@article{DoscheKumkeLoehmannsroebenetal.2004, author = {Dosche, Carsten and Kumke, Michael Uwe and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Ariese, Freek and Bader, Arjen N. and Gooijer, Cees and Miljanic, Ognjen S. and Iwamoto, M. and Vollhardt, K. Peter C. and Puchta, Ralph and Hommes, N. J. R. V.}, title = {Deuteration effects on the vibronic structure of the fluorescence spectra and the internal conversion rates of triangular [4]phenylene}, issn = {1463-9076}, year = {2004}, abstract = {Deuteration effects on the vibronic structure of the emission and excitation spectra of triangular [ 4] phenylene (D-3h [4]phenylene) were studied using laser-excited Shpol'skii spectroscopy (LESS) in an octane matrix at 4.2 K. For correct assignment of the vibrational modes, the experimental results were compared with calculated frequencies (B3LYP/6-31G*). CH vibrations were identified by their characteristic isotopic shifts in the spectra of deuterated triangular [4]phenylenes. Two CC stretching modes, at 100 cm(-1) and 1176 cm(-1), suitable as probes for bond strength changes in the excited state, were identified. The isotope effect on the internal conversion rates of triangular [4] phenylene was evaluated from measurements of temperature dependent lifetime. Isotope dependency and the magnitude of the internal conversion rates indicate that internal conversion in triangular [4] phenylene is most likely induced by CH vibrations. The results obtained by LESS and lifetime measurements were compared with PM3 PECI calculations of the excited state structure. The theoretical results and the relation between ground and excited state vibration energies of the 1176 cm(-1) probe vibration indicate a reduction of bond alternation of the central cyclohexatriene ring in the excited state}, language = {en} } @misc{DoscheKumkeLoehmannsroebenetal.2004, author = {Dosche, Carsten and Kumke, Michael Uwe and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Ariese, F. and Bader, Arjen N. and Gooijer, C. and Miljanic, O. S. and Iwamoto, M. and Vollhardt, K. Peter C. and Puchta, R. ; van Eikema Hommes, N. J. R.}, title = {Deuteration effects on the vibronic structure of the fluorescence spectra and the internal conversion rates of triangular [4]Phenylene}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-11881}, year = {2004}, abstract = {Deuteration effects on the vibronic structure of the emission and excitation spectra of triangular [4]phenylene (D3h[4]phenylene) were studied using laser-excited Shpolskii spectroscopy (LESS) in an octane matrix at 4.2 K. For correct assignment of the vibrational modes, the experimental results were compared with calculated frequencies (B3LYP/6-31G*). CH vibrations were identified by their characteristic isotopic shifts in the spectra of deuterated triangular [4]phenylenes. Two CC stretching modes, at 100 cm-1 and 1176 cm-1, suitable as probes for bond strength changes in the excited state, were identified. The isotope effect on the internal conversion rates of triangular [4]phenylene was evaluated from measurements of temperature dependent lifetime. Isotope dependency and the magnitude of the internal conversion rates indicate that internal conversion in triangular [4]phenylene is most likely induced by CH vibrations. The results obtained by LESS and lifetime measurements were compared with PM3 PECI calculations of the excited state structure. The theoretical results and the relation between ground and excited state vibration energies of the 1176 cm-1 probe vibration indicate a reduction of bond alternation of the central cyclohexatriene ring in the excited state.}, language = {de} } @misc{DoscheLoehmannsroebenBieseretal.2002, author = {Dosche, Carsten and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Bieser, A. and Dosa, P. I. and Han, S. and Iwamoto, M. and Schleifenbaum, A. and Vollhardt, K. Peter C.}, title = {Photophysical properties of [N]phenylenes}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-11936}, year = {2002}, abstract = {In the present study, photophysical properties of [N]phenylenes were studied by means of stationary and time-resolved absorption and fluorescence spectroscopy (in THF at room temperature). For biphenylene (1) and linear [3]phenylene (2a), internal conversion (IC) with quantum yields ΦIC > 0.99 is by far the dominant mechanism of S1 state deactivation. Angular [3]phenylene (3a), the zig-zag [4]- and [5]phenylenes (3b), (3c), and the triangular [4]phenylene (4) show fluorescence emission with fluorescence quantum yieds and lifetimes between ΦF = 