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In both eukaryotic and prokaryotic DNA sequences of 30-100 base-pairs rich in AT base-pairs have been identified at which the double helix preferentially unwinds. Such DNA unwinding elements are commonly associated with origins for DNA replication and transcription, and with chromosomal matrix attachment regions. Here we present a quantitative study of local DNA unwinding based on extensive single DNA plasmid imaging. We demonstrate that long-lived single-stranded denaturation bubbles exist in negatively supercoiled DNA, at the expense of partial twist release. Remarkably, we observe a linear relation between the degree of supercoiling and the bubble size, in excellent agreement with statistical modelling. Furthermore, we obtain the full distribution of bubble sizes and the opening probabilities at varying salt and temperature conditions. The results presented herein underline the important role of denaturation bubbles in negatively supercoiled DNA for biological processes such as transcription and replication initiation in vivo.
A series of new monocationic iridium(III) complexes [Ir((CN)-N-boolean AND)(2)((NN)-N-boolean AND)]PF6 with "large-surface" alpha,alpha'-diimin ligands (NN)-N-boolean AND (dap = 1,12-diazaperylene, dmedap = 2,11-dimethyl-1,12-diazaperylene, dipdap = 2,11-diisopropyl-1,12-diazaperylene) and different cyclometalating ligands (CN)-N-boolean AND (piq = 1-phenylisoquinoline, bzq = benzo[h]quinoline, ppz = 1-phenylpyrazole, thpy = 2-(2-thienyl)pyridine, ppy = 2-phenylpyridine, meppy = 2-(4-methylphenyl)pyridine, dfppy = 2-(2,4-difluorophenyl)pyridine) were synthesized. The solid structures of the complexes [Ir(piq)(2)(dap)]PF6, [Ir(bzq)(2)(dap)]PF6, [Ir(ppy)(2)(dipdap)]PF6, [Ir(piq)(2)(dmedap)]PF6, [Ir(ppy)(2)(dap)]PF6 and [Ir(ppz)(2)(dap)]PF6 are reported. In [Ir(piq)(2)(dap)]PF6, the dap ligand and one of the piq ligands of each cationic complex are involved in pi-pi stacking interactions forming supramolecular channels running along the crystallographic c axis. In the crystalline [Ir(bzq)(2)(dap)]PF6 pi-pi stacking interactions between the metal complexes lead to the formation of a 2D layer structure. In addition, CH-pi interactions were found in all compounds, which are what stabilizes the solid structure. In particular, a significant number of them were found in [Ir(piq)(2)(dap)]PF6 and [Ir(bzq)(2)(dap)]PF6. The crystal structures of [Ir(ppy)(2)(dipdap)]PF6 and [Ir(ppy)(2)(dmedap)]PF6 are also presented, being the first examples of bis-cyclometalated iridium(III) complexes with phenanthroline-type alpha,alpha'-diimin ligands bearing bulky alkyl groups in the neighbourhood of the N-donor atoms. These ligands implicate a distorted octahedral coordination geometry that in turn destabilized the Ir-N-N boolean AND N bonds. The new iridium (III) complexes are not luminescent. All compounds show an electrochemically irreversible anodic peak between 1.15 and 1.58 V, which is influenced by the different cyclometalated ligands. All of the new complexes show two reversible successive one-electron "large-surface" ligand-centred reductions around -0.70 V and -1.30 V. Electrospray ionisation mass spectrometry (ESI-MS) and collision induced decomposition (CID) measurements were used to investigate the stability of the new complexes. Thereby, the stability agreed well with the order of the Ir-N-N boolean AND N bond lengths.
