@phdthesis{Zarafshani2012, author = {Zarafshani, Zoya}, title = {Chain-end functionalization and modification of polymers using modular chemical reactions}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-59723}, school = {Universit{\"a}t Potsdam}, year = {2012}, abstract = {Taking advantage of ATRP and using functionalized initiators, different functionalities were introduced in both α and ω chain-ends of synthetic polymers. These functionalized polymers could then go through modular synthetic pathways such as click cycloaddition (copper-catalyzed or copper-free) or amidation to couple synthetic polymers to other synthetic polymers, biomolecules or silica monoliths. Using this general strategy and designing these co/polymers so that they are thermoresponsive, yet bioinert and biocompatible with adjustable cloud point values (as it is the case in the present thesis), the whole generated system becomes "smart" and potentially applicable in different branches. The applications which were considered in the present thesis were in polymer post-functionalization (in situ functionalization of micellar aggregates with low and high molecular weight molecules), hydrophilic/hydrophobic tuning, chromatography and bioconjugation (enzyme thermoprecipitation and recovery, improvement of enzyme activity). Different α-functionalized co/polymers containing cholesterol moiety, aldehyde, t-Boc protected amine, TMS-protected alkyne and NHS-activated ester were designed and synthesized in this work.}, language = {en} } @article{ZamagniMuttiKosir2012, author = {Zamagni, Jessica and Mutti, Maria and Kosir, Adrijan}, title = {The evolution of mid paleocene-early eocene coral communities how to survive during rapid global warming}, series = {Palaeogeography, palaeoclimatology, palaeoecology : an international journal for the geo-sciences}, volume = {317}, journal = {Palaeogeography, palaeoclimatology, palaeoecology : an international journal for the geo-sciences}, number = {2}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0031-0182}, doi = {10.1016/j.palaeo.2011.12.010}, pages = {48 -- 65}, year = {2012}, abstract = {Today, diverse communities of zooxanthellate corals thrive, but do not build reef, under a wide range of environmental conditions. In these settings they inhabit natural bottom communities, sometimes forming patch-reefs, coral carpets and knobs. Episodes in the fossil record, characterized by limited coral-reef development but widespread occurrence of coral-bearing carbonates, may represent the fossil analogs of these non-reef building, zooxanthellate coral communities. If so, the study of these corals could have valuable implications for paleoenvironmental reconstructions. Here we focus on the evolution of early Paleogene corals as a fossil example of coral communities mainly composed by zooxanthellate corals (or likely zooxanthellate), commonly occurring within carbonate biofacies and with relatively high diversity but with a limited bioconstructional potential as testified by the reduced record of coral reefs. We correlate changes of bioconstructional potential and community compositions of these fossil corals with the main ecological/environmental conditions at that time. The early Paleogene greenhouse climate was characterized by relatively short pulses of warming with the most prominent occurring at the Paleocene-Eocene boundary (PETM event), associated with high weathering rates, nutrient fluxes, and pCO(2) levels. A synthesis of coral occurrences integrated with our data from the Adriatic Carbonate Platform (SW Slovenia) and the Minervois region (SW France), provides evidence for temporal changes in the reef-building capacity of corals associated with a shift in community composition toward forms adapted to tolerate deteriorating sea-water conditions. During the middle Paleocene coral-algal patch reefs and barrier reefs occurred from shallow-water settings, locally with reef-crest structures. A first shift can be traced from middle Paleocene to late Paleocene, with small coral-algal patch reefs and coral-bearing mounds development in shallow to intermediate water depths. In these mounds corals were highly subordinated as bioconstructors to other groups tolerant to higher levels of trophic resources (calcareous red algae, encrusting foraminifera, microbes, and sponges). A second shift occurred at the onset of the early Eocene with a further reduction of coral framework-building capacity. These coral communities mainly formed knobs in shallow-water, turbid settings associated with abundant foraminiferal deposits. We suggest that environmental conditions other than high temperature determined a combination of interrelated stressors that limited the coral-reef construction. A continuous enhancement of sediment load/nutrients combined with geochemical changes of ocean waters likely displaced corals as the main bioconstructors during the late Paleocene-early Eocene times. Nonetheless, these conditions did not affect the capacity of some corals to colonize the substrate, maintain biodiversity, and act as locally important carbonate-sediment producers, suggesting broad environmental tolerance limits of various species of corals. The implications of this study include clues as to how both ancient and modern zooxanthellate corals could respond to changing climate.