TY - JOUR
A1 - Tavernaro, Isabella
A1 - Sander, P. C.
A1 - Andresen, Elina
A1 - Schedler, U.
A1 - Resch-Genger, Ute
T1 - Expanding the Toolbox of Simple, Cost-Efficient, and Automatable Methods for Quantifying Surface Functional Groups on Nanoparticles� Potentiometric Titration
N2 - Measuring surface functional groups (FGs) on nanomaterials (NMs) is essential for designing dispersible and stable NMs with tailored and predictable functionality. FG screening and quantification also plays a critical role for subsequent processing steps, NM long-term stability, quality control of NM production, and risk assessment studies and enables the implementation of sustainable and safe(r)-by-design concepts. This calls for simple and cost-efficient methods for broadly utilized FGs that can be ideally automated to speed up FG screening, monitoring, and quantification. To expand our NM surface analysis toolbox, focusing on simple methods and broadly available, cost-efficient instrumentation, we explored a NM-adapted pH titration method with potentiometric and optical readout for measuring the total number of (de)protonable FGs on representatively chosen commercial and custom-made aminated silica nanoparticles (SiO2 NPs). The accuracy and robustness of our stepwise optimized workflows was assessed by several operators in two laboratories and method validation was done by cross-comparison with two analytical methods relying on different signal generation principles. This included traceable, chemo-selective quantitative nuclear magnetic resonance spectroscopy (qNMR) and thermogravimetric analysis (TGA), providing the amounts of amino silanes released by particle dissolution and the total mass of the surface coatings. A comparison of the potentiometric titration results with the reporter-specific amounts of surface amino FGs determined with the previously automated fluorescamine (Fluram) assay highlights the importance of determining both quantities for surface-functionalized NMs. In the future, combined NM surface analysis with optical assays and pH titration will simplify quality control of NM production processes and stability studies and can yield large data sets for NM grouping that facilitates further developments in regulation and standardization.
KW - Quality assurance
KW - Fluorescence
KW - Nano
KW - Particle
KW - Synthesis
KW - Characterization
KW - Advanced material
KW - Surface
KW - Standardization
KW - Reference material
KW - Functional group
KW - Quantification
KW - Coating
KW - Automation
KW - Potentiometry
KW - Method
KW - Validation
KW - Optical assay
KW - Fluram
KW - Fluorescamine
KW - qNMR
KW - Comparison
KW - ILC
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-642371
DO - https://doi.org/10.1021/acsmeasuresciau.5c00062
SN - 2694-250X
SP - 1
EP - 13
PB - American Chemical Society
CY - Washington, DC
AN - OPUS4-64237
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Richter, Maria
A1 - Güttler, Arne
A1 - Pauli, Jutta
A1 - Vogel, K.
A1 - Homann, Christian
A1 - Würth, Christian
A1 - Resch-Genger, Ute
T1 - Extending certified spectral fluorescence standards for the calibration and performance validation of fluorescence instruments to the NIR—closing the gap from 750 to 940 nm with two novel NIR dyes
N2 - Fluorescence techniques such as fluorescence spectroscopy, microfluorometry, and fluorescence microscopy, providing spectral, intensity, polarization, and lifetime information, are amongst the most broadly utilized analytical methods in the life and materials sciences. However, the measured fluorescence data contain sample- and instrument-specific contributions, which hamper their comparability across instruments and laboratories. Comparable, instrument-independent fluorescence data require the determination of the fluorescence instrument’s wavelength-dependent spectral responsivity, also termed emission correction curve, for the same instrument settings as those used for the fluorescence measurements as a prerequisite for the subsequent correction of the measured instrument-specific data. Such a spectral correction is essential for the performance comparison of different fluorescent labels and reporters, quantitative fluorescence measurements, the determination of the fluorescence quantum yield, and the spectroscopic measure for the fluorescence efficiency of a fluorophore. Simple-to-use tools for obtaining emission correction curves are chromophore-based reference materials (RMs), referred to as fluorescence standards, with precisely known, preferably certified instrument-independent fluorescence spectra. However, for the increasingly used near-infrared (NIR) wavelength region >700 nm, at present, no spectral fluorescence standards are available. To close this gap, we developed two novel spectral fluorescence standards, BAM F007 and BAM-F009, with broad emission bands from about 580 to 940 nm in ethanolic solution. These liquid fluorescence standards currently under certification, which will be released in 2025, will expand the wavelength range of the already available certified Calibration Kit BAM F001b-F005b from about 300–730 to 940 nm. In this research article, we will detail the criteria utilized for dye and matrix selection and the homogeneity and stability tests accompanying dye certification as well as the calculation of the wavelength-dependent uncertainty budgets of the emission spectra BAM F007 and BAM-F009, determined with the traceably calibrated BAM reference spectrofluorometer. These fluorescence standards can provide the basis for comparable fluorescence measurements in the ultraviolet, visible, and NIR for the fluorescence community.
KW - Quality assurance
KW - Reference material
KW - Fluorescence
KW - Dye
KW - Traceability
KW - Metrology
KW - Calibration
KW - Reference data
KW - Reference product
KW - Digital certificate
KW - NIR
KW - Instrument performance validation
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-626317
DO - https://doi.org/10.1007/s00216-024-05723-w
SN - 1618-2650
SP - 1
EP - 15
PB - Springer
AN - OPUS4-62631
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Deumer, J.
