Dimers of Dipyrrometheneboron Difluoride (BODIPY) with Light Spectroscopic Applications in Chemistry and Biology
详细信息 查看全文
- 作者：Fredrik Bergströ ; m ; Ilya Mikhalyov ; Peter Hä ; gglö ; f ; Rü ; diger Wortmann ; Tor Ny ; and Lennart B.-Å ; . Johansson
- 刊名：Journal of the American Chemical Society
- 出版年：2002
- 出版时间：January 16, 2002
- 年：2002
- 卷：124
- 期：2
- 页码：196 - 204
- 全文大小：180K
- 年卷期：v.124,no.2(January 16, 2002)
- ISSN：1520-5126
文摘
A ground-state dimer (denoted <B>DI) exhibiting a strong absorption maximum at 477 nm (
= 97 000M-1cm-1) can form between adjacent BODIPY groups attached to mutant forms of the protein, plasminogenactivator inhibitor type 1 (PAI-1). No fluorescence from excited DI was detected. A locally high concentrationof BODIPY groups was also achieved by doping lipid phases (micelles, vesicles) with BODIPY-labeledlipids. In addition to an absorption band located at about 480 nm, a new weak absorption band is alsoobserved at ca. 570 nm. Both bands are ascribed to the formation of BODIPY dimers of differentconformation (DI and DII). Contrary to DI in PAI-1, the DII aggregates absorbing at 570 nm are emitting lightobserved as a broad band centered at about 630 nm. The integrated absorption band of DI is about twicethat of the monomer, which is compatible with exciton coupling within a dimer. The Förster radius of electronicenergy transfer between a BODIPY excited monomer and the ground-state dimer (DI) is 57 ± 2 Å. A simplemodel of exciton coupling suggests that in DI two BODIPY groups are stacked on top of each other in asandwich-like configuration with parallel electronic transition dipoles. For DII the model suggests that theS0 
S1 transition dipoles are collinear. An explanation for the previously reported (J. Am. Chem. Soc.1994, 116, 7801) exceptional light spectroscopic properties of BODIPY is also presented. These are ascribedto the extraordinary electric properties of the BODIPY chromophore. First, changes of the permanent electricdipole moment (
-0.05 D) and polarizability (-26 × 10-40 C m2 V-1) between the ground and the firstexcited states are small. Second, the S0 
S1 electronic transition dipole moments are perpendicular to.
= 97 000M-1cm-1) can form between adjacent BODIPY groups attached to mutant forms of the protein, plasminogenactivator inhibitor type 1 (PAI-1). No fluorescence from excited DI was detected. A locally high concentrationof BODIPY groups was also achieved by doping lipid phases (micelles, vesicles) with BODIPY-labeledlipids. In addition to an absorption band located at about 480 nm, a new weak absorption band is alsoobserved at ca. 570 nm. Both bands are ascribed to the formation of BODIPY dimers of differentconformation (DI and DII). Contrary to DI in PAI-1, the DII aggregates absorbing at 570 nm are emitting lightobserved as a broad band centered at about 630 nm. The integrated absorption band of DI is about twicethat of the monomer, which is compatible with exciton coupling within a dimer. The Förster radius of electronicenergy transfer between a BODIPY excited monomer and the ground-state dimer (DI) is 57 ± 2 Å. A simplemodel of exciton coupling suggests that in DI two BODIPY groups are stacked on top of each other in asandwich-like configuration with parallel electronic transition dipoles. For DII the model suggests that theS0 S1 transition dipoles are collinear. An explanation for the previously reported (J. Am. Chem. Soc.1994, 116, 7801) exceptional light spectroscopic properties of BODIPY is also presented. These are ascribedto the extraordinary electric properties of the BODIPY chromophore. First, changes of the permanent electricdipole moment ( -0.05 D) and polarizability (-26 × 10-40 C m2 V-1) between the ground and the firstexcited states are small. Second, the S0 S1 electronic transition dipole moments are perpendicular to.