}, language = {en} } @article{ZamagniMuttiBallatoetal.2012, author = {Zamagni, Jessica and Mutti, Maria and Ballato, Paolo and Kosir, Adrijan}, title = {The Paleocene-Eocene thermal maximum (PETM) in shallow-marine successions of the Adriatic carbonate platform (SW Slovenia)}, series = {Geological Society of America bulletin}, volume = {124}, journal = {Geological Society of America bulletin}, number = {7-8}, publisher = {American Institute of Physics}, address = {Boulder}, issn = {0016-7606}, doi = {10.1130/B30553.1}, pages = {1071 -- 1086}, year = {2012}, abstract = {The Paleocene-Eocene thermal maximum represents one of the most rapid and extreme warming events in the Cenozoic. Shallow-water stratigraphic sections from the Adriatic carbonate platform offer a rare opportunity to learn about the nature of Paleocene-Eocene thermal maximum and the effects on shallow-water ecosystems. We use carbon and oxygen isotope stratigraphy, in conjunction with detailed larger benthic foraminiferal biostratigraphy, to establish a high-resolution paleoclimatic record for the Paleocene-Eocene thermal maximum. A prominent negative excursion in delta C-13 curves of bulk-rock (similar to 1 parts per thousand-3 parts per thousand), matrix (similar to 4 parts per thousand), and foraminifera (similar to 6 parts per thousand) is interpreted as the carbon isotope excursion during the Paleocene-Eocene thermal maximum. The strongly C-13-depleted delta(1)d(3)C record of our shallow-marine carbonates compared to open-marine records could result from organic matter oxidation, suggesting intensified weathering, runoff, and organic matter flux. The Ilerdian larger benthie foraminiferal turnover is documented in detail based on high-resolution correlation with the carbon isotopic excursion. The turnover is described as a two-step process, with the first step (early Ilerdian) marked by a rapid diversification of small alveolinids and nummulitids with weak adult dimorphism, possibly as adaptations to fluctuating Paleocene-Eocene thermal maximum nutrient levels, and a second step (middle Ilerdian) characterized by a further specific diversification, increase of shell size, and well-developed adult dimorphism. Within an evolutionary scheme controlled by long-term biological processes, we argue that high seawater temperatures could have stimulated the early Ilerdian rapid specific diversification. Together, these data help elucidate the effects of global warming and associated feedbacks in shallow-water ecosystems, and by inference, could serve as an assessment analog for future changes.}, language = {en} } @article{ZakrevskyyRichterZakrevskaetal.2012, author = {Zakrevskyy, Yuriy and Richter, Marcel and Zakrevska, Svitlana and Lomadze, Nino and von Klitzing, Regine and Santer, Svetlana}, title = {Light-controlled reversible manipulation of microgel particle size using azobenzene-containing surfactant}, series = {Advanced functional materials}, volume = {22}, journal = {Advanced functional materials}, number = {23}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1616-301X}, doi = {10.1002/adfm.201200617}, pages = {5000 -- 5009}, year = {2012}, abstract = {The light-induced reversible switching of the swelling of microgel particles triggered by photo-isomerization and binding/unbinding of a photosensitive azobenzene-containing surfactant is reported. The interactions between the microgel (N-isopropylacrylamide, co-monomer: allyl acetic acid, crosslinker: N,N'-methylenebisacrylamide) and the surfactant are studied by UV-Vis spectroscopy, dynamic and electrophoretic light scattering measurements. Addition of the surfactant above a critical concentration leads to contraction/collapse of the microgel. UV light irradiation results in trans-cis isomerization of the azobenzene unit incorporated into the surfactant tail and causes an unbinding of the more hydrophilic cis isomer from the microgel and its reversible swelling. The reversible contraction can be realized by blue light irradiation that transfers the surfactant back to the more hydrophobic trans conformation, in which it binds to the microgel. The phase diagram of the surfactant-microgel interaction and transitions (aggregation, contraction, and precipitation) is constructed and allows prediction of changes in the system when the concentration of one or both components is varied. Remote and reversible switching between different states can be realized by either UV or visible light irradiation.