A1 - Andresen, Elina
A1 - Gollwitzer, C.
A1 - Schürmann, R.
A1 - Resch-Genger, Ute
T1 - Adding More Shape to Nanoscale Reference Materials-LiYF4:Yb,Tm Bipyramids as Standards for Sizing Methods and Particle Number Concentration
N2 - The increasing industrial use of nanomaterials calls for the reliable characterization of their physicochemical key properties like size, size distribution, shape, and surface chemistry, and test and reference materials (RMs) with sizes and shapes, closely matching real-world nonspheric nano-objects. An efficient strategy to minimize efforts in producing nanoscale RMs (nanoRMs) for establishing, validating, and standardizing methods for characterizing nanomaterials are multimethod nanoRMs.
Ideal candidates are lanthanide-based, multicolor luminescent, and chemically inert nanoparticles (NPs) like upconversion nanoparticles (UCNPs), which can be prepared in different sizes, shapes, and chemical composition with various surface coatings. This makes UCNPs interesting candidates as standards not only for sizing methods, but also for element-analytical methods like laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), quantitative bioimaging methods like X-ray fluorescence computed tomography (XFCT), and luminescence methods and correlative measurements.
Here, we explore the potential of two monodisperse LiYF4:Yb,Tm bipyramids with peak-to-peak distances of (43 ± 2) nm and (29 ± 2) nm as size standards for small-angle X-ray scattering (SAXS) and tools for establishing and validating the sophisticated simulations required for the analysis of SAXS data derived from dispersions of nonspheric nano-objects. These SAXS studies are supplemented by two-dimensional (2D)-transmission electron microscopy measurements of the UCNP bipyramids. Additionally, the particle number concentration of cyclohexane dispersions of these UCNP bipyramids is determined by absolute SAXS measurements, complemented by gravimetry, thermogravimetric analysis (TGA), and inductively coupled plasma optical emission spectrometry (ICP-OES). This approach enables traceable particle number concentration measurements of ligand-capped nonspheric particles with unknown chemical composition.
KW - Fluorescence
KW - Upconversion nanoparticles
KW - SAXS
KW - Particle number concentration
KW - Reference material
KW - Traceability
KW - Quality assurance
KW - Quantum yield
KW - Spectroscopy
KW - Synthesis
KW - Quantification
KW - NanoRM
KW - Nano
KW - Particle
KW - Bipyramid
KW - Reference data
KW - Simulation
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-617940
DO - https://doi.org/10.1021/acs.analchem.4c03641
SP - 1
EP - 8
PB - ACS Publications
AN - OPUS4-61794
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Resch-Genger, Ute
A1 - Carl, F.
A1 - Grauel, Bettina
A1 - Pons, Monica
A1 - Würth, Christian
A1 - Haase, M.
T1 - LiYF4:Yb/LiYF4 and LiYF4:Yb,Er/LiYF4 core/shell nanocrystals with luminescence decay times similar to YLF laser crystals and the upconversion quantum yield of the Yb,Er doped nanocrystals
N2 - We developed a procedure to prepare luminescent LiYF4:Yb/LiYF4 and LiYF4:Yb,Er/LiYF4 core/shell nanocrystals with a size of approximately 40 nm revealing luminescence decay times of the dopant ions that approach those of high-quality laser crystals of LiYF4:Yb (Yb:YLF) and LiYF4:Yb,Er (Yb,Er:YLF) with identical doping concentrations. As the luminescence decay times of Yb3+ and Er3+ are known to be very sensitive to the presence of quenchers, the long decay times of the core/shell nanocrystals indicate a very low number of defects in the core particles and at the core/shell interfaces. This improvement in the performance was achieved by introducing two important modifications in the commonly used oleic acid based synthesis. First, the shell was prepared via anewly developed method characterized by a very low nucleation rate for particles of pure LiYF4 shell material. Second, anhydrous acetates were used as precursors and additional drying steps were applied to reduce the incorporation of OH− in the crystal lattice, known to quench the emission of Yb3+ ions. Excitation power density (P)-dependent absolute measurements of the upconversion luminescence quantum yield (Φ,UC) of LiYF4:Yb,Er/LiYF4 core/shell particles reveal a maximum value of 1.25% at P of 180 W·cm−2.
Although lower than the values reported for NaYF4:18%Yb,2%Er core/shell nanocrystals with comparable sizes, these Φ, UC values are the highest reported so far for LiYF4:18%Yb,2%Er/LiYF4 nanocrystals without additional dopants. Further improvements May nevertheless be possible by optimizing the dopant concentrations in the LiYF4 nanocrystals.
KW - Nano
KW - Crystal
KW - Quantum yield
KW - LiYF4
KW - Synthesis
KW - Lifetime
KW - Fluorescence
KW - NIR
KW - Photoluminescence
KW - Lanthanide
KW - Upconversion nanoparticle
KW - Nanomaterial
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-515395
DO - https://doi.org/10.1007/s12274-020-3116-y
SN - 1998-0124
VL - 14
IS - 3
SP - 797
EP - 806
PB - Springer
AN - OPUS4-51539
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Biesen, L.
