Confinement-Driven Photophysics in Cages, Covalent−Organic Frameworks, Metal–Organic Frameworks, and DNA
| Autor: | Mark D. Smith, Maksymilian Chruszcz, Karthikeyan Mythreye, Otega A. Ejegbavwo, Seok W Choi, Martín S. Faillace, Ekaterina A. Dolgopolova, Allison M. Rice, Gabrielle A. Leith, Natalia B. Shustova, Anna A. Berseneva, Sophya Garashchuk, Haley N. Gregory |
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| Rok vydání: | 2020 |
| Předmět: |
Light
Intercalation (chemistry) Molecular Conformation 010402 general chemistry Photochemistry 01 natural sciences Biochemistry Catalysis Colloid and Surface Chemistry Humans Confined space Conformational isomerism Metal-Organic Frameworks Fluorescent Dyes Triazines Hydrogen bond Chemistry Imidazoles DNA General Chemistry Chromophore Fluorescence Intercalating Agents 0104 chemical sciences Covalent bond Metal-organic framework HeLa Cells |
| Zdroj: | Journal of the American Chemical Society. 142:4769-4783 |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | Photophysics tunability through alteration of framework aperture (metal-organic framework (MOF) = variable; guest = constant) was probed for the first time in comparison with previously explored concepts (MOF = constant; guest = variable). In particular, analysis of the confinement effect on a photophysical response of integrated 5-(3-chlorobenzylidene)-2,3-dimethyl-3,5-dihydro-4H-imidazol-4-one (Cl-BI) chromophore allowed us to establish a photophysics-aperture relationship. To shed light on the observed correlation, the framework confined environment was replicated using a molecular cage, Pd6(TPT)4 (TPT = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine), thus allowing for utilization of crystallography, spectroscopy, and theoretical simulations to reveal the effect a confined space has on the chromophore's molecular conformation (including disruption of strong hydrogen bonding and novel conformer formation) and any associated changes on a photophysical response. Furthermore, the chosen Cl-oHBI@Pd6(TPT)4 (Cl-oHBI = 5-(5-chloro-2-hydroxybenzylidene)-2,3-dimethyl-3,5-dihydro-4H-imidazol-4-one, chromophore) system was applied as a tool for targeted cargo delivery of a chromophore to the confined space of DNA, which resulted in promotion of chromophore-DNA interactions through a well-established intercalation mechanism. Moreover, the developed principles were applied toward utilizing a HBI-based chromophore as a fluorescent probe on the example of macrophage cells. For the first time, suppression of non-radiative decay pathways of a chromophore was tested by anchoring the chromophore to a framework metal node, portending a potential avenue to develop an alternative to natural biomarkers. Overall, these studies are among the first attempts to demonstrate the unrevealed potential of a confined scaffold environment for tailoring a material's photophysical response. |
| Databáze: | OpenAIRE |
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