@article{KruegerLinker2021, author = {Kr{\"u}ger, Tobias and Linker, Torsten}, title = {Synthesis of gamma-spirolactams by Birch reduction of arenes}, series = {European journal of organic chemistry}, volume = {2021}, journal = {European journal of organic chemistry}, number = {10}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1099-0690}, doi = {10.1002/ejoc.202100056}, pages = {1585 -- 1591}, year = {2021}, abstract = {A convenient method for the synthesis of gamma-spirolactams in only three steps is described. Birch reduction of inexpensive and commercially available aromatic carboxylic acids in the presence of chloroacetonitrile affords nitriles in moderate to good yields. Suitable precursors are methyl-substituted benzoic acids, naphthoic, and anthroic acid. Subsequent catalytic hydrogenation proceeds smoothly with PtO2 or Raney Ni as catalysts and lactams are isolated in excellent yields and stereoselectivities. Thus, up to 3 new stereogenic centers can be constructed as sole diastereomers from achiral benzoic acids. Furthermore, it is possible to control the degree of saturation at different pressures, affording products with 0, 1, or 2 double bonds. Overall, more than 15 new gamma-spirolactams have been synthesized in analytically pure form.}, language = {en} } @article{FudickarMetzMaiLindeetal.2021, author = {Fudickar, Werner and Metz, Melanie and Mai-Linde, Yasemin and Kr{\"u}ger, Tobias and Kelling, Alexandra and Sperlich, Eric and Linker, Torsten}, title = {Influence of functional groups on the ene reaction of singlet oxygen with 1,4-cyclohexadienes}, series = {Photochemistry and photobiology : the official journal of the American Society for Photobiology}, volume = {97}, journal = {Photochemistry and photobiology : the official journal of the American Society for Photobiology}, number = {6}, publisher = {Wiley}, address = {Malden, Mass.}, issn = {0031-8655}, doi = {10.1111/php.13422}, pages = {1289 -- 1297}, year = {2021}, abstract = {The photooxygenation of 1,4-cyclohexadienes has been studied with a special focus on regio- and stereoselectivities. In all examples, only the methyl-substituted double bond undergoes an ene reaction with singlet oxygen, to afford hydroperoxides in moderate to good yields. We explain the high regioselectivities by a "large-group effect" of the adjacent quaternary stereocenter. Nitriles decrease the reactivity of singlet oxygen, presumably by quenching, but can stabilize proposed per-epoxide intermediates by polar interactions resulting in different stereoselectivities. Spiro lactams and lactones show an interesting effect on regio- and stereoselectivities of the ene reactions. Thus, singlet oxygen attacks the double bond preferentially anti to the carbonyl group, affording only one regioisomeric hydroperoxide. If the reaction occurs from the opposite face, the other regioisomer is exclusively formed by severe electrostatic repulsion in a perepoxide intermediate. We explain this unusual behavior by the fixed geometry of spiro compounds and call it a "spiro effect" in singlet oxygen ene reactions.}, language = {en} } @article{KruegerVorndranLinker2009, author = {Kr{\"u}ger, Tobias and Vorndran, Katja and Linker, Torsten}, title = {Regioselective arene functionalization : simple substitution of carboxylate by alkyl groups}, issn = {0947-6539}, doi = {10.1002/chem.200901774}, year = {2009}, abstract = {Arenes with various alkyl side-chains were synthesized in high yields and excellent regioselectivities. Starting from toluic and naphthoic acids, the carboxylate group was conveniently substituted by alkyl halides by Birch reduction and subsequent decarbonylation. The method is characterized by inexpensive starting materials and reagents, and methylation of arenes was realized. Besides simple alkyl substituents, the scope of arene functionalization was extended by benzyl, fluoro, amino, and ester groups. We were able to control the alkylation of 1-naphthoic acid during Birch reduction by the addition of tert-butanol. This allowed the regioselective synthesis of mono and bis-substituted naphthalenes from the same starting material.