}, language = {en} } @article{ZakrevskyyRitschelDoscheetal.2012, author = {Zakrevskyy, Y. and Ritschel, T. and Dosche, C. and L{\"o}hmannsr{\"o}ben, Hans-Gerd}, title = {Quantitative calibration - and reference-free wavelength modulation spectroscopy}, series = {Infrared physics \& technology}, volume = {55}, journal = {Infrared physics \& technology}, number = {2-3}, publisher = {Elsevier}, address = {Amsterdam}, issn = {1350-4495}, doi = {10.1016/j.infrared.2011.12.001}, pages = {183 -- 190}, year = {2012}, abstract = {A unified model for quantitative description of harmonic spectra of gases obtained by wavelength modulation spectroscopy (WMS) technique is presented. In the model, both intensity modulation (IM) and frequency modulation (FM) of the laser emission are taken into account using minimum number of parameters. For the first time, the static behavior of a laser is described as a limiting case of its dynamic response. Laser and its driver are considered as a single device converting applied bias to laser emission. This allows application of the model to any type of laser and the introduced parameters can be assigned to the corresponding laser and/or driver properties. The approach was tested using a distributed feedback (DFB) laser spectrometer. Correctness of the proposed model is justified by very good agreement between the measured and modeled/fitted spectra, which allowed evaluation of the setup performance and assessment of modulation parameters of the DFB laser. An algorithm to minimize the time of numerical calculation of harmonic spectra using numerically approximated Voigt lineshape function was developed. Absolute values of the absorption line parameters (line strength and line width) were obtained from a single calibration- and reference-free spectrum scan with accuracy better than 0.1\%.}, language = {en} } @article{ZaklanCullmannNeumannetal.2012, author = {Zaklan, Aleksandar and Cullmann, Astrid and Neumann, Anne and von Hirschhausen, Christian}, title = {The globalization of steam coal markets and the role of logistics an empirical analysis}, series = {Energy economics}, volume = {34}, journal = {Energy economics}, number = {1}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0140-9883}, doi = {10.1016/j.eneco.2011.03.001}, pages = {105 -- 116}, year = {2012}, abstract = {In this paper, we provide a comprehensive multivariate cointegration analysis of three parts of the steam coal value chain - export, transport and import prices. The analysis is based on a rich dataset of international coal prices: in particular, we combine data on steam coal prices with freight rates, covering the period December 2001 until August 2009 at weekly frequency. We then test whether the demand and supply side components of steam coal trade are consistently integrated with one another. In addition, export and import prices as well as freight rates for individual trading routes, across regions and globally are combined. We find evidence of significant yet incomplete integration. We also find heterogeneous short-term dynamics of individual markets. Furthermore, we examine whether logistics enter coal price dynamics through transportation costs, which are mainly determined by oil prices. Our results suggest that this is generally not the case.}, language = {en} } @phdthesis{Zakharova2012, author = {Zakharova, Anna}, title = {Bifurcations in deterministic and stochastic systems and applications to biology}, address = {Potsdam}, pages = {VI, 69 S.}, year = {2012}, language = {en} } @article{ZaccheusBroekerLundborgetal.2012, author = {Zaccheus, Mona V. and Br{\"o}ker, Nina Kristin and Lundborg, Magnus and Uetrecht, Charlotte and Barbirz, Stefanie and Widmalm, Goran}, title = {Structural studies of the O-antigen polysaccharide from Escherichia coli TD2158 having O18 serogroup specificity and aspects of its interaction with the tailspike endoglycosidase of the infecting bacteriophage HK620}, series = {Carbohydrate research}, volume = {357}, journal = {Carbohydrate research}, number = {8}, publisher = {Elsevier}, address = {Oxford}, issn = {0008-6215}, doi = {10.1016/j.carres.2012.05.022}, pages = {118 -- 125}, year = {2012}, abstract = {We have analyzed the O-antigen polysaccharide of the previously uncharacterized Escherichia coli strain TD2158 which is a host