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We report the synthesis of free 1,6,7,12-tetraazaperylene (tape). Tape was obtained from 1,1'-bis-2,7-naphthyridine by potassium promoted cyclization followed by oxidation with air. Mono-and dinuclear ruthenium(II) 1,6,7,12-tetraazaperylene complexes of the general formulas [Ru(L-L)(2)(tape)](PF6)(2), [1] (PF6)(2)-[5](PF6)(2), and [{Ru(L-L)(2)}(2)(mu-tape)](PF6)(4), [6](PF6)(4)-[10](PF6)(4), with{L-L = phen, bpy, dmbpy (4,4'-dimethyl-2,2'-bipyridine), dtbbpy (4,4'-ditertbutyl-2,2'-bipyridine) and tmbpy (4,4' 5,5'-tetramethyl-2,2'- bipyridine)}, respectively, were synthesized. The X-ray structures of tape center dot 2CHCl(3) and the mononuclear complexes [Ru(bpy)(2)(tape)](PF6)(2)center dot 0.5CH(3)CN center dot 0.5toluene, [Ru(dmbpy)(2)(tape)] (PF6)(2)center dot 2toluene and [Ru(dtbbpy)(2)(tape)](PF6)(2) center dot 3acetone center dot 0.5H(2)O were solved. The UV-vis absorption spectra and the electrochemical behavior of the ruthenium(II) tape complexes were explored and compared with the data of the analogous dibenzoeilatin (dbneil), 2,2'-bipyrimidine (bpym) and tetrapyrido [3,2-a:2',3'-c:3 '',2''-h:2''',3'''-j] phenazin (tpphz) species.
Background: The goal was to study lipid profiles (TG, TC, LDL, HDL), effects on serum leptin, and fat tissue adiponectin, and resistin as well as body weight effects of Shan He Jian Fei Granules (SHJFG) in rats on a high fat diet.
Methods: Rats were randomly divided into five groups: normal control group fed with normal fat diet, rats on high fat diet receiving low dosage, middle dosage, high dosage of Shan He Jian Fei Granules (SHJFG) as well as a high fat diet group receiving placebo. Rats were treated for 8 weeks. Body weight and naso-anal length of each rat were recorded and Lee's index was calculated. Serum TG, TC, LDL, HDL and leptin concentrations were analyzed. The gene expressions of adiponectin and resistin in adipose tissues were tested by RT-PCR.
Results: Compared to the high-fat diet group, body weights, Lee's indexes, weight of fat tissues and serum TG, TC, LDL and leptin of SHJFG groups significantly decreased (p<0.05), whereas mRNA expressions of adiponectin and resistin of SHJFG groups significantly increased (p<0.05).
Conclusions: SHJFG could significantly lower body weight and serum TG, TC, and LDL of obese rats. The effects of SHJFG in lowering leptin synthesis and raising mRNA expression of adiponectin and resistin in fat tissues may act as part of the mechanisms in lowering body weight of obese rats. Further studies are needed to demonstrate whether SHJFG may also reduce overall cardiovascular morbidity and mortality like other lipid lowering drugs.
The minima on the potential energy surface of 1,2-bis(o-carboxyphenoxy)ethane (CPE) molecule in its electronic ground state were searched by a molecular dynamics simulation performed with MM2 force field. For each of the found minimum-energy conformers, the corresponding equilibrium geometry, charge distribution, HOMO-LUMO energy gap, force field, vibrational normal modes and associated IR and Raman spectral data were determined by means of the density functional theory (DFT) based electronic structure calculations carried out by using B3LYP method and various Pople-style basis sets. The obtained theoretical data confirmed the significant effects of the intra- and inter-molecular hydrogen bonding interactions on the conformational structure, force field, and group vibrations of the molecule. The same data have also revealed that two of the determined stable conformers, both of which exhibit pseudo-crown structure, are considerably more favorable in energy to the others and accordingly provide the major contribution to the experimental spectra of CPE. In the light of the improved vibrational spectral data obtained within the "SQM FF" methodology and "Dual Scale Factors" approach for the monomer and dimer forms of these two conformers, a reliable assignment of the fundamental bands observed in the experimental room-temperature IR and Raman spectra of the molecule was given, and the sensitivities of its group vibrations to conformation, substitution and dimerization were discussed.
In mobile telecommunication networks the trend for an increasing heterogeneity of access networks, the convergence with fixed networks as well as with the Internet are apparent. The resulting future converged network with an expected wide variety of services and a possibly stiff competition between the different market participants as well as legal issues will bring about requirements for charging systems that demand for more flexibility, scalability and efficiency than is available in today's systems. This article surveys recent developments in charging and billing architectures comprising both standardisation work as well as research projects. The second main contribution of this article is a comparison of key features of these developments thus giving a list of essential charging and billing ingredients for tomorrow's communication and service environments.
