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New regime of anomalous penetration of relativistically strong laser radiation into an overdense plasma

It is shown that penetration of relativistically intense laser light into an overdense plasma, accessible by self-induced transparency, occurs over a finite length only. The penetration length depends crucially on the overdense plasma parameter and increases with increasing incident intensity after exceeding the threshold for self-induced transparency. Exact analytical solutions describing the plasma-field distributions are presented.     

Insight into the catalytic mechanism of vanadium haloperoxidases. DFT investigation of vanadium cofactor reactivity

Density functional theory (DFT) has been used to investigate the catalytic properties of the isolated vanadium cofactor found in vanadium haloperoxidases, with a particular emphasis on the steps going from the resting form of the cofactor to the peroxo complex. Computation of transition states, intermediate species, and UV-vis spectra, as well as comparison of reaction energies, demonstrated the important role of protonation in cofactor activation. This illustrates that the resting form of the vanadium cofactor reacts with hydrogen peroxide according to a mechanism that implies formation of an aqua complex, release of the apical water molecule according to a dissociative pathway, and binding of hydrogen peroxide to vanadium. This process leads to a side-on peroxo species corresponding to the peroxo form observed in the enzyme. In addition, it appears that an acid-base catalysts strongly accelerates the conversion to the side-on peroxo form. The comparison of computed and experimental UV-vis spectra corroborated the proposed reaction pathway and allowed us to explain the effects of the vanadium ligands on the electronic properties of the cofactor.     

Pressure broadening of the NH3 pure rotation line (JI = 0 → JF = 1) perturbed by inert gases (He,Ne, Ar,Kr)

We have calculated the linewidths of the NH₃ pure rotation line (J_I = 0 → J_F = 1) perturbed by inert gases (He, Ne, Ar, Kr) using a convergent impact theory. We have taken into account the dipole-induced dipole, quadrupole-induced dipole and dispersion terms of Krishnaji and Prakash and the dispersion term of Tipping and Herman. Our theoretical results and those obtained with the Anderson and Tsao and Curnette theory are compared with experimental results.     

Probing the effects of one-electron reduction and protonation on the electronic properties of the Fe-S clusters in the active-ready form of [FeFe]-hydrogenases. A QM/MM investigation

A QM/MM investigation of the active-ready (H(ox)) form of [FeFe]-hydrogenase from D. desulfuricans, in which the electronic properties of all Fe-S clusters (H, F and F') have been simultaneously described using DFT, was carried out with the aim of disclosing a possible interplay between the H-cluster and the accessory iron-sulfur clusters in the initial steps of the catalytic process leading to H(2) formation. It turned out that one-electron addition to the active-ready form leads to reduction of the F'-cluster and not of the H-cluster. Protonation of the H-cluster in H(ox) is unlikely, and in any case it would not trigger electron transfer from the accessory Fe(4)S(4) clusters to the active site. Instead, one-electron reduction and protonation of the active-ready form trigger electron transfer within the protein, a key event in the catalytic cycle. In particular, protonation of the H-cluster after one-electron reduction of the enzyme lowers the energy of the lowest unoccupied molecular orbitals localized on the H-cluster to such an extent that a long-range electron transfer from the F'-cluster towards the H-cluster itself is allowed.