TY - JOUR A1 - Matiushkina, Anna A1 - Abram, Sarah-Luise A1 - Tavernaro, Isabella A1 - Richstein, R. A1 - Reithofer, M. R. A1 - Andresen, Elina A1 - Michaelis, Matthias A1 - Koch, Matthias A1 - Resch-Genger, Ute T1 - Quantifying Citrate Surface Ligands on Iron Oxide Nanoparticles with TGA, CHN Analysis, NMR, and RP-HPLC with UV Detection N2 - Although citrate is frequently used as a surface ligand for nanomaterials (NMs) such as metal, metal oxide, and lanthanide-based NMs in hydrophilic environments due to its biocompatibility and simple replacement by other more strongly binding ligands in postsynthetic surface modification reactions, its quantification on NM surfaces has rarely been addressed. Here, we present a multimethod approach for citrate quantification on iron oxide nanoparticles (IONPs) broadly applied in the life and material sciences. Methods explored include thermogravimetric (TGA) and elemental (CHN) analysis, providing citrate-nonspecific information on the IONP coating, simple photometry, and citrate-selective reversed-phase high-performance liquid chromatography (RP-HPLC) with absorption (UV) detection and quantitative nuclear magnetic resonance spectroscopy (qNMR). Challenges originating from the strongly absorbing magnetic NM and paramagnetic iron species interfering with optical and NMR Methods were overcome by suitable sample preparation workflows. Our multimethod approach to citrate quantification highlights the advantages of combining specific and unspecific methods for characterizing NM Surface chemistry and method cross-validation. It also demonstrates that chemically nonselective measurements can favor an overestimation of the amount of a specific surface ligand by signal contributions from molecules remaining on the NM surface, e.g., from particle synthesis, such as initially employed ligands and/or surfactants. Our results emphasize the potential of underexplored selective RPHPLC for quantifying ligands on NMs, which does not require a multistep sample preparation workflow such as qNMR for many NMs and provides a higher sensitivity. These findings can pave the road to future applications of versatile HPLC methods in NM characterization. KW - Advanced material KW - Functional group KW - Iron oxide KW - Ligand KW - Nano KW - Particle KW - Quantification KW - Surface analysis PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-648632 DO - https://doi.org/10.1021/acs.analchem.5c03024 SN - 0003-2700 VL - 97 IS - 36 SP - 19627 EP - 19634 PB - American Chemical Society (ACS) CY - Washington, DC AN - OPUS4-64863 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Andresen, Elina A1 - Resch-Genger, Ute A1 - Michaelis, Matthias A1 - Prinz, Carsten A1 - Würth, Christian T1 - Time-resolved luminescence spectroscopy for monitoring the stability and dissolution behaviour of upconverting nanocrystals with different surface coatings† N2 - We demonstrate the potential of time-resolved luminescence spectroscopy for the straightforward assessment and in situ monitoring of the stability of upconversion nanocrystals (UCNPs). Therefore, we prepared hexagonal NaYF4:Yb3+,Er3+ UCNPs with various coatings with a focus on phosphonate ligands of different valency, using different ligand exchange procedures, and studied their dissolution behaviour in phosphate-buffered saline (PBS) dispersions at 20 °C and 37 °C with various analytical methods. The amount of the released UCNPs constituting fluoride ions was quantified by potentiometry using a Fluoride ion-sensitive electrode and particle disintegration was confirmed by transmission electron microscopy studies of the differently aged UCNPs. In parallel, the luminescence features of the UCNPs were measured with special emphasis on the lifetime of the sensitizer emission to demonstrate its suitability as Screening parameter for UCNP stability and changes in particle composition. The excellent correlation between the changes in luminescence lifetime and fluoride concentration highlights the potential of our luminescence lifetime method for UCNP stability screening and thereby indirect monitoring of the release of potentially hazardous fluoride ions during uptake and dissolution in biological systems. Additionally, the developed in situ optical method was used to distinguish the dissolution dynamics of differently sized and differently coated UCNPs. KW - Fluorescence KW - Lifetime KW - Method KW - Quantification KW - Stability KW - Coating KW - Surface chemistry KW - Lanthanide KW - Fluoride KW - Electrochemistry KW - ICP-OES KW - Upconversion KW - Nano KW - Particle KW - Aging KW - Quality assurance KW - TEM PY - 2020 DO - https://doi.org/10.1039/d0nr02931a VL - 12 IS - 23 SP - 12589 EP - 12601 PB - Royal Society od Chemistry AN - OPUS4-52088 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -