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th  - 1987 - 51st ENC Conference

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WKIO<br />

IH, IsC, AND ISN NMR STUDIES OF METAL COMPLEXES OF BLEOMYCIN<br />

Ian J. Mclennan* Michael P Gamcslk, Susanta K. Sarkar, Ad Bax t , and<br />

I °<br />

Jerry D. Gllckson, Depar ~ment of Radiology, The Johns Hopkins University<br />

School of Medicine, Baltimore MD 21205 and SNatlonal Institutes of Heal<strong>th</strong>,<br />

Be<strong>th</strong>esda MD 20892.<br />

The solution conformation of <strong>th</strong>e Zn(II) bleomycin complex has been<br />

studied by ZH, IsC, and ISN NMR. As part of <strong>th</strong>e study we have performed<br />

rotating frame NOE experiments in bo<strong>th</strong> H20 and D20. The Zn(II) bleomycln<br />

complex has been found to be partlcularly amenable to rotating frame<br />

experiments since <strong>th</strong>e TlP'S of <strong>th</strong>e complex are long (-50ms) at 4°C. The<br />

complete assignment of <strong>th</strong>e IH spectrum of <strong>th</strong>e Zn(II) bleomycln complex has<br />

been accomplished by COSY-llke experiments utilizing Hartman-Hahn<br />

polarization transfer. The complete assignment of <strong>th</strong>e IsC spectrum of <strong>th</strong>e<br />

Zn(II) bleomycin complex has been accomplished using <strong>th</strong>e RELAY me<strong>th</strong>od<br />

(Lerner and Bax (1986) J. Magn. Reson. 69, 375). The assignment of <strong>th</strong>e<br />

peptide amlde nitrogens in free bleomycin and <strong>th</strong>e Zn(II) bleomycin complex<br />

was accomplished by IH-16N multiple quantum experiments. The results from<br />

<strong>th</strong>ese experiments are discussed in terms of a probable solution<br />

conformation of <strong>th</strong>e Zn(II) bleomycln complex.

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