Ruthenium(III) Polyaminocarboxylate Complexes: Efficient and Effective Nitric Oxide Scavengers
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- 作者：Beth R. Cameron ; Marilyn C. Darkes ; Helen Yee ; Micki Olsen ; Simon P. Fricker ; Renato T. Skerlj ; Gary J. Bridger ; Nathan A. Davies ; Michael T. Wilson ; David J. Rose ; and Jon Zubieta
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：March 24, 2003
- 年：2003
- 卷：42
- 期：6
- 页码：1868 - 1876
- 全文大小：164K
- 年卷期：v.42,no.6(March 24, 2003)
- ISSN：1520-510X
文摘
The preparation of two RuIII polyaminocarboxylate complexes, AMD6245 and AMD6221, and their nitrosyl analogues,AMD6204, AMD6263, and AMD3689, is described. The compounds are characterized by IR, ES-MS, and 13C and15N NMR spectroscopy where appropriate and cyclic voltammetry. The crystal structures for AMD6245, AMD6263,and AMD3689 are presented. AMD6245 (C10H14N2O9Ru) crystallized in the P21/c space group with a = 8.4382(2)Å, b = 8.8304(2) Å, c = 17.6321(4) Å, 
= 99.603
, V = 1295.3(2) Å3, and Z = 4. AMD6263 (C10H14N3O10Ru)crystallized in the P21/c space group with a = 9.9043(4) Å, b = 13.1144(3) Å, c = 12.0914(4) Å, = 100.191,V = 1545.8(5) Å3, and Z = 4. AMD3689 (C14H24.56N4O13.28Ru) crystallized in the P
space group with a = 8.838(2) Å, b = 9.452(3) Å, c = 13.419(4) Å, 
= 78.413(6), = 75.804(6), 
= 73.562(6), V = 1031.8(5) Å3,and Z = 2. The reaction of AMD6245 and AMD6221 with nitric oxide is investigated using EPR spectroscopy andstopped flow kinetics. Upon reaction with NO, a linear, diamagnetic {RuNO}6 complex is formed. The substitutionreaction of AMD6245 with NO proceeds with a second-order rate constant of 2.24 × 107 M-1 s-1 at 7.3 C (pH= 7.4; 50 mM phosphate buffer). The substitution reaction of AMD6221 with NO proceeds with a second-orderrate constant of 3 × 105 M-1 s-1 at 20 C (pH = 7.4; 50 mM phosphate buffered saline). The NO scavengingability was assessed using a RAW264 murine macrophage assay by measuring the difference in nitrite producedbetween untreated control cells and treated cells. At 100 
M AMD6245 has [NO2-] = 12.5 M less than theuntreated cells and AMD6221 has [NO2-] = 37.6 M less than the untreated cells. There is an insignificantdifference in the amount of nitrite produced between AMD6263 or AMD3689 treated cells and untreated cells.
= 99.603, V = 1295.3(2) Å3, and Z = 4. AMD6263 (C10H14N3O10Ru)crystallized in the P21/c space group with a = 9.9043(4) Å, b = 13.1144(3) Å, c = 12.0914(4) Å, = 100.191,V = 1545.8(5) Å3, and Z = 4. AMD3689 (C14H24.56N4O13.28Ru) crystallized in the P space group with a = 8.838(2) Å, b = 9.452(3) Å, c = 13.419(4) Å, = 78.413(6), = 75.804(6), = 73.562(6), V = 1031.8(5) Å3,and Z = 2. The reaction of AMD6245 and AMD6221 with nitric oxide is investigated using EPR spectroscopy andstopped flow kinetics. Upon reaction with NO, a linear, diamagnetic {RuNO}6 complex is formed. The substitutionreaction of AMD6245 with NO proceeds with a second-order rate constant of 2.24 × 107 M-1 s-1 at 7.3 C (pH= 7.4; 50 mM phosphate buffer). The substitution reaction of AMD6221 with NO proceeds with a second-orderrate constant of 3 × 105 M-1 s-1 at 20 C (pH = 7.4; 50 mM phosphate buffered saline). The NO scavengingability was assessed using a RAW264 murine macrophage assay by measuring the difference in nitrite producedbetween untreated control cells and treated cells. At 100 M AMD6245 has [NO2-] = 12.5 M less than theuntreated cells and AMD6221 has [NO2-] = 37.6 M less than the untreated cells. There is an insignificantdifference in the amount of nitrite produced between AMD6263 or AMD3689 treated cells and untreated cells.