X-ray absorption spectroscopy of Cu amyloid-β peptide (Aβ) under in situ electrochemical control (XAS-EC) has allowed elucidation of the redox properties of Cu bound to truncated peptide forms. The Cu binding environment is significantly different for the Aβ and the N-truncated Aβ, Aβ, and Aβ (Aβ) peptides, where the N-truncated sequence (FRH) provides the high-affinity amino-terminal copper nickel (ATCUN) binding motif. Low temperature (ca. 10 K) XAS measurements show the adoption of identical Cu ATCUN-type binding sites (Cu) by the first three amino acids (FRH) and a longer-range interaction modeled as an oxygen donor ligand, most likely water, to give a tetragonal pyramid geometry in the Aβ peptides not previously reported. Both XAS-EC and EPR measurements show that Cu:Aβ can be reduced at mildly reducing potentials, similar to that of Cu:Aβ. Reduction of peptides lacking the HH residues, Cu:Aβ, require far more forcing conditions, with metallic copper the only metal-based reduction product. The observations suggest that reduction of Cu species at mild potentials is possible, although the rate of reduction is significantly enhanced by involvement of HH. XAS-EC analysis reveals that, following reduction, the peptide acts as a terdentate ligand to Cu (H, H together with the linking amide oxygen atom). Modeling of the EXAFS is most consistent with coordination of an additional water oxygen atom to give a quasi-tetrahedral geometry. XAS-EC analysis of oxidized Cu:Aβ gives structural parameters consistent with crystallographic data for a five-coordinate Cu complex and the Cu complex. The structural results suggest that Cu and the oxidation product are both accommodated in an ATCUN-like binding site.

The most accurate measurements of the mass attenuation coefficient for metals at low temperature for the zinc K-edge from 9.5 keV to 11.5 keV at temperatures of 10 K, 50 K, 100 K and 150 K using the hybrid technique are reported. This is the first time transition metal X-ray absorption fine structure (XAFS) has been studied using the hybrid technique and at low temperatures. This is also the first hybrid-like experiment at the Australian Synchrotron. The measured transmission and fluorescence XAFS spectra are compared and benchmarked against each other with detailed systematic analyses. A recent method for modelling self-absorption in fluorescence has been adapted and applied to a solid sample. The XAFS spectra are analysed using eFEFFIT to provide a robust measurement of the evolution of nanostructure, including such properties as net thermal expansion and mean-square relative displacement. This work investigates crystal dynamics, nanostructural evolution and the results of using the Debye and Einstein models to determine atomic positions. Accuracies achieved, when compared with the literature, exceed those achieved by both relative and differential XAFS, and represent a state-of-the-art for future structural investigations. Bond length uncertainties are of the order of 20–40 fm.

Measurements of mass attenuation coefficients and X-ray absorption fine structure (XAFS) of zinc selenide (ZnSe) are reported to accuracies typically better than 0.13%. The high accuracy of the results presented here is due to our successful implementation of the X-ray extended range technique, a relatively new methodology, which can be set up on most synchrotron X-ray beamlines. 561 attenuation coefficients were recorded in the energy range 6.8–15 keV with measurements concentrated at the zinc and selenium pre-edge, near-edge and fine-structure absorption edge regions. This accuracy yielded detailed nanostructural analysis of room-temperature ZnSe with full uncertainty propagation. Bond lengths, accurate to 0.003 Å to 0.009 Å, or 0.1% to 0.3%, are plausible and physical. Small variation from a crystalline structure suggests local dynamic motion beyond that of a standard crystal lattice, noting that XAFS is sensitive to dynamic correlated motion. The results obtained in this work are the most accurate to date with comparisons with theoretically determined values of the attenuation showing discrepancies from literature theory of up to 4%, motivating further investigation into the origin of such discrepancies.

We present a method to explore the effect of fluorescence on X‐ray attenuation measurements obtained from X‐ray absorption spectroscopy (XAS). We use the X‐ray extended range technique‐like method (XERT‐like). The experimental setup includes different sized apertures to control the number of secondary X‐rays entering the detector. Comparison of attenuation measurements produced with different aperture combination permit investigation of the effect of fluorescence radiation. In this work, fluorescence has a large impact on the attenuation measurements of thick zinc foils. The correction is energy‐dependent and sample thickness‐dependent and changes the structure and relative amplitudes of oscillations in the near‐edge region. Correction for this systematic is important for absolute measurement, for edge‐jump and edge characterization, and for near‐edge structure and amplitudes. A significant background scattering due to zinc fluorescence from the beamline optics was identified and treated for the first time. The model theory fits the experimental measurements well. The resulting correction is most significant for thicker foils with the 50 μm sample experiencing a shift in attenuation of up to 15.5% for the largest aperture while the 25 and 10 μm samples saw corrections of up to 0.153 and 0.00639% respectively. The standard error from the dispersion and variance was reduced by up to 50.5% after the correction for the 50 μm sample. This enables high‐accuracy data and theoretical and experimental analysis to below 0.03% accuracy. The technology is advanced. There is a cost in preparation and measurement time of less than a factor of two, and the principles are clear and can be routinely implemented on any beamline. This paper focuses on the model and parameters for fluorescence.

The first X-ray Extended Range Technique (XERT)-like experiment at the Australian Synchrotron, Australia, is presented. In this experiment X-ray mass attenuation coefficients are measured across an energy range including the zinc K-absorption edge and X-ray absorption fine structure (XAFS). These high-accuracy measurements are recorded at 496 energies from 8.51 keV to 11.59 keV. The XERT protocol dictates that systematic errors due to dark current nonlinearities, correction for blank measurements, full-foil mapping to characterize the absolute value of attenuation, scattering, harmonics and roughness are measured over an extended range of experimental parameter space. This results in data for better analysis, culminating in measurement of mass attenuation coefficients across the zinc K-edge to 0.023–0.036% accuracy. Dark current corrections are energy- and structure-dependent and the magnitude of correction reached 57% for thicker samples but was still large and significant for thin samples. Blank measurements scaled thin foil attenuation coefficients by 60–500%; and up to 90% even for thicker foils. Full-foil mapping and characterization corrected discrepancies between foils of up to 20%, rendering the possibility of absolute measurements of attenuation. Fluorescence scattering was also a major correction. Harmonics, roughness and bandwidth were explored. The energy was calibrated using standard reference foils. These results represent the most extensive and accurate measurements of zinc which enable investigations of discrepancies between current theory and experiments. This work was almost fully automated from this first experiment at the Australian Synchrotron, greatly increasing the possibility for large-scale studies using XERT.