1,069 research outputs found
Scaling Behaviour and Complexity of the Portevin-Le Chatelier Effect
The plastic deformation of dilute alloys is often accompanied by plastic
instabilities due to dynamic strain aging and dislocation interaction. The
repeated breakaway of dislocations from and their recapture by solute atoms
leads to stress serrations and localized strain in the strain controlled
tensile tests, known as the Portevin-Le Chatelier (PLC) effect. In this present
work, we analyse the stress time series data of the observed PLC effect in the
constant strain rate tensile tests on Al-2.5%Mg alloy for a wide range of
strain rates at room temperature. The scaling behaviour of the PLC effect was
studied using two complementary scaling analysis methods: the finite variance
scaling method and the diffusion entropy analysis. From these analyses we could
establish that in the entire span of strain rates, PLC effect showed Levy walk
property. Moreover, the multiscale entropy analysis is carried out on the
stress time series data observed during the PLC effect to quantify the
complexity of the distinct spatiotemporal dynamical regimes. It is shown that
for the static type C band, the entropy is very low for all the scales compared
to the hopping type B and the propagating type A bands. The results are
interpreted considering the time and length scales relevant to the effect.Comment: 35 pages, 6 figure
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The sensitivity of the colour of dust in MSG-SEVIRI Desert Dust infrared composite imagery to surface and atmospheric conditions
Infrared "Desert Dust" composite imagery taken by the Spinning Enhanced Visible and InfraRed Imager (SEVIRI), onboard the Meteosat Second Generation (MSG) series of satellites above the equatorial East Atlantic, has been widely used for more than a decade to identify and track the presence of dust storms from and over the Sahara Desert, the Middle East, and southern Africa. Dust is characterised by distinctive pink colours in the Desert Dust false-colour imagery; however, the precise colour is influenced by numerous environmental properties, such as the surface thermal emissivity and skin temperature, the atmospheric water vapour content, the quantity and height of dust in the atmosphere, and the infrared optical properties of the dust itself. For this paper, simulations of SEVIRI infrared measurements and imagery have been performed using a modelling system, which combines dust concentrations simulated by the aerosol transport model COSMO-MUSCAT (COSMO: COnsortium for Small-scale MOdelling; MUSCAT: MUltiScale Chemistry Aerosol Transport Model) with radiative transfer simulations from the RTTOV (Radiative Transfer for TOVS) model. Investigating the sensitivity of the synthetic infrared imagery to the environmental properties over a 6-month summertime period from 2011 to 2013, it is confirmed that water vapour is a major control on the apparent colour of dust, obscuring its presence when the moisture content is high. Of the three SEVIRI channels used in the imagery (8.7, 10.8, and 12.0 μm), the channel at 10.8 μm has the highest atmospheric transmittance and is therefore the most sensitive to the surface skin temperature. A direct consequence of this sensitivity is that the background desert surface exhibits a strong diurnal cycle in colour, with light blue colours possible during the day and purple hues prevalent at night. In dusty scenes, the clearest pink colours arise from high-altitude dust in dry atmospheres. Elevated dust influences the dust colour primarily by reducing the contrast in atmospheric transmittance above the dust layer between the SEVIRI channels at 10.8 and 12.0 μm, thereby boosting red and pink colours in the imagery. Hence, the higher the dust altitude, the higher the threshold column moisture needed for dust to be obscured in the imagery: for a sample of dust simulated to have an aerosol optical depth (AOD) at 550 nm of 2-3 at an altitude of 3-4 km, the characteristic colour of the dust may only be impaired when the total column water vapour is particularly moist ('39 mm). Meanwhile, dust close to the surface (altitude < 1 km) is only likely to be apparent when the atmosphere is particularly dry and when the surface is particularly hot, requiring column moisture/13 mm and skin temperatures '314 K, and is highly unlikely to be apparent when the skin temperature is/300 K. Such low-altitude dust will regularly be almost invisible within the imagery, since it will usually be beneath much of the atmospheric water vapour column. It is clear that the interpretation of satellite-derived dust imagery is greatly aided by knowledge of the background environment
Nanomechanical and thermophoretic analyses of the nucleotide-dependent interactions between the AAA+ subunits of magnesium chelatase
In chlorophyll biosynthesis, the magnesium
chelatase enzyme complex catalyzes the insertion of a Mg2+
ion into protoporphyrin IX. Prior to this event, two of the three
subunits, the AAA+ proteins ChlI and ChlD, form a ChlID−
MgATP complex. We used microscale thermophoresis to
directly determine dissociation constants for the I-D subunits
from Synechocystis, and to show that the formation of a ChlID−
MgADP complex, mediated by the arginine finger and the
sensor II domain on ChlD, is necessary for the assembly of the
catalytically active ChlHID−MgATP complex. The N-terminal
AAA+ domain of ChlD is essential for complex formation, but
some stability is preserved in the absence of the C-terminal
integrin domain of ChlD, particularly if the intervening polyproline linker region is retained. Single molecule force spectroscopy
(SMFS) was used to determine the factors that stabilize formation of the ChlID−MgADP complex at the single molecule level;
