TY - JOUR A1 - Kage, Daniel A1 - Fischer, Linn A1 - Hoffmann, Katrin A1 - Thiele, T. A1 - Schedler, U. A1 - Resch-Genger, Ute T1 - Close spectroscopic look at dye-stained polymer microbeads JF - The Journal of Physical Chemistry C N2 - Dye-stained micrometer-sized polymer beads are important tools in the life sciences with applications in biomedical, biochemical, and clinical research. Here, bead-based assays are increasingly used, for example, in DNA sequencing and the detection of autoimmune diseases or pathogenic microorganisms. Moreover, stained beads are employed as calibration tools for fluorescence microscopy and flow cytometry methods with increasing complexity. To address the requirements concerning the relevant fluorescence features, the spectroscopic properties of representative polymer beads with diameters ranging from about 1 to 10 μm stained with varying concentrations of rhodamine 6G were systematically assessed. The observed dependence of the spectral properties, fluorescence decay kinetics, and fluorescence quantum yields on bead size and dye loading concentration is attributed to different fluorescence characteristics of fluorophores located in the particle core and near-surface dye molecules. Supported by the fluorescence anisotropy measurements, the origin of the observed alteration of fluorescence features is ascribed to a combination of excitation energy transfer and polarity-related effects that are especially pronounced at the interface of the bead and the surrounding medium. The results of our studies underline the need to carefully control and optimize all Parameters that can affect the fluorescence properties of the dye-stained beads. KW - Fluorophore KW - Polymer particles KW - Photophysics KW - Life sciences KW - Standards PY - 2018 DO - https://doi.org/10.1021/acs.jpcc.8b02546 SN - 1932-7447 VL - 122 IS - 24 SP - 12782 EP - 12791 PB - ACS Publications CY - Washington, DC AN - OPUS4-45453 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kaiser, M. A1 - Würth, Christian A1 - Kraft, Marco A1 - Hyppänen, I. A1 - Soukka, T. A1 - Resch-Genger, Ute T1 - Power-dependent upconversion quantum yield of NaYF4:Yb3+,Er3+ nano- and micrometer-sized particles – measurements and simulations JF - Nanoscale N2 - Photophysical studies of nonlinear lanthanide-doped photon upconverting nanoparticles (UCNPs) increasingly used in biophotonics and photovoltaics require absolute measurements of the excitation power density (P)-dependent upconversion luminescence (UCL) and luminescence quantum yields (ΦUC) for quantifying the material performance, UCL deactivation pathways, and possible enhancement factors. We present here the P-dependence of the UCL spectra, ΦUC, and slope factors of the different emission bands of representative 25 nm-sized oleate-capped β-NaYF4:17% Yb3+, 3% Er3+ UCNPs dispersed in toluene and as powder as well as ΦUC of 3 μm-sized upconversion particles (UCμP), all measured with a newly designed integrating sphere setup, enabling controlled variation of P over four orders of magnitude. This includes quantifying the influence of the beam shape on the measured ΦUC and comparison of experimental ΦUC with simulations utilizing the balancing power density model of the Andersson-Engels group and the simulated ΦUC of UCμP from the Berry group, underpinned by closely matching decay kinetics of our UC material. We obtained a maximum ΦUC of 10.5% for UCμP and a ΦUC of 0.6% and 2.1% for solid and dispersed UCNPs, respectively. Our results suggest an overestimation of the contribution of the purple and an underestimation of that of the red emission of β-NaYF4:Yb3+,Er3+: microparticles by the simulations of the Berry group. Moreover, our measurements can be used as a guideline to the absolute determination of UCL and ΦUC KW - Upconversion KW - Photophysics KW - Nanoparticles PY - 2017 DO - https://doi.org/10.1039/c7nr02449e VL - 9 IS - 28 SP - 10051 EP - 10058 PB - The Royal Society of Chemistry AN - OPUS4-41550 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Brömme, T. A1 - Schmitz, C. A1 - Oprych, D. A1 - Wenda, A. A1 - Strehmel, V. A1 - Grabolle, Markus A1 - Resch-Genger, Ute A1 - Ernst, S. A1 - Reiner, K. A1 - Keil, D. A1 - Lüs, P. A1 - Baumann, H. A1 - Strehmel, B. T1 - Digital imaging of lithographic materials by radical photopolymerization and photonic baking with NIR diode lasers JF - Chemical engineering & technology N2 - Photo-initiated cross-linking of multifunctional acrylic esters in polymeric binders was investigated based on digital imaging using the Computer-to-Plate (CtP) technology applying laser exposure in the near-infrared (NIR). Generation of initiating radicals occurs by electron transfer from the excited state of the NIR-sensitizer to the radical generator, an onium salt. Iodonium salts derived from several borates and those with the bis(trifluoromethylsulfonyl)imide anion resulted in lithographic materials with high sensitivity. Photo-induced electron transfer plays a major function to generate initiating radicals by a sensitized mechanism but thermal events also influence sensitivity of the coating. Internal conversion was the major deactivation pathway while a certain fraction of NIR-dye fluorescence was also available. A line shape focused laser system with emission in the NIR was successfully used to bake the materials. KW - Iodonium KW - Near-infrared laser KW - Photonic baking KW - Photophysics KW - Photopolymer PY - 2016 DO - https://doi.org/10.1002/ceat.201500453 SN - 0930-7516 SN - 1521-4125 VL - 39 IS - 1 SP - 13 EP - 25 