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Vittitow, Joseph Lawrence 2011-05-07T13:28:35Z 2011-05-07T13:28:35Z 10000-01-01 1989 An infrared-monitored flash-photolysis apparatus capable of measuring absorbance changes to 10$\sp{-3}$OD over a time range from 10$\mu$s to 10s is described. Measurements made on this apparatus, combined with slower measurements made on a Fourier-transform infrared spectrometer, of the CO-rebinding kinetics of the A$\sb0$, A$\sb1$, and A$\sb3$ conformations of sperm-whale myoglobin (Mb) at atmospheric pressure and neutral pH are reported. The A$\sb0$, A$\sb1$, and A$\sb3$ rebinding kinetics are shown to be non-exponential and parameterized by activation-enthalpy distributions differing in prefactor $k\sb0\ (\log(k\sb0/s)$ = 10.8, 9.3, and 9.8 for the A$\sb0$, A$\sb1$, and A$\sb3$ conformations, respectively) and peak activation-enthalpy $H\sb{p}\ (H\sb{p} = 10.4$, 9.6, and 17.6 kJ/M, respectively). "CO-rebinding kinetics of MbCO ensembles prepared along different paths in the pressure-temperature plane (""freeze"" and ""squeeze-freeze-release"" ensembles) monitored at two frequencies within the A$\sb1$ band are also reported. No differences between kinetics monitored at 1943.0cm$\sp{-1}$ and 1947.5cm$\sp{-1}$, and none between the kinetics of the freeze and squeeze-freeze-release ensembles, are resolved. The large uncertainty in the determination of the peak $H\sb{p}$ of the activation-enthalpy distribution ($H\sb{p}$ = 15 (+8,$-$7)kJ/M for the squeeze-freeze-release ensemble monitored at 1943.0cm$\sp{-1}$) suggests limits of the capability of the apparatus, which are discussed in terms of time resolution." Made available in DSpace on 2011-05-07T13:28:35Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9011062.pdf: 2085300 bytes, checksum: 03ce4ae399fb79ba187656caca234151 (MD5) Previous issue date: 1989 Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:55:15Z Item is restricted indefinitely. Restriction data tranferred 2014-07-01T11:25:44-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission ETDs are only available to UIUC Users without author permission U of I Only AAI9011062 (UMI)AAI9011062 http://hdl.handle.net/2142/22089 eng Copyright 1989 Vittitow, Joseph Lawrence Physics, Molecular Biophysics, General Infrared-monitored flash-photolysis of carboxymyoglobin text Physics Physics University of Illinois at Urbana-Champaign Dissertation Ph.D.