TY - JOUR A1 - Fa, X. A1 - Lin, Sh. A1 - Yang, J. A1 - Shen, Ch. A1 - Liu, Y. A1 - Gong, Y. A1 - Qin, A. A1 - Ou, Jun A1 - Resch-Genger, Ute T1 - −808 nm-activated Ca2+ doped up-conversion nanoparticles that release no inducing liver cancer cell (HepG2) apoptosis N2 - Anear-infrared (NIR) light-triggered release method for nitric oxide (NO) was developed utilizing core/shell NaYF4: Tm/Yb/Ca@NaGdF4:Nd/Yb up-conversion nanoparticles (UCNPs) bearing a mesoporous silica (mSiO2) shell loaded with theNOdonor S-nitroso-N-acetyl-DL-penicillamine (SNAP). To avoid overheating in biological samples, Nd3+ was chosen as a sensitizer, Yb3+ ions as the bridging sensitizer, andTm3+ ions as UV-emissive activator while co-doping with Ca2+ was done to enhance the luminescence of the activatorTm3+.NOrelease from SNAP was triggered by an NIR-UV up-conversion process, initiated by 808nmlight absorbed by the Nd3+ ions.NOrelease was confirmed by the Griess method. Under 808nmirradiation, the viability of the liver cancer cell line HepG2 significantly decreased with increasing UCNPs@mSiO2-SNAP concentration. For a UCNPs@mSiO2-SNAP concentration of 200 μgml−1, the cell survival probability was 47%. These results demonstrate that UCNPs@mSiO2-SNAP can induce the release of apoptosis-inducingNOby NIR irradiation. KW - Nano KW - Nanomaterial KW - Upconversion nanoparticle KW - Lanthanide KW - Photoluminescence KW - Quantum yield KW - Photophysics KW - Lifetime KW - Sensor KW - Excitation power density KW - Brightness KW - NIR KW - Mechanism KW - Triggered KW - Release KW - Cell KW - PDT KW - Dye KW - Therapy KW - Surface KW - Coating PY - 2022 DO - https://doi.org/10.1088/2050-6120/ac5524 VL - 10 IS - 2 SP - 1 EP - 9 PB - IOP Publishing AN - OPUS4-54842 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Tavernaro, Isabella T1 - Where Do We Stand – Quantifying Amino Groups on Silica (Nano)Particles N2 - Industry and regulators are increasingly requesting validated and standardized measurement protocols to support the manufacturing, quality control, and safe use of engineered nanomaterials. Addressing a remaining gap in method development and standardization for nanomaterial characterization, we investigated in a bilateral comparison various methods commonly used for surface functional group quantification, like quantitative nuclear magnetic resonance (qNMR) spectroscopy, x-ray photoelectron spectroscopy (XPS), and optical assays. These results demonstrate not only an influence of the size and synthesis methods on the number of surface functional groups for differently sized commercial and in-house synthesized silica nanoparticles but also on their functionality. T2 - Kickoff-Meeting SMURFnano CY - Berlin, Germany DA - 09.07.2024 KW - Nano KW - Particles KW - Silica KW - Synthesis KW - Quantification KW - Functional groups KW - Quality assurance KW - Reference material KW - Interlaboratory comparison KW - Method KW - Uncertainty KW - Sensor KW - Surface analysis PY - 2024 AN - OPUS4-62164 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Grauel, Bettina A1 - Würth, Christian A1 - Homann, C. A1 - Krukewitt, Lisa A1 - Andresen, Elina A1 - Roik, Janina A1 - Recknagel, Sebastian A1 - Haase, M. A1 - Resch-Genger, Ute T1 - Volume and surface effects on two-photonic and three-photonic processes in dry co-doped upconversion nanocrystals N2 - 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. KW - Nano KW - Nanomaterial KW - Upconversion KW - Nanoparticle KW - Lanthanide KW - Photoluminescence KW - Quantum yield KW - Pphotophysics KW - Lifetime KW - Sensor KW - Excitation KW - Power density KW - Single particle KW - Brightness KW - NIR KW - Mechanism KW - Modeling KW - Simulation KW - Energy transfer PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-535317 DO - https://doi.org/10.1007/s12274-021-3727-y SN - 1998-0124 VL - 15 IS - 3 SP - 2362 EP - 2373 PB - Springer AN - OPUS4-53531 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Resch-Genger, Ute T1 - Tumore abbilden, Biomarker nachweisen, Messungen standardisieren N2 - Zu den am häufigsten eingesetzten Analysemethoden in den Lebens- und Materialwissenschaften gehören Lumineszenzmethoden. Sie nutzen die Emission von Licht nach Absorption von Energie, um Signale zu erzeugen, und umfassen spektroskopische und mikroskopische Messungen. KW - Quality assurance KW - Sensor KW - Imaging KW - Reference material KW - Nano KW - Particle KW - Nanomaterial KW - Upconversion KW - Nanoparticle KW - Lanthanide KW - Photoluminescence KW - Quantum yield KW - Photophysics KW - Lifetime KW - Excitation KW - Power density KW - Single particle KW - Brightness KW - NIR PY - 2021 SP - 75 EP - 77 PB - GDCH AN - OPUS4-53526 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR ED - Resch-Genger, Ute ED - Koch, Matthias ED - Meermann, Björn ED - Weller, Michael G. T1 - Topical collection: Analytical methods and applications in the materials and life sciences N2 - 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. T2 - 150 years BAM: Science with impact CY - Berlin, Germany DA - 01.01.2021 KW - 150th anniversary KW - ABC KW - Analysis KW - Analytical sciences KW - BAM KW - Collection KW - Environment KW - Fluorescence KW - Life sciences KW - Limit of detection KW - Material sciences KW - Method KW - Nanoparticle KW - Pollutant KW - Quality assurance KW - Reference material KW - Sensor KW - Special issue KW - Bundesanstalt für Materialforschung und -prüfung KW - Jahrestag PY - 2022 UR - https://link.springer.com/journal/216/topicalCollection/AC_16a2ef9b81853377e321ef84d9c4a431 SN - 1618-2642 SN - 1618-2650 VL - 414 SP - 4267 EP - 4529 PB - Springer CY - Berlin AN - OPUS4-55670 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Radunz, Sebastian A1 - Kraus, Werner A1 - Bischoff, F. A. A1 - Emmerling, Franziska A1 - Resch-Genger, Ute A1 - Tschiche, Harald T1 - Temperature- and Structure-Dependent Optical Properties and Photophysics of BODIPY Dyes N2 - We report on the temperature- and structural-dependent optical properties and photophysics of a set of boron dipyrromethene (BODIPY) dyes with different substitution patterns of their meso-aryl subunit. Single-crystal Xray diffraction analysis of the compounds enabled a classification of the dyes into a sterically hindered and a unhindered group. The steric hindrance refers to a blocked rotational motion of the aryl subunit around the bond connecting this moiety to the meso-position of the BODIPY core. The energy barriers related to this rotation were simulated by DFT calculations. As follows from the relatively low rotational barrier calculated to about 17 kcal/mol, a free rotation is only possible for sterically unhindered compounds. Rotational barriers of more than 40 kcal/mol determined for the sterically hindered compounds suggest an effective freezing of the rotational motion in These molecules. With the aid of temperature-dependent spectroscopic measurements, we could show that the ability to rotate directly affects the optical properties of our set of BODIPY dyes. This accounts for the strong temperature dependence of the fluorescence of the sterically unhindered compounds which show a drastic decrease in fluorescence quantum yield and a significant shortening in fluorescence lifetime upon heating. The optical properties of the sterically hindered compounds, however, are barely affected by temperature. Our results suggest a nonradiative deactivation of the first excited singlet state of the sterically unhindered compounds caused by a conical intersection of the potential energy surfaces of the Ground and first excited state which is accessible by rotation of the meso-subunit. This is in good agreement with previously reported deactivation mechanisms. In addition, our results suggest the presence of a second nonradiative depopulation pathway of the first excited singlet state which is particularly relevant for the sterically hindered compounds. KW - Fluorescence KW - Sensor KW - Switch KW - pH KW - BODIPY KW - Dye KW - Probe KW - Synthesis KW - Photophysics KW - Mechanism PY - 2020 DO - https://doi.org/10.1021/acs.jpca.9b11859 SN - 1089-5639 VL - 124 IS - 9 SP - 1787 EP - 1797 PB - American Chemical Society AN - OPUS4-50639 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bandi, V.G. A1 - Luciano, M.P. A1 - Saccomano, M. A1 - Patel, N.L. A1 - Bischof, Th. S. A1 - Lingg, J.G.P. A1 - Tsrunchev, P.T. A1 - Nix, M.N. A1 - Ruehle, Bastian A1 - Sanders, C. A1 - Riffle, L. A1 - Robinson, C.M. A1 - Difilippantonio, S. A1 - Kalen, J.D. A1 - Resch-Genger, Ute A1 - Ivanic, J. A1 - Bruns, O.T. A1 - Schnermann, M. T1 - Targeted multicolor in vivo imaging over 1,000 nm enabled by nonamethine cyanines N2 - Recent progress has shown that using wavelengths between 1,000 and 2,000 nm, referred to as the shortwave-infrared or near-infrared (NIR)-II range, can enable high-resolution in vivo imaging at depths not possible with conventional optical wavelengths. However, few bioconjugatable probes of the type that have proven invaluable for multiplexed imaging in the visible and NIR range are available for imaging these wavelengths. Using rational design, we have generated persulfonated indocyanine dyes with absorbance maxima at 872 and 1,072 nm through catechol-ring and