ChlD was attached to an atomic force microscope (AFM) probe in two different orientations, and the ChlI subunits were
tethered to a silica surface; the probability of subunits interacting more than doubled in the presence of MgADP, and we show
that the N-terminal AAA+ domain of ChlD mediates this process, in agreement with the microscale thermophoresis data. Analysis
of the unbinding data revealed a most probable interaction force of around 109 pN for formation of single ChlID−MgADP
complexes. These experiments provide a quantitative basis for understanding the assembly and function of the Mg chelatase
complex
The molecular basis of phosphite and hypophosphite recognition by ABC-transporters
Inorganic phosphate is the major bioavailable form of the essential nutrient phosphorus. However, the concentration of phosphate in most natural habitats is low enough to limit microbial growth. Under phosphate-depleted conditions some bacteria utilise phosphite and hypophosphite as alternative sources of phosphorus, but the molecular basis of reduced phosphorus acquisition from the environment is not fully understood. Here, we present crystal structures and ligand binding affinities of periplasmic binding proteins from bacterial phosphite and hypophosphite ATP-binding cassette transporters. We reveal that phosphite and hypophosphite specificity results from a combination of steric selection and the presence of a P-H…π interaction between the ligand and a conserved aromatic residue in the ligand-binding pocket. The characterisation of high affinity and specific transporters has implications for the marine phosphorus redox cycle, and might aid the use of phosphite as an alternative phosphorus source in biotechnological, industrial and agricultural applications
The ChlD subunit links the motor and porphyrin binding subunits of magnesium chelatase
Magnesium chelatase initiates chlorophyll biosynthesis, catalysing the MgATP2- dependent insertion of a Mg2+ ion into protoporphyin IX. The catalytic core of this large enzyme complex consists of three subunits: Bch/ChlI, Bch/ChlD and Bch/ChlH (in bacteriochlorophyll and chlorophyll producing species respectively). The D and I subunits are members of the AAA+ (ATPases associated with various cellular activities) superfamily of enzymes, and they form a complex that binds to H, the site of metal ion insertion. In order to investigate the physical coupling between ChlID and ChlH in vivo and in vitro , ChlD was FLAG-tagged in the cyanobacterium Synechocystis sp. PCC 6803 and co-immunoprecipitation experiments showed interactions with both ChlI and ChlH. Co-production of recombinant ChlD and ChlH in Escherichia coli yielded a ChlDH. Quantitative analysis using microscale thermophoresis (MST) showed magnesium-dependent binding ( K d 331 ± 58 nM) between ChlD and H. The physical basis for a ChlD-H interaction was investigated using chemical crosslinking coupled with mass spectrometry (XL-MS), together with modifications that either truncate ChlD or modify single residues. We found that the C-terminal integrin I domain of ChlD governs association with ChlH, the Mg2+ dependence of which also mediates the cooperative response of the Synechocystis chelatase to magnesium. Our work, showing the interaction site between the AAA+ motor and the chelatase domain of magnesium chelatase, will be essential for understanding how free energy from the hydrolysis of ATP on the AAA+ ChlI subunit is transmitted via the bridging subunit ChlD to the active site on ChlH
Elucidating the crystal-chemistry of Jbel Rhassoul stevensite (Morocco) by advanced analytical techniques
The composition of Rhassoul clay is controversial regarding the nature of the puremineral clay fraction which is claimed to be stevensite rather than saponite. In this study, the raw and mineral fractions were characterized using various techniques including Fourier transform infrared spectroscopy and magic angle spinning nuclear magnetic resonance (MAS NMR). The isolated fine clay mineral fraction contained a larger amount of Al (>1 wt.%) than that reported for other stevensite occurrences. The 27Al MAS NMR technique confirmed that the mineral is stevensite in which the Al is equally split between the tetrahedral and octahedral coordination sites. The 29Si NMR spectrum showed a single unresolved resonance indicating little or no short-range ordering of silicon. The chemical composition of the stevensite from Jbel Rhassoul was determined to be ((Na0.25K0.20 (Mg5.04Al0.37Fe0.20&0.21)5.61(Si7.76Al0.24)8O20(OH)4). This formula differs from previous compositions described from this locality and shows it to be an Al-bearing lacustrine clay mineral
The influence of dust optical properties on the colour of simulated MSG-SEVIRI Desert Dust infrared imagery
Satellite imagery of atmospheric mineral dust is sensitive to the optical properties of the dust, governed by the mineral refractive indices, particle size, and particle shape. In infrared channels the imagery is also sensitive to the dust layer height and to the surface and atmospheric environment. Simulations of mineral dust in infrared "Desert Dust" imagery from the Spinning Enhanced Visible and InfraRed Imager (SEVIRI) have been performed, using the COSMO-MUSCAT (COSMO: COnsortium for Small-scale MOdelling; MUSCAT: MUltiScale Chemistry Aerosol Transport Model) dust transport model and the Radiative Transfer for TOVS (RTTOV) program, in order to investigate the sensitivity of the imagery to assumed dust properties. This paper introduces the technique and performs initial validation and comparisons with SEVIRI measurements over North Africa for daytime hours during 6 months covering June and July of 2011–2013. Using T-matrix scattering theory and assuming the dust particles to be spherical or spheroidal, wavelength- and size-dependent dust extinction values are calculated for a number of different dust refractive index databases, along with several values of the particle aspect ratio, denoting the particle shape. The consequences for the infrared extinction values of both the particle shape and the particle orientation are explored: this analysis shows that as the particle asphericity increases, the extinctions increase if the particles are aligned horizontally, and decrease if they are aligned vertically. Randomly oriented spheroidal particles have very similar infrared extinction properties as spherical particles, whereas the horizontally and vertically aligned particles can be considered to be the upper and lower bounds on the extinction values. Inputting these values into COSMO-MUSCAT-RTTOV, it is found that spherical particles do not appear to be sufficient to describe fully the resultant colour of the dust in the infrared imagery. Comparisons of SEVIRI and simulation colours indicate that of the dust types tested, the dust refractive index dataset produced by Volz (1973) shows the most similarity in the colour response to dust in the SEVIRI imagery, although the simulations have a smaller range of colour than do the observations. It is also found that the thermal imagery is most sensitive to intermediately sized particles (radii between 0.9 and 2.6µm): larger particles are present in too small a concentration in the simulations, as well as with insufficient contrast in extinction between wavelength channels, to have much ability to perturb the resultant colour in the SEVIRI dust imagery
Porphyrin Binding to Gun4 protein, Facilitated by a Flexible Loop, Controls Metabolite Flow through the Chlorophyll Biosynthetic Pathway
In oxygenic phototrophs, chlorophylls, hemes and bilins are synthesized by a common branched pathway. Given the phototoxic nature of tetrapyrroles, this pathway must be tightly regulated and an important regulatory role is attributed to Mgchelatase enzyme at the branching between the heme and chlorophyll pathway. Gun4 is a porphyrin-binding protein known to stimulate in vitro the Mg-chelatase activity but how the Gun4-porphyrin complex acts in the cell was
unknown. To address this issue we first performed simulations to determine the porphyrin-docking mechanism to the
cyanobacterial Gun4 structure. After correcting crystallographic loop contacts, we determined the binding site for Mgprotoporphyrin IX. It revealed that the orientation of 6/7 loop is critical for the binding and the magnesium ion held within the porphyrin is coordinated by Asn211 residue. We also identified the basis for stronger binding in the Gun4-1 variant and for weaker binding in the W192A mutant. The W192A-Gun4 was further characterized in Mg-chelatase assay showing that tight porphyrin-binding in Gun4 facilitates its interaction with the Mg-chelatase ChlH
subunit. Finally, we introduced the W192A mutation into Synechocystis 6803 cells and show that the Gun4-porphyrin complex is important for the accumulation of ChlH and for channeling metabolites into the chlorophyll biosynthetic pathway.This work was supported by project P501/12/G055 of the Czech Science Foundation, and by the National Programme of Sustainability I (LO1416) and by ERC 2009-Adg25027-PELE (to V.G). J.K. was supported by project Algain (EE2.3.30.0059). N.B.P.A., P.A.D., A.A.B. and C.N.H. thank
the Biotechnology and Biological Sciences Research Council (BBSRC) U.K. for funding, under award numbers BB/G021546/1 and BB/M000265/1. CNH was also supported by an Advanced Award 338895 from the European Research Council.Peer ReviewedPostprint (author's final draft
Relaxation oscillations and negative strain rate sensitivity in the Portevin - Le Chatelier effect
A characteristic feature of the Portevin - Le Chatelier effect or the jerky
flow is the stick-slip nature of stress-strain curves which is believed to
result from the negative strain rate dependence of the flow stress. The latter
is assumed to result from the competition of a few relevant time scales
controlling the dynamics of jerky flow. We address the issue of time scales and
its connection to the negative strain rate sensitivity of the flow stress
within the framework of a model for the jerky flow which is known to reproduce
several experimentally observed features including the negative strain rate
sensitivity of the flow stress. We attempt to understand the above issues by
analyzing the geometry of the slow manifold underlying the relaxational
oscillations in the model. We show that the nature of the relaxational
oscillations is a result of the atypical bent geometry of the slow manifold.
The analysis of the slow manifold structure helps us to understand the time
scales operating in different regions of the slow manifold. Using this
information we are able to establish connection with the strain rate
sensitivity of the flow stress. The analysis also helps us to provide a proper
dynamical interpretation for the negative branch of the strain rate
sensitivity.Comment: 7 figures, To appear in Phys. Rev.
Existence of radial stationary solutions for a system in combustion theory
In this paper, we construct radially symmetric solutions of a nonlinear
noncooperative elliptic system derived from a model for flame balls with
radiation losses. This model is based on a one step kinetic reaction and our
system is obtained by approximating the standard Arrehnius law by an ignition
nonlinearity, and by simplifying the term that models radiation. We prove the
existence of 2 solutions using degree theory
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