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J. Biochem, 1988, Vol. 103, No. 6 979-985
© 1988 Japanese Biochemical Society

research-article

4-Vinyl and 2, 4-Divinyl Deuteration Effects on the Low Frequency Resonance Raman Bands of Myoglobin: Correlation with the Structure of Vinyl Group1

Kiyoshi Uchida, Yuko Susai, Eri Hirotani, Takuma Kimura, Takaaki Yoneya, Hideo Takeuchi and Issei Harada2

Pharmaceutical Institute, Tohoku University Sendai, Miyagi 980

2To whom correspondence should be addressed.

Resonance Raman spectra of myoglobin (Mb) reconstituted with 4-vinyl and 2, 4-divinyl deuterated protoheme IX were studied in several oxidation, spin, and ligation states (deoxyMb, MbO2, MbCO, metMbH2O, and metMbCN-) with special attention to the low frequency vibrations. Frequency shifts observed on deuteration enabled us to assign some Raman bands to vibrations specifically involving the 2- or 4-vinyl group. The most significant deuteration effect was found for a band around 410 cm–1 in the ferrous state, which loses intensity on 4-vinyl deuteration and is ascribed to a porphyrin in-plane vibration strongly coupled with the skeletal bend of the vinyl group at position 4. Such strong coupling implies that the vinyl group lies in the same plane as the pyrrole II ring, as in the crystalline state. Thus, frequency shifts on vinyl deuteration may be useful as a probe of the orientation of the vinyl group. Resonance Raman spectra of Mb coordinated with various sizes of isocyanides are interpreted in terms of vinyl orientational changes induced by ligation.

1This work was supported by a Grant-in-Aid for Scientific Research (No. 58780250) from the Ministry of Education, Science and Culture of Japan, by a research grant from the Naito Foundation, and by a research grant from the Takeda Science Foundation.


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