Figure 1
(a) RR spectra measured from a ferric AxCYTcp crystal at 100 K. The redox marker ν4 and the core size markers ν3, ν2 and ν10 are clearly defined. (b) X-ray-reduction kinetic series of 20 s RR measurements. The first spectrum is shown in blue, with reduction essentially complete after an absorbed X-ray dose of ∼0.19 MGy. The inset shows the dose-dependent change in the bands at 1371 cm−1 (red) and 1352 cm−1 (blue). (c) RR spectra of ferric, chemically reduced, laser-reduced and X-ray-reduced crystals. Several spectra for each state were measured before X-ray exposure to ensure that no laser effects were apparent (except for the laser-reduced data) and only a single spectrum for each state is presented here. Data from a ferric crystal (black) were measured over 30 s at ∼2 mW, data from an X-ray-reduced crystal (green) over 20 s at ∼0.88 mW and data from a chemically reduced crystal (red) over 30 s at ∼2 mW. The laser-reduced spectrum shown (orange) was the final spectrum of a series of 20 × 30 s at ∼4.8 mW. Raman shifts measured from all three ferrous crystals are consistent within experimental error with solution data for the ferrous form of AxCYTcp (Table 1). |