Excited-state dynamics of isolated DNA bases: a case study of adenine.

We present a summary of recent advances in the understanding of the UV photophysics of the isolated DNA base adenine, emphasizing a discussion of the mechanisms behind the ultrafast relaxation following excitation to the pipi* band. Drawing on our femtosecond time-resolved photoelectron spectroscopy experiments, we discuss differences in the ultrafast relaxation of adenine and 9-methyladenine and consider the relative merits of the various proposed mechanisms.

Ab initio molecular dynamics and time-resolved photoelectron spectroscopy of electronically excited uracil and thymine.

The reaction dynamics of excited electronic states in nucleic acid bases is a key process in DNA photodamage. Recent ultrafast spectroscopy experiments have shown multicomponent decays of excited uracil and thymine, tentatively assigned to nonadiabatic transitions involving multiple electronic states. Using both quantum chemistry and first principles quantum molecular dynamics methods we show that a true minimum on the bright S2 electronic state is responsible for the first step that occurs on a femtosecond time scale.

Loop formation in unfolded polypeptide chains on the picoseconds to microseconds time scale.

Intrachain loop formation allows unfolded polypeptide chains to search for favorable interactions during protein folding. We applied triplet-triplet energy transfer between a xanthone moiety and naphthylalanine to directly measure loop formation in various unfolded polypeptide chains with loop regions consisting of polyserine, poly(glycine-serine) or polyproline. By combination of femtosecond and nanosecond laserflash experiments loop formation could be studied over many orders of magnitude in time from picoseconds to microseconds.

1B2(1Sigma(u)+) excited state decay dynamics in CS2.

The authors report time resolved photoelectron spectra of the (1)B(2)((1)Sigma(u) (+)) state of CS(2) at pump wavelengths in the region of 200 nm. In contrast to previous studies, the authors find that the predissociation dynamics is not well described by a single exponential decay. Biexponential modeling of the authors' data reveals a rapid decay pathway (tau<50 fs), in addition to a longer lived channel (tau approximately 350-650 fs) that displays a marked change in apparent lifetime when the polarization of the pump laser is rotated with respect to that of the probe.

Primary processes underlying the photostability of isolated DNA bases: adenine.

The UV chromophores in DNA are the nucleic bases themselves, and it is their photophysics and photochemistry that govern the intrinsic photostability of DNA. Because stability is related to the conversion of dangerous electronic to less-dangerous vibrational energy, we study ultrafast electronic relaxation processes in the DNA base adenine. We excite adenine, isolated in a molecular beam, to its pipi* state and follow its relaxation dynamics using femtosecond time-resolved photoelectron spectroscopy.

A conformational two-state peptide model system containing an ultrafast but soft light switch.

Combining an azobenzene chromophore with the bis-cysteinyl active-site sequence of the protein disulfide isomerase (PDI) we constructed a simple but promising model for allosteric conformational rearrangements. Paralleling cellular signaling events, an external trigger, here absorption of a photon, leads to a structural change in one part of the molecule, namely the azobenzene-based chromophore. The change in geometry translates to the effector site, in our case the peptide sequence, where it modifies covalent and nonbonded interactions and thus leads to a conformational rearrangement.

Ultrafast spectroscopy reveals subnanosecond peptide conformational dynamics and validates molecular dynamics simulation.

Femtosecond time-resolved spectroscopy on model peptides with built-in light switches combined with computer simulation of light-triggered motions offers an attractive integrated approach toward the understanding of peptide conformational dynamics. It was applied to monitor the light-induced relaxation dynamics occurring on subnanosecond time scales in a peptide that was backbone-cyclized with an azobenzene derivative as optical switch and spectroscopic probe. The femtosecond spectra permit the clear distinguishing and characterization of the subpicosecond photoisomerization of the chromophore, the subsequent dissipation of vibrational energy, and the subnanosecond conformational relaxation of the peptide.