Reversible Low-Light Induced Photoswitching of Crowned Spiropyran-DO3A Complexed with Gadolinium(III) Ions 英文参考文献.docVIP

Molecules 2012, 17, 6605-6624; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Reversible Low-Light Induced Photoswitching of Crowned Spiropyran-DO3A Complexed with Gadolinium(III) Ions Klaus Kruttwig 1, Diego R. Yankelevich 2, Chantal Brueggemann 3, Chuqiao Tu 1, Noelle L’Etoile 3, André Knoesen 2 and Angelique Y. Louie 1,* 1 Department of Biomedical Engineering, University of California, Davis, CA 95616, USA 2 Department of Electrical and Computer Engineering, University of California, Davis, CA 95616, USA 3 Department of Cell and Tissue Biology, University of California, San Francisco, CA 94143, USA * Author to whom correspondence should be addressed; E-Mail: aylouie@; Tel.: +1-530-752-7134; Fax: +1-530-752-5739. Received: 26 March 2012; in revised form: 11 May 2012 / Accepted: 25 May 2012 / Published: 31 May 2012 Abstract: Photoswitchable spiropyran has been conjugated to the crowned ring system DO3A, which improves its solubility in dipolar and polar media and stabilizes the merocyanine isomer. Adding the lanthanide ion gadolinium(III) to the macrocyclic ring system leads to a photoresponsive magnetic resonance imaging contrast agent that displays an increased spin-lattice relaxation time (T1) upon visible light stimulation. In this work, the photoresponse of this photochromic molecule to weak light illumination using blue and green light emitting diodes was investigated, simulating the emission spectra from bioluminescent enzymes. Photon emission rate of the light emitting diodes was changed, from 1.75 × 1016 photons·s?1 to 2.37 × 1012 photons·s?1. We observed a consistent visible light-induced isomerization of the merocyanine to the spiropyran form with photon fluxes as low as 2.37 × 1012 photons·s?1 resulting in a relaxivity change of the compound. This demonstrates the potential for use of the described imaging probes in low l