Temperature dependence of the spinS=1/2 fluctuation rate and the low-spin versus high-spin transition in native chloroperoxidase |
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Authors: | C E Schulz P Osmulski Y -M Xia P G Debrunner |
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Institution: | (1) Physics Department, Knox College, 61401 Galesburg, IL, USA;(2) Physics Department, University of Illinois at Urbana-Champaign, 61801, IL, USA |
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Abstract: | We analyzed two preparations of native, low-spin ferric chloroperoxides as a function of temperature with the following results. (i) The spin lattice transition rateW(T) is relative slow, following a power lawW=0.035 (T/K)4.98 (rad/s) for one of the samples. (ii) The quadrupole splitting is strongly temperature dependent, dropping from ¦ E
Q¦ 2.94 mm/s at 100 K to 2 mm/s at 250 K. (iii) Starting at 190 K, the low-spin heme iron in frozen adqueous solution converts reversibly to a high-spin form, reaching 40% high-spin at 250 K. The two forms appear to be in thermal equilibrium, (iv) Optical data indicate that in a 70% glycerol glass, the conversion starts at lower temperature and reaches 50% highspin at 190 K.Supported in part by GM 49513 and GM 16406. |
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