of bacteriophage HK620. This bacteriophage recognizes and cleaves the polysaccharide with its tailspike protein (TSP). The polysaccharide preparation as well as oligosaccharides obtained from HK620TSP endoglycosidase digests were analyzed with NMR spectroscopy. Additionally, sugar analysis was performed on the O-antigen polysaccharide and MALDI-TOF MS was used in oligosaccharide analysis. The present study revealed a heterogeneous polysaccharide with a hexasaccharide repeating unit of the following structure: alpha-D-Glcp-(1 -> 6) vertical bar vertical bar 2)-alpha-L-Rhap-(1 -> 6)-alpha-D-Glcp-(1 -> 4)-alpha-D-Galp-(1 -> 3)-alpha-D-GlcpNAc- (1 ->vertical bar beta-D-Glcp/beta-D-GlcpNAc-(1 -> 3) A repeating unit with a D-GlcNAc substitution of D-Gal has been described earlier as characteristic for serogroup O18A1. Accordingly, we termed repeating units with D-Glc substitution at D-Gal as O18A2. NMR analyses of the polysaccharide confirmed that O18A1- and O18A2-type repeats were present in a 1:1 ratio. However, HK620TSP preferentially bound the D-GlcNAc- substituted O18A1-type repeating units in its high affinity binding pocket with a dissociation constant of 140 mu M and disfavored the O18A2-type having a beta-D-Glcp-(1 -> 3)-linked group. As a result, in hexasaccharide preparations, O18A1 and O18A2 repeats were present in a 9: 1 ratio stressing the clear preference of O18A1- type repeats to be cleaved by HK620TSP.}, language = {en} } @article{YinLinker2012, author = {Yin, Jian and Linker, Torsten}, title = {Recent advances in the stereoselective synthesis of carbohydrate 2-C-analogs}, series = {Organic \& biomolecular chemistry : an international journal of synthetic, physical and biomolecular organic chemistry}, volume = {10}, journal = {Organic \& biomolecular chemistry : an international journal of synthetic, physical and biomolecular organic chemistry}, number = {12}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1477-0520}, doi = {10.1039/c2ob06529k}, pages = {2351 -- 2362}, year = {2012}, abstract = {C-branched carbohydrates are of current interest for glycochemistry, are widely found in nature and serve as important subunits in many antibiotics, bacterial polysaccharides and macrolides. Among C-functionalized saccharides, 2-C-branched carbohydrates represent challenging structures for synthetic chemists, since in contrast to C-glycosides they are not easily accessible from glycosyl bromides or other simple precursors. In this perspective we want to summarize recent approaches to 2-C-branched carbohydrates over the past fifteen years. The two main strategies are based on ring-opening of 1,2-cyclopropanated carbohydrates by various reagents, as well as radical additions to glycals and further transformations, developed in our group. Both methods are characterized by high stereoselectivities and good yields and give access to a broad variety of functionalized carbohydrate 2-C-analogs.}, language = {en} } @article{YarmanGroebeNeumannetal.2012, author = {Yarman, Aysu and Gr{\"o}be, Glenn and Neumann, Bettina and Kinne, Mathias and Gajovic-Eichelmann, Nenad and Wollenberger, Ursula and Hofrichter, Martin and Ullrich, Rene and Scheibner, Katrin and Scheller, Frieder W.}, title = {The aromatic peroxygenase from Marasmius rutola-a new enzyme for biosensor applications}, series = {Analytical \& bioanalytical chemistry}, volume = {402}, journal = {Analytical \& bioanalytical chemistry}, number = {1}, publisher = {Springer}, address = {Heidelberg}, issn = {1618-2642}, doi = {10.1007/s00216-011-5497-y}, pages = {405 -- 412}, year = {2012}, abstract = {The aromatic peroxygenase (APO; EC 1.11.2.1) from the agraric basidomycete Marasmius rotula (MroAPO) immobilized at the chitosan-capped gold-nanoparticle-modified glassy carbon electrode displayed a pair of redox peaks with a midpoint potential of -278.5 mV vs. AgCl/AgCl (1 M KCl) for the Fe(2+)/Fe(3+) redox couple of the heme-thiolate-containing protein. MroAPO oxidizes aromatic substrates such as aniline, p-aminophenol, hydroquinone, resorcinol, catechol, and paracetamol by means of hydrogen peroxide. The substrate spectrum overlaps with those of cytochrome P450s and plant peroxidases which are relevant in environmental analysis and drug monitoring. In M. rotula peroxygenase-based enzyme electrodes, the signal is generated by the reduction of electrode-active reaction products (e.g., p-benzoquinone and p-quinoneimine) with electro-enzymatic recycling of the analyte. In these enzyme electrodes, the signal reflects the conversion of all substrates thus representing an overall parameter in complex media. The performance of these sensors and their further development are discussed.}, language = {en} }