Time-resolved photoelectron spectroscopy of adenine and adenosine in aqueous solution

Buchner, Franziska; Ritze, H.‐H.; Lahl, Jan; Lübcke, A.

doi:10.1039/c3cp51057c

Cited by 44 publications

(77 citation statements)

References 41 publications

(71 reference statements)

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“…EDHE pathways can be enhanced through a suppression of the adiabatic ionization potential (IP) in H2O, 34 which recent experiments and calculations suggest is reduced by ~1 eV relative to the gas phase. [51][52][53] Related EDHE behavior has been observed for aqueous 2-aminopurine (a structural isomer of Ade), albeit initiated through two-photon absorption at 266 nm. 54 Herein, we present new TEAS and transient vibrational absorption spectroscopy (TVAS) studies, which aim to reveal whether N-H bond fission (mediated by the 1 πσ* state) is active in aqueous Ade after photoexcitation at 266 nm and 220 nm.…”

Section: Introductionmentioning

confidence: 89%

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On the Participation of Photoinduced N–H Bond Fission in Aqueous Adenine at 266 and 220 nm: A Combined Ultrafast Transient Electronic and Vibrational Absorption Spectroscopy Study

et al. 2014

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Section: Introductionmentioning

confidence: 89%

“…Considering the latter pathway, it is noteworthy that recent high-level theory 51 and experiment 52,53 show that Ade's IP is only suppressed to 7.5 eV in water (cf. 8.48 eV in the gas phase 85,86 …”

Section: B Transient Vibrational Absorption Of Deprotonated Adenine mentioning

confidence: 99%

On the Participation of Photoinduced N–H Bond Fission in Aqueous Adenine at 266 and 220 nm: A Combined Ultrafast Transient Electronic and Vibrational Absorption Spectroscopy Study

et al. 2014

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“…In the case of adenine, there is agreement that the biexponential decay components of ca. 0.2 ps and 8.4 ps in aqueous solution should be assigned to the decay of the singlet state in the N9H and N7H tautomers, respectively [73,88,132,133]. Transient absorption experiments show that these lifetimes are solventdependent, increasing to ca.…”

Section: Time-resolved Photophysical Properties Of the Nucleic Acid Mmentioning

confidence: 97%

Photochemistry of Nucleic Acid Bases and Their Thio- and Aza-Analogues in Solution

Pollum

Martínez‐Fernández

Crespo‐Hernández

2014

Topics in Current Chemistry

108

200

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The steady-state and time-resolved photochemistry of the natural nucleic acid bases and their sulfur- and nitrogen-substituted analogues in solution is reviewed. Emphasis is given to the experimental studies performed over the last 3-5 years that showcase topical areas of scientific inquiry and those that require further scrutiny. Significant progress has been made toward mapping the radiative and nonradiative decay pathways of nucleic acid bases. There is a consensus that ultrafast internal conversion to the ground state is the primary relaxation pathway in the nucleic acid bases, whereas the mechanism of this relaxation and the level of participation of the (1)πσ*, (1) nπ*, and (3)ππ* states are still matters of debate. Although impressive research has been performed in recent years, the microscopic mechanism(s) by which the nucleic acid bases dissipate excess vibrational energy to their environment, and the role of the N-glycosidic group in this and in other nonradiative decay pathways, are still poorly understood. The simple replacement of a single atom in a nucleobase with a sulfur or nitrogen atom severely restricts access to the conical intersections responsible for the intrinsic internal conversion pathways to the ground state in the nucleic acid bases. It also enhances access to ultrafast and efficient inter-system crossing pathways that populate the triplet manifold in yields close to unity. Determining the coupled nuclear and electronic pathways responsible for the significantly different photochemistry in these nucleic acid base analogues serves as a convenient platform to examine the current state of knowledge regarding the photodynamic properties of the DNA and RNA bases from both experimental and computational perspectives. Further investigations should also aid in forecasting the prospective use of sulfur- and nitrogen-substituted base analogues in photochemotherapeutic applications.

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“…33 The dynamics of dAMP -have been measured by transient absorption and fluorescence upconversion in aqueous solution by a number of groups, 2,3,32 and recently time-resolved photoelectron spectroscopy of solvated adenosine has been reported. 35 The most recent solutionphase measurements reported a biexponential decay with lifetimes of the slower (i = 2) component as τ 2 = 340 fs for dAMP -(following excitation at 260 nm). 32 Given the differences in environments 8 and experimental techniques, the agreement of this timescale with our results is remarkable.…”

mentioning

confidence: 99%

Mapping the Ultrafast Dynamics of Adenine onto Its Nucleotide and Oligonucleotides by Time-Resolved Photoelectron Imaging

Chatterley

West

Roberts

et al. 2014

J. Phys. Chem. Lett.

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Publisher's copyright statement:This document is the Accepted Manuscript version of a Published Work that appeared in nal form in The Journal of Physical Chemistry Letters, copyright c American Chemical Society after peer review and technical editing by the publisher. To access the nal edited and published work see http://pubs.acs.org/doi/abs/10.1021/jz500264c. Additional information:Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. AbstractThe intrinsic photo-physics of nucleobases and nucleotides following UV absorption presents a key reductionist step towards understanding the complex photo-damage mechanisms occurring in DNA. Adenine in particular has been the focus of intense investigation, where there has been a long-standing uncertainty about the mechanism and how the dynamics of adenine correlate to those of its more biologically relevant nucleotide and oligonucleotides in aqueous solution. Here we report on time-resolved photoelectron imaging of the deprotonated 3'-deoxyadenosine-5'-monophosphate nucleotide and the adenosine di-and tri-nucleotides. Through a comparison of gas and solution phase experiments and available theoretical studies, we show that the dynamics of the base are insensitive to the surrounding environment and that the decay of the adenine base within a nucleotide probably involves internal conversion from the initially populated 1 ππ* states. This is in agreement with some recent theoretical studies. The relaxation dynamics of the adenosine oligonucleotides are very similar to those of the nucleobase, in contrast to the aqueous the oligonucleotides, where a fraction of the ensemble forms long-lived excimer states that are delocalised over two bases. 3The absorption of ultraviolet (UV) radiation by DNA can lead to biological damage including strand breaks and mutations that can ultimately lead to photolesions, transcription errors and cancer. 1 Despite the efficient UV absorption, mediated by the optically bright 1 ππ* states localised on the four DNA nucleobases, the photodamage quantum yield in DNA is low (<1%). 2,3 This photostability is governed by the non-radiative decay mechanisms that enable the nucleobases to assimilate and dispose of the potentially harmful electronic energy in a non-destructive fashion.Gaining a molecular level understanding of these processes has been a long-standing goal, not only because of its role in radiation damage of DNA, but also to assess why nature has evolved using such a select number of molecular building blocks to define the genetic code. 4 Much of the expe...

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Time-resolved photoelectron spectroscopy of adenine and adenosine in aqueous solution

Cited by 44 publications

References 41 publications

On the Participation of Photoinduced N–H Bond Fission in Aqueous Adenine at 266 and 220 nm: A Combined Ultrafast Transient Electronic and Vibrational Absorption Spectroscopy Study

On the Participation of Photoinduced N–H Bond Fission in Aqueous Adenine at 266 and 220 nm: A Combined Ultrafast Transient Electronic and Vibrational Absorption Spectroscopy Study

Photochemistry of Nucleic Acid Bases and Their Thio- and Aza-Analogues in Solution

Mapping the Ultrafast Dynamics of Adenine onto Its Nucleotide and Oligonucleotides by Time-Resolved Photoelectron Imaging

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