamics are influenced by nanoparticle architecture, doping concentration, and the microenvironment. We will discuss how time resolved measurements can help to understand the fundamental photophysical mechanisms and discuss differences to other nanocrystals like quantum dots.
AbstractWe report on gold clusters with around 62 gold atoms and a diameter of 1.15±0.10 nm. Dispersions of the clusters are long‐term stable for two years at ambient conditions. The synthesis was performed by mixing tetrachloroauric acid (HAuCl4 ⋅ 3 H2O) with the ionic liquid 1‐ethyl‐3‐methylimidazolium dicyanamide ([Emim][DCA]) at temperatures of 20 to 80 °C. Characterization was performed with small‐angle X‐ray scattering (SAXS), UV‐Vis spectroscopy, and MALDI‐TOF mass spectrometry. A three‐stage model is proposed for the formation of the clusters, in which cluster growth from gold nuclei takes place according to the Lifshitz‐Slyozov‐Wagner (LSW) model followed by oriented attachment to form colloidal stable clusters.
New insights into pertinent Fe-complexes for the synthesis of iron via the instant polyol process
(2023)
Chemically synthesized iron is in demand for biomedical applications due to its large saturation magnetization compared to iron oxides. The polyol process, suitable for obtaining Co and Ni particles and their alloys, is laborious in synthesizing Fe. The reaction yields iron oxides, and the reaction pathway remains unexplored. This study shows that a vicinal polyol, such as 1,2-propanediol, is suitable for obtaining Fe rather than 1,3-propanediol owing to the formation of a reducible Fe intermediate complex. X-ray absorption spectroscopy analysis reveals the ferric octahedral geometry and tetrahedral geometry in the ferrous state of the reaction intermediates in 1,2-propanediol and 1,3-propanediol, respectively. The final product obtained using a vicinal polyol is Fe with a γ-Fe2O3 shell, while the terminal polyol is favourable for Fe3O4. The distinct Fe–Fe and Fe–O bond lengths suggest the presence of a carboxylate group and a terminal alkoxide ligand in the intermediate of 1,2-propanediol. A large Fe–Fe bond distance suggests diiron complexes with bidentate carboxylate bridges. Prominent high-spin and low-spin states indicate the possibility of transition, which favors the reduction of iron ions in the reaction using 1,2-propanediol.
Heterogeneous sandwich immunoassays are widely used for biomarker detection in bioanalysis and medical diagnostics. The high analyte sensitivity of the current “gold standard” enzyme-linked immunosorbent assay (ELISA) originates from the signal-generating enzymatic amplification step, yielding a high number of optically detectable reporter molecules. For future point-of-care testing (POCT) and point-of-need applications, there is an increasing interest in more simple detection strategies that circumvent time-consuming and temperature-dependent enzymatic reactions. A common concept to aim for detection limits comparable to those of enzymatic amplification reactions is the usage of polymer nanoparticles (NP) stained with a large number of chromophores. We explored different simple NP-based signal amplification strategies for heterogeneous sandwich immunoassays
that rely on an extraction-triggered release step of different types of optically detectable reporters. Therefore, streptavidinfunctionalized polystyrene particles (PSP) are utilized as carriers for (i) the fluorescent dye coumarin 153 (C153) and (ii) hemin (hem) molecules catalyzing the luminol reaction enabling chemiluminescence (CL) detection. Additionally, (iii) NP labeling with hemin-based microperoxidase MP11 was assessed. For each amplification approach, the PSP was first systematically optimized regarding size, loading concentration, and surface chemistry. Then, for an immunoassay for the inflammation marker C- eactive protein (CRP), the analyte sensitivity achievable with optimized PSP
ystems was compared with the established ELISA concept for photometric and CL detection. Careful optimization led to a limit of detection (LOD) of 0.1 ng/mL for MP11-labeled PSP and CL detection, performing similarly well to a photometric ELISA (0.13 ng/mL), which demonstrates the huge potential of our novel assay concept.
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., Eu and Ho, is described using a novel strategy that uses the ratio of IS elements and LA-ICP-TOFMS analysis. To achieve this, an internal standard layer is deposited onto microscope slides containing either gelatin calibration standards or Euand Ho-tagged cell samples. This IS layer contains both gallium (Ga) and indium (In).
Monitoring either element as an IS individually showed significant variability in intensity signal between sample or standards prepared across multiple microscope slides, which is indicative of the difficulties in producing a homogeneous film at intracellular resolution.
However, normalization of the lanthanide signal to the ratio of the IS elements improved the calibration correlation coefficients from 0.9885 to 0.9971 and 0.9805 to 0.9980 for Eu and Ho, respectively, while providing a consistent signal to monitor the ablation behavior between standards and samples. By analyzing an independent quality control (QC) gelatin sample spiked with Eu and Ho, it was observed that without normalization to the IS ratio the concentrations of Eu and Ho were highly biased by approximately 20% in comparison to the expected values.
Similarly, this overestimation was also observed in the lanthanide concentration distribution of the cell samples in comparison with
the normalized data.
Reducing the size of upconversion nanoparticles (UCNPs) down to a few nm yields luminescent materials containing a very small number of emitters.
Considering the bottom limit of one activator per particle ultrasmall UCNPs offer an unprecedented platform to study the contributions of the energy transfers at play in upconversion luminescence. Maintaining detectable emission despite the limited number of emitting ions and the high surface-to-volume ratio requires suitable particle architectures.
Na(Gd-Yb)F4:Tm3+ emissive sub-3 nm diameter 𝜷-phase UCNPs are prepared using a gadolinium-rich composition in situ mixing of the precursors and a microwave high-temperature cycling sequence allowing precise control of the particle size and dispersity. These cores are coated with a NaGdF4 inert shell to minimize the deleterious influence of surface quenching (SQ).
Time-resolved luminescence measurements combining standard NIR excitation of the Yb3+ sensitizer and direct UV excitation of the Tm3+ activator are performed to quantify cross relaxation and surface quenching processes.
The fine tuning of the number of activators per particle via an optimized synthesis pathway along with the use of an appropriate excitation scheme enabled to provide an accurate analysis of the different mechanisms at play in these model nanoparticles and to characterize the structure of the core-shell architecture.