aryl-ring fusion, respectively, onto the nonamethine scaffold. Multiplexed two-color and three-color in vivo imaging using monoclonal antibody and dextran conjugates in several tumor models illustrate the benefits of concurrent labeling of the tumor and healthy surrounding tissue and lymphatics. These efforts are enabled by complementary advances in a custom-built NIR/shortwave-infrared imaging setup and software package for multicolor real-time imaging. KW - Photoluminescence KW - Fluorescence KW - Dye KW - Cyanine KW - Antibody KW - Bioconjugate KW - Conjugate KW - Quantum yield KW - Photophysics KW - Lifetime KW - Sensor KW - NIR KW - SWIR KW - Mechanism KW - Imaging KW - Application KW - Contrast agent KW - Bioimaging PY - 2021 DO - https://doi.org/10.1038/s41592-022-01394-6 VL - 19 IS - 3 SP - 353 EP - 358 PB - Nature Research AN - OPUS4-54465 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Le Guevel, X. A1 - Wegner, Karl David A1 - Würth, Christian A1 - Baulin, V. A. A1 - Musnier, B. A1 - Josserand, V. A1 - Resch-Genger, Ute A1 - Koll, J-C T1 - Tailoring the SWIR emission of gold nanoclusters by surface ligand rigidification and their application in 3D bioimaging N2 - The influence of solvent polarity and surface ligand rigidification on the SWIR emission profile of gold nanoclusters with an anistropic surface was investigated. A strong enhancement of the SWIR emission band at 1200 nm was observed when measuring in different local environments: in solution, in polymer composites, and in solids. SWIR in vivo imaging of mice assisted by deep learning after intravenous administration of these gold nanoclusters provides high definition pseudo-3D views of vascular blood vessels. KW - Nano KW - Nanomaterial KW - Metal cluster KW - Photoluminescence KW - Quantum yield KW - Photophysics KW - Lifetime KW - Sensor KW - NIR KW - SWIR KW - Ligand KW - Gold KW - Mechanism KW - Charge transfer KW - Enhancement strategy KW - Imaging KW - Application KW - Contrast agent PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-543582 DO - https://doi.org/10.1039/D1CC06737K VL - 58 IS - 18 SP - 2967 EP - 2970 PB - RSC AN - OPUS4-54358 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bertorelle, F. A1 - Wegner, Karl David A1 - Berkulic, M. P. A1 - Fakhouri, H. A1 - Comby-Zerbino, C. A1 - Sagar, A. A1 - Bernadó, P. A1 - Resch-Genger, Ute A1 - Bonacic-Koutecký, V. A1 - Le Guével, X. A1 - Antoine, R. T1 - Tailoring the NIR-II Photoluminescence of Single Thiolated Au25 Nanoclusters by Selective Binding to Proteins N2 - Atomically precise gold nanoclusters are a fascinating class of nanomaterials that exhibit molecule-like properties and have outstanding photoluminescence (PL). Their ultrasmall size, molecular chemistry, and biocompatibility make them extremely appealing for selective biomolecule labeling in investigations of biological mechanisms at the cellular and anatomical levels. In this work, we report a simple route to incorporate a preformed Au25 nanocluster into a model bovine serum albumin (BSA) protein. A new approach combining small-angle X-ray scattering and molecular modeling provides a clear localization of a single Au25 within the protein to a cysteine residue on the gold nanocluster surface. Attaching Au25 to BSA strikingly modifies the PL properties with enhancement and a redshift in the second near-infrared (NIR-II) window. This study paves the way to conrol the design of selective sensitive probes in biomolecules through a ligand-based strategy to enable the optical detection of biomolecules in a cellular environment by live imaging. KW - Fluorescence KW - Aggregation KW - Signal enhancement KW - Cluster KW - Nano KW - Metal KW - NIRII KW - SWIR KW - Sensor KW - Quantum yield KW - Lifetime KW - Photophysics KW - Synthesis KW - Protein KW - Imaging KW - Bioimaging KW - Ligand KW - Gold PY - 2022 DO - https://doi.org/10.1002/chem.202200570 SN - 1521-3765 VL - 28 IS - 39 SP - 1 EP - 8 PB - Wiley-VCH CY - Weinheim AN - OPUS4-55077 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nirmalananthan-Budau, Nithiya A1 - Budau, J. H. A1 - Moldenhauer, Daniel A1 - Hermann, G. A1 - Kraus, Werner A1 - Hoffmann, Katrin A1 - Paulus, Beate A1 - Resch-Genger, Ute T1 - Substitution pattern controlled aggregation-induced emission in donor-acceptor-donor dyes with one and two propeller-like triphenylamine donors N2 - 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. 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 DO - https://doi.org/10.1039/d0cp00413h VL - 22 IS - 25 SP - 14142 EP - 14154 AN - OPUS4-50967 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -