985 resultados para POLAR MONOMERS
Resumo:
An improved method for the detection of pressed hazelnut oil in admixtures with virgin olive oil by analysis of polar components is described. The method. which is based on the SPE-based isolation of the polar fraction followed by RP-HPLC analysis with UV detection. is able to detect virgin olive oil adulterated with pressed hazelnut oil at levels as low as 5% with accuracy (90.0 +/- 4.2% recovery of internal standard), good reproducibility (4.7% RSD) and linearity (R-2: 0.9982 over the 5-40% adulteration range). An international ring-test of the developed method highlighted its capability as 80% of the samples were, on average, correctly identified despite the fact that no training samples were provided to the participating laboratories. However, the large variability in marker components among the pressed hazelnut oils examined prevents the use of the method for quantification of the level of adulteration. (C) 2003 Elsevier Ltd. All rights reserved.
Resumo:
The concentration of hydroxytyrosol (3,4-DHPEA) and its secoiridoid derivatives (3,4-DHPEA-EDA and 3,4-DHPEA-EA) in virgin olive oil decreased rapidly when the oil was repeatedly used for preparing french fries in deep-fat frying operations. At the end of the first frying process (10 min at 180 degreesC), the concentration of the dihydroxyphenol components was reduced to 50-60% of the original value, and after six frying operations only about 10% of the initial components remained. However, tyrosol (p-HPEA) and its derivatives (p-HPEA-EDA and p-HPEA-EA) in the oil were much more stable during 12 frying operations. The reduction in their original concentration was much smaller than that for hydroxytyrosol and its derivatives and showed a roughly linear relationship with the number of frying operations. The antioxidant activity of the phenolic extract measured using the DPPH test rapidly diminished during the first six frying processes, from a total antioxidant activity higher than 740,mumol of Trolox/kg down to less than 250 mumol/kg. On the other hand, the concentration of polar compounds, oxidized triacylglycerol monomers (oxTGs), dimeric TGs, and polymerized TGs rapidly increased from the sixth frying operation onward, when the antioxidant activity of the phenolic extract was very low, and as a consequence the oil was much more susceptible to oxidation. The loss of antioxidant activity in the phenolic fraction due to deep-fat frying was confirmed by the storage oil and oil-in-water emulsions containing added extracts from olive oil used for 12 frying operations.
Resumo:
An important step in liposome characterization is to determine the location of a drug within the liposome. This work thus investigated the interaction of dipalmitoylphosphatidylcholine liposomes with drugs of varied water solubility, polar surface area (PSA) and partition coefficient using high sensitivity differential scanning calorimetry. Lipophilic estradiol (ES) interacted strongest with the acyl chains of the lipid membrane, followed by the somewhat polar 5-fluorouracil (5-FU). Strongly hydrophilic mannitol (MAN) showed no evidence of interaction but water soluble polymers inulin (IN) and an antisense oligonucleotide (OLG), which have very high PSAs, interacted with the lipid head groups. Accordingly, the drugs could be classified as: hydrophilic ones situated in the aqueous core and which may interact with the head groups; those located at the water-bilayer interface with some degree of penetration into the lipid bilayer; those lipophilic drugs constrained within the bilayer. (c) 2004 Elsevier B.V. All rights reserved.
Resumo:
Every winter, the high-latitude oceans are struck by severe storms that are considerably smaller than the weather-dominating synoptic depressions1. Accompanied by strong winds and heavy precipitation, these often explosively developing mesoscale cyclones—termed polar lows1—constitute a threat to offshore activities such as shipping or oil and gas exploitation. Yet owing to their small scale, polar lows are poorly represented in the observational and global reanalysis data2 often used for climatological investigations of atmospheric features and cannot be assessed in coarse-resolution global simulations of possible future climates. Here we show that in a future anthropogenically warmed climate, the frequency of polar lows is projected to decline. We used a series of regional climate model simulations to downscale a set of global climate change scenarios3 from the Intergovernmental Panel of Climate Change. In this process, we first simulated the formation of polar low systems in the North Atlantic and then counted the individual cases. A previous study4 using NCEP/NCAR re-analysis data5 revealed that polar low frequency from 1948 to 2005 did not systematically change. Now, in projections for the end of the twenty-first century, we found a significantly lower number of polar lows and a northward shift of their mean genesis region in response to elevated atmospheric greenhouse gas concentration. This change can be related to changes in the North Atlantic sea surface temperature and mid-troposphere temperature; the latter is found to rise faster than the former so that the resulting stability is increased, hindering the formation or intensification of polar lows. Our results provide a rare example of a climate change effect in which a type of extreme weather is likely to decrease, rather than increase.
Resumo:
The budgets of seven halogenated gases (CFC-11, CFC-12, CFC-113, CFC-114, CFC-115, CCl4 and SF6) are studied by comparing measurements in polar firn air from two Arctic and three Antarctic sites, and simulation results of two numerical models: a 2-D atmospheric chemistry model and a 1-D firn diffusion model. The first one is used to calculate atmospheric concentrations from emission trends based on industrial inventories; the calculated concentration trends are used by the second one to produce depth concentration profiles in the firn. The 2-D atmospheric model is validated in the boundary layer by comparison with atmospheric station measurements, and vertically for CFC-12 by comparison with balloon and FTIR measurements. Firn air measurements provide constraints on historical atmospheric concentrations over the last century. Age distributions in the firn are discussed using a Green function approach. Finally, our results are used as input to a radiative model in order to evaluate the radiative forcing of our target gases. Multi-species and multi-site firn air studies allow to better constrain atmospheric trends. The low concentrations of all studied gases at the bottom of the firn, and their consistency with our model results confirm that their natural sources are small. Our results indicate that the emissions, sinks and trends of CFC-11, CFC-12, CFC-113, CFC-115 and SF6 are well constrained, whereas it is not the case for CFC-114 and CCl4. Significant emission-dependent changes in the lifetimes of halocarbons destroyed in the stratosphere were obtained. Those result from the time needed for their transport from the surface where they are emitted to the stratosphere where they are destroyed. Efforts should be made to update and reduce the large uncertainties on CFC lifetimes.
Resumo:
The mean state, variability and extreme variability of the stratospheric polar vortices, with an emphasis on the Northern Hemisphere vortex, are examined using 2-dimensional moment analysis and Extreme Value Theory (EVT). The use of moments as an analysis to ol gives rise to information about the vortex area, centroid latitude, aspect ratio and kurtosis. The application of EVT to these moment derived quantaties allows the extreme variability of the vortex to be assessed. The data used for this study is ECMWF ERA-40 potential vorticity fields on interpolated isentropic surfaces that range from 450K-1450K. Analyses show that the most extreme vortex variability occurs most commonly in late January and early February, consistent with when most planetary wave driving from the troposphere is observed. Composites around sudden stratospheric warming (SSW) events reveal that the moment diagnostics evolve in statistically different ways between vortex splitting events and vortex displacement events, in contrast to the traditional diagnostics. Histograms of the vortex diagnostics on the 850K (∼10hPa) surface over the 1958-2001 period are fitted with parametric distributions, and show that SSW events comprise the majority of data in the tails of the distributions. The distribution of each diagnostic is computed on various surfaces throughout the depth of the stratosphere, and shows that in general the vortex becomes more circular with higher filamentation at the upper levels. The Northern Hemisphere (NH) and Southern Hemisphere (SH) vortices are also compared through the analysis of their respective vortex diagnostics, and confirm that the SH vortex is less variable and lacks extreme events compared to the NH vortex. Finally extreme value theory is used to statistically mo del the vortex diagnostics and make inferences about the underlying dynamics of the polar vortices.
