DNA-Based Assemblies for Photochemical Upconversion
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- 作者：Saymore Mutsamwira ; Eric W. Ainscough ; Ashton C. Partridge ; Peter J. Derrick ; Vyacheslav V. Filichev
- 刊名：Journal of Physical Chemistry B
- 出版年：2015
- 出版时间：November 5, 2015
- 年：2015
- 卷：119
- 期：44
- 页码：14045-14052
- 全文大小：518K
- ISSN：1520-5207
文摘
In the present study DNA was used as a scaffold for the supramolecular assembly of organic chromophores for photochemical upconversion (PUC). Initially, a green-to-blue PUC was observed using free chromophores in solution: tris(2,2鈥?bipyridine)ruthenium(II), [Ru(bpy)3]2+, which acts as a long-wavelength absorber (位ex = 500 nm), and an in situ energy donor to an acceptor (R)-1-O-[4-(1-pyrenylethynyl)phenylmethyl]glycerol (PEPy or TINA monomer), which acts as an annihilator and short-wavelength photoemitter (位em = 420 nm). Then, DNA duplexes possessing TINA monomers were synthesized, and complexes with [Ru(bpy)3]2+ were investigated. In contrast to the dynamic interactions of [Ru(bpy)3]2+ with TINA monomer free in solution, ground-state complex formation was the predominant mechanism of interaction between [Ru(bpy)3]2+ and DNA duplexes bearing two TINA monomers at the 5鈥?ends as shown by fluorescence, circular dichroism (CD), and UV鈥搗is spectroscopy studies. The use of TINA-modified DNAs led to PUC occurring at concentrations significantly lower than that for free chromophores in solution: 2.5 渭M [Ru(bpy)3]2+ and 5.0 渭M TINA-modified duplex in the DNA-based systems in aqueous buffer versus 46 渭M [Ru(bpy)3]2+ and 4.6 mM TINA monomer for the free donor and acceptor in DCM, respectively. Providing vast capabilities of DNA in the development of novel photonic systems as a result of the controllable organization of various chromophores, this study opens a new perspective for the development of DNA-based light-harvesting systems using PUC.