}, language = {en} } @article{KumkeEidnerKrueger2005, author = {Kumke, Michael Uwe and Eidner, Sascha and Kr{\"u}ger, Tobias}, title = {Fluorescence quenching and luminescence sensitization in complexes of Tb3+ and Eu3+ with humic substances}, year = {2005}, abstract = {Intrinsic fluorescence quenching of humic substances (HS) and the sensitization of Ln(3+) luminescence (Ln3+ Tb3+, Eu3+) in HS complexes were investigated. Both measurements yielded complementary information on the complexation of metals by HS. Large differences between fulvic acids(FA)and humic acids (HA) were found. From time-resolved luminescence measurements it is concluded that a combination of energy transfer and energy back transfer between HS and Ln(3+) is responsible for the observed luminescence decay characteristics. In the case of Eu3+, an additional participation of charge-transfer states is suggested. A new concept for the evaluation of the sensitized luminescence decays of Ln(3+) was adapted}, language = {en} } @article{KruegerBramborgKellingetal.2021, author = {Kr{\"u}ger, Tobias and Bramborg, Andrea and Kelling, Alexandra and Sperlich, Eric and Linker, Torsten}, title = {Birch Reduction of Arenes as an Easy Entry to γ-Spirolactones}, series = {European journal of organic chemistry}, volume = {2021}, journal = {European journal of organic chemistry}, number = {46}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-193X}, doi = {10.1002/ejoc.202101018}, pages = {6383 -- 6391}, year = {2021}, abstract = {A convenient method for the synthesis of γ-spirolactones in only 2-3 steps is described. Birch reduction of inexpensive and commercially available aromatic carboxylic acids in the presence of ethylene oxide affords hydroxy acids, which undergo direct lactonization during work-up. Suitable precursors are methyl-substituted benzoic acids, naphthoic, and dicarboxylic acids. Subsequent hydrogenation proceeds smoothly with Pd/C as catalyst and saturated γ-spirolactones are isolated in excellent yields and stereoselectivities. Thus, up to 3 new stereogenic centers can be constructed as sole diastereomers from achiral benzoic acids. Furthermore, it is possible to control the degree of saturation with Raney nickel or Wilkinson's catalyst to obtain products with 1 double bond. Overall, more than 30 new γ-spirolactones have been synthesized in analytically pure form.}, language = {en} } @article{KruegerKellingSchildeetal.2016, author = {Kr{\"u}ger, Tobias and Kelling, Alexandra and Schilde, Uwe and Linker, Torsten}, title = {Simple Synthesis of gamma-Spirolactams by Birch Reduction of Benzoic Acids}, series = {European journal of organic chemistry}, journal = {European journal of organic chemistry}, number = {6}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-193X}, doi = {10.1002/ejoc.201601650}, pages = {1074 -- 1077}, year = {2016}, abstract = {A convenient synthesis of gamma-spirolactams in only two steps was developed. Birch reduction of benzoic acids and immediate alkylation with chloroacetonitrile afforded cyclohexadienes in high yields. The products could be isolated by crystallization on a large scale in analytically pure form. Subsequent hydrogenation with platinum(IV) oxide as the catalyst reduced the nitrile functionality and the double bonds in the same step with excellent stereoselectivity. The relative configurations were determined unequivocally by X-ray analyses. Direct cyclization of the intermediary formed amino acids afforded the desired gamma-spirolactams in excellent overall yields. The procedure is characterized by few steps, cheap reagents, and can be performed on a large scale, interesting for industrial processes.