@article{KlaumuenzerKroenerLischkaetal.2012,
  author    = {Klaum{\"u}nzer, Bastian and Kr{\"o}ner, Dominik and Lischka, Hans and Saalfrank, Peter},
  title     = {Non-adiabatic excited state dynamics of riboflavin after photoexcitation},
  series = {Physical chemistry, chemical physics : a journal of European Chemical Societies},
  volume    = {14},
  journal   = {Physical chemistry, chemical physics : a journal of European Chemical Societies},
  number    = {24},
  publisher = {Royal Society of Chemistry},
  address   = {Cambridge},
  issn      = {1463-9076},
  doi       = {10.1039/c2cp40978j},
  pages     = {8693 -- 8702},
  year      = {2012},
  abstract  = {Flavins are chromophores in light-gated enzymes and therefore central in many photobiological processes. To unravel the optical excitation process as the initial, elementary step towards signal transduction, detailed ultrafast (femtosecond) experiments probing the photo-activation of flavins have been carried out recently [Weigel et al., J. Phys. Chem. B, 2011, 115, 3656-3680.]. The present paper contributes to a further understanding and interpretation of these experiments by studying the post-excitation vibrational dynamics of riboflavin (RF) and microsolvated riboflavin, RF center dot 4H(2)O, using first principles non-adiabatic molecular dynamics. By analyzing the characteristic atom motions and calculating time-resolved stimulated emission spectra following pi pi* excitation, it is found that after optical excitation C-N and C-C vibrations in the isoalloxazine rings of riboflavin set in. The Franck-Condon (vertically excited) state decays within about 10 fs, in agreement with experiment. Anharmonic coupling leads to Intramolecular Vibrational energy Redistribution (IVR) on the timescale of about 80-100 fs, first to (other) C-C stretching modes of the isoalloxazine rings, then by energy spread over the whole molecule, including low-frequency in-plane modes. The IVR is accompanied by a red-shift and broadening of the emission spectrum. When RF is microsolvated with four water molecules, an overall redshift of optical spectra by about 20 nm is observed but the relaxation dynamics is only slightly affected. For several trajectories, a tendency for hydrogen transfer from water to flavin-nitrogen (N-5) was found.},
  language  = {en}
}
@article{SpillingSchulzPauletal.2016,
  author    = {Spilling, Kristian and Schulz, Kai G. and Paul, Allanah J. and Boxhammer, Tim and Achterberg, Eric Pieter and Hornick, Thomas and Lischka, Silke and Stuhr, Annegret and Bermudez, Rafael and Czerny, Jan and Crawfurd, Kate and Brussaard, Corina P. D. and Grossart, Hans-Peter and Riebesell, Ulf},
  title     = {Effects of ocean acidification on pelagic carbon fluxes in a mesocosm experiment},
  series = {Biogeosciences},
  volume    = {13},
  journal   = {Biogeosciences},
  publisher = {Copernicus},
  address   = {G{\"o}ttingen},
  issn      = {1726-4170},
  doi       = {10.5194/bg-13-6081-2016},
  pages     = {6081 -- 6093},
  year      = {2016},
  abstract  = {About a quarter of anthropogenic CO2 emissions are currently taken up by the oceans, decreasing seawater pH. We performed a mesocosm experiment in the Baltic Sea in order to investigate the consequences of increasing CO2 levels on pelagic carbon fluxes. A gradient of different CO2 scenarios, ranging from ambient (similar to 370 mu atm) to high (similar to 1200 mu atm), were set up in mesocosm bags (similar to 55m(3)). We determined standing stocks and temporal changes of total particulate carbon (TPC), dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), and particulate organic carbon (POC) of specific plankton groups. We also measured carbon flux via CO2 exchange with the atmosphere and sedimentation (export), and biological rate measurements of primary production, bacterial production, and total respiration. The experiment lasted for 44 days and was divided into three different phases (I: t0-t16; II: t17-t30; III: t31-t43). Pools of TPC, DOC, and DIC were approximately 420, 7200, and 25 200 mmol Cm-2 at the start of the experiment, and the initial CO2 additions increased the DIC pool by similar to 7\% in the highest CO2 treatment. Overall, there was a decrease in TPC and increase of DOC over the course of the experiment. The decrease in TPC was lower, and increase in DOC higher, in treatments with added CO2. During phase I the estimated gross primary production (GPP) was similar to 100 mmol C m(-2) day(-1), from which 75-95\% was respired, similar to 1\% ended up in the TPC (including export), and 5-25\% was added to the DOC pool. During phase II, the respiration loss increased to similar to 