TY - JOUR A1 - Mirskova, Anna N. A1 - Adamovich, Sergey N. A1 - Mirskov, Rudolf G. A1 - Schilde, Uwe T1 - Reaction of pharmacological active tris-(2-hydroxyethyl)ammonium 4-chlorophenylsulfanylacetate with ZnCl2 or NiCl2: first conversion of a protic ionic liquid into metallated ionic liquid JF - CHEMISTRY CENTRAL JOURNAL N2 - The reaction of pharmacological active protic ionic liquid tris-(2-hydroxyethyl)ammonium 4-chlorophenylsulfanylacetate H+N(CH2CH2OH)(3) center dot (-OOCCH2SC6H4Cl-4) (1) with zinc or nickel chloride in a ratio of 2:1 affords stable at room temperature powder-like adducts [H+N(CH2CH2OH)(3)](2) center dot [M(OOCCH2SC6H4Cl-4)(2)Cl-2](2-), M = Zn (2), Ni (3). By recrystallization from aqueous alcohol compound 2 unexpectedly gives Zn(OOCCH2SC6H4Cl-4)(2) center dot 2H(2)O (4). Unlike 2, compound 3 gives crystals [N(CH2CH2OH)(3)](2)Ni2+ center dot [-OOCCH2SC6H4Cl-4](2) (5), which have a structure of metallated ionic liquid. The structure of 5 has been proved by X-ray diffraction analysis. It is the first example of the conversion of a protic ionic liquid into potentially biological active metallated ionic liquid (1 -> 3 -> 5). Y1 - 2013 U6 - https://doi.org/10.1186/1752-153X-7-34 SN - 1752-153X VL - 7 PB - BIOMED CENTRAL LTD CY - LONDON ER - TY - JOUR A1 - Dahl, Jan-Ulrik A1 - Radon, Christin A1 - Bühning, Martin A1 - Nimtz, Manfred A1 - Leichert, Lars I. A1 - Denis, Yann A1 - Jourlin-Castelli, Cecile A1 - Iobbi-Nivol, Chantal A1 - Mejean, Vincent A1 - Leimkühler, Silke T1 - The Sulfur Carrier Protein TusA Has a Pleiotropic Role in Escherichia coli That Also Affects Molybdenum Cofactor Biosynthesis JF - JOURNAL OF BIOLOGICAL CHEMISTRY N2 - The Escherichia coli L-cysteine desulfurase IscS mobilizes sulfur from L-cysteine for the synthesis of several biomolecules such as iron-sulfur (FeS) clusters, molybdopterin, thiamin, lipoic acid, biotin, and the thiolation of tRNAs. The sulfur transfer from IscS to various biomolecules is mediated by different interaction partners (e.g. TusA for thiomodification of tRNAs, IscU for FeS cluster biogenesis, and ThiI for thiamine biosynthesis/tRNA thiolation), which bind at different sites of IscS. Transcriptomic and proteomic studies of a Delta tusA strain showed that the expression of genes of the moaABCDE operon coding for proteins involved in molybdenum cofactor biosynthesis is increased under aerobic and anaerobic conditions. Additionally, under anaerobic conditions the expression of genes encoding hydrogenase 3 and several molybdoenzymes such as nitrate reductase were also increased. On the contrary, the activity of all molydoenzymes analyzed was significantly reduced in the Delta tusA mutant. Characterization of the Delta tusA strain under aerobic conditions showed an overall low molybdopterin content and an accumulation of cyclic pyranopterin monophosphate. Under anaerobic conditions the activity of nitrate reductase was reduced by only 50%, showing that TusA is not essential for molybdenum cofactor biosynthesis. We present a model in which we propose that the direction of sulfur transfer for each sulfur-containing biomolecule is regulated by the availability of the interaction partner of IscS. We propose that in the absence of TusA, more IscS is available for FeS cluster biosynthesis and that the overproduction of FeS clusters leads to a modified expression of several genes. Y1 - 2013 U6 - https://doi.org/10.1074/jbc.M112.431569 SN - 0021-9258 VL - 288 IS - 8 SP - 5426 EP - 5442 PB - AMER SOC BIOCHEMISTRY MOLECULAR BIOLOGY INC CY - BETHESDA ER - TY - JOUR A1 - Inal, Sahika A1 - Koelsch, Jonas D. A1 - Chiappisi, Leonardo A1 - Kraft, Mario A1 - Gutacker, Andrea A1 - Janietz, Dietmar A1 - Scherf, Ullrich A1 - Gradzielski, Michael A1 - Laschewsky, André A1 - Neher, Dieter T1 - Temperature-Regulated Fluorescence Characteristics of Supramolecular Assemblies Formed By a Smart Polymer and a Conjugated Polyelectrolyte JF - MACROMOLECULAR CHEMISTRY AND PHYSICS N2 - Aqueous mixtures of a coumarin-labeled non-ionic thermoresponsive copolymer and a cationic polythiophene exhibit marked changes in their fluorescence properties upon heating. At room temperature, emission from the label is significantly quenched due to energy transfer to the conjugated polyelectrolyte. Heating the mixture reduces the energy-transfer efficiency markedly, resulting in a clearly visible change of the emission color. Although the two macromolecules associate strongly at room temperature, the number of interacting sites is largely reduced upon the phase transition. Crucially, the intermolecular association does not suppress the responsiveness of the smart polymer, meaning that this concept should be applicable to chemo- or bioresponsive polymers with optical read-out, for example, as a sensor device. KW - aqueous solutions KW - conjugated polyelectrolytes KW - fluorescence (or Forster) KW - resonance energy transfer KW - phase transitions KW - thermoresponsive polymers Y1 - 2013 U6 - https://doi.org/10.1002/macp.201200493 SN - 1022-1352 VL - 214 IS - 4 SP - 435 EP - 445 PB - WILEY-V C H VERLAG GMBH CY - WEINHEIM ER - TY - JOUR A1 - Winkler, M. A1 - Kofod, G. A1 - Krastev, R. A1 - Stoeckle, S. A1 - Abel, M. W. T1 - Exponentially Fast Thinning of Nanoscale Films by Turbulent Mixing JF - PHYSICAL REVIEW LETTERS N2 - Films are nanoscopic elements of foams, emulsions, and suspensions that form a paradigm for nanochannel transport that eventually tests the limits of hydrodynamic descriptions. Here, we study the collapse of a freestanding film to its equilibrium. The generation of nanoscale films usually is a slow linear process; using thermal forcing we find unprecedented dynamics with exponentially fast thinning. The complex interplay of thermal convection, interface, and gravitational forces yields optimal turbulent mixing and transport. Domains of collapsed film are generated, elongated, and convected in a beautiful display of chaotic mixing. With a time scale analysis, we identify mixing as the dominant dynamical process responsible for exponential thinning. DOI: 10.1103/PhysRevLett.110.094501 Y1 - 2013 U6 - https://doi.org/10.1103/PhysRevLett.110.094501 SN - 0031-9007 VL - 110 IS - 9 PB - AMER PHYSICAL SOC CY - COLLEGE PK ER - TY - JOUR A1 - Schick, Daniel A1 - Bojahr, Andre A1 - Herzog, Marc A1 - Gaal, P. A1 - Vrejoiu, I. A1 - Bargheer, Matias T1 - Following Strain-Induced Mosaicity Changes of Ferroelectric Thin Films by Ultrafast Reciprocal Space Mapping JF - Physical review letters N2 - We investigate coherent phonon propagation in a thin film of ferroelectric PbZr0.2Ti0.8O3 (PZT) by ultrafast x-ray diffraction experiments, which are analyzed as time-resolved reciprocal space mapping in order to observe the in-and out-of-plane structural dynamics, simultaneously. The mosaic structure of the PZT leads to a coupling of the excited out-of-plane expansion to in-plane lattice dynamics on a picosecond time scale, which is not observed for out-of-plane compression. Y1 - 2013 U6 - https://doi.org/10.1103/PhysRevLett.110.095502 SN - 0031-9007 SN - 1079-7114 VL - 110 IS - 9 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Eliazar, Iddo A1 - Metzler, Ralf T1 - Anomalous statistics of random relaxations in random environments JF - Physical review : E, Statistical, nonlinear and soft matter physics N2 - We comprehensively analyze the emergence of anomalous statistics in the context of the random relaxation ( RARE) model [Eliazar and Metzler, J. Chem. Phys. 137, 234106 ( 2012)], a recently introduced versatile model of random relaxations in random environments. The RARE model considers excitations scattered randomly across a metric space around a reaction center. The excitations react randomly with the center, the reaction rates depending on the excitations' distances from this center. Relaxation occurs upon the first reaction between an excitation and the center. Addressing both the relaxation time and the relaxation range, we explore when these random variables display anomalous statistics, namely, heavy tails at zero and at infinity that manifest, respectively, exceptionally high occurrence probabilities of very small and very large outliers. A cohesive set of closed-form analytic results is established, determining precisely when such anomalous statistics emerge. Y1 - 2013 U6 - https://doi.org/10.1103/PhysRevE.87.022141 SN - 1539-3755 SN - 1550-2376 VL - 87 IS - 2 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Feudel, Fred A1 - Seehafer, Norbert A1 - Tuckerman, Laurette S. A1 - Gellert, Marcus T1 - Multistability in rotating spherical shell convection JF - Physical review : E, Statistical, nonlinear and soft matter physics N2 - The multiplicity of stable convection patterns in a rotating spherical fluid shell heated from the inner boundary and driven by a central gravity field is presented. These solution branches that arise as rotating waves (RWs) are traced for varying Rayleigh number while their symmetry, stability, and bifurcations are studied. At increased Rayleigh numbers all the RWs undergo transitions to modulated rotating waves (MRWs) which are classified by their spatiotemporal symmetry. The generation of a third frequency for some of the MRWs is accompanied by a further loss of symmetry. Eventually a variety of MRWs, three-frequency solutions, and chaotic saddles and attractors control the dynamics for higher Rayleigh numbers. Y1 - 2013 U6 - https://doi.org/10.1103/PhysRevE.87.023021 SN - 1539-3755 VL - 87 IS - 2 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Lin, Yue A1 - Berger, Uta A1 - Grimm, Volker A1 - Huth, Franka A1 - Weiner, Jacob T1 - Plant interactions alter the predictions of metabolic scaling theory JF - PLoS one N2 - Metabolic scaling theory (MST) is an attempt to link physiological processes of individual organisms with macroecology. It predicts a power law relationship with an exponent of -4/3 between mean individual biomass and density during density-dependent mortality (self-thinning). Empirical tests have produced variable results, and the validity of MST is intensely debated. MST focuses on organisms' internal physiological mechanisms but we hypothesize that ecological interactions can be more important in determining plant