}, language = {en} } @article{JedrusikBodeStudenckaSmolkaetal.2013, author = {Jedrusik-Bode, Monika and Studencka, Maja and Smolka, Christian and Baumann, Tobias and Schmidt, Henning and Kampf, Jan and Paap, Franziska and Martin, Sophie and Tazi, Jamal and M{\"u}ller, Kristian M. and Kr{\"u}ger, Marcus and Braun, Thomas and Bober, Eva}, title = {The sirtuin SIRT6 regulates stress granule formation in C. elegans and mammals}, series = {Journal of cell science}, volume = {126}, journal = {Journal of cell science}, number = {22}, publisher = {Company of Biologists Limited}, address = {Cambridge}, issn = {0021-9533}, doi = {10.1242/jcs.130708}, pages = {5166 -- +}, year = {2013}, abstract = {SIRT6 is a NAD(+)-dependent deacetylase that modulates chromatin structure and safeguards genomic stability. Until now, SIRT6 has been assigned to the nucleus and only nuclear targets of SIRT6 are known. Here, we demonstrate that in response to stress, C. elegans SIR-2.4 and its mammalian orthologue SIRT6 localize to cytoplasmic stress granules, interact with various stress granule components and induce their assembly. Loss of SIRT6 or inhibition of its catalytic activity in mouse embryonic fibroblasts impairs stress granule formation and delays disassembly during recovery, whereas deficiency of SIR-2.4 diminishes maintenance of P granules and decreases survival of C. elegans under stress conditions. Our findings uncover a novel, evolutionary conserved function of SIRT6 in the maintenance of stress granules in response to stress.}, language = {en} } @article{NeffevonRuestenLangeBrauneetal.2014, author = {Neffe, Axel T. and von R{\"u}sten-Lange, Maik and Braune, Steffen and L{\"u}tzow, Karola and Roch, Toralf and Richau, Klaus and Kr{\"u}ger, Anne and Becherer, Tobias and Th{\"u}nemann, Andreas F. and Jung, Friedrich and Haag, Rainer and Lendlein, Andreas}, title = {Multivalent grafting of hyperbranched oligo- and polyglycerols shielding rough membranes to mediate hemocompatibility}, series = {Journal of materials chemistry : B, Materials for biology and medicine}, volume = {2}, journal = {Journal of materials chemistry : B, Materials for biology and medicine}, number = {23}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2050-750X}, doi = {10.1039/c4tb00184b}, pages = {3626 -- 3635}, year = {2014}, abstract = {Hemocompatible materials are needed for internal and extracorporeal biomedical applications, which should be realizable by reducing protein and thrombocyte adhesion to such materials. Polyethers have been demonstrated to be highly efficient in this respect on smooth surfaces. Here, we investigate the grafting of oligo- and polyglycerols to rough poly(ether imide) membranes as a polymer relevant to biomedical applications and show the reduction of protein and thrombocyte adhesion as well as thrombocyte activation. It could be demonstrated that, by performing surface grafting with oligo-and polyglycerols of relatively high polydispersity (>1.5) and several reactive groups for surface anchoring, full surface shielding can be reached, which leads to reduced protein adsorption of albumin and fibrinogen. In addition, adherent thrombocytes were not activated. This could be clearly shown by immunostaining adherent proteins and analyzing the thrombocyte covered area. The presented work provides an important strategy for the development of application relevant hemocompatible 3D structured materials.}, language = {en} } @misc{NeffevonRuestenLangeBrauneetal.2014, author = {Neffe, Axel T. and von R{\"u}sten-Lange, Maik and Braune, Steffen and L{\"u}tzow, Karola and Roch, Toralf and Richau, Klaus and Kr{\"u}ger, Anne and Becherer, Tobias and Th{\"u}nemann, Andreas F. and Jung, Friedrich and Haag, Rainer and Lendlein, Andreas}, title = {Multivalent grafting of hyperbranched oligo- and polyglycerols shielding rough membranes to mediate hemocompatibility}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-99444}, year = {2014}, abstract = {Hemocompatible materials are needed for internal and extracorporeal biomedical applications, which should be realizable by reducing protein and thrombocyte adhesion to such materials. Polyethers have been demonstrated to be highly efficient in this respect on smooth surfaces. Here, we