Throwing light on dark states of α-oligothiophenes of chain lengths 2 to 6: radical anion photoelectron spectroscopy and excited-state theory.

In this work, we apply photodetachment photoelectron spectroscopy (PD-PES) on radical anions to access the lowest excited electronic states of neutral α-oligothiophenes nT (n = 2-6, where n denotes the number of thiophene rings) in the gas phase. Besides electron affinities, the spectra provide the energies of the T(1) and T(2) states which are otherwise difficult to investigate in neutral molecules due to spin selection rules. The assignment of the spectra is assisted by quantum chemical calculations using a combined density functional theory and multi-reference configuration interaction approach. For all α-oligothiophenes investigated in this work, the T(2) state is situated below S(1). In the gas phase, the S(1) state energies lie higher than in non-polar solution (0.2 to 0.4 eV). The geometry optimizations show that the S(0) state and especially the excited states gain planarity with increasing chain length. A non-planar structure or out-of-plane vibrational activity is needed to allow an efficient intersystem crossing (ISC) dynamics from S(1) to T(2), followed by internal conversion to T(1). Our theoretical calculations predict that in 6T a doubly excited state becomes nearly isoenergetic to S(1). This state is not observed by PD-PES, which is explained by the analysis of the calculated contributing electron configurations.

Ultrafast dynamics in thiophene investigated by femtosecond pump probe photoelectron spectroscopy and theory.

A hybrid of a time-of-flight mass spectrometer and a time-of-flight "magnetic-bottle type" photoelectron (PE) spectrometer is used for fs pump-probe investigations of the excited state dynamics of thiophene. A resonant two-photon ionization spectrum of the onset of the excited states has been recorded with a tunable UV laser of 190 fs pulse width. With the pump laser set to the first intense transition we find by UV probe ionization first a small time shift of the maxima in the PE spectrum and then a fast decay to a low constant intensity level. The fitted time constants are 80+/-10 fs, and 25+/-10 fs, respectively. Theoretical calculations show that upon geometry relaxation the electronic state order changes and conical intersections between excited states exist. We use the vertical state order S1, S2, S3 to define the terms S1, S2, and S3 for the characterization of the electron configuration of these states. On the basis of our theoretical result we discuss the electronic state order in the UV spectra and identify in the photoelectron spectrum the origin of the first cation excited state D1. The fast excited state dynamics agrees best with a vibrational dynamics in the photo-excited S1 (80+/-10 fs) and an ultrafast decay via a conical intersection, presumably a ring opening to the S3 state (25+/-10 fs). The subsequently observed weak constant signal is taken as an indication, that in the gas phase the ring-closure to S0 is slower than 50 ps. An ultrafast equilibrium between S1 and S2 before ring opening is not supported by our data.

Dissociation kinetics of peptide ions.

The dissociation of peptide ions has been found to have ultrafast components that in many ways are uniquely different from typical unimolecular kinetics. As such, some peptide reactions provide new channels, which do not conform to statistical models of reaction kinetics. When the dissociation rates are in the 100 fs range, they are in a time scale where statistical methods do not yet apply, although molecules that have not yet dissociated will later in time undergo statistical redistribution of their excess energy, which, however, may not lead to noticeable reactivity within the experimental time frames for large peptides and hence are simply dissipative. This work is meant to reconcile the long time statistical results of Lifshitz et al. (2003) with the work of Schlag et al. (1995/6) that suggests an alternate parallel and much faster time scale for dissociation. It is argued that the two sets of results and interpretations augment one another and in fact open up a most interesting new field of peptide kinetics in addition to the unimolecular behavior, which becomes de facto arrested by the shear size of the molecule being unable to find a transition state on any reasonable time scale.

Femtosecond dynamics after ionization: 2-phenylethyl-N,N-dimethylamine as a model system for nonresonant downhill charge transfer in peptides.

The cation of 2-phenylethyl-N,N-dimethylamine (PENNA) offers two local sites for the charge: the amine group and 0.7 eV higher in energy the phenyl chromophore. In this paper, we investigate the dynamics of the charge transfer (CT) from the phenyl to the amine site. We present a femtosecond resonant two-color photoionization spectrum which shows that the femtosecond pump laser pulse is resonant in the phenyl chromophore. As shown previously with resonant wavelengths the aromatic phenyl chromophore can be then selectively ionized. Because the state "charge in the phenyl chromophore" is the first excited state in the PENNA cation, it can relax to the lower-energetic state "charge in the amine site". To follow this CT dynamics, femtosecond probe photoabsorption of green light (vis) is used. The vis light is absorbed by the charged phenyl chromophore, but not by the neutral phenyl and the neutral or cationic amine group. Thus, the absorption of vis photons of the probe laser pulse is switched off by the CT process. For detection of the resonant absorption of two or more vis photons in the cation the intensity of a fragmentation channel is monitored which opens only at high internal energy. The CT dynamics in PENNA cations has a time constant of 80 +/- 28 fs and is therefore not a purely electronic process. Because of its structural similarity to phenylalanine, PENNA is a model system for a downhill charge transfer in peptide cations.

Ethnic variation in the skin irritation response.

