Search

X-ray absorption spectroscopy (XAS) is a promising technique for determining structural information from sensitive biological samples, but high-accuracy X-ray absorption fine structure (XAFS) requires corrections of systematic errors in experimental data. Low-temperature XAS and room-temperature X-ray absorption spectro-electrochemical (XAS-EC) measurements of N-truncated amyloid-β samples were collected and corrected for systematic effects such as dead time, detector efficiencies, monochromator glitches, self-absorption, radiation damage and noise at higher wavenumber ( k ). A new protocol was developed using extended X-ray absorption fine structure (EXAFS) data analysis for monitoring radiation damage in real time and post-analysis. The reliability of the structural determinations and consistency were validated using the XAS measurement experimental uncertainty. The correction of detector pixel efficiencies improved the fitting χ 2 by 12%. An improvement of about 2.5% of the structural fitting was obtained after dead-time corrections. Normalization allowed the elimination of 90% of the monochromator glitches. The remaining glitches were manually removed. The dispersion of spectra due to self-absorption was corrected. Standard errors of experimental measurements were propagated from pointwise variance of the spectra after systematic corrections. Calculated uncertainties were used in structural refinements for obtaining precise and reliable values of structural parameters including atomic bond lengths and thermal parameters. This has permitted hypothesis testing., (© Ruwini S. K. Ekanayake et al. 2024.)

The design and performance of an electrochemical cell and solution flow system optimized for the collection of X-ray absorption spectra from solutions of species sensitive to photodamage is described. A combination of 3D CAD and 3D printing techniques facilitates highly optimized design with low unit cost and short production time. Precise control of the solution flow is critical to both minimizing the volume of solution needed and minimizing the photodamage that occurs during data acquisition. The details of an integrated four-syringe stepper-motor-driven pump and associated software are described. It is shown that combined electrochemical and flow control can allow repeated measurement of a defined volume of solution, 100 µl, of samples sensitive to photoreduction without significant change to the X-ray absorption near-edge structure and is demonstrated by measurements of copper(II) complexes. The flow in situ electrochemical cell allows the collection of high-quality X-ray spectral measurements both in the near-edge region and over an extended energy region as is needed for structural analysis from solution samples. This approach provides control over photodamage at a level at least comparable with that achieved using cryogenic techniques and at the same time eliminates problems associated with interference due to Bragg peaks.

Structure factors for small hydrothermally grown yttrium and holmium orthoferrites, RFeO(3) (R = Y, Ho), were measured with focused synchrotron radiation at wavelengths of 0.70 and 0.84 A using both scintillation and high-speed avalanche photodiode (APD) detectors. Resulting APD Deltarho images showed striking correlations between aspherical electron densities around Fe and rare-earth metals. Approximate high symmetry in the Deltarho images indicates that cations deform the electron density far more strongly than the O atoms. The Ho-Fe magnetic interactions appear to affect the electron density distribution of the Fe atoms and the magnetic phase transitions. Space group Pnma, orthorhombic, YFeO3 (APD): Mr = 192.76, a = 5.5931 (3), b = 7.6102 (4), c = 5.2806 (3) A, V = 224.77 (2) A(3), Z = 4, Dx = 5.695 Mg m(-3), mu(0.84) = 15.56 mm(-1), F(000) = 356, T = 293 K, R = 0.045, wR = 0.073, S = 4.83 (9) for 1282 unique reflections; HoFeO3 (APD): Mr = 268.78, a = 5.5922 (3), b = 7.6157 (5), c = 5.2798 (3) A, V = 224.86 (2) A(3), Z = 4, D(x) = 7.939 Mg m(-3), mu(0.84) = 61.98 mm(-1), F(000) = 356, T = 293 K, R = 0.036, wR = 0.037, S = 3.07 (6) for 1284 unique reflections.