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-35303 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Otto, S. A1 - Grabolle, Markus A1 - Förster, C. A1 - Kreitner, C. A1 - Resch-Genger, Ute A1 - Heinze, K. T1 - [Cr(ddpd)2]3+: A molecular, water-soluble, highly NIR-emissive ruby analogue JF - Angewandte Chemie / International Edition N2 - Bright, long-lived emission from first-row transition-metal complexes is very challenging to achieve. Herein, we present a new strategy relying on the rational tuning of energy levels. With the aid of the large N-Cr-N bite angle of the tridentate ligand ddpd (N,N′-dimethyl-N,N′-dipyridine-2-ylpyridine-2,6-diamine) and its strong σ-donating capabilities, a very large ligand-field splitting could be introduced in the chromium(III) complex [Cr(ddpd)2]3+, that shifts the deactivating and photoreactive 4T2 state well above the emitting 2E state. Prevention of back-intersystem crossing from the 2E to the 4T2 state enables exceptionally high near-infrared phosphorescence quantum yields and lifetimes for this 3d metal complex. The complex [Cr(ddpd)2](BF4)3 is highly water-soluble and very stable towards thermal and photo-induced substitution reactions and can be used for fluorescence intensity- and lifetime-based oxygen sensing in the NIR. KW - Chromium complexes KW - Intersystem crossing KW - Ligand-field splitting KW - NIR luminescence KW - Photophysics PY - 2015 DO - https://doi.org/10.1002/anie.201504894 SN - 1433-7851 SN - 1521-3773 SN - 0570-0833 VL - 54 IS - 39 SP - 11572 EP - 11576 PB - Wiley-VCH CY - Weinheim AN - OPUS4-35084 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wang, Y.-W. A1 - Descalzo López, Ana Belén A1 - Shen, Z. A1 - You, X.-Z. A1 - Rurack, Knut T1 - Dihydronaphthalene-fused Boron-dipyrromethene (BODIPY) dyes: insight into the electronic and conformational tuning modes of BODIPY fluorophores JF - Chemistry - A European journal N2 - A new series of boron-dipyrromethene (BDP, BODIPY) dyes with dihydronaphthalene units fused to the β-pyrrole positions (1 a-d, 2) has been synthesised and spectroscopically investigated. All the dyes, except pH-responsive 1 d in polar solvents, display intense emission between 550-700 nm. Compounds 1 a and 1 b with a hydrogen atom and a methyl group in the meso position of the BODIPY core show spectroscopic properties that are similar to those of rhodamine 101, thus rendering them potent alternatives to the positively charged rhodamine dyes as stains and labels for less polar environments or for the dyeing of latex beads. Compound 1 d, which carries an electron-donating 4-(dimethylamino)phenyl group in the meso position, shows dual fluorescence in solvents more polar than dibutyl ether and can act as a pH-responsive "light-up" probe for acidic pH. Correlation of the pKa data of 1 d and several other meso-(4-dimethylanilino)-substituted BODIPY derivatives allowed us to draw conclusions on the influence of steric crowding at the meso position on the acidity of the aniline nitrogen atom. Preparation and investigation of 2, which carries a nitrogen instead of a carbon as the meso-bridgehead atom, suggests that the rules of colour tuning of BODIPYs as established so far have to be reassessed; for all the reported couples of meso-C- and meso-N-substituted BODIPYs, the exchange leads to pronounced redshifts of the spectra and reduced fluorescence quantum yields. For 2, when compared with 1 a, the opposite is found: negligible spectral shifts and enhanced fluorescence. Additional X-ray crystallographic analysis of 1 a and quantum chemical modelling of the title and related compounds employing density functional theory granted further insight into the features of such sterically crowded chromophores. KW - Dyes/pigments KW - Fluorescent probes KW - Photophysics KW - Protonation KW - Boron PY - 2010 DO - https://doi.org/10.1002/chem.200902527 SN - 0947-6539 SN - 1521-3765 VL - 16 IS - 9 SP - 2887 EP - 2903 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-20957 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Li, Yanqin A1 - Bricks, J.L. A1 - Resch-Genger, Ute A1 - Spieles, Monika A1 - Rettig, W. T1 - CT-Operated Bifunctional Fluorescent Probe Based on a Pretwisted Donor-Donor-Biphenyl JF - Journal of fluorescence N2 - Taking into account the structural requirements for TICT-type sensor molecules, a general synthetic route to derive pH and cation-responsive pretwisted donor (D)–donor (D) biphenyls (b) equipped with donor receptors is developed and a first model compound containing a mono aza-15-crown-5 and a DMA receptor is synthesized, see Scheme 1. The spectroscopic properties of this new bifunctional D–D biphenyl are studied in the non-polar and polar solvents cyclohexane, acetonitrile, and methanol. Protonation as well as complexation studies are performed with the representative metal ions Na(I), K(I), Ca(II), Ag(I), Zn(II), Cd(II), Hg(II), and Pb(II) to reveal the potential of this molecule for communication of whether none, only one, or both binding sites are engaged in analyte coordination by spectroscopically distinguishable outputs. The results are compared to those obtained with closely related donor (D)–acceptor (A) substituted biphenyl-type sensor molecules and are discussed within the framework of neutral and ionic D – A biphenyls. KW - Fluorescent probe KW - Biphenyl KW - TICT KW - Photophysics KW - Bifunctional PY - 2006 SN - 1053-0509 SN - 1573-4994 VL - 16 IS - 3 SP - 337 EP - 348 PB - Plenum Publ. Corp. CY - New York, NY AN - OPUS4-14198 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -