26 resultados para Ionic radius
Resumo:
The concept of “distance to instability” of a system matrix is generalized to system pencils which arise in descriptor (semistate) systems. Difficulties arise in the case of singular systems, because the pencil can be made unstable by an infinitesimal perturbation. It is necessary to measure the distance subject to restricted, or structured, perturbations. In this paper a suitable measure for the stability radius of a generalized state-space system is defined, and a computable expression for the distance to instability is derived for regular pencils of index less than or equal to one. For systems which are strongly controllable it is shown that this measure is related to the sensitivity of the poles of the system over all feedback matrices assigning the poles.
Resumo:
The influence of a non-ionic polymeric surfactant on the self-assembly of a peptide amphiphile (PA) that forms nanotapes is investigated using a combination of microscopic, scattering and spectroscopic techniques. Mixtures of Pluronic copolymer P123 with the PA C16-KTTKS in aqueous solution were studied at a fixed concentration of the PA at which it is known to self-assemble into extended nanotapes, but varying P123 concentration. We find that P123 can disrupt the formation of C16- KTTKS nanotapes, leading instead to cylindrical nanofibril structures. The spherical micelles formed by P123 at room temperature are disrupted in the presence of the PA. There is a loss of cloudiness in the solutions as the large nanotape aggregates formed by C16-KTTKS are broken up, by P123 solubilization. At least locally, b-sheet structure is retained, as confirmed by XRD and FTIR spectroscopy, even for solutions containing 20 wt% P123. This indicates, unexpectedly, that peptide secondary structure can be retained in solutions with high concentration of non-ionic surfactant. Selfassembly in this system exhibits slow kinetics towards equilibrium, the initial self-assembly being dependent on the order of mixing. Heating above the lipid chain melting temperature assists in disrupting trapped non-equilibrium states.
Resumo:
The use of ionic self-assembly, a facile noncovalent approach, to access non-conventional block copolymer morphologies, including tetragonal and helical structures, from a combination of polyferrocenylsilane diblock copolymer polyelectrolytes and AOT-based surfactants, is described.
Resumo:
A record of dust deposition events between 2009 and 2012 on Mt. Elbrus, Caucasus Mountains derived from a snow pit and a shallow ice core is presented for the first time for this region. A combination of isotopic analysis, SEVIRI red-green-blue composite imagery, MODIS atmospheric optical depth fields derived using the Deep Blue algorithm, air mass trajectories derived using the HYSPLIT model and analysis of meteorological data enabled identification of dust source regions with high temporal (hours) and spatial (cf. 20–100 km) resolution. Seventeen dust deposition events were detected; fourteen occurred in March–June, one in February and two in October. Four events originated in the Sahara, predominantly in north-eastern Libya and eastern Algeria. Thirteen events originated in the Middle East, in the Syrian Desert and northern Mesopotamia, from a mixture of natural and anthropogenic sources. Dust transportation from Sahara was associated with vigorous Saharan depressions, strong surface winds in the source region and mid-tropospheric south-westerly flow with daily winds speeds of 20–30 m s−1 at 700 hPa level and, although these events were less frequent, they resulted in higher dust concentrations in snow. Dust transportation from the Middle East was associated with weaker depressions forming over the source region, high pressure centered over or extending towards the Caspian Sea and a weaker southerly or south-easterly flow towards the Caucasus Mountains with daily wind speeds of 12–18 m s−1 at 700 hPa level. Higher concentrations of nitrates and ammonium characterise dust from the Middle East deposited on Mt. Elbrus in 2009 indicating contribution of anthropogenic sources. The modal values of particle size distributions ranged between 1.98 μm and 4.16 μm. Most samples were characterised by modal values of 2.0–2.8 μm with an average of 2.6 μm and there was no significant difference between dust from the Sahara and the Middle East.
Resumo:
We explore the influence of the choice of attenuation factor on Katz centrality indices for evolving communication networks. For given snapshots of a network observed over a period of time, recently developed communicability indices aim to identify best broadcasters and listeners in the network. In this article, we looked into the sensitivity of communicability indices on the attenuation factor constraint, in relation to spectral radius (the largest eigenvalue) of the network at any point in time and its computation in the case of large networks. We proposed relaxed communicability measures where the spectral radius bound on attenuation factor is relaxed and the adjacency matrix is normalised in order to maintain the convergence of the measure. Using a vitality based measure of both standard and relaxed communicability indices we looked at the ways of establishing the most important individuals for broadcasting and receiving of messages related to community bridging roles. We illustrated our findings with two examples of real-life networks, MIT reality mining data set of daily communications between 106 individuals during one year and UK Twitter mentions network, direct messages on Twitter between 12.4k individuals during one week.
Resumo:
In this article, we investigate how the choice of the attenuation factor in an extended version of Katz centrality influences the centrality of the nodes in evolving communication networks. For given snapshots of a network, observed over a period of time, recently developed communicability indices aim to identify the best broadcasters and listeners (receivers) in the network. Here we explore the attenuation factor constraint, in relation to the spectral radius (the largest eigenvalue) of the network at any point in time and its computation in the case of large networks. We compare three different communicability measures: standard, exponential, and relaxed (where the spectral radius bound on the attenuation factor is relaxed and the adjacency matrix is normalised, in order to maintain the convergence of the measure). Furthermore, using a vitality-based measure of both standard and relaxed communicability indices, we look at the ways of establishing the most important individuals for broadcasting and receiving of messages related to community bridging roles. We compare those measures with the scores produced by an iterative version of the PageRank algorithm and illustrate our findings with two examples of real-life evolving networks: the MIT reality mining data set, consisting of daily communications between 106 individuals over the period of one year, a UK Twitter mentions network, constructed from the direct \emph{tweets} between 12.4k individuals during one week, and a subset the Enron email data set.
Resumo:
The factors influencing the formation of water-in-134a-propellant microemulsions using the fluorinated ionic surfactants ammonium perfluorooctanoate, ammonium perfluoroheptanoate, and sodium perfluorooctanoate has been determined. None of the fluorinated ionic surfactants could be used to prepare clear, one-phase systems when used as sole surfactant, but they could be when combined with a short-chain fluoro- or hydrocarbon alcohol in surfactant:cosurfactant weight-mixing ratios (K(m)) in the range 1:2 to 2:1. When hydrocarbon alcohols were used this clear region extended over a wide range of compositions and was confirmed by means of photon correlation spectroscopy (PCS) to contain microemulsion droplets in the propellant-rich part of the phase diagram. PCS studies performed in the presence of the water-soluble drug terbutaline sulfate showed that it was possible to solubilize the drug within water-in-propellant microemulsion droplets. These studies confirm for the first time that it is possible to prepare water-in-propellant 134a microemulsions using fluorinated ionic surfactants and to solubilize water-soluble drugs within these systems.
Resumo:
Stalagmites are natural archives containing detailed information on continental climate variability of the past. Microthermometric measurements of fluid inclusion homogenisation temperatures allow determination of stalagmite formation temperatures by measuring the radius of stable laser-induced vapour bubbles inside the inclusions. A reliable method for precisely measuring the radius of vapour bubbles is presented. The method is applied to stalagmite samples for which the formation temperature is known. An assessment of the bubble radius measurement accuracy and how this error influences the uncertainty in determining the formation temperature is provided. We demonstrate that the nominal homogenisation temperature of a single inclusion can be determined with an accuracy of ±0.25 °C, if the volume of the inclusion is larger than 105 μm3. With this method, we could measure in a proof-of-principle investigation that the formation temperature of 10–20 yr old inclusions in a stalagmite taken from the Milandre cave is 9.87 ± 0.80 °C, while the mean annual surface temperature, that in the case of the Milandre cave correlates well with the cave temperature, was 9.6 ± 0.15 °C, calculated from actual measurements at that time, showing a very good agreement. Formation temperatures of inclusions formed during the last 450 yr are found in a temperature range between 8.4 and 9.6 °C, which corresponds to the calculated average surface temperature. Paleotemperatures can thus be determined within ±1.0 °C.
Resumo:
The products of reactions of the pharmaceutical amide carbamazepine (CBZ) with strong acids under aqueous conditions were investigated by both powder and single crystal X-ray diffraction. Despite previous claims to the contrary, it was found that salt forms with CBZ protonated at the amide O atom could be isolated from reactions with both HCl and HBr. These forms include the newly identified hydrate phase [CBZ(H)][Cl]·H O. Reactions with other mineral acids (HI and HBF ) gave ionic cocrystalline (ICC) forms (CBZ· [acridinium][I ]·2.5I and CBZ·[H O ] [BF ] ·H O) as well as the salt form CBZ·[CBZ(H)][BF ]·0.5H O. Reaction 2 4 3 2 5 2 0.25 4 0.25 2 4 2 of CBZ with a series of sulfonic acids also gave salt forms, namely, [CBZ(H)][O SC H ], [CBZ(H)][O SC H (OH)]· 3 6 5 3 6 4 0.5H O, [CBZ(H)] [O SCH CH SO ], and [CBZ(H)][O SC H (OH) (COOH)]·H O. CBZ and protonated CBZ(H) 2 2 3 2 2 3 3 6 3 2 moieties can be differentiated in the solid state both by changes to molecular geometry and by differing packing preferences
Resumo:
Although liquid matrix-assisted laser desorption/ionization (MALDI) has been used in mass spectrometry (MS) since the early introduction of MALDI, its substantial lack of sensitivity compared to solid (crystalline) MALDI was for a long time a major hurdle to its analytical competitiveness. In the last decade, this situation has changed with the development of new sensitive liquid matrices, which are often based on a binary matrix acid/base system. Some of these matrices were inspired by the recent progress in ionic liquid research, while others were developed from revisiting previous liquid MALDI work as well as from a combination of these two approaches. As a result, two high-performing liquid matrix classes have been developed, the ionic liquid matrices (ILMs) and the liquid support matrices (LSMs), now allowing MS measurements at a sensitivity level that is very close to the level of solid MALDI and in some cases even surpasses it. This chapter provides some basic information on a selection of highly successful representatives of these new liquid matrices and describes in detail how they are made and applied in MALDI MS analysis.