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71.
We present the simplest discrete model to date that leads to synchronization of stochastic phase-coupled oscillators. In the mean field limit, the model exhibits a Hopf bifurcation and global oscillatory behavior as coupling crosses a critical value. When coupling between units is strictly local, the model undergoes a continuous phase transition which we characterize numerically using finite-size scaling analysis. In particular, the onset of global synchrony is marked by signatures of the XY universality class, including the appropriate classical exponents beta and nu, a lower critical dimension d(lc) = 2, and an upper critical dimension d(uc) = 4. 相似文献
72.
Michael Zech Matthias Saurer Mario Tuthorn Katja Rinne Roland A. Werner Rolf Siegwolf 《Isotopes in environmental and health studies》2013,49(4):492-502
Although the instrumental coupling of gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-Py-IRMS) for compound-specific δ18O analysis has been commercially available for more than a decade, this method has been hardly applied so far. Here we present the first GC-Py-IRMS δ18O results for trimethylsilyl-derivatives of plant sap-relevant sugars and a polyalcohol (glucose, fructose, sucrose, raffinose and pinitol). Particularly, we focus on sucrose, which is assimilated in leaves and which is the most important transport sugar in plants and hence of utmost relevance in plant physiology and paleoclimate studies. Replication measurements of sucrose standards and concentration series indicate that the GC-Py-IRMS δ18O measurements are not stable over time and that they are amount (area) dependent. We, therefore, suggest running sample batch replication measurements in alternation with standard concentration series of reference material. This allows for carrying out (i) a drift correction, (ii) a calibration against reference material and (iii) an amount (area) correction. Tests with 18O-enriched water do not provide any evidence for oxygen isotope exchange reactions affecting sucrose and raffinose. We present the first application of GC-Py-IRMS δ18O analysis for sucrose from needle extract (soluble carbohydrate) samples. The obtained δ18Osucrose/ Vienna Standard Mean Ocean Water (VSMOW) values are more positive and vary in a wider range (32.1–40.1 ‰) than the δ18Obulk/ VSMOW values (24.6–27.2 ‰). Furthermore, they are shown to depend on the climate parameters maximum day temperature, relative air humidity and cloud cover. These findings suggest that δ18Osucrose of the investigated needles very sensitively reflects the climatically controlled evaporative 18O enrichment of leaf water and thus highlights the great potential of GC-Py-IRMS δ18Osucrose analysis for plant physiology and paleoclimate studies. 相似文献
73.
Fan (in Southeast Asian Bull Math 25, 217–221, 2001) determines the endomorphism type of a finite projective plane. In this note we show that Fan’s result actually characterizes the class of projective planes among the finite bipartite graphs of diameter three. In fact, this will follow from a generalization of Fan’s theorem and its converse to all finite bipartite graphs with diameter d and girth g such that (1) d + 1<g≤2d, and (2) every pair of adjacent edges is contained in a circuit of length g. 相似文献
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Roy A. Meoded Dr. Reiko Ueoka Dr. Eric J. N. Helfrich Dr. Katja Jensen Nancy Magnus Prof. Dr. Birgit Piechulla Prof. Dr. Jörn Piel 《Angewandte Chemie (International ed. in English)》2018,57(36):11644-11648
Enzymatic core components from trans‐acyltransferase polyketide synthases (trans‐AT PKSs) catalyze exceptionally diverse biosynthetic transformations to generate structurally complex bioactive compounds. Here we focus on a group of oxygenases identified in various trans‐AT PKS pathways, including those for pederin, oocydins, and toblerols. Using the oocydin pathway homologue (OocK) from Serratia plymuthica 4Rx13 and N‐acetylcysteamine (SNAC) thioesters as test surrogates for acyl carrier protein (ACP)‐tethered intermediates, we show that the enzyme inserts oxygen into β‐ketoacyl moieties to yield malonyl ester SNAC products. Based on these data and the identification of a non‐hydrolyzed oocydin congener with retained ester moiety, we propose a unified biosynthetic pathway of oocydins, haterumalides, and biselides. By providing access to internal ester, carboxylate pseudostarter, and terminal hydroxyl functions, oxygen insertion into polyketide backbones greatly expands the biosynthetic scope of PKSs. 相似文献
78.
Enzymatic or In Vivo Installation of Propargyl Groups in Combination with Click Chemistry for the Enrichment and Detection of Methyltransferase Target Sites in RNA
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79.
Schwaighofer A Schroeter T Mika S Hansen K Ter Laak A Lienau P Reichel A Heinrich N Müller KR 《Journal of chemical information and modeling》2008,48(4):785-796
Metabolic stability is an important property of drug molecules that should-optimally-be taken into account early on in the drug design process. Along with numerous medium- or high-throughput assays being implemented in early drug discovery, a prediction tool for this property could be of high value. However, metabolic stability is inherently difficult to predict, and no commercial tools are available for this purpose. In this work, we present a machine learning approach to predicting metabolic stability that is tailored to compounds from the drug development process at Bayer Schering Pharma. For four different in vitro assays, we develop Bayesian classification models to predict the probability of a compound being metabolically stable. The chosen approach implicitly takes the "domain of applicability" into account. The developed models were validated on recent project data at Bayer Schering Pharma, showing that the predictions are highly accurate and the domain of applicability is estimated correctly. Furthermore, we evaluate the modeling method on a set of publicly available data. 相似文献
80.
A CE-MS method was developed and validated for the quantitative analysis of negatively charged metabolites by making use of the high mass accuracy and the quantitation capabilities of a TOF mass analyzer in combination with automated feature extraction and database search. Metabolites of the central carbon metabolism were quantified with an LOD and lower LOQ (LLOQ) of 0.2-2 and 1-4 microM, respectively. The method was used to elucidate metabolic changes in the Escherichia coli deletion mutant PntAB-UdhA that lacks nicotinamide nucleotide transhydrogenase function, under both stationary and exponential growth conditions. The reproducibility of metabolite extraction and CE-TOF-MS analysis ranged from 3.7 to 22.7 and 7.9 to 22.6%, respectively, while the biological variance was 3.4-31.3%. We observed significant differences in metabolite abundance, particularly in the citrate cycle, between wild-type and mutant E. coli. Overall, more than 600 features were found by automated feature detection, which resulted in approximately 150 high-confidence metabolite identifications. Concomitant analyses with two different GC-MS methods allowed not only crossvalidation of the quantitative results obtained by the various methods, but also led to a more comprehensive coverage of the E. coli metabolome. 相似文献