0.07 for (3a) and 0.21 for (3c) and τF = 20 ns for (3a) and 81 ns for (4). Also, compounds (3) and (4) exhibit triplet formation upon photoexcitation with quantum yields as high as ΦISC = 0.45 for (3c). The strong differences in the fluorescence properties and in the triplet fromation efficiencies between (1) and (2a) on one hand and (3) and (4) on the other are related to the remarkable variation of the internal conversion (IC) rate constants kIC. A tentative classification of (1) and (2a) as "fast IC compounds", with kIC > 109 s-1, and of (3) and (4) as "slow IC compounds", with kIC ≈ 107 s-1, is suggested. This classification cannot simply be related to H{\"u}ckel's rule-type concepts of aromaticity, because the group of "fast IC compounds" consists of "antiaromatic" (1) and "aromatic" (2a), and the group of "slow IC compounds" consists of "antiaromatic" (3b), (4) and "aromatic" (3a), (3c). The IC in the [N]phenylenes is discussed within the framework of the so-called energy gap law established for non-radiative processes in benzenoid hydrocarbons.}, language = {en} } @misc{DoscheMicklerLoehmannsroebenetal.2007, author = {Dosche, Carsten and Mickler, Wulfhard and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Agenet, Nicolas and Vollhardt, K. Peter C.}, title = {Photoinduced electron transfer in [N]phenylenes}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-12463}, year = {2007}, abstract = {First studies of electron transfer in [N]phenylenes were performed in bimolecular quenching reactions of angular [3]- and triangular [4]phenylene with various electron acceptors. The relation between the quenching rate constants kq and the free energy change of the electron transfer (ΔG0CS ) could be described by the Rehm-Weller equation. From the experimental results, a reorganization energy λ of 0.7 eV was derived. Intramolecular electron transfer reactions were studied in an [N]phenylene bichomophore and a corresponding reference compound. Fluorescence lifetime and quantum yield of the bichromophor display a characteristic dependence on the solvent polarity, whereas the corresponding values of the reference compound remain constant. From the results, a nearly isoenergonic ΔG0CS can be determined. As the triplet quantum yield is nearly independent of the polarity, charge recombination leads to the population of the triplet state.}, language = {en} } @article{HilleLahnLoehmannsroebenetal.2009, author = {Hille, Carsten and Lahn, Mattes and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Dosche, Carsten}, title = {Two-photon fluorescence lifetime imaging of intracellular chloride in cockroach salivary glands}, issn = {1474-905X}, doi = {10.1039/B813797H}, year = {2009}, language = {en} } @article{MareljaChowdhuryDoscheetal.2013, author = {Marelja, Zvonimir and Chowdhury, Mita Mullick and Dosche, Carsten and Hille, Carsten and Baumann, Otto and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Leimk{\"u}hler, Silke}, title = {The L-cysteine desulfurase NFS1 is localized in the cytosol where it provides the sulfur for molybdenum cofactor biosynthesis in humans}, series = {PLoS one}, volume = {8}, journal = {PLoS one}, number = {4}, publisher = {PLoS}, address = {San Fransisco}, issn = {1932-6203}, doi = {10.1371/journal.pone.0060869}, pages = {13}, year = {2013}, abstract = {In humans, the L-cysteine desulfurase NFS1 plays a crucial role in the mitochondrial iron-sulfur cluster biosynthesis and in the thiomodification of mitochondrial and cytosolic tRNAs. We have previously demonstrated that purified NFS1 is able to transfer sulfur to the C-terminal domain of MOCS3, a cytosolic protein involved in molybdenum cofactor biosynthesis and tRNA thiolation. However, no direct evidence existed so far for the interaction of NFS1 and MOCS3 in the cytosol of human cells. Here, we present direct data to show the interaction of NFS1 and MOCS3 in the cytosol of human cells using Forster resonance energy transfer and a split-EGFP system. The colocalization of NFS1 and MOCS3 in the cytosol was confirmed by immunodetection of fractionated cells and localization studies using confocal fluorescence microscopy. Purified NFS1 was used to reconstitute the lacking molybdoenzyme activity of the Neurospora crassa nit-1 mutant, giving additional evidence that NFS1 is the sulfur donor for Moco biosynthesis in eukaryotes in general.}, language = {en} } @article{DoscheLoehmannsroebenBieseretal.2002, author = {Dosche, Carsten and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Bieser, A. and Dosa, P. I. and Han, S. and Iwamoto, M. and Schleifenbaum, A. and Vollhardt, K. Peter C.