investigate the grafting of oligo- and polyglycerols to rough poly(ether imide) membranes as a polymer relevant to biomedical applications and show the reduction of protein and thrombocyte adhesion as well as thrombocyte activation. It could be demonstrated that, by performing surface grafting with oligo- and polyglycerols of relatively high polydispersity (>1.5) and several reactive groups for surface anchoring, full surface shielding can be reached, which leads to reduced protein adsorption of albumin and fibrinogen. In addition, adherent thrombocytes were not activated. This could be clearly shown by immunostaining adherent proteins and analyzing the thrombocyte covered area. The presented work provides an important strategy for the development of application relevant hemocompatible 3D structured materials.}, language = {en} } @article{AbdallaAbramowskiAharonianetal.2016, author = {Abdalla, Hassan E. and Abramowski, Attila and Aharonian, Felix A. and Benkhali, Fai{\c{c}}al Ait and Akhperjanian, A. G. and Ang{\"u}ner, Ekrem Oǧuzhan and Arrieta, M. and Aubert, Pierre and Backes, Michael and Balzer, Arnim and Barnard, Michelle and Becherini, Yvonne and Tjus, Julia Becker and Berge, David and Bernhard, Sabrina and Bernl{\"o}hr, K. and Birsin, E. and Blackwell, R. and Bottcher, Markus and Boisson, Catherine and Bolmont, J. and Bordas, Pol and Bregeon, Johan and Brun, Francois and Brun, Pierre and Bryan, Mark and Bulik, Tomasz and Capasso, M. and Carr, John and Casanova, Sabrina and Chakraborty, N. and Chalme-Calvet, R. and Chaves, Ryan C. G. and Chen, Andrew and Chevalier, J. and Chretien, M. and Colafrancesco, Sergio and Cologna, Gabriele and Condon, B. and Conrad, Jan and Couturier, C. and Cui, Y. and Davids, I. D. and Degrange, B. and Deil, Christoph and deWilt, P. and Djannati-Atai, Arache and Domainko, Wilfried and Donath, Axel and Dubus, Guillaume and Dutson, Kate and Dyks, J. and Dyrda, M. and Edwards, T. and Egberts, Kathrin and Eger, P. and Ernenwein, J. -P. and Eschbach, S. and Farnier, C. and Fegan, Stuart and Fernandes, M. V. and Fiasson, A. and Fontaine, G. and Foerster, A. and Funk, S. and F{\"u}ßling, Matthias and Gabici, Stefano and Gajdus, M. and Gallant, Y. A. and Garrigoux, T. and Giavitto, Gianluca and Giebels, B. and Glicenstein, J. F. and Gottschall, Daniel and Goyal, A. and Grondin, M. -H. and Grudzinska, M. and Hadasch, Daniela and Hahn, J. and Hawkes, J. and Heinzelmann, G. and Henri, Gilles and Hermann, G. and Hervet, Olivier and Hillert, A. and Hinton, James Anthony and Hofmann, Werner and Hoischen, Clemens and Holler, M. and Horns, D. and Ivascenko, Alex and Jacholkowska, A. and Jamrozy, Marek and Janiak, M. and Jankowsky, D. and Jankowsky, Felix and Jingo, M. and Jogler, Tobias and Jouvin, Lea and Jung-Richardt, Ira and Kastendieck, M. A. and Katarzynski, Krzysztof and Katz, Uli and Kerszberg, D. and Khelifi, B. and Kieffer, M. and King, J. and Klepser, S. and Klochkov, Dmitry and Kluzniak, W. and Kolitzus, D. and Komin, Nu. and Kosack, K. and Krakau, S. and Kraus, Michael and Krayzel, F. and Kruger, P. P. and Laffon, H. and Lamanna, G. and Lau, Jeanie and Lees, J. -P. and Lefaucheur, J. and Lefranc, V. and Lemiere, A. and Lemoine-Goumard, M. and Lenain, J. -P. and Leser, Eva and Lohse, Thomas and Lorentz, M. and Lui, R. and Lypova, Iryna and Marandon, Vincent and Marcowith, Alexandre and Mariaud, C. and Marx, R. and Maurin, G. and Maxted, N. and Mayer, Michael and Meintjes, Petrus Johannes and Menzler, U. and Meyer, Manuel and Mitchell, A. M. W. and Moderski, R. and Mohamed, M. and Mora, K. and Moulin, Emmanuel and Murach, T. and de Naurois, Mathieu and Niederwanger, F. and Niemiec, J. and Oakes, L. and Odaka, Hirokazu and Ohm, Stefan and Oettl, S. and Ostrowski, M. and Oya, I. and Padovani, Marco and Panter, M. and Parsons, R. D. and Arribas, M. Paz and Pekeur, N. W. and Pelletier, G. and Petrucci, P. -O. and Peyaud, B. and Pita, S. and Poon, Helen and Prokhorov, Dmitry and Prokoph, Heike and Puehlhofer, Gerd and Punch, Michael and Quirrenbach, Andreas and Raab, S. and Reimer, Anita and Reimer, Olaf and Renaud, M. and de los Reyes, R. and Rieger, Frank and Romoli, Carlo and Rosier-Lees, S. and Rowell, G. and Rudak, B. and Rulten, C. B. and Sahakian, V. and Salek, David and Sanchez, David A. and Santangelo, Andrea and Sasaki, Manami and Schlickeiser, Reinhard and Schussler, F. and Schulz, Andreas and Schwanke, U. and Schwemmer, S. and Seyffert, A. S. and Shafi, N. and Simoni, R. and Sol, H. and Spanier, Felix and Spengler, G. and Spiess, F. and Stawarz, Lukasz and Steenkamp, R. and Stegmann, Christian and Stinzing, F. and Stycz, K. and Sushch, Iurii and Tavernet, J. -P. and Tavernier, T. and Taylor, A. M. and Terrier, R. and Tluczykont, Martin and Trichard, C. and Tuffs, R. and van der Walt, Johan and van Eldik, Christopher and van Soelen, Brian and Vasileiadis, Georges and Veh, J. and Venter, C. and Viana, A. and Vincent, P. and Vink, Jacco and Voisin, F. and Voelk, Heinrich J. and Vuillaume, Thomas and Wadiasingh, Z. and Wagner, Stefan J. and Wagner, P. and Wagner, R. M. and White, R. and Wierzcholska, Alicja and Willmann, P. and Woernlein, A. and Wouters, Denis and Yang, R. and Zabalza, Victor and Zaborov, D. and Zacharias, M. and Zdziarski, A. A. and Zech, Andreas and Zefi, F. and Ziegler, A. and Zywucka, Natalia}, title = {Search for Dark Matter Annihilations towards the Inner Galactic Halo from 10 Years of Observations with HESS}, series = {Physical review letters}, volume = {117}, journal = {Physical review letters}, publisher = {American Physical Society}, address = {College Park}, organization = {HESS Collaboration}, issn = {0031-9007}, doi = {10.1103/PhysRevLett.117.111301}, pages = {6}, year = {2016}, abstract = {The inner region of the Milky Way halo harbors a large amount of dark matter (DM). Given its proximity, it is one of the most promising targets to look for DM. We report on a search for the annihilations of DM particles using gamma-ray observations towards the inner 300 pc of the Milky Way, with the H.E.S.S. array of ground-based Cherenkov telescopes. The analysis is based on a 2D maximum likelihood method using Galactic Center (GC) data accumulated by H.E.S.S. over the last 10 years (2004-2014), and does not show any significant gamma-ray signal above background. Assuming Einasto and Navarro-Frenk-White DM density profiles at the GC, we derive upper limits on the annihilation cross section . These constraints are the strongest obtained so far in the TeV DM mass range and improve upon previous limits by a factor 5. For the Einasto profile, the constraints reach values of 6 x 10(-26) cm(3) s(-1) in the W+W- channel for a DM particle mass of 1.5 TeV, and 2 x 10(-26) cm(3) s(-1) in the tau(+)tau(-) channel for a 1 TeV mass. For the first time, ground-based gamma-ray observations have reached sufficient sensitivity to probe values expected from the thermal relic density for TeV DM particles.}, language = {en} } @article{KleinpeterHeydenreichKochetal.2017, author = {Kleinpeter, Erich and Heydenreich, Matthias and Koch, Andreas and Krtitschka, Angela and Kr{\"u}ger, Tobias and Linker, Torsten}, title = {NMR spectroscopic conformational analysis of 4-methylene-cyclohexyl pivalateThe effect of sp(2) hybridization}, series = {Magnetic resonance in chemistry}, volume = {55}, journal = {Magnetic resonance in chemistry}, publisher = {Wiley}, address = {Hoboken}, issn = {0749-1581}, doi = {10.1002/mrc.4630}, pages = {1073 -- 1078}, year = {2017}, abstract = {The conformational equilibrium of the axial/equatorial conformers of 4-methylene-cyclohexyl pivalate is studied by dynamic NMR spectroscopy in a methylene chloride/freon mixture. At 153K, the ring interconversion gets slow on the nuclear magnetic resonance timescale, the conformational equilibrium (-G degrees) can be examined, and the barrier to ring interconversion (G(\#)) can be determined. The structural influence of sp(2) hybridization on both G degrees and G(\#) of the cyclohexyl moiety can be quantified.}, language = {en} }