mass-density relationships induced by density. We employ an individual-based model of plant stand development that includes three elements: a model of individual plant growth based on MST, different modes of local competition (size-symmetric vs. -asymmetric), and different resource levels. Our model is consistent with the observed variation in the slopes of self-thinning trajectories. Slopes were significantly shallower than -4/3 if competition was size-symmetric. We conclude that when the size of survivors is influenced by strong ecological interactions, these can override predictions of MST, whereas when surviving plants are less affected by interactions, individual-level metabolic processes can scale up to the population level. MST, like thermodynamics or biomechanics, sets limits within which organisms can live and function, but there may be stronger limits determined by ecological interactions. In such cases MST will not be predictive. Y1 - 2013 U6 - https://doi.org/10.1371/journal.pone.0057612 SN - 1932-6203 VL - 8 IS - 2 PB - PLoS CY - San Fransisco ER - TY - JOUR A1 - Bauer, Barbara A1 - Sommer, Ulrich A1 - Gaedke, Ursula T1 - High predictability of spring phytoplankton biomass in mesocosms at the species, functional group and community level JF - Freshwater biology N2 - 1. Models aim to predict phytoplankton dynamics based on observed initial conditions and a set of equations and parameters. However, our knowledge about initial conditions in nature is never perfect. Thus, if phytoplankton dynamics are sensitive to small variations in initial conditions, they are difficult to predict. 2. We used time-series data from indoor mesocosm experiments with natural phyto- and zooplankton communities to quantify the extent to which small initial differences in the species, functional group and community biomass in parallel treatments were amplified or buffered over time. We compared the differences in dynamics between replicates and among all mesocosms of 1year. 3. Temperature-sensitive grazing during the exponential growth phase of phytoplankton caused divergence. In contrast, negative density dependence caused convergence. 4. Mean differences in biomass between replicates were similar for all hierarchical levels. This indicates that differences in their initial conditions were amplified to the same extent. Even though large differences in biomass occasionally occurred between replicates for a short time, dynamics returned to the same path at all hierarchical levels. This suggests that internal feedback mechanisms make the spring development of phytoplankton highly predictable. KW - divergence KW - hierarchical level KW - mesocosms KW - predictability KW - replicates Y1 - 2013 U6 - https://doi.org/10.1111/j.1365-2427.2012.02780.x SN - 0046-5070 VL - 58 IS - 3 SP - 588 EP - 596 PB - Wiley-Blackwell CY - Hoboken ER - TY - JOUR A1 - Zakharova, A. A1 - Nikoloski, Zoran A1 - Koseska, Aneta T1 - Dimensionality reduction of bistable biological systems JF - Bulletin of mathematical biology : official journal of the Society for Mathematical Biology N2 - Time hierarchies, arising as a result of interactions between system's components, represent a ubiquitous property of dynamical biological systems. In addition, biological systems have been attributed switch-like properties modulating the response to various stimuli across different organisms and environmental conditions. Therefore, establishing the interplay between these features of system dynamics renders itself a challenging question of practical interest in biology. Existing methods are suitable for systems with one stable steady state employed as a well-defined reference. In such systems, the characterization of the time hierarchies has already been used for determining the components that contribute to the dynamics of biological systems. However, the application of these methods to bistable nonlinear systems is impeded due to their inherent dependence on the reference state, which in this case is no longer unique. Here, we extend the applicability of the reference-state analysis by proposing, analyzing, and applying a novel method, which allows investigation of the time hierarchies in systems exhibiting bistability. The proposed method is in turn used in identifying the components, other than reactions, which determine the systemic dynamical properties. We demonstrate that in biological systems of varying levels of complexity and spanning different biological levels, the method can be effectively employed for model simplification while ensuring preservation of qualitative dynamical properties (i.e., bistability). Finally, by establishing a connection between techniques from nonlinear dynamics and multivariate statistics, the proposed approach provides the basis for extending reference-based analysis to bistable systems. KW - Bistability KW - Time-scales hierarchy KW - Similarity transformation KW - Canonical correlation analysis KW - Dimensionality reduction Y1 - 2013 U6 - https://doi.org/10.1007/s11538-013-9807-8 SN - 0092-8240 VL - 75 IS - 3 SP - 373 EP - 392 PB - Springer CY - New York ER -