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-1 (in ref 1a), respectively, the intensity of Soret of PEG-HRP compound I in benzene (Figure 4) is greater than we expected. Since the extinction coefficient of compound I for PEG-HRP in buffer is approximately half of that of ferric PEG-HRP (Figure 3), the nature of compound I in organic media could be different.
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31
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note
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obs2) to accumulate compound I. The results are consistent with the hypothesis that bulky substrates cannot readily reach the heme of PEG-HRP in organic solvents. However, the spectrum generated with the alkyl hydroperoxide is the same as that with hydrogen peroxide.
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32
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3543024000
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note
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2 in benzene at 7.5°C was also found to be nonlinear, and the rate of compound I formation reached a plateau when more than 10 equiv of hydrogen peroxide were used.
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33
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0000160591
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3543027553
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note
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The amount of water in PEG-HRP benzene solution was 109 ± 3 ppm, when 1 μM of PEG-HRP in dry benzene (water content 4.4 ± 0.3 ppm) was prepared.
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37
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3543031144
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note
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Soret (ferric) = 0.82, 0.71. and 0.66 in the presence of 142, 216, and 305 ppm of water in chlorobenzene, respectively).
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38
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