There is a widespread, but largely unsubstantiated, view that certain skin types may be more susceptible to the effect of skin irritants than others. One expression of this would be that certain ethnic groups may also be more likely to experience skin irritation. As a consequence, when evaluating the skin compatibility of substances/preparations, these differences may need to be taken into account. However, other evidence indicates that, within any particular group, inter-individual variation is likely to be much larger than the differences between means for distinct groups. In this study, we have investigated 2 carefully matched panels of Caucasian and Japanese women volunteers to determine their topical irritant reaction, both acute and cumulative, to a range of materials. The results indicated that the acute irritant response tended to be greater in the Japanese panel and this reached statistical significance with the stronger irritants. Cumulative irritation was investigated only with the weaker irritants and, although again the trend was to a higher response in Japanese compared to Caucasian panelists, this rarely reached significance. Nevertheless, where risk assessment for skin irritation was critical, then at the population level, these differences might be relevant, both for safety in use of substances and products and for skin acceptability.

Investigation of charge localization and charge delocalization in model molecules by multiphoton ionization photoelectron spectroscopy and DFT calculations.

In this work we focus on the question to which degree a surplus charge is localized or delocalized in extended molecular systems. Molecules consisting of a flexible tail and the benzene chromophore, such as n-propylbenzene, 2-phenylethyl alcohol and 2-phenylethylamine, are used as model molecules. Their S0-S1 resonance enhanced multiphoton ionization (MPI) spectra containing origin transitions of different conformers appear at similar wavelengths. This shows, that in the neutral the electronic excitation is localized at the benzene chromophore. Geometry differences between the neutral and the cation can be qualitatively derived from intensities of vibrational transitions or the onset behavior in MPI high-resolution photoelectron (MPI-PE) spectra. We identify two possible reasons for structural changes: Charge-dipole interaction and charge delocalization. Whereas both effects can be active for the folded gauche conformers, the charge-dipole interaction is expected to be small for the extended anti conformers and geometry changes are attributed to charge delocalization. Density functional calculations of structures and energies qualitatively confirm the experimental results for all molecules and their conformers. They predict charge delocalization into the end group of below 20% for n-propylbenzene and 2-phenylethyl alcohol. In the case of 2-phenylethylamine the charge is equally shared by the near-isoenergetic charge sites of the benzene chromophore and the amine group.

Electron solvation in finite systems: femtosecond dynamics of iodide. (Water)n anion clusters

Electron solvation dynamics in photoexcited anion clusters of I-(D2O)n=4-6 and I-(H2O)4-6 were probed by using femtosecond photoelectron spectroscopy (FPES). An ultrafast pump pulse excited the anion to the cluster analog of the charge-transfer-to-solvent state seen for I- in aqueous solution. Evolution of this state was monitored by time-resolved photoelectron spectroscopy using an ultrafast probe pulse. The excited n = 4 clusters showed simple population decay, but in the n = 5 and 6 clusters the solvent molecules rearranged to stabilize and localize the excess electron, showing characteristics associated with electron solvation dynamics in bulk water. Comparison of the FPES of I-(D2O)n with I-(H2O)n indicates more rapid solvation in the H2O clusters.

Dynamical principles in biological processes.

The purpose of this paper is to propose certain dynamical principles in biological systems, which can be used to explain the effectiveness of charge transfer or excitation transfer in biological systems. Some of these systems are accessible experimentally.

Energetics of photoinduced electron transfer in the indole.O2 cluster in gas phase: possible consequences for photoexcited tryptophan in solution.

A direct process for an activationless electron transfer from photoexcited tryptophan to molecular oxygen is proposed. By photodetachment of mass-selected indole+.O2- clusters in gas phase a neutral indole+.O2- charge-separated exciplex state is found at 2.25 +/- 0.2 eV above the neutral ground state. By theory also, the existence of an excited charge separated state at 3.05 +/- 0.2 eV is postulated. In gas phase both charge-separated cluster states are energetically below the first singlet states 1Lb and 1La and the lower even below the first triplet state T1 of indole. In gas-phase clusters these energetics imply a very efficient quenching of photoexcited indole by fast electron transfer to oxygen. We discuss a similar mechanism for tryptophan.O2 in aqueous environment and find it without activation barrier and presumably extremely fast. In the collisional tryptophan*-O2 complex the efficiency and the time scale of the charge transfer process should be mostly solvent independent. In polar solvent a complete charge separation and free superoxide formation are expected. We correlate this model with previous fluorescence and phosphorescence quenching data of excited tryptophan by O2 and propose electron transfer to be the relevant process.

Antineoplastic activity of benzimidazo[1,2-b]-isoquinolines, indolo[2,3-b]quinolines, and pyridocarbazoles.

Substituted pyrido[3,4-b]carbazoles, pyrido[2,3-b]carbazoles, indolo[2,3-b]quinolines, and benzimidazo[1,2-b]-isoquinolines were synthesized and evaluated for biological activity. Several methylated derivatives of these heterocyclic compounds had similar activity to ellipticine as mammalian topoisomerase II inhibitors. Methylated derivatives of these heterocyclic compounds were also highly active in vitro, inhibiting the growth of several human tumor cell lines. These data demonstrate that the antineoplastic activity associated with ellipticine can be retained within a wide variety of analogous heterocyclics.