TY - JOUR A1 - Hennig, Andreas A1 - Borcherding, H. A1 - Jäger, Christian A1 - Hatami, Soheil A1 - Würth, Christian A1 - Hoffmann, Angelika A1 - Hoffmann, Katrin A1 - Thiele, T. A1 - Schedler, U. A1 - Resch-Genger, Ute T1 - Scope and limitations of surface functional quantification methods: exploratory study with poly(acrylic acid)-grafted micro- and nanoparticles JF - Journal of the American chemical society N2 - The amount of grafted poly(acrylic acid) on poly(methyl methacrylate) micro- and nanoparticles was quantified by conductometry, 13C solid-state NMR, fluorophore labeling, a supramolecular assay based on high-affinity binding of cucurbit[7]uril, and two colorimetric assays based on toluidine blue and nickel complexation by pyrocatechol violet. The methods were thoroughly validated and compared with respect to reproducibility, sensitivity, and ease of use. The results demonstrate that only a small but constant fraction of the surface functional groups is accessible to covalent surface derivatization independently of the total number of surface functional groups, and different contributing factors are discussed that determine the number of probe molecules which can be bound to the polymer surface. The fluorophore labeling approach was modified to exclude artifacts due to fluorescence quenching, but absolute quantum yield measurements still indicate a major uncertainty in routine fluorescence-based surface group quantifications, which is directly relevant for biochemical assays and medical diagnostics. Comparison with results from protein labeling with streptavidin suggests a porous network of poly(acrylic acid) chains on the particle surface, which allows diffusion of small molecules (cutoff between 1.6 and 6.5 nm) into the network. KW - Polymers KW - Surface groups KW - Quantification KW - Fluorescence PY - 2012 DO - https://doi.org/10.1021/ja302649g SN - 0002-7863 SN - 1520-5126 VL - 134 IS - 19 SP - 8268 EP - 8276 PB - American Chemical Society CY - Washington, DC AN - OPUS4-26002 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hatami, Soheil A1 - Würth, Christian A1 - Kaiser, Martin A1 - Leubner, S. A1 - Gabriel, S. A1 - Bahrig, L. A1 - Lesnyak, V. A1 - Pauli, Jutta A1 - Gaponik, N. A1 - Eychmüller, A. A1 - Resch-Genger, Ute T1 - Absolute photoluminescence quantum yields of IR26 and IR-emissive Cd1-xHgxTe and PbS quantum dots - method- and material-inherent challenges JF - Nanoscale N2 - Bright emitters with photoluminescence in the spectral region of 800–1600 nm are increasingly important as optical reporters for molecular imaging, sensing, and telecommunication and as active components in electrooptical and photovoltaic devices. Their rational design is directly linked to suitable methods for the characterization of their signal-relevant properties, especially their photoluminescence quantum yield (Φf). Aiming at the development of bright semiconductor nanocrystals with emission >1000 nm, we designed a new NIR/IR integrating sphere setup for the wavelength region of 600–1600 nm. We assessed the performance of this setup by acquiring the corrected emission spectra and Φf of the organic dyes Itrybe, IR140, and IR26 and several infrared (IR)-emissive Cd1-xHgxTe and PbS semiconductor nanocrystals and comparing them to data obtained with two independently calibrated fluorescence instruments absolutely or relative to previously evaluated reference dyes. Our results highlight special challenges of photoluminescence studies in the IR ranging from solvent absorption to the lack of spectral and intensity standards together with quantum dot-specific challenges like photobrightening and photodarkening and the size-dependent air stability and photostability of differently sized oleate-capped PbS colloids. These effects can be representative of lead chalcogenides. Moreover, we redetermined the Φf of IR26, the most frequently used IR reference dye, to 1.1 × 10-3 in 1,2-dichloroethane DCE with a thorough sample reabsorption and solvent absorption correction. Our results indicate the need for a critical reevaluation of Φf values of IR-emissive nanomaterials and offer guidelines for improved Φf measurements. PY - 2015 DO - https://doi.org/10.1039/c4nr04608k SN - 2040-3364 SN - 2040-3372 VL - 7 IS - 1 SP - 133 EP - 143 PB - RSC Publ. CY - Cambridge AN - OPUS4-32408 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -