The structure of adenine monohydrates studied by femtosecond multiphoton ionization detected IR spectroscopy and quantum chemical calculations

Nosenko, Yevgeniy; Kunitski, Maksim; Riehn, Christoph; Harbach, Philipp H. P.; Dreuw, Andreas; Brutschy, Bernhard

doi:10.1039/b914236c

Cited by 23 publications

(35 citation statements)

References 55 publications

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“…The resulting loss of conformational selectivity of the excitation step caused by the large spectral linewidth must be compensated for by additional diagnostics. Coupling of ns-IR excitation with femtosecond detection is a way to fix the issue: this has been done on DNA bases, their hydrates [213] or on water dimer and complexes of flexible systems [214]. However, in addition to the selective ns-IR excitation, distinguishing several conformers also requires a selective detection.…”

Section: Photophysics Of Aromatic Residues In Model Peptidesmentioning

confidence: 99%

Isolated Neutral Peptides

Gloaguen

Mons

2014

Topics in Current Chemistry

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This chapter examines the structural characterisation of isolated neutral amino-acids and peptides. After a presentation of the experimental and theoretical state-of-the-art in the field, a review of the major structures and shaping interactions is presented. Special focus is made on conformationally-resolved studies which enable one to go beyond simple structural characterisation; probing flexibility and excited-state photophysics are given as examples of promising future directions.

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Section: Photophysics Of Aromatic Residues In Model Peptidesmentioning

confidence: 99%

Isolated Neutral Peptides

Gloaguen

Mons

2014

Topics in Current Chemistry

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“…Furthermore, even if the triplet state is populated in the adenine and The participation of πσ* states in the excited-state dynamics of the monomers is a matter of intense debate [1,4,6,7,81,88,111,[145][146][147][148][149]. The population of 1 πσ* states has been proposed to play a role in the excited-state dynamics of adenine and guanine monomers in solution, particularly at high excitation energies [81,88,[145][146][147]. A recent study by Cheng and co-workers [81] continues to add fuel to this discussion.…”

Section: Adenine and Guanine Monomersmentioning

confidence: 99%

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

Pollum

Martínez‐Fernández

Crespo‐Hernández

2014

Topics in Current Chemistry

111

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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“…And the mechanisms regarding photostability of DNA vary significantly upon hydration. For molecular level understanding, gas-phase infrared spectroscopic study of hydrated biomolecules is highly powerful as it provides information on the hydration sites, structure of relevant clusters, binding energies, vibrational frequencies, and spectral shift of electronic states [29][30][31][32][33][34]. Nonetheless, experimental results on the structures of microhydrated nucleobases are rather limited.…”

Section: Introductionmentioning

confidence: 98%