A1 - Nirmalananthan-Budau, Nithiya
A1 - Hoffmann, Katrin
A1 - Resch-Genger, Ute
A1 - Müller, T. J. J.
T1 - Solid-State Emissive Aroyl-S,N-Ketene Acetals with Tunable
N2 - 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.
KW - Nano
KW - Nanoparticle
KW - Photoluminescence
KW - Fluorescence
KW - Quantum yield
KW - Photophysics
KW - Lifetime
KW - Sensor
KW - dye
KW - Enhancement
KW - Particle
KW - Polarity
KW - AIE
KW - Aggregation
KW - Aggregation-induced emission
KW - Solid state emission
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-509072
DO - https://doi.org/10.1002/anie.201916396
VL - 59
IS - 25
SP - 10037
EP - 10041
PB - Wiley Online Libary
AN - OPUS4-50907
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Denißen, M.
A1 - Hannen, R.
A1 - Itskalov, D.
A1 - Biesen, L.
A1 - Nirmalananthan-Budau, Nithiya
A1 - Hoffmann, Katrin
A1 - Reiss, G. J.
A1 - Resch-Genger, Ute
A1 - Müller, T. J. J.
T1 - One-pot synthesis of a white-light emissive bichromophore operated by aggregation-induced dual emission (AIDE) and partial energy transfer
N2 - 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.
KW - Energy transfer
KW - Nano
KW - Nanoparticle
KW - Photoluminescence
KW - Fluorescence
KW - Quantum yield
KW - Photophysics
KW - Lifetime
KW - Sensor
KW - Dye
KW - Enhancement
KW - Particle
KW - Polarity
KW - AIE
KW - Aggregation
KW - Aggregation-induced emission
KW - Solid state emission
KW - Merocyanine
PY - 2020
DO - https://doi.org/10.1039/d0cc03451g
VL - 56
IS - 54
SP - 7407
PB - Royal Society of Chemistry
AN - OPUS4-50936
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Biesen, L.
A1 - May, L.
A1 - Nirmalananthan-Budau, Nithiya
A1 - Hoffmann, Katrin
A1 - Resch-Genger, Ute
A1 - Müller, T. J. J.
T1 - Communication of Bichromophore Emission upon Aggregation – Aroyl-S,N-ketene Acetals as Multifunctional Sensor Merocyanines
N2 - Aroyl-S,N-ketene acetal-based bichromophores can be readily synthesized in a consecutive three-component synthesis in good to excellent yields by condensation of aroyl chlorides and an N-(p-bromobenzyl) 2-methyl benzothiazolium salt followed by a Suzuki coupling, yielding a library of 31 bichromophoric fluorophores with substitution patterntunable emission properties. Varying both chromophores enables different communication pathways between the chromophores, exploiting aggregation-induced emission (AIE) and energy transfer (ET) properties, and thus, furnishing aggregation-based fluorescence switches. Possible applications range from fluorometric analysis of alcoholic beverages to pH sensors.
KW - Dye
KW - Fluorescence
KW - Aggregation induced emission
KW - Signal enhancement
KW - Energy transfer
KW - Switch
KW - Sensor
KW - Quantum yield
KW - Lifetime
KW - Photophysics
KW - Synthesis
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-531123
DO - https://doi.org/10.1002/chem.202102052
VL - 27
IS - 53
SP - 13426
EP - 13434
PB - Wiley-VCH
AN - OPUS4-53112
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Frenzel, F.
A1 - Fiedler, S.
A1 - Bardan, A.
A1 - Güttler, Arne
A1 - Würth, Christian
A1 - Resch-Genger, Ute
T1 - Influence of Measurement Geometry and Blank on Absolute Measurements of Photoluminescence Quantum Yields of Scattering Luminescent Films
N2 - For a series of 500 μm-thick polyurethane films containing different concentrations of luminescent and scattering YAG:Ce microparticles, we systematically explored and quantified pitfalls of absolute measurements of photoluminescence quantum yields (Φf) for often employed integrating sphere (IS) geometries, where the sample is placed either on a sample holder at the bottom of the IS surface or mounted in the IS center. Thereby, the influence of detection and illumination geometry and sample position was examined using blanks with various scattering properties for measuring the number of photons absorbed by the sample. Our results reveal that (i) setup configurations where the scattering sample is mounted in the IS center and (ii) transparent blanks can introduce systematic errors in absolute Φf measurements.
For strongly scattering, luminescent samples, this can result in either an under- or overestimation of the absorbed photon flux and hence an under- or overestimation of Φf. The size of these uncertainties depends on the scattering properties of the sample and instrument parameters, such as sample position, IS size, wavelength-dependent reflectivity of the IS surface coating, and port configuration. For accurate and reliable absolute Φf measurements, we recommend (i) a blank with scattering properties closely matching those of the sample to realize similar distributions of the diffusely scattered excitation photons within the IS, and (ii) a sufficiently high sample absorption at the excitation wavelength. For IS setups with center-mounted samples, measurement geometries should be utilized that prevent the loss of excitation photons by reflections from the sample out of the IS.
