title: Switching on the fluorescence of 2-aminopurine by site-selective microhydration.
abstract: 2-Aminopurine (2 AP) is a fluorescent isomer of adenine and has a fluorescence lifetime of ~11 ns in water. It is widely used in biochemical settings as a site-specific fluorescent probe of DNA and RNA structure and base-flipping and -folding. These assays assume that 2 AP is intrinsically strongly fluorescent. Here, we show this not to be the case, observing that gas-phase, jet-cooled 2-aminopurine and 9-methyl-2-aminopurine have very short fluorescence lifetimes (156 ps and 210 ps, respectively); they are, to all intents and purposes, non-fluorescent. We find that the lifetime of 2-aminopurine increases dramatically when it is part of a hydrate cluster, 2 AP · (H2O)n, where n = 1-3. Not only does it depend on the presence of water molecules, it also depends on the specific hydrogen-bonding site to which they attach and on the number of H2O molecules at that site. We selectively microhydrate 2-aminopurine at its sugar-edge, cis-amino or trans-amino sites and see that its fluorescence lifetime increases by 4, 50 and 95 times (to 14.5 ns), respectively.
authors.affiliation: Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland.
authors.forename: Simon
authors.initials: S
authors.lastname: Lobsiger
authors.affiliation: Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland.
authors.forename: Susan
authors.initials: S
authors.lastname: Blaser
authors.affiliation: 1] Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland [2] Department of Atomic and Molecular Physics, Manipal University, Manipal-576104, Karnataka, India.
authors.forename: Rajeev K
authors.initials: RK
authors.lastname: Sinha
authors.affiliation: Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland.
authors.forename: Hans-Martin
authors.initials: HM
authors.lastname: Frey
authors.affiliation: Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland.
authors.forename: Samuel
authors.initials: S
authors.lastname: Leutwyler
mesh_terms: D015075:2-Aminopurine / Q000737:chemistry*; D005740:Gases / Q000737:chemistry; D006860:Hydrogen Bonding; D007477:Ions / Q000737:chemistry; D007536:Isomerism; D011789:Quantum Theory; D013050:Spectrometry, Fluorescence; D013997:Time Factors; D014867:Water / Q000737:chemistry
chemical_list: D005740:Gases; D007477:Ions; D014867:Water; D015075:2-Aminopurine