Elemental analysis methods based on X-ray fluorescence spectrometry (XRF) can offer several advantages, such as rapid multi-element detection and/or non-destructive information. XRF in total reflection set-up (TXRF) achieves high sensitivity down to pg, while the use of an X-ray beam focused to a few micrometres for excitation (μXRF) allows the laterally resolved study of elements.
First, we present the development and validation of a reliable method based on TXRF analysis for the accurate quantification of iron and other trace metals in a variety of biological samples, including spleen and liver cells, liver and placental tissues, and bone marrow-derived macrophages1,2. We show that a fast and simple one-point calibration by addition of an internal standard provides reliable multi-element analysis in minute sample quantities after minimal sample preparation. The method was validated over a wide concentration range for several biometals using (GFAAS) as a reference method study and by studying the bovine liver standard reference material (SRM 1577c, NIST). Quantitative recoveries (92-106%) demonstrate the suitability of the developed method. The detection limits for the smallest sample quantities are in the low picogram range. Furthermore, the simplicity of the procedure is highly advantageous in terms of the sustainability of biometal trace determination compared to standard methods.
Secondly, the application of μXRF for metal detection in various materials used in energy research, such as nanomaterials and polymer membranes for artificial photosynthesis, is reported3,4. Multi-element analysis provides information on the local concentration and distribution of the actives elements of molecular components in such composite materials. In this context, the design and construction of a μXRF measurement cell is described, which allows the study of the stability/degradation of matrix-embedded light-driven catalysts in native (wet) polymer membranes. Calibration strategies for quantitative elemental mapping in complex matrices are also presented.
1) Gruber, A. et al., 2020. Total reflection X-ray fluorescence spectrometry for trace determination of iron and some additional elements in biological samples. Anal Bioanal Chem 412, 6419–6429. https://doi.org/10.1007/s00216-020-02614-8
2) Hauser, S. et al., 2022. Determination of trace elements in placenta by total reflection X-ray fluorescence spectrometry: effects of sampling and sample preparation. Anal Bioanal Chem 414, 4519 4529. https://doi.org/10.1007/s00216 022 04112 5
3) Benndorf, S. et al. al., 2023. Covalent Functionalization of CdSe Quantum Dot Films with Molecular [FeFe] Hydrogenase Mimics for Light-Driven Hydrogen Evolution. ACS Appl. Mater. Interfaces 15, 18889–18897. https://doi.org/10.1021/acsami.3c00184
4) Kund, J. et al. al., 2023. Multimodal Analysis of Light‐Driven Water Oxidation in Nanoporous Block Copolymer Membranes. Angew Chem Int Ed 62, e202217196. https://doi.org/10.1002/anie.202217196