KW - Quality assurance
KW - Fluorescence
KW - Nano
KW - Particle
KW - Quantum yield
KW - Characterization
KW - Silica
KW - Scattering
KW - Uncertainty
KW - Film
KW - Pphosphor
KW - YAG:Ce
KW - LED
KW - Converter material
KW - Solid material
KW - Polymer
KW - Composite material
KW - Advanced material
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-638304
DO - https://doi.org/10.1021/acs.analchem.4c06726
SN - 1520-6882
SP - 1
EP - 8
PB - ACS Publications
AN - OPUS4-63830
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Xu, R.
A1 - Teich, W.
A1 - Frenzel, Florian
A1 - Hoffmann, Katrin
A1 - Radke, J.
A1 - Rösler, J.
A1 - Faust, K.
A1 - Blank, A.
A1 - Brandenburg, S.
A1 - Misch, M.
A1 - Vajkoczy, P.
A1 - Onken, J. S.
A1 - Resch-Genger, Ute
T1 - Optical characterization of sodium fluorescein in vitro and ex vivo
N2 - Objective: The utilization of fluorescein-guided biopsies and resection has been recently discussed as a suitable strategy to improve and expedite operative techniques for the resection of central nervous system (CNS) tumors. However, little is known about the optical properties of sodium fluorescein (NaFl) in human tumor tissue and their potential impact on ex vivo analyses involving fluorescence-based methods.
Methods: Tumor tissue was obtained from a study cohort of an observational study on the utilization of fluorescein-guided biopsy and resection (n=5). The optical properties of fluorescein-stained tissue were compared to the optical features of the dye in vitro and in control samples consisting of tumor tissue of high-grade glioma patients (n=3) without intravenous (i.v.) application of NaFl. The dye-exposed tumor tissues were used for optical measurements to confirm the detectability of NaFl emission ex vivo. The tissue samples were fixed in 4%PFA, immersed in 30% sucrose, embedded in Tissue-Tek OCT compound, and cut to 10 mm cryosections. Spatially resolved emission spectra from tumor samples were recorded on representative slides with a Confocal Laser Scanning Microscope FV1000 (Olympus GmbH, Hamburg, Germany) upon excitation with lexc = 488 nm.
Results: Optical measurements of fluorescein in 0.9% sodium chloride (NaCl) under in vitro conditions showed an absorption maximum of lmax abs = 479 nm as detected with spectrophotometer Specord 200 and an emission peak at lmax em = 538 nm recorded with the emCCD detection system of a custom-made microscope-based single particle setup using a 500 nm long-pass filter. Further measurements revealed pH- and concentration-dependent emission spectra of NaFl. Under ex vivo conditions, confocal laser scanning microscopy of fluorescein tumor samples revealed a slight bathochromic shift and a broadening of the emission band.
Conclusion: Tumor uptake of NaFl leads to changes in the optical properties – a bathochromic shift and broadening of the emission band – possibly caused by the dye’s high pH sensitivity and concentration-dependent reabsorption acting as an innerfilter of the dye’s emission, particularly in the short wavelength region of the Emission spectrum where absorption and fluorescence overlap. Understanding the ex vivo optical properties of fluorescein is crucial for testing and validating its further applicability as an optical probe for intravital microscopy, immunofluorescence localization studies, and flow cytometry analysis.
KW - Fluorescence
KW - Optical probe
KW - Sensor
KW - Fluorescein
KW - PH
KW - Imaging
KW - Tissue
KW - Cancer
KW - Medical diagnostics
KW - Tumor
KW - In vivo
KW - Ex vivo
KW - Quantum yield
KW - Dye
KW - Quality assurance
KW - Microscopy
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-527843
DO - https://doi.org/10.3389/fonc.2021.654300
SN - 2234-943X
VL - 11
SP - 1
EP - 8
PB - Frontiers Media
CY - Lausanne
AN - OPUS4-52784
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kage, Daniel
A1 - Hoffmann, Katrin
A1 - Borcherding, H.
A1 - Schedler, U.
A1 - Resch-Genger, Ute
T1 - Lifetime encoding in flow cytometry for bead‑based sensing of biomolecular interaction
N2 - To demonstrate the potential of time-resolved flow cytometry (FCM) for bioanalysis, clinical diagnostics, and optically encoded bead-based assays, we performed a proof-of-principle study to detect biomolecular interactions utilizing fluorescence lifetime (LT)-encoded micron-sized polymer beads bearing target-specific bioligands and a recently developed prototype lifetime flow cytometer (LT-FCM setup). This instrument is equipped with a single excitation light source and different fluorescence detectors, one operated in the photon-counting mode for time-resolved measurements of fluorescence decays and three detectors for conventional intensity measurements in different spectral windows. First, discrimination of bead-bound biomolecules was demonstrated in the time domain exemplarily for two targets, Streptavidin (SAv) and the tumor marker human chorionic gonadotropin (HCG). In a second step, the determination of biomolecule concentration levels was addressed representatively for the inflammation-related biomarker tumor necrosis factor (TNF-α) utilizing fluorescence intensity measurements in a second channel of the LT-FCM instrument. Our results underline the applicability of LT-FCM in the time domain for measurements of biomolecular interactions in suspension assays. In the future, the combination of spectral and LT encoding and multiplexing and the expansion of the time scale from the lower nanosecond range to the longer nanosecond and the microsecond region is expected to provide many distinguishable codes. This enables an increasing degree of multiplexing which could be attractive for high throughput screening applications.
