Radical Stabilization Energies for Enzyme Engineering: Tackling the Substrate Scope of the Radical Enzyme QueE.

Experimental assessment of catalytic reaction mechanisms and profiles of radical enzymes can be severely challenging due to the reactive nature of the intermediates and sensitivity of cofactors such as iron-sulfur clusters. Here, we present an enzyme-directed computational methodology for the assessment of thermodynamic reaction profiles and screening for radical stabilization energies (RSEs) for the assessment of catalytic turnovers in radical enzymes. We have applied this new screening method to the radical -adenosylmethione enzyme 7-carboxy-7-deazaguanine synthase (QueE), following a detailed molecular dynamics (MD) analysis that clarifies the role of both specific enzyme residues and bound Mg, Ca, or Na.

Quantum chemical calculations of tryptophan → heme electron and excitation energy transfer rates in myoglobin.

The development of optical multidimensional spectroscopic techniques has opened up new possibilities for the study of biological processes. Recently, ultrafast two-dimensional ultraviolet spectroscopy experiments have determined the rates of tryptophan → heme electron transfer and excitation energy transfer for the two tryptophan residues in myoglobin (Consani et al., Science, 2013, 339, 1586).

Idiopathic (unexplained) pulmonary embolism is associated with an impaired prognosis compared to other entities of pulmonary embolism.

In patients following acute pulmonary embolism, little is known about long-term prognosis attributed to individual risk factors and entities of pulmonary embolism. The aim of our study was to identify predictors of long-term mortality and morbidity, taking into account precipitating causes and entities of pulmonary embolism, especially in cases of idiopathic pulmonary embolism. We reviewed the records of 257 consecutive patients presenting with acute pulmonary embolism in the emergency room of the University Hospital in Frankfurt between 1997 and 2006.

Rostro-caudal gradual loss of cellular diversity within the periventricular regions of the ventricular system.

Neurogenesis occurs constitutively within the periventricular region (PVR) of the lateral ventricles (LV) of the adult mammalian brain. The occurrence of adult neurogenesis within the PVR outside the neurogenic niche of the LV remains controversial, but neural stem cells can be isolated from PVR of the whole ventricular system. The histological basis of this phenomenon including the regional differences of cellular phenotypes within the PVRs is still enigmatic.

Incidence, clinical characteristics, and long-term prognosis of travel-associated pulmonary embolism.

Aims: Prolonged air travel is considered a risk factor for pulmonary embolism (PE). The clinical characteristics as well as the long-term prognosis of patients suffering from travel-associated PE ('economy-class syndrome', ECS) remain largely unknown. Owing to its proximity, our hospital is the primary referral centre for Frankfurt Airport, Europe's third-largest airport.

Lithium intercalation of phenyl-capped aniline dimers: a study by photoelectron spectroscopy and quantum chemical calculations.

Structural and electronic properties of pristine and lithium-intercalated, phenyl-capped aniline dimers as a model for the lithium-polyaniline system have been studied by photoelectron spectroscopy and quantum chemical calculations. It was found that the electronic structure of reduced and oxidized forms of oligoanilines is only weakly affected by isomerism. Upon intercalation, charge transfer from the Li-atoms is remarkable and highly localized at N-atomic sites, where configurations are energetically favored in which both N atoms of the dimers are bound to Li atoms.

Vibronic coupling in the ground and excited states of oligoacene cations.

The vibrational coupling in the ground and excited states of positively charged naphthalene, anthracene, tetracene, and pentacene molecules is studied on the basis of a joint experimental and theoretical study of ionization spectra using high-resolution gas-phase photoelectron spectroscopy and first-principles correlated quantum-mechanical calculations. Our theoretical and experimental results reveal that, while the main contribution to relaxation energy in the ground state of oligoacene systems comes from high-energy vibrations, the excited-state relaxation energies show a significant redistribution toward lower-frequency vibrations. A direct correlation is found between the nature of the vibronic interaction and the pattern of the electronic state structure.

Vibronic coupling in the ground and excited states of the naphthalene cation.

The hole-vibrational coupling in naphthalene is studied using high-resolution gas-phase photoelectron spectroscopy and density functional theory calculations (DFT), and a remarkable increase of the coupling with low-frequency vibrations is observed in the excited states.