Metamorphic studies in the cover sequences of the Bitlis complex allow the thermal evolution of the massif to be constrained using metamorphic index minerals. Regionally distributed metamorphic index minerals such as glaucophane, carpholite, relics of carpholite in chloritoid-bearing schists and pseudomorphs after aragonite in marbles record a LT-HP evolution:This demonstrates that the Bitlis complex was subducted and stacked to form a nappe complex during the closure of the Neo-Tethys. During late Cretaceous to Cenozoic evolution the Bitlis complex experienced peak metamorphism of 1.0-1.1 GPa at 350-400 degrees C. During the retrograde evolution temperatures remained below 460 degrees C. Ar-39/Ar-40 dating of white mica in different parageneses from the Bitlis complex reveals a 74-79 Ma (Campanian) date of peak metamorphism and rapid exhumation to an almost isothermal greenschist stage at 67-70 Ma (Maastrichtian). The HP Eocene flysch escaped the greenschist facies stage and were exhumed under very cold conditions. These single stage evolutions contrast with the multistage evolution reported further north from the Amassia-Stepanavan Suture in Armenia. Petrological investigations and isotopic dating show that the collision of Arabia with Eurasia resulted in an assemblage of different blocks derived from the northern as well as from the southern plate and a set of subduction zones producing HP rocks with diverse exhumation histories.
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.
Recent observations and modeling studies emphasize the crucial role of fracture mechanics for the stability of ice shelves and thereby the evolution of ice sheets. Here we introduce a macroscopic fracture-density field into a prognostic continuum ice-flow model and compute its evolution incorporating the initiation and growth of fractures as well as their advection with two-dimensional ice flow. To a first approximation, fracture growth is assumed to depend on the spreading rate only, while fracture initiation is defined in terms of principal stresses. The inferred fracture-density fields compare well with observed elongate surface structures. Since crevasses and other deep-reaching fracture structures have been shown to influence the overall ice-shelf dynamics, we propose the fracture-density field introduced here be used as a measure for ice softening and decoupling of the ice flow in fracture-weakened zones. This may yield more accurate and realistic velocity patterns in prognostic simulations. Additionally, the memory of past fracture events links the calving front to the upstream dynamics. Thus the fracture-density field proposed here may be employed in fracture-based calving parameterizations. The aim of this study is to introduce the field and investigate which of the observed surface structures can be reproduced by the simplest physically motivated fracture source terms.
We investigated EEG-power and EEG-coherence changes in a unimodal and a crossmodal matching-to-sample working memory task with either visual or kinesthetic stimuli. Angle-shaped trajectories were used as stimuli presented either as a moving dot on a screen or as a passive movement of a haptic device. Effects were evaluated during the different phases of encoding, maintenance, and recognition. Alpha power was modulated during encoding by the stimulus modality, and in crossmodal conditions during encoding and maintenance by the expected modality of the upcoming test stimulus. These power modulations were observed over modality-specific cortex regions. Systematic changes of coherence for crossmodal compared to unimodal tasks were not observed during encoding and maintenance but only during recognition. There, coherence in the theta-band increased between electrode sites over left central and occipital cortex areas in the crossmodal compared to the unimodal conditions. The results underline the importance of modality-specific representations and processes in unimodal and crossmodal working memory tasks. Crossmodal recognition of visually and kinesthetically presented object features seems to be related to a direct interaction of somatosensory/motor and visual cortex regions by means of long-range synchronization in the theta-band and such interactions seem to take place at the beginning of the recognition phase, i.e. when crossmodal transfer is actually necessary.
Thawing of permafrost and the associated release of carbon constitutes a positive feedback in the climate system, elevating the effect of anthropogenic GHG emissions on global-mean temperatures. Multiple factors have hindered the quantification of this feedback, which was not included in climate carbon-cycle models which participated in recent model intercomparisons (such as the Coupled Carbon Cycle Climate Model Intercomparison Project - (CMIP)-M-4). There are considerable uncertainties in the rate and extent of permafrost thaw, the hydrological and vegetation response to permafrost thaw, the decomposition timescales of freshly thawed organic material, the proportion of soil carbon that might be emitted as carbon dioxide via aerobic decomposition or as methane via anaerobic decomposition, and in the magnitude of the high latitude amplification of global warming that will drive permafrost degradation. Additionally, there are extensive and poorly characterized regional heterogeneities in soil properties, carbon content, and hydrology. Here, we couple a new permafrost module to a reduced complexity carbon-cycle climate model, which allows us to perform a large ensemble of simulations. The ensemble is designed to span the uncertainties listed above and thereby the results provide an estimate of the potential strength of the feedback from newly thawed permafrost carbon. For the high CO2 concentration scenario (RCP8.5), 33-114 GtC (giga tons of Carbon) are released by 2100 (68% uncertainty range). This leads to an additional warming of 0.04-0.23 degrees C. Though projected 21st century permafrost carbon emissions are relatively modest, ongoing permafrost thaw and slow but steady soil carbon decomposition means that, by 2300, about half of the potentially vulnerable permafrost carbon stock in the upper 3 m of soil layer (600-1000 GtC) could be released as CO2, with an extra 1-4% being released as methane. Our results also suggest that mitigation action in line with the lower scenario RCP3-PD could contain Arctic temperature increase sufficiently that thawing of the permafrost area is limited to 9-23% and the permafrost-carbon induced temperature increase does not exceed 0.04-0.16 degrees C by 2300.