A number of ionogels - silica-ionic liquid (IL) hybrid materials - were synthesized and studied for their ionic conductivity. The materials are based on a sulfonated IL, 1-methyl-3-(3-sulfopropyl-)-imidazolium p-toluenesulfonate, [PmimSO(3)H][PTS], which contains a sulfonic acid/sulfonate group both in the IL anion and in the side chain of the IL cation. By way of the sulfonate-sulfonic acid proton transfer, the IL imparts the ionogel with a high ionic conductivity of ca. 10(-2) S cm(-1) in the as-synthesized state at 120 degrees C and 10(-3) S cm(-1) in the dry state at 120 degrees C. The ionogels are stable up to ca. 150 degrees C in dynamic thermogravimetric analysis. This suggests that these materials, which are relatively cheap and easily fabricated, could find application in fuel cells in intermediate temperature ranges where many other membrane materials are not suitable.
The sediment flux through Himalayan rivers directly impacts water quality and is important for sustaining agriculture as well as maintaining drinking-water and hydropower generation. Despite the recent increase in demand for these resources, little is known about the triggers and sources of extreme sediment flux events, which lower water quality and account for extensive hydropower reservoir filling and turbine abrasion. Here, we present a comprehensive analysis of the spatiotemporal trends in suspended sediment flux based on daily data during the past decade (2001-2009) from four sites along the Sutlej River and from four of its main tributaries. In conjunction with satellite data depicting rainfall and snow cover, air temperature and earthquake records, and field observations, we infer climatic and geologic controls of peak suspended sediment concentration (SSC) events. Our study identifies three key findings: First, peak SSC events (a parts per thousand yen 99th SSC percentile) coincide frequently (57-80%) with heavy rainstorms and account for about 30% of the suspended sediment flux in the semi-arid to arid interior of the orogen. Second, we observe an increase of suspended sediment flux from the Tibetan Plateau to the Himalayan Front at mean annual timescales. This sediment-flux gradient suggests that averaged, modern erosion in the western Himalaya is most pronounced at frontal regions, which are characterized by high monsoonal rainfall and thick soil cover. Third, in seven of eight catchments, we find an anticlockwise hysteresis loop of annual sediment flux variations with respect to river discharge, which appears to be related to enhanced glacial sediment evacuation during late summer. Our analysis emphasizes the importance of unconsolidated sediments in the high-elevation sector that can easily be mobilized by hydrometeorological events and higher glacial-meltwater contributions. In future climate change scenarios, including continuous glacial retreat and more frequent monsoonal rainstorms across the Himalaya, we expect an increase in peak SSC events, which will decrease the water quality and impact hydropower generation.
Whereas the US President signed the Kyoto Protocol, the failure of the US Congress to ratify it seriously hampered subsequent international climate cooperation. This recent US trend, of signing environmental treaties but failing to ratify them, could thwart attempts to come to a future climate agreement. Two complementary explanations of this trend are proposed. First, the political system of the US has distinct institutional features that make it difficult for presidents to predict whether the Senate will give its advice and consent to multilateral environmental agreements (MEAs) and whether Congress will pass the required enabling legislation. Second, elected for a fixed term, US presidents might benefit politically from supporting MEAs even when knowing that legislative support is not forthcoming. Four policy implications are explored, concerning the scope for unilateral presidential action, the potential for bipartisan congressional support, the effectiveness of a treaty without the US, and the prospects for a deep, new climate treaty.
Policy relevance
Why does the failure of US ratification of multilateral environmental treaties occur? This article analyses the domestic political mechanisms involved in cases of failed US ratification. US non-participation in global environmental institutions often has serious ramifications. For example, it sharply limited Kyoto's effectiveness and seriously hampered international climate negotiations for years. Although at COP 17 in Durban the parties agreed to negotiate a new agreement by 2015, a new global climate treaty may well trigger a situation resembling the one President Clinton faced in 1997 when he signed Kyoto but never obtained support for it in the Senate. US failure to ratify could thwart future climate agreements.
