title: G-Quadruplex Supramolecular Assemblies in Photochemical Upconversion.
abstract: Parallel, tetramolecular G-quadruplex (G4) DNA possessing TINA monomer, (R)-1-O-[4-(1-pyrenylethynyl)phenylmethyl]glycerol, were synthesised and evaluated in complexes with tris(2,2'-bipyridine)ruthenium(II), [Ru(bpy)3 ](2+) , and the Zn(2+) derivative of 5,10,15,20-tetrakis-(1-methyl-4-pyridyl)-21 H,23H-porphine, ZnTMpyP4. UV/Vis, fluorescence, and circular dichroism (CD) spectroscopy showed that the use of G4-DNA as a template resulted in the effective communication between the ligands and the TINA molecule that was covalently attached to the 5'-end and between T and dG at the 5'-end of the dTG4 T sequence. Only one G4-DNA possessing the TINA molecule at the 5'-end of the dTG4 T sequence was able to yield a green-to-blue photochemical upconversion (PUC, λem =420 nm) in the presence of [Ru(bpy)3 ](2+) upon excitation at 500 nm. Different DNA secondary structures can thus be used in DNA-based assemblies for PUC and the way of attachment of chromophores to DNA plays a pivotal role for the creation of a photosynthetic centre.
authors.affiliation: Institute of Fundamental Sciences, Massey University, Private Bag 11 222, Palmerston North, 4442, New Zealand.
authors.forename: Saymore
authors.initials: S
authors.lastname: Mutsamwira
authors.affiliation: Institute of Fundamental Sciences, Massey University, Private Bag 11 222, Palmerston North, 4442, New Zealand.
authors.forename: Eric W
authors.initials: EW
authors.lastname: Ainscough
authors.affiliation: Institute of Fundamental Sciences, Massey University, Private Bag 11 222, Palmerston North, 4442, New Zealand.|Department of Physics and School of Engineering, The University of Auckland, 20 Symonds Street, Auckland, New Zealand.
authors.forename: Ashton C
authors.initials: AC
authors.lastname: Partridge
authors.affiliation: Institute of Fundamental Sciences, Massey University, Private Bag 11 222, Palmerston North, 4442, New Zealand.|Department of Physics and School of Engineering, The University of Auckland, 20 Symonds Street, Auckland, New Zealand.
authors.forename: Peter J
authors.initials: PJ
authors.lastname: Derrick
authors.affiliation: Institute of Fundamental Sciences, Massey University, Private Bag 11 222, Palmerston North, 4442, New Zealand. v.filichev@massey.ac.nz.
authors.forename: Vyacheslav V
authors.identifier: http://orcid.org/0000-0002-7383-3025
authors.initials: VV
authors.lastname: Filichev
mesh_terms: D002942:Circular Dichroism; D056831:Coordination Complexes / Q000737:chemistry*; D004247:DNA; D054856:G-Quadruplexes; D005990:Glycerol / Q000031:analogs & derivatives* / Q000737:chemistry; D008024:Ligands; D008027:Light; D008665:Metalloporphyrins / Q000737:chemistry*; D009690:Nucleic Acid Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D055668:Photochemical Processes; D010788:Photosynthesis; D011721:Pyrenes / Q000737:chemistry*; D013050:Spectrometry, Fluorescence; D013056:Spectrophotometry, Ultraviolet
chemical_list: C507245:(R)-1-O-(4-(1-pyrenylethynyl)phenylmethyl)glycerol; D056831:Coordination Complexes; D008024:Ligands; D008665:Metalloporphyrins; D009942:Organometallic Compounds; D011721:Pyrenes; C474397:ruthenium tris(2,2'-bpyridyl)(ClO4)2(H2O); C568449:zinc(II) 5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin; D004247:DNA; D005990:Glycerol
keywords: G4-DNA; energy upconversion; fluorescence; pyrene; triplet-triplet annihilation