KW - Fluorescence
KW - Sensor
KW - Assay
KW - Protein
KW - Multiplexing
KW - Flow cytometry
KW - Barcoding
KW - Lifetime
KW - Dye
KW - Bead
KW - Bead-based assay
KW - Method
KW - Quantification
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-516007
DO - https://doi.org/10.1038/s41598-020-76150-x
VL - 10
IS - 1
SP - 19477
PB - Nature
AN - OPUS4-51600
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Srivastava, Priyanka
A1 - Fürstenwerth, Paul Christian
A1 - Witte, J. F.
A1 - Resch-Genger, Ute
T1 - Synthesis and spectroscopic characterization of a fluorescent phenanthrene-rhodamine dyad for ratiometric measurements of acid pH values
N2 - We present the rational design, synthesis and spectroscopic characterization of a novel dual excitation, three color emitting, pH-responsive fluorescent probe consisting of two phenanthrene and one rhodamine B units linked by click chemistry. The rhodamine moiety, excitable at λEx = 315 nm and at λEx = 560 nm in its ring-opened form, provides the pH-responsive fluorophore, while the pH-insensitive phenanthrene, excited at λEx = 315 nm, serves as inert internal reference, The presence of two phenanthrene moieties enables a blue monomer and a blueish green excimer emission at 351 nm and 500 nm, respectively. Opening of the rhodamine B spirolactam ring at an acidic pH below 5.0 (pKa = 2.59 ± 0.04) switches on its emission at 580 nm. Simultaneously, the phenanthrene excimer emission decreases caused by a change in orientation of the phenanthrene units, while the monomer emission is barely affected. This sensor design enables ratiometric measurements in the low acidic pH range utilizing the intensity ratios of the rhodamine B and phenanthrene excimer emission at 580 nm and 500 nm. Alternatively, also the intensity ratios of the rhodamine B and the phenanthrene monomer emission could be exploited or the sum of the phenanthrene monomer and excimer fluorescence. To the best of our knowledge, this is the first report of ratiometric sensing utilizing such a versatile type of tricolor emissive dyad probe bearing phenanthrene moieties and showing phenanthrene monomer and excimer emission.
KW - Fluorescence
KW - Optical probe
KW - Sensor
KW - Dye
KW - Rhodamine
KW - Synthesis
KW - Photophysics
KW - PH
KW - Quantum yield
KW - Quality assurance
KW - Mechanism
KW - Chemodosimeter
KW - Phenanthrene
KW - Ratiometric
KW - Dyad
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-530554
DO - https://doi.org/10.1039/d1nj01573g
SN - 1144-0546
VL - 45
IS - 31
SP - 13755
EP - 13762
PB - Royal Society of Chemistry
AN - OPUS4-53055
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wasternack, J.
A1 - Schröder, H. V.
A1 - Witte, J. F.
A1 - Ilisson, M.
A1 - Hupatz, H.
A1 - Hille, J. F.
A1 - Gaedke, M.
A1 - Valkonen, A. M.
A1 - Sobottka, S.
A1 - Krappe, A.
A1 - Schubert, M.
A1 - Paulus, B.
A1 - Rissanen, K.
A1 - Sarkar, B.
A1 - Eigler, S.
A1 - Resch-Genger, Ute
A1 - Schalley, C. A.
T1 - Switchable protection and exposure of a sensitive squaraine dye within a redox active rotaxane
N2 - In nature,molecular environments in proteins can sterically protect and stabilize reactive species such as organic radicals through non-covalent interactions.Here, wereport a near-infrared fluorescent rotaxane in which the stabilization of a chemically labile squaraine fluorophore by the coordination of a tetralactam macrocycle can be controlled chemically and electrochemically. The rotaxane can be switched between two co-conformations inwhich thewheel either stabilizes or exposes the fluorophore. Coordination by the wheel affects the squaraine’s stability across four redox states and renders the radical anion significantly more stable—by a factor of 6.7—than without protection by a mechanically bonded wheel. Furthermore, the fluorescence properties can be tuned by the redox reactions in a stepwise manner. Mechanically interlockedmolecules provide an excellent scaffold to stabilize and selectively expose reactive species in a co-conformational switching process controlled by external stimuli.
KW - Fluorescence
KW - Dye
KW - Sensor
KW - Quantum yield
KW - Spectroscopy
KW - Photophysics
KW - Synthesis
KW - Squaraine
KW - Switch
KW - Redox-active
KW - Rotaxane
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-614959
DO - https://doi.org/10.1038/s42004-024-01312-1
VL - 7
SP - 1
EP - 11
AN - OPUS4-61495
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Ramirez, Alejandra
A1 - Pauli, Jutta
A1 - Crasselt, C.
A1 - Simon, S.
A1 - Schmidt, W.
A1 - Resch-Genger, Ute
T1 - The effect of a polycarboxylate ether on C3A / CaSO4.2H2O passivation monitored by optical spectroscopy
N2 - Polycarboxylate ethers (PCEs) are widely used in construction, but the exact nature of their interaction with cement is still debated. Aiming at a better understanding of the role of tricalcium Aluminate (C3A) in cement hydration, we assessed the potential of optical spectroscopy in combination with a water-soluble fluorescent organic reporter dye (S0586) to monitor the early hydration of C3A in the presence of 26 wt% CaSO4.2H2O (C3A26G-S) with and without PCE. As optical methods, steady-state fluorescence and diffuse reflectance (UV–VisDR) spectroscopy were employed. Phase characterization and particle size distribution were performed with in-situ X-ray diffraction (in-situ XRD) and dynamic light scattering (DLS). Our results show that fluorescence and UV–VisDR spectroscopy can be used to monitor the formation of metastable phases by the disaggregation of the dye S0586 in a cement paste as well as changes in ettringite formation. Addition of PCE slowed down the disaggregation of the dye as reflected by the corresponding changes of the dyes absorption and fluorescence. This prolonged induction period is a well-known side effect of PCEs and agrees with previous reported calorimetric studies and the Inhibition of gypsum dissolution observed by in-situ XRD. This demonstrates that fluorescence and UV–VisDR spectroscopy together with a suitable optical probe can provide deeper insights into the influence of PCE on C3A-gypsum hydration which could be e.g., utilized as screening method for comparing the influences
of different types of PCEs.
KW - Fluorescence
KW - Cement
KW - Nano
KW - Particle
KW - Optical spectroscopy
KW - PCE
KW - XRD
KW - Calorimetry
KW - Monitoring
KW - Diffuse
KW - Reflection
KW - Phase
KW - Dye
KW - Optical probe
KW - Cyanine
KW - Sensor
KW - Method
KW - Analysis
PY - 2020
DO - https://doi.org/10.1016/j.conbuildmat.2020.121856
VL - 270
SP - 121856
PB - Elsevier Ltd.
AN - OPUS4-52118
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Hudson, A.D.
A1 - Jamieson, O.
A1 - Crapnell, R.D.
A1 - Rurack, Knut
A1 - Soares, T.C.C.
A1 - Mecozzi, F.
A1 - Laude, A.
A1 - Gruber, J.
A1 - Novakovic, K.
A1 - Peeters, M.
T1 - Dual detection of nafcillin using a molecularly imprinted polymer-based platform coupled to thermal and fluorescence read-out
N2 - Reported here is the production of molecularly imprinted polymer (MIP) films, integrating a fluorescent moiety that serves as both an element for template interaction and signalling, for the thermal and optical detection of the beta-lactam antibiotic nafcillin. Fluorescein methacrylate (FluMa) was synthesized and introduced during the molecular imprinting process as the sole monomer and in a 1 : 1 mixture with methacrylic acid (MAA), allowing to draw first conclusions on the MIP formation potential of such a rather large and rigid monomer. At first, MIP microparticles containing FluMa were prepared by free radical polymerisation. Optical batch rebinding experiments revealed that FluMa can act as a functional monomer for selective detection of nafcillin; however, the addition of MAA as co-monomer significantly improved performance. Subsequently, thin MIP films containing FluMa were deposited onto functionalised glass slides and the influence of porogen, drying time, and monomer composition was studied. These MIP-functionalised glass electrodes were mounted into a customised 3D-printed flow cell, where changes in the liquid were either evaluated with a thermal device or using fluorescence bright field microscopy. Thermal analysis demonstrated that multiple MIP layers enhanced sensor specificity, with detection in the environmentally relevant range. The fluorescence bright field microscope investigations validated these results, showing an increase in the fluorescence intensity upon exposure of the MIP-functionalised glass slides to nafcillin solutions. These are promising results for developing a portable sensor device that can be deployed for antibiotics outside of a dedicated laboratory environment, especially if sensor design and fluorophore architecture are optimised.
KW - Molecularly Imprinted Polymers
KW - Fluorescence
KW - Antibiotics
KW - Heat-transfer Measurements
KW - Thin films
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-540044
DO - https://doi.org/10.1039/D1MA00192B
VL - 2
IS - 15
SP - 5105
EP - 5115
PB - Royal Society of Chemistry
CY - Cambridge
AN - OPUS4-54004
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Homann, Christian
A1 - Peeters, Régis
A1 - Mirmajidi, Hana
A1 - Berg, Jessica
A1 - Fay, Michael
A1 - Rodrigues, Lucas Carvalho Veloso
A1 - Radicchi, Eros
A1 - Jain, Akhil
A1 - Speghini, Adolfo
A1 - Hemmer, Eva
T1 - Rapid microwave-assisted synthesis of morphology-controlled luminescent lanthanide-doped Gd2O2S nanostructures
N2 - Gadolinium oxysulfide (Gd2O2S) is an attractive material of demonstrated suitability for a variety of imaging applications, leveraging its magnetic, scintillating, and luminescent properties, particularly when doped with optically active lanthanide ions (Ln3+). For many of these applications, control over size and morphology at the nanoscale is crucial. This study demonstrates the rapid microwave-assisted Synthesis of colloidal Ln2O2S (Ln = Gd and dopants Yb, Er, Tb) nanostructures in as little as 20 min. Structural characterization using X-ray diffraction analysis (XRD), Raman spectroscopy, as well as Transmission electron microscopy (TEM), including elemental mapping via energy dispersive X-ray spectroscopy (EDS), unveiled the key role of elemental sulphur (S8) in the reaction mixtures for materials growth. By systematically varying the Ln-to-S ratio from 1 : 0.5 to 1 : 15, controlled morphologies ranging from triangular nanoplatelets to berry- and flower-like shapes were achieved. Doping with Er3+/Yb3+ endowed the nano-triangles with upconverting and near-infrared emitting properties. Tb3+-doped Gd2O2S exhibited the characteristic green Tb3+ emission under UV excitation, while also showing X-ray excited optical luminescence (XEOL), rendering the material interesting as a potential nano-scintillator.
