Advances in element speciation analysis of biomedical samples using synchrotron-based techniques

Abstract

Advances in element speciation analysis of biomedical samples using synchrotron-based techniques. Trends in Analytical Chemistry, Elsevier, 2018, 104, pp. Highlights principle of direct element speciation with synchrotron X-ray absorption spectroscopy (XAS)  experimental modalities for bulk-and micro-XAS speciation and their limitations  review (2012-2017) of XAS in pharmacology, metals and nanoparticles toxicology, physiopathology  future directions and developments of XAS speciation for biomedical research AbstractSynchrotron-radiation X-ray absorption spectroscopy (XAS) is a direct method for speciation analysis with atomic resolution, providing information about the local chemical environment of the probed element. This article gives an overview of the basic principles of XAS and its application to element speciation in biomedical research. The basic principle and experimental modalities of XAS are introduced, followed by a discussion of both its limitations, such as beam damage or detection limits, and practical advices to improve experiments. An updated review of biomedical studies involving XAS published over the last 5 years is then provided, paying special attention to metal-based drug biotransformation, metal and nanoparticle toxicology, and element speciation in cancer, neurological, and general pathophysiology. Finally, trends and future developments such as hyphenated methods, in situ correlative imaging and speciation, in vivo X-ray Absorption Near Edge Spectroscopy (XANES), full-field XANES, and X-ray Free Electron Laser (XFEL) XAS are presented.

Mapping Chemical Elements and Iron Oxidation States in the Substantia Nigra of 6-Hydroxydopamine Lesioned Rats Using Correlative Immunohistochemistry With Proton and Synchrotron Micro-Analysis

“…This result is in good agreement with XAS and Mössbauer spectroscopy data obtained on human PD cryogenically processed tissues (Griffiths et al, 1999; Chwiej et al, 2007; Wypijewska et al, 2010). Overall these results suggest that low temperature sample environment is highly advocated for micro-XAS speciation of Fe, as also suggested by previous studies of biological samples due to their sensitivity to X-ray irradiation (Bacquart et al, 2007; Ortega, 2011; Porcaro et al, 2018). Our data also indicate that Fe was present exclusively at Fe(III) oxidation state in all samples, and with a XANES spectral signature similar to that of ferritin.…”

“…X-ray microanalysis using proton or synchrotron radiation microbeams can be employed to image Fe and other elements content with great sensitivity and quantitative accuracy within local microscopic regions (Ortega et al, 2009; Collingwood and Davidson, 2014; Pushie et al, 2014; Collingwood and Adams, 2017). In addition, micro-XANES can be used to identify Fe(II) and Fe(III) from differences in their absorption edge energies and pre-edge features (Ortega et al, 2012; Collingwood and Davidson, 2014; Collingwood and Adams, 2017; Porcaro et al, 2018). The determination of chemical element distributions in brain regions requires the use of non-denaturating sample preparation methods usually based on cryogenic protocols of tissue fixation.…”

XANES Measurements for Studies of Adsorbed Protein Layers at Liquid Interfaces

“…X-ray absorption spectroscopy (XAS) expands opportunities to characterize the local structure of the absorbing sites in biological materials. Analysis of XAS spectra for metalloproteins and metal-protein complexes allows one to obtain detailed information about the 3D geometry of a metal site, the number and type of ligands, metal-ligand distances, and the oxidation state of metal ions [ 4 , 5 , 6 , 7 , 8 ]. Metalloproteins play a key role in many vital biological processes, such as enzymatic catalysis, gas transport, electron transfer, and redox signal transmission.…”

A mail-in and user facility for X-ray absorption near-edge structure: the CEI-XANES laboratory X-ray spectrometer at the University of Washington

“…X-ray absorption spectroscopy (XAS) exhibits a global intellectual reach, with more than 100 endstations or beamlines at synchrotron or free-electron laser facilities world-wide. This has led to continual scientific impact across numerous disciplines (Bunker, 2010;de Groot & Kotani, 2008), with XAS playing an especially central role in research in catalysis (Caudillo-Flores et al, 2018;Thomas & Sankar, 2001), electrical energy storage (McBreen et al, 1988;McBreen, 2009;Cheng et al, 2017;Li et al, 2018), environmental sciences (Ma et al, 2019), fundamental chemistry and physics (Young, 2014), biochemistry (Sarangi, 2013;Porcaro et al, 2018;Kowalska & DeBeer, 2015), and heavy-element chemistry (Kosog et al, 2012;Shi et al, 2014). Much of the highest profile contemporary research does require the full brilliance, time resolution or other extreme performance metrics of these light sources, but a considerable fraction of ongoing excellent work does not.…”