100\% of GPP at the ambient CO2 concentration, whereas respiration was lower (85-95\% of GPP) in the highest CO2 treatment. Bacterial production was similar to 30\% lower, on average, at the highest CO2 concentration than in the controls during phases II and III. This resulted in a higher accumulation of DOC and lower reduction in the TPC pool in the elevated CO2 treatments at the end of phase II extending throughout phase III. The "extra" organic carbon at high CO2 remained fixed in an increasing biomass of small-sized plankton and in the DOC pool, and did not transfer into large, sinking aggregates. Our results revealed a clear effect of increasing CO2 on the carbon budget and mineralization, in particular under nutrient limited conditions. Lower carbon loss processes (respiration and bacterial remineralization) at elevated CO2 levels resulted in higher TPC and DOC pools than ambient CO2 concentration. These results highlight the importance of addressing not only net changes in carbon standing stocks but also carbon fluxes and budgets to better disentangle the effects of ocean acidification.},
  language  = {en}
}
@misc{SpillingSchulzPauletal.2016,
  author    = {Spilling, Kristian and Schulz, Kai Georg and Paul, Allanah J. and Boxhammer, Tim and Achterberg, Eric Pieter and Hornick, Thomas and Lischka, Silke and Stuhr, Annegret and Berm{\´u}dez, Rafael and Czerny, Jan and Crawfurd, Kate and Brussaard, Corina P. D. and Grossart, Hans-Peter and Riebesell, Ulf},
  title     = {Effects of ocean acidification on pelagic carbon fluxes in a mesocosm experiment},
  series = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  journal   = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  number    = {544},
  issn      = {1866-8372},
  doi       = {10.25932/publishup-41183},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-411835},
  pages     = {13},
  year      = {2016},
  abstract  = {About a quarter of anthropogenic CO2 emissions are currently taken up by the oceans, decreasing seawater pH. We performed a mesocosm experiment in the Baltic Sea in order to investigate the consequences of increasing CO2 levels on pelagic carbon fluxes. A gradient of different CO2 scenarios, ranging from ambient (similar to 370 mu atm) to high (similar to 1200 mu atm), were set up in mesocosm bags (similar to 55m(3)). We determined standing stocks and temporal changes of total particulate carbon (TPC), dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), and particulate organic carbon (POC) of specific plankton groups. We also measured carbon flux via CO2 exchange with the atmosphere and sedimentation (export), and biological rate measurements of primary production, bacterial production, and total respiration. The experiment lasted for 44 days and was divided into three different phases (I: t0-t16; II: t17-t30; III: t31-t43). Pools of TPC, DOC, and DIC were approximately 420, 7200, and 25 200 mmol Cm-2 at the start of the experiment, and the initial CO2 additions increased the DIC pool by similar to 7\% in the highest CO2 treatment. Overall, there was a decrease in TPC and increase of DOC over the course of the experiment. The decrease in TPC was lower, and increase in DOC higher, in treatments with added CO2. During phase I the estimated gross primary production (GPP) was similar to 100 mmol C m(-2) day(-1), from which 75-95\% was respired, similar to 1\% ended up in the TPC (including export), and 5-25\% was added to the DOC pool. During phase II, the respiration loss increased to similar to 100\% of GPP at the ambient CO2 concentration, whereas respiration was lower (85-95\% of GPP) in the highest CO2 treatment. Bacterial production was similar to 30\% lower, on average, at the highest CO2 concentration than in the controls during phases II and III. This resulted in a higher accumulation of DOC and lower reduction in the TPC pool in the elevated CO2 treatments at the end of phase II extending throughout phase III. The "extra" organic carbon at high CO2 remained fixed in an increasing biomass of small-sized plankton and in the DOC pool, and did not transfer into large, sinking aggregates. Our results revealed a clear effect of increasing CO2 on the carbon budget and mineralization, in particular under nutrient limited conditions. Lower carbon loss processes (respiration and bacterial remineralization) at elevated CO2 levels resulted in higher TPC and DOC pools than ambient CO2 concentration. These results highlight the importance of addressing not only net changes in carbon standing stocks but also carbon fluxes and budgets to better disentangle the effects of ocean acidification.},
  language  = {en}
}