Blanco-Rodríguez Ana María, Busby Michael, Gradinaru Cristian, Crane Brian R, Di Bilio Angel J, Matousek Pavel, Towrie Michael, Leigh Brian S, Richards John H, Vlcek Antonín, Gray Harry B
School of Biological and Chemical Sciences, Queen Mary, University of London, UK.
J Am Chem Soc. 2006 Apr 5;128(13):4365-70. doi: 10.1021/ja057451+.
The triplet metal-to-ligand charge transfer ((3)MLCT) dynamics of two structurally characterized Re(I)(CO)(3)(phen)(HisX)-modified (phen = 1,10-phenanthroline; X = 83, 109) Pseudomonas aeruginosa azurins have been investigated by picosecond time-resolved infrared (TRIR) spectroscopy in aqueous (D(2)O) solution. The (3)MLCT relaxation dynamics exhibited by the two Re(I)-azurins are very different from those of the sensitizer Re(I)(CO)(3)(phen)(im) (im = imidazole). Whereas the Re(I)(CO)(3) intramolecular vibrational relaxation in Re(I)(CO)(3)(phen)(HisX)Az (4 ps) is similar to that of Re(I)(CO)(3)(phen)(im) (2 ps), the medium relaxation is much slower ( approximately 250 vs 9.5 ps); the 250-ps relaxation is attributable to reorientation of D(2)O molecules as well as structural reorganization of the rhenium chromophore and nearby polar amino acids in each of the modified proteins.
通过皮秒时间分辨红外（TRIR）光谱法在重水溶液（D₂O）中研究了两种结构特征明确的铼（I）（CO）₃（邻菲罗啉）（组氨酸X）修饰的（邻菲罗啉 = 1,10 - 菲咯啉；X = 83, 109）铜绿假单胞菌天青蛋白的三重态金属到配体电荷转移（(³)MLCT）动力学。这两种铼（I）-天青蛋白表现出的(³)MLCT弛豫动力学与敏化剂铼（I）（CO）₃（邻菲罗啉）（咪唑）（咪唑 = 咪唑）的弛豫动力学非常不同。虽然铼（I）（CO）₃在铼（I）（CO）₃（邻菲罗啉）（组氨酸X）天青蛋白中的分子内振动弛豫时间（4皮秒）与铼（I）（CO）₃（邻菲罗啉）（咪唑）的弛豫时间（2皮秒）相似，但介质弛豫要慢得多（约250皮秒对9.5皮秒）；250皮秒的弛豫归因于D₂O分子的重新取向以及铼发色团和每个修饰蛋白中附近极性氨基酸的结构重组。