Land use is increasingly recognized as a major driver of biodiversity and ecosystem functioning in many current research projects. In grasslands, land use is often classified by categorical descriptors such as pastures versus meadows or fertilized versus unfertilized sites. However, to account for the quantitative variation of multiple land-use types in heterogeneous landscapes, a quantitative, continuous index of land-use intensity (LUI) is desirable. Here we define such a compound, additive LUI index for managed grasslands including meadows and pastures. The LUI index summarizes the standardized intensity of three components of land use, namely fertilization, mowing, and livestock grazing at each site. We examined the performance of the LUI index to predict selected response variables on up to 150 grassland sites in the Biodiversity Exploratories in three regions in Germany(Alb, Hainich, Schorlheide). We tested the average Ellenberg nitrogen indicator values of the plant community, nitrogen and phosphorus concentration in the aboveground plant biomass, plant-available phosphorus concentration in the top soil, and soil C/N ratio, and the first principle component of these five response variables.
The LUI index significantly predicted the principal component of all five response variables, as well as some of the individual responses. Moreover, vascular plant diversity decreased significantly with LUI in two regions (Alb and Hainich).
Inter-annual changes in management practice were pronounced from 2006 to 2008, particularly due to variation in grazing intensity. This rendered the selection of the appropriate reference year(s) an important decision for analyses of land-use effects, whereas details in the standardization of the index were of minor importance. We also tested several alternative calculations of a LUI index, but all are strongly linearly correlated to the proposed index.
The proposed LUI index reduces the complexity of agricultural practices to a single dimension and may serve as a baseline to test how different groups of organisms and processes respond to land use. In combination with more detailed analyses, this index may help to unravel whether and how land-use intensities, associated disturbance levels or other local or regional influences drive ecological processes.
Magnetotactic bacteria produce chains of magnetite nanoparticles, which are called magnetosomes and are used for navigational purposes. We use these cells as a biological template to prepare a hollow hybrid material based on silica and magnetite, and show that the synthetic route is nondestructive as the material conserves the cell morphology as well as the alignment of the magnetic particles. The hybrid material can be resuspended in aqueous solution, and can be shown to orient itself in an external magnetic field. We anticipate that chemical modification of the silica can be used to functionalize the material surface in order to obtain multifunctional materials with specialized applications, e.g. targeted drug delivery.
Virtual 3D city models serve as an effective medium with manifold applications in geoinformation systems and services. To date, most 3D city models are visualized using photorealistic graphics. But an effective communication of geoinformation significantly depends on how important information is designed and cognitively processed in the given application context. One possibility to visually emphasize important information is based on non-photorealistic rendering, which comprehends artistic depiction styles and is characterized by its expressiveness and communication aspects. However, a direct application of non-photorealistic rendering techniques primarily results in monotonic visualization that lacks cartographic design aspects. In this work, we present concepts for cartography-oriented visualization of virtual 3D city models. These are based on coupling non-photorealistic rendering techniques and semantics-based information for a user, context, and media-dependent representation of thematic information. This work highlights challenges for cartography-oriented visualization of 3D geovirtual environments, presents stylization techniques and discusses their applications and ideas for a standardized visualization. In particular, the presented concepts enable a real-time and dynamic visualization of thematic geoinformation.
A membrane of a dielectric elastomer coated with compliant electrodes may form wrinkles as the applied voltage is ramped up. We present a combination of experiment and theory to investigate the transition to wrinkles using a clamped membrane subject to a constant force and a voltage ramp. Two types of transitions are identified. In type-I transition, the voltage-stretch curve is N-shaped, and flat and wrinkled regions coexist in separate areas of the membrane. The type-I transition progresses by nucleation of small wrinkled regions, followed by the growth of the wrinkled regions at the expense of the flat regions, until the entire membrane is wrinkled. By contrast, in type-II transition, the voltage-stretch curve is monotonic, and the entire flat membrane becomes wrinkled with no nucleation barrier. The two types of transitions are analogous to the first and the second order phase transitions. While the type-I transition is accompanied by a jump in the vertical displacement, type-II transition is accompanied by a continuous change in the vertical displacement. Such transitions may enable applications in muscle-like actuation and energy harvesting, where large deformation and large energy of conversion are desired.