Resumo:
We outline a method to determine the direction of solar open flux transport that results from the opening of magnetic clouds (MCs) by interchange reconnection at the Sun based solely on in-situ observations. This method uses established findings about i) the locations and magnetic polarities of emerging MC footpoints, ii) the hemispheric dependence of the helicity of MCs, and iii) the occurrence of interchange reconnection at the Sun being signaled by uni-directional suprathermal electrons inside MCs. Combining those observational facts in a statistical analysis of MCs during solar cycle 23 (period 1995 – 2007), we show that the time of disappearance of the northern polar coronal hole (1998 – 1999), permeated by an outward-pointing magnetic field, is associated with a peak in the number of MCs originating from the northern hemisphere and connected to the Sun by outward-pointing magnetic field lines. A similar peak is observed in the number of MCs originating from the southern hemisphere and connected to the Sun by inward-pointing magnetic field lines. This pattern is interpreted as the result of interchange reconnection occurring between MCs and the open field lines of nearby polar coronal holes. This reconnection process closes down polar coronal hole open field lines and transports these open field lines equatorward, thus contributing to the global coronal magnetic field reversal process. These results will be further constrainable with the rising phase of solar cycle 24.
Resumo:
We have examined the atmospheric water cycle of both Polar Regions, pole wards of 60°N and 60°S, using the ERA-Interim re-analysis and high-resolution simulations with the ECHAM5 model for both the present and future climate based on the IPCC, A1B scenario, representative of the last three decades of the 21st century. The annual precipitation in ERA-Interim amounts to ~17000 km3 and is more or less the same in the Arctic and the Antarctic, but it is composed differently. In the Arctic the annual evaporation is some 8000 km3 but some 3000 km3 less in the Antarctica where the net horizontal transport is correspondingly larger. The net water transport of the model is more intense than in ERA-Interim, in the Arctic the difference is 2.5% and in the Antarctic it is 6.2%. Precipitation and net horizontal transport in the Arctic has a maximum in August and September. Evaporation peaks in June and July. The seasonal cycle is similar in Antarctica with the highest precipitation in the austral autumn. The largest net transport occurs at the end of the major extra-tropical storm tracks in the Northern Hemisphere such as the eastern Pacific and eastern north Atlantic. The variability of the model is virtually identical to that of the re-analysis and there are no changes in variability between the present climate and the climate at the end of the 21st century when normalized with the higher level of moisture. The changes from year to year are substantial with the 20 and 30-year records being generally too short to identify robust trends in the hydrological cycle. In the A1B climate scenario the strength of the water cycle increases by some 25% in the Arctic and by 19% in the Antarctica, as measured by annual precipitation. The increase in the net horizontal transport is 29% and 22% respectively, and the increase in evaporation correspondingly less. The net transport follows closely the Clausius-Clapeyron relation. There is 2 a minor change in the annual cycle of the Arctic atmospheric water cycle with the maximum transport and precipitation occurring later in the year. There is a small imbalance of some 4-6% between the net transport and precipitation minus evaporation. We suggest that this is mainly due to the fact the transport is calculated from instantaneous 6-hourly data while precipitation and evaporation is accumulated over a 6 hour period. The residual difference is proportionally similar for all experiments and hardly varies from year to year.
Resumo:
A number of poleward moving events were observed between 1130 and 1300 UT on 11 February 2004, during periods of southward interplanetary magnetic field (IMF), while the steerable antenna of the European Incoherent Scatter (EISCAT) Svalbard radar (ESR)and the Tromsø VHF radar pointed nearly northward at low elevation. In this interval, simultaneous SuperDARN CUTLASS Finland radar measurements showed poleward moving radar aurora forms (PMRAFs) which appeared very similar to the density enhancements observed by the ESR northward pointing antenna. These events appeared quasiperiodically with a period of about 10 min. Comparing the observations from the above three radars, it is inferred that there is an almost one‐to‐one correspondence between the poleward moving plasma concentration enhancements (PMPCEs) observed by the ESR and the VHF radar and the PMRAFs measured by the CUTLASS Finland radar. These observations are consistent with the interpretation that the polar cap patch material was generated by photoionization at subauroral latitudes and that the plasma was structured by bursts of magnetopause reconnection giving access to the polar cap. There is clear evidence that plasma structuring into patches was dependent on the variability in IMF |By|. The duration of these events implies that the average evolution time of the newly opened flux tubes from the subauroral region to the polar cap was about 33 min.
Resumo:
A developing polar low is targeted with dropsonde observations to improve the forecast of its landfall. Accurately forecasting a polar low's strength and location remains a challenge; polar lows form over the ocean in poorly observed regions, therefore initial condition errors may contribute significantly to forecast error. The targeted polar low formed in the Norwegian Sea on 3 March 2008, during the Norwegian IPY-THORPEX field campaign. Two flights, six hours apart, released dense networks of dropsondes into a sensitive region covering the polar low and Arctic front to its west. The impact of the targeted observations is assessed using the limited-area Met Office Unified Model and three-dimensional variational (3D-Var) data assimilation scheme. Forecasts were verified using ECMWF analysis data, which show good agreement with both dropsonde data from a flight through the mature polar low, and 10 m QuikSCAT winds. The impact of the targeted data moved southwards with the polar low as it developed and then hit the Norwegian coast after 24 hours. The results show that the forecast of the polar low is sensitive to the initial conditions; targeted observations from the first flight did not improve the forecast, but those from the second flight clearly improved the forecast polar low position and intensity. However, caution should be applied to attributing the forecast improvement to the assimilation of the targeted observations from a single case-study, especially in this case as the forecast improvement is moderate relative to the spread from an operational ensemble forecast
Resumo:
A pharmacokinetic hypothesis of stratum corneum with two parallel pathways, lipophilic and porous hydrophilic, is not well documented yet. Still questionable is the localization of the pores, and the present experiments were designed to elucidate the contribution of extracellular lipids and intracellular keratin to the structure of this pathway. Percutaneous penetration of baclofen, a model zwitterion, was studied in vitro using human cadaver skin. Aqueous or ethanolic saturated solutions of the drug (Cs = 4.6 and 0.4 mg/ mL, respectively) were applied on the skin that was pretreated with: methanol/chloroform (Me/Ch) or acetone-chloroform (Ac/Ch) (1:1) mixtures, or with these solvents followed by 0.2% solution of sodium lauryl sulfate (SLS). As controls, baclofen penetration through the intact full-thickness skin was determined, and the fluxes were 0.18 ±0.08 and 0.14 ±0.07 µg/cm2/h for aqueous and ethanolic solutions, respectively. When Me/Ch was used for 1 h, an expected increase of the penetration was observed, but the lag time, Tlag, was still nearly 20 h. When the less polar mixture, Ac/Ch, was used, no flux enhancement was observed, and with ethanol as the vehicle, decreased penetration was even noted. No effect on baclofen penetration was observed when SLS was used for 1 h after delipidization of the skin was done with either the Me/Ch or Ac/Ch mixture. The results suggest that the polar pathway may be located intercellularly and comprises aqueous regions surrounded by polar lipids, which create the walls of such microchannels.
Resumo:
The structure of the Arctic stratospheric polar vortex in three chemistry–climate models (CCMs) taken from the CCMVal-2 intercomparison is examined using zonal mean and geometric-based methods. The geometric methods are employed by taking 2D moments of potential vorticity fields that are representative of the polar vortices in each of the models. This allows the vortex area, centroid location and ellipticity to be determined, as well as a measure of vortex filamentation. The first part of the study uses these diagnostics to examine how well the mean state, variability and extreme variability of the polar vortices are represented in CCMs compared to ERA-40 reanalysis data, and in particular for the UMUKCA-METO, NIWA-SOCOL and CCSR/NIES models. The second part of the study assesses how the vortices are predicted to change in terms of the frequency of sudden stratospheric warmings and their general structure over the period 1960–2100. In general, it is found that the vortices are climatologically too far poleward in the CCMs and produce too few large-scale filamentation events. Only a small increase is observed in the frequency of sudden stratospheric warming events from the mean of the CCMVal-2 models, but the distribution of extreme variability throughout the winter period is shown to change towards the end of the twentyfirst century.