KW - Upconversion
KW - Microwave-assisted synthesis
KW - Synthesis
KW - Fluorescence
KW - Nano
KW - Particle
KW - NIR
KW - XRD
KW - X-ray fluoressence
KW - Morphology control
KW - Raman
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-647907
DO - https://doi.org/10.1039/D5TC01646K
SN - 2050-7526
VL - 13
IS - 35
SP - 18492
EP - 18507
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-64790
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Jiang, Shan
A1 - Gawlitza, Kornelia
A1 - Rurack, Knut
T1 - Dual-Fluorescent Nanoparticle Probes Consisting of a Carbon Nanodot Core and a Molecularly Imprinted Polymer Shell
N2 - Dual-fluorescent molecularly imprinted nanoparticles with a red-emissive carbon nanodot-doped silica core and a chlorogenic acid-imprinted fluorescent polymer layer are prepared and their use in ratiometric fluorometric analysis is described. Nanoparticle probes consisting of a shielded and stably emitting core and a shell with embedded binding sites that indicates the presence of an analyte with a change in emission allow for internally referenced measurements potentially accounting for detrimental influences from instrument drifts, light source fluctuations or sensor materials-related inhomogeneities.
KW - Molecular imprinting
KW - Fluorescence
KW - Core-shell particles
KW - Chlorogenic acid
KW - Ratiometric measurement
PY - 2021
DO - https://doi.org/10.1007/978-1-0716-1629-1_17
VL - 2359
SP - 195
EP - 208
PB - Springer
CY - Humana, New York, NY
AN - OPUS4-53336
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Srivastava, Priyanka
A1 - Tavernaro, Isabella
A1 - Genger, C.
A1 - Welker, P.
A1 - Huebner, Oskar
A1 - Resch-Genger, Ute
T1 - Multicolor Polystyrene Nanosensors for the Monitoring of Acidic, Neutral, and Basic pH Values and Cellular Uptake Studies
N2 - A first tricolor fluorescent pH nanosensor is presented, which was rationally designed from biocompatible carboxylated polystyrene nanoparticles and two analyte-responsive molecular fluorophores. Its fabrication involved particle staining with a blue-red-emissive dyad, consisting of a rhodamine moiety responsive to acidic pH values and a pH-inert quinoline fluorophore, followed by the covalent attachment of a fluorescein dye to the particle surface that signals neutral and basic pH values with a green fluorescence. These sensor particles change their fluorescence from blue to red and green, depending on the pH and excitation wavelength, and enable ratiometric pH measurements in the pH range of 3.0−9.0. The localization of the different sensor dyes in the particle core and at the particle surface was confirmed with fluorescence microscopy utilizing analogously prepared polystyrene microparticles. To show the application potential of these polystyrene-based multicolor sensor particles, fluorescence microscopy studies with a human A549 cell line were performed, which revealed the cellular uptake of the pH nanosensor and the differently colored emissions in different cell organelles, that is, compartments of the endosomal-lysosomal pathway. Our results demonstrate the underexplored potential of biocompatible polystyrene particles for multicolor and multianalyte sensing and bioimaging utilizing hydrophobic and/or hydrophilic stimuli-responsive luminophores.
KW - Microparticle
KW - Fluorescence
KW - Sensor
KW - pH
KW - Quantum yield
KW - Multiplexing
KW - Imaging
KW - Cell
KW - Quality assurance
KW - Nano
KW - Polymer
KW - Bioimaging
KW - Particle
KW - Application
PY - 2022
DO - https://doi.org/10.1021/acs.analchem.2c00944
VL - 94
IS - 27
SP - 9656
EP - 9664
PB - ACS
AN - OPUS4-55365
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Witte, F.
A1 - Rietsch, P.
A1 - Sinha, S.
A1 - Krappe, A.
A1 - Joswig, J.-O.
A1 - Götze, J. P.
A1 - Nirmalananthan-Budau, Nithiya
A1 - Resch-Genger, Ute
A1 - Eigler, S.
A1 - Paulus, B.
T1 - Fluorescence Quenching in J‑Aggregates through the Formation of Unusual Metastable Dimers
N2 - Molecular aggregation alters the optical properties of a system as fluorescence may be activated or quenched. This is usually described within the well-established framework of H- and J-aggregates. While H-aggregates show nonfluorescent blueshifted absorption bands with respect to the isolated monomer, Jaggregates are fluorescent displaying a redshifted peak. In this publication, we employ a combined approach of experiment and theory to study the complex aggregation features and photophysical properties of diaminodicyanoquinone derivatives, which show unusual and puzzling nonfluorescent redshifted Absorption bands upon aggregation. Our theoretical analysis demonstrates that stable aggregates do not account for the experimental observations.
