Model Compounds for the T State of Hemoglobin
O2binding to a series of ferrous and cobaltous ``picket fence'' porphyrins is reported. N-Methylimidazole and covalently attached imidazoles give O2binding to ferrous porphyrins with Δ H degrees = -16.2 kcal/mol (-67.7 kJ/mol) and Δ S degrees = -40 eu (standard state, 1 atmosphere O2). Sim...
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Published in | Proceedings of the National Academy of Sciences - PNAS Vol. 75; no. 2; pp. 564 - 568 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
United States
National Academy of Sciences of the United States of America
01.02.1978
National Acad Sciences |
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Abstract | O2binding to a series of ferrous and cobaltous ``picket fence'' porphyrins is reported. N-Methylimidazole and covalently attached imidazoles give O2binding to ferrous porphyrins with Δ H degrees = -16.2 kcal/mol (-67.7 kJ/mol) and Δ S degrees = -40 eu (standard state, 1 atmosphere O2). Similar studies with cobaltous porphyrins yield Δ H degrees = -12.8 kcal/mol (-53.5 kJ/mol) and Δ S degrees = -39 eu. These values match well those of myoglobin and isolated subunits of hemoglobin and their cobalt reconstituted analogues. 1,2-Dimethylimidazole has been successfully used to mimic the presumed restraint of T state hemoglobin. In direct analogy to the decreased cooperativity shown by cobalt-substituted hemoglobin, model cobalt porphyrins show a smaller decrease in O2affinity than the analogous iron porphyrins when the axial base is hindered. Thermodynamic data are presented. The molecular mechanism of cooperativity in hemoglobin is discussed. |
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AbstractList | O2 binding to a series of ferrous and cobaltous "picket fence" porphyrins is reported. N-Methylimidazole and covalently attached imidazoles gives O2 binding to ferrous porphyrins with deltaH degrees =-16.2 kcal/mol (-67.7 kJ/mol) and deltaS degrees =-40 eu (standard state, 1 atmosphere O2). Similar studies with cobaltous porphyrins yield deltaH degrees =- 12.8 kcal/mol (-53.5 kJ/mol) and deltaS degrees =- 39 eu. These values match well those of myoglobin and isolated subunits of hemoglobin and their cobalt reconstituted analogues. 1,2-Dimethylimidazole has been successfully used to mimic the presumed restraint of T state hemoglobin. In direct analogy to the decreased cooperativity shown by cobalt-substituted hemoglobin, model cobalt porphyrins show a smaller decrease in O2 affinity than the analogous iron porphyrins when the axial base is hindered. Thermodynamic data are presented. The molecular mechanism of cooperativity in hemoglobin is discussed. O2binding to a series of ferrous and cobaltous ``picket fence'' porphyrins is reported. N-Methylimidazole and covalently attached imidazoles give O2binding to ferrous porphyrins with Δ H degrees = -16.2 kcal/mol (-67.7 kJ/mol) and Δ S degrees = -40 eu (standard state, 1 atmosphere O2). Similar studies with cobaltous porphyrins yield Δ H degrees = -12.8 kcal/mol (-53.5 kJ/mol) and Δ S degrees = -39 eu. These values match well those of myoglobin and isolated subunits of hemoglobin and their cobalt reconstituted analogues. 1,2-Dimethylimidazole has been successfully used to mimic the presumed restraint of T state hemoglobin. In direct analogy to the decreased cooperativity shown by cobalt-substituted hemoglobin, model cobalt porphyrins show a smaller decrease in O2affinity than the analogous iron porphyrins when the axial base is hindered. Thermodynamic data are presented. The molecular mechanism of cooperativity in hemoglobin is discussed. |
Author | Suslick, Kenneth S. Brauman, John I. Doxsee, Kenneth M. Halbert, Thomas R. Collman, James P. |
Author_xml | – sequence: 1 givenname: James P. surname: Collman fullname: Collman, James P. – sequence: 2 givenname: John I. surname: Brauman fullname: Brauman, John I. – sequence: 3 givenname: Kenneth M. surname: Doxsee fullname: Doxsee, Kenneth M. – sequence: 4 givenname: Thomas R. surname: Halbert fullname: Halbert, Thomas R. – sequence: 5 givenname: Kenneth S. surname: Suslick fullname: Suslick, Kenneth S. |
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Snippet | O2binding to a series of ferrous and cobaltous ``picket fence'' porphyrins is reported. N-Methylimidazole and covalently attached imidazoles give O2binding to... O2 binding to a series of ferrous and cobaltous "picket fence" porphyrins is reported. N-Methylimidazole and covalently attached imidazoles gives O2 binding to... |
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SubjectTerms | Cobalt Hemoglobins Imidazoles Iron Metalloporphyrins Models, Chemical Myoglobin Oxygen Oxygen - blood Phosphates Picket fences Porphyrins Porphyrins - metabolism Protein Binding |
Title | Model Compounds for the T State of Hemoglobin |
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