}, title = {Photophysical properties of [N]phenylenes}, year = {2002}, language = {en} } @article{DoscheMicklerLoehmannsroebenetal.2007, author = {Dosche, Carsten and Mickler, Wulfhard and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Agenet, Nicolas and Vollhardt, K. Peter C.}, title = {Photoinduced electron transfer in [N]phenylenes}, issn = {1010-6030}, doi = {10.1016/j.jphotochem.2006.12.038}, year = {2007}, abstract = {First studies of electron transfer in [N]phenylenes were performed in bimolecular quenching reactions of angular [3]- and triangular [4]phenylene with various electron acceptors. The relation between the quenching rate constants k(q) and the free energy change of the electron transfer (Delta G(CS)(0)) could be described by the Rehm- Weller equation. From the experimental results, a reorganization energy lambda of 0.7 eV was derived. Intramolecular electron transfer reactions were studied in an [N]phenylene bichomophore and a corresponding reference compound. Fluorescence lifetime and quantum yield of the bichromophor display a characteristic dependence on the solvent polarity, whereas the corresponding values of the reference compound remain constant. From the results, a nearly isoenergonic charge separation process can be determined. As the triplet quantum yield is nearly independent of the polarity, charge recombination leads to the population of the triplet state.}, language = {en} } @article{KumkeDoscheFlehretal.2006, author = {Kumke, Michael Uwe and Dosche, Carsten and Flehr, Roman and Trowitzsch-Kienast, Wolfram and L{\"o}hmannsr{\"o}ben, Hans-Gerd}, title = {Spectroscopic characterization of the artificial siderophore pyridinochelin}, issn = {0939-5075}, year = {2006}, language = {en} } @article{RiebeZuehlkeZenichowskietal.2011, author = {Riebe, Daniel and Z{\"u}hlke, Martin and Zenichowski, Karl and Beitz, Toralf and Dosche, Carsten and L{\"o}hmannsr{\"o}ben, Hans-Gerd}, title = {Characterization of rhodamine 6G release in electrospray ionization by means of spatially resolved fluorescence spectroscopy}, series = {Zeitschrift f{\"u}r physikalische Chemie : international journal of research in physical chemistry and chemical physics}, volume = {225}, journal = {Zeitschrift f{\"u}r physikalische Chemie : international journal of research in physical chemistry and chemical physics}, number = {9-10}, publisher = {De Gruyter Oldenbourg}, address = {M{\"u}nchen}, issn = {0942-9352}, doi = {10.1524/zpch.2011.0149}, pages = {1055 -- 1072}, year = {2011}, abstract = {In the present work, the density distribution of rhodamine 6G ions (R6G) in the gas phase and the droplets of an electrospray plume was studied by spatial and spectral imaging. The intention is to contribute to the fundamental understanding of the release mechanism of gaseous R6G in the electrospray ionization (ESI) process. Furthermore, the influence of ESI-parameters on the release efficiency of R6G, e. g. solvent flow, R6G and salt concentration were examined via direct fluorescence imaging of R6G. A solvent-shift of the fluorescence maximum,lambda(max) = 555 nm in methanolic solution and lambda(max) = 505 nm in gas phase, allows the discrimination between solvated and gaseous R6G. Two experimental setups were used for our measurements. In the first experiment, the R6G fluorescence and the light scattered from the spray plume were imaged in two spatial dimensions using a tunable wavelength filter. The second experiment was designed for obtaining 1-dimensional spatially resolved emission spectra of the spray. Here, the intensity distribution of solvated and gaseous R6G as well as scattered light (lambda = 355 nm) were measured simultaneously. The results show the distribution of gaseous R6G in the plane, orthogonal to the ESI capillary, decreasing slightly towards the spray center and showing maxima at the cone margins. The distribution of gaseous R6G confirms the preferred release of gaseous ions from nano-droplets, indicating the ion evaporation model (IEM) to be the dominating release mechanism. Up to now, only a few fluorescence spectra of ionic compounds in the gas phase were published because the measurement of emission spectra of mass-selected ions in an ion trap is experimentally challenging. The fluorescence spectrum of gaseous lucigenin at atmospheric pressure is reported for the first time. This spectrum of lucigenin in the gas phase exhibits a blue shift of about Delta lambda = 10 nm in comparison to the corresponding spectrum in methanol.}, language = {en} }