Unraveling the Effect on Luminescent Properties by Postsynthetic Covalent and Noncovalent Grafting of gfp Chromophore Analogues in Nanoscale MOF-808
Ashish Singh, Sanchita Karmakar, Irine Maria Abraham, Darsi Rambabu, Dhwanit Dave, Ravi Manjithaya, Tapas Kumar Maji
Abstract
Here, we demonstrate mimicking of photophysical properties of native green fluorescent protein (gfp) by immobilizing the gfp chromophore analogues in nanoscale MOF-808 and further exploring the bioimaging applications. The two virtually nonfluorescent gfp chromophore analogues carrying different functionalities, BDI-AE (COOH/COOMe) and BDI-EE (COOMe/COOMe) were immobilized in nanosized MOF-808 via postsynthetic modification. An 1H NMR and IR study confirms that BDI-AE was coordinated in NMOF-808, whereas BDI-EE was just noncovalently encapsulated. Interestingly, the extremely weakly fluorescent monomers BDI-AE and BDI-EE (QY = 0.01–0.03%, lifetime = 0.01–0.03 ns) showed a 102-fold increase in quantum efficiency with a significantly longer excited-state lifetime (QY = 1.8–5.6%, lifetime 0.89–1.49 ns) after immobilization in the NMOF-808 scaffold. Moreover, BDI-AE@MOF-808 has 4 times higher quantum efficiency as well as longer excited-state lifetime in comparison to BDI-EE@NMOF-808 due to the rigidity imposed in the chromophore upon coordination with Zr4+ in the former case. Further, a cell viability test performed for BDI-AE@NMOF-808 in HeLa cells confirmed the nontoxic nature of the material and, more importantly, bioimaging applications have also been explored successfully.