Instead, we propose an unprecedented mechanism involving metastable dimeric species formed from stable dimers to generate nonfluorescent J-aggregates. These results represent a novel kind of aggregation-induced optical effect and may have Broad implications for the photophysics of dye aggregates.
KW - Fluorescence
KW - Llifetime
KW - Dye
KW - Quantum yield
KW - Label
KW - Reporter
KW - Aggregation
KW - Monomer
KW - Heory
KW - Mechanism
KW - photophysics
PY - 2021
DO - https://doi.org/10.1021/acs.jpcb.1c01600
SN - 1520-5207
VL - 125
IS - 17
SP - 4438
EP - 4446
PB - ACS Publikations
AN - OPUS4-52619
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Billimoria, K.
A1 - Diaz Fernandez, Y. A.
A1 - Andresen, Elina
A1 - Sorzabal-Bellido, I.
A1 - Huelga-Suarez, G.
A1 - Bartczak, D.
A1 - Ortiz de Solórzano, C.
A1 - Resch-Genger, Ute
A1 - Goenaga Infante, H.
T1 - The potential of bioprinting for preparation of nanoparticle-based calibration standards for LA-ICP-ToF-MS quantitative imaging
N2 - This paper discusses the feasibility of a novel strategy based on the combination of bioprinting nano-doping technology and laser ablation-inductively coupled plasma time-of-flight mass spectrometry analysis for the preparation and characterization of gelatin- based multi-element calibration standards suitable for quantitative imaging. To achieve this, lanthanide up-conversion nanoparticles were added to a gelatin matrix to produce the bioprinted calibration standards. The features of this bioprinting approach were com- pared with manual cryosectioning standard preparation, in terms of throughput, between batch repeatability and elemental signal homogeneity at 5 μm spatial resolution. By using bioprinting, the between batch variability for three independent standards of the same concentration of 89 Y (range 0–600 mg/kg) was reduced to 5% compared to up to 27% for cryosectioning. On this basis, the relative standard deviation ( RSD ) obtained between three independent calibration slopes measured within 1 day also reduced from 16% (using cryosectioning ) to 5% (using bioprinting), supporting the use of a single standard preparation replicate for each of the concentrations to achieve good calibration performance using bioprinting. This helped reduce the analysis time by approximately 3-fold. With cryosectioning each standard was prepared and sectioned individually, whereas using bio-printing it was possible to have up to six different standards printed simultaneously, reducing the preparation time from approximately 2 h to under 20 min (by approxi- mately 6-fold). The bio-printed calibration standards were found stable for a period of 2 months when stored at ambient temperature and in the dark.
KW - Environmental analysis
KW - LA-ICP-MS
KW - Lanthanide
KW - Tag
KW - Fluorescence
KW - Nanoparticles
KW - Reference material
KW - Quality assurance
KW - 3D-printing
KW - Synthesis
KW - Production
KW - Multimodal
PY - 2022
DO - https://doi.org/10.1093/mtomcs/mfac088
SN - 1756-591X
VL - 14
IS - 12
SP - 1
EP - 9
PB - Oxford University Press
CY - Oxford
AN - OPUS4-57018
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Pauli, J.
A1 - Güttler, Arne
A1 - Schneider, T.
A1 - Würth, Christian
A1 - Resch-Genger, Ute
T1 - Fluorescence Quantum Yield Standards for the UV/Visible/NIR: Development, Traceable Characterization, and Certification
N2 - The rational design of next generation molecular and nanoscale reporters and the comparison of different emitter classes require the determination of the fluorometric key performance parameter fluorescence quantum yield (Φf), i.e., the number of emitted photons per number of absorbed photons. Main prerequisites for reliable Φf measurements, which are for transparent luminophore solutions commonly done relative to a reference, i.e., a fluorescence quantum yield standard of known Φf, are reliable and validated instrument calibration procedures to consider wavelength-, polarization-, and time-dependent instrument specific signal contributions, and sufficiently well characterized fluorescence quantum yield standards. As the standard’s Φf value directly contributes to the calculation of the sample’s Φf, its accuracy presents one of the main sources of uncertainty of relative Φf measurements. To close this gap, we developed a first set of 12 fluorescence quantum yield standards, which absorb and emit in the wavelength region of 330−1000 nm and absolutely determined their Φf values with two independently calibrated integrating sphere setups.
Criteria for standard selection and the configuration of these novel fluorescence reference materials are given, and the certification procedure is presented including homogeneity and stability studies and the calculation of complete uncertainty budgets for the certified Φf values. The ultimate goal is to provide the community of fluorescence users with available reference materials as a basis for an improved comparability and reliability of quantum yield data since the measurement of this spectroscopic key property is an essential part of the characterization of any new emitter.
KW - Optical spectroscopy
KW - Traceability
KW - Reference product
KW - Dye
KW - Fluorescence
KW - Quantum yield
KW - Reference material
KW - Reference data
KW - Certification
KW - Quality assurance
PY - 2023
DO - https://doi.org/10.1021/acs.analchem.2c05530
VL - 95
SP - 5671
EP - 5677
PB - American Chemical Society
AN - OPUS4-58151
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -