Microwave-assisted hydrogel synthesis: a new method for crosslinking polymers in aqueous solutions

It has been found that hydrogels may be formed by microwave irradiation of aqueous solutions containing appropriate combinations of polymers. This new method of hydrogel synthesis yields sterile hydrogels without the use of monomers, eliminating the need for the removal of unreacted species from the final product. Results for two particularly successful combinations, poly(vinyl alcohol) with either poly(acrylic acid) or poly(methylvinylether-alt-maleic anhydride), are presented. Irradiation using temperatures of 100–150 °C was found to yield hydrogels with large equilibrium swelling degrees of 500–1000 g g−1. Material leached from both types of hydrogel shows little cytotoxicity towards HT29 cells.

An efficient and rapid microwave-assisted synthesis of 1-acetyl-1H-indol-3-YL acetates

An efficient and rapid synthesis of 1-acetyl-1H-indol-3-yl acetate 1 and its derivatives 7 via the microwave-assisted cyclisation and decarboxylation of 2-[(carboxymethyl)amino]benzoic acids 5 is described. The latter were left to react with acetic anhydride using triethylamine as the base and were subjected to microwave irradiation for 1 minute, at 80 °C with initial power of 300 W. The target 1-acetyl-1H-indol-3-yl acetate 1 and derivatives 7 were isolated in 34-71% yield. In particular, synthesis of 1-acetyl-6-(trifluoromethyl)-1H-indol-3-yl acetate 7f and 1-acetyl-3-methyl-1H-indol-3-yl acetate 7h is reported for the first time.

Rapid synthesis of carbohydrate derivatives, including mimetics of c-linked disaccharides and c-Linked aza disaccharides, using the Hetero-Diels−Alder Reaction

In this work we demonstrate the value of performing a Hetero Diels-Alder reaction (HDAR) between Danishefsky’s diene and a range of aldehydes or imines, under microwave irradiation. By using a range of aldehydes and imines, including those derived from carbohydrates, access to functionalised 2,3-dihydro-4H-pyran-4-ones or 2,3-dihydro-4-pyridinones in good to excellent synthetic yields is possible. A particular strength of the methodology is its ability to access mimetics of C-linked disaccharides and C-linked aza disaccharides, targets of current therapeutic interest, in a rapid, convenient and diastereoselective manner. The effect of high pressure on the HDARs involving carbohydrate derived aldehydes and imines is also explored, with enhancement in yields occurring for the aldehyde substrates. Finally, HDARs using carbohydrate derived ketones, enones and enals are described under a range of conditions. Optimum results were obtained under high pressure conditions, with highly functionalized carbohydrate derivatives being afforded, in good yields, in this way.

Equatorial Kelvin waves as revealed by EOS Microwave Limb Sounder observations and European Centre for Medium-Range Weather Forecasts analyses: Evidence for slow Kelvin waves of zonal wave number 3

[1] Temperature and ozone observations from the Microwave Limb Sounder (MLS) on the EOS Aura satellite are used to study equatorial wave activity in the autumn of 2005. In contrast to previous observations for the same season in other years, the temperature anomalies in the middle and lower tropical stratosphere are found to be characterized by a strong wave-like eastward progression with zonal wave number equal to 3. Extended empirical orthogonal function (EOF) analysis reveals that the wave 3 components detected in the temperature anomalies correspond to a slow Kelvin wave with a period of 8 days and a phase speed of 19 m/s. Fluctuations associated with this Kelvin wave mode are also apparent in ozone profiles. Moreover, as expected by linear theory, the ozone fluctuations observed in the lower stratosphere are in phase with the temperature perturbations, and peak around 20–30 hPa where the mean ozone mixing ratios have the steepest vertical gradient. A search for other Kelvin wave modes has also been made using both the MLS observations and the analyses from one experiment where MLS ozone profiles are assimilated into the European Centre for Medium-Range Weather Forecasts (ECMWF) data assimilation system via a 6-hourly 3D var scheme. Our results show that the characteristics of the wave activity detected in the ECMWF temperature and ozone analyses are in good agreement with MLS data.

Four-dimensional variational assimilation of ozone profiles from the Microwave Limb Sounder on the Aura satellite

Ozone profiles from the Microwave Limb Sounder (MLS) onboard the Aura satellite of the NASA's Earth Observing System (EOS) were experimentally added to the European Centre for Medium-range Weather Forecasts (ECMWF) four-dimensional variational (4D-var) data assimilation system of version CY30R1, in which total ozone columns from Scanning Imaging Absorption Spectrometer for Atmospheric CHartographY (SCIAMACHY) onboard the Envisat satellite and partial profiles from the Solar Backscatter Ultraviolet (SBUV/2) instrument onboard the NOAA-16 satellite have been operationally assimilated. As shown by results for the autumn of 2005, additional constraints from MLS data significantly improved the agreement of the analyzed ozone fields with independent observations throughout most of the stratosphere, owing to the daily near-global coverage and good vertical resolution of MLS observations. The largest impacts were seen in the middle and lower stratosphere, where model deficiencies could not be effectively corrected by the operational observations without the additional information on the ozone vertical distribution provided by MLS. Even in the upper stratosphere, where ozone concentrations are mainly determined by rapid chemical processes, dense and vertically resolved MLS data helped reduce the biases related to model deficiencies. These improvements resulted in a more realistic and consistent description of spatial and temporal variations in stratospheric ozone, as demonstrated by cases in the dynamically and chemically active regions. However, combined assimilation of the often discrepant ozone observations might lead to underestimation of tropospheric ozone. In addition, model deficiencies induced large biases in the upper stratosphere in the medium-range (5-day) ozone forecasts.

The effects of scene heterogeneity on soil moisture retrieval from passive microwave data

The s–x model of microwave emission from soil and vegetation layers is widely used to estimate soil moisture content from passive microwave observations. Its application to prospective satellite-based observations aggregating several thousand square kilometres requires understanding of the effects of scene heterogeneity. The effects of heterogeneity in soil surface roughness, soil moisture, water area and vegetation density on the retrieval of soil moisture from simulated single- and multi-angle observing systems were tested. Uncertainty in water area proved the most serious problem for both systems, causing errors of a few percent in soil moisture retrieval. Single-angle retrieval was largely unaffected by the other factors studied here. Multiple-angle retrievals errors around one percent arose from heterogeneity in either soil roughness or soil moisture. Errors of a few percent were caused by vegetation heterogeneity. A simple extension of the model vegetation representation was shown to reduce this error substantially for scenes containing a range of vegetation types.

Effects of sub-pixel heterogeneity on the retrieval of soil moisture from passive microwave radiometry

A simple formulation relating the L-band microwave brightness temperature detected by a passive microwave radiometer to the near surface soil moisture was developed using MICRO-SWEAT, a coupled microwave emission model and soil-vegetation-atmosphere-transfer (SVAT) scheme. This simple model provides an ideal tool with which to explore the impact of sub-pixel heterogeneity on the retrieval of soil moisture from microwave brightness temperatures. In the case of a bare soil pixel, the relationship between apparent emissivity and surface soil moisture is approximately linear, with the clay content of the soil influencing just the intercept of this relationship. It is shown that there are no errors in the retrieved soil moisture from a bare soil pixel that is heterogeneous in soil moisture and texture. However, in the case of a vegetated pixel, the slope of the relationship between apparent emissivity and surface soil moisture decreases with increasing vegetation. Therefore for a pixel that is heterogeneous in vegetation and soil moisture, errors can be introduced into the retrieved soil moisture. Generally, under moderate conditions, the retrieved soil moisture is within 3% of the actual soil moisture. Examples illustrating this discussion use data collected during the Southern Great Plains '97 Experiment (SGP97).

A sensitivity analysis of soil moisture retrieval from the t-w microwave emission model

The potential of the τ-ω model for retrieving the volumetric moisture content of bare and vegetated soil from dual polarisation passive microwave data acquired at single and multiple angles is tested. Measurement error and several additional sources of uncertainty will affect the theoretical retrieval accuracy. These include uncertainty in the soil temperature, the vegetation structure and consequently its microwave singlescattering albedo, and uncertainty in soil microwave emissivity based on its roughness. To test the effects of these uncertainties for simple homogeneous scenes, we attempt to retrieve soil moisture from a number of simulated microwave brightness temperature datasets generated using the τ-ω model. The uncertainties for each influence are estimated and applied to curves generated for typical scenarios, and an inverse model used to retrieve the soil moisture content, vegetation optical depth and soil temperature. The effect of each influence on the theoretical soil moisture retrieval limit is explored, the likelihood of each sensor configuration meeting user requirements is assessed, and the most effective means of improving moisture retrieval indicated.

Evaluation of a large-eddy model simulation of a mixed-phase altocumulus cloud using microwave radiometer, lidar and Doppler radar data

Using the Met Office large-eddy model (LEM) we simulate a mixed-phase altocumulus cloud that was observed from Chilbolton in southern England by a 94 GHz Doppler radar, a 905 nm lidar, a dual-wavelength microwave radiometer and also by four radiosondes. It is important to test and evaluate such simulations with observations, since there are significant differences between results from different cloud-resolving models for ice clouds. Simulating the Doppler radar and lidar data within the LEM allows us to compare observed and modelled quantities directly, and allows us to explore the relationships between observed and unobserved variables. For general-circulation models, which currently tend to give poor representations of mixed-phase clouds, the case shows the importance of using: (i) separate prognostic ice and liquid water, (ii) a vertical resolution that captures the thin layers of liquid water, and (iii) an accurate representation the subgrid vertical velocities that allow liquid water to form. It is shown that large-scale ascents and descents are significant for this case, and so the horizontally averaged LEM profiles are relaxed towards observed profiles to account for these. The LEM simulation then gives a reasonable. cloud, with an ice-water path approximately two thirds of that observed, with liquid water at the cloud top, as observed. However, the liquid-water cells that form in the updraughts at cloud top in the LEM have liquid-water paths (LWPs) up to half those observed, and there are too few cells, giving a mean LWP five to ten times smaller than observed. In reality, ice nucleation and fallout may deplete ice-nuclei concentrations at the cloud top, allowing more liquid water to form there, but this process is not represented in the model. Decreasing the heterogeneous nucleation rate in the LEM increased the LWP, which supports this hypothesis. The LEM captures the increase in the standard deviation in Doppler velocities (and so vertical winds) with height, but values are 1.5 to 4 times smaller than observed (although values are larger in an unforced model run, this only increases the modelled LWP by a factor of approximately two). The LEM data show that, for values larger than approximately 12 cm s(-1), the standard deviation in Doppler velocities provides an almost unbiased estimate of the standard deviation in vertical winds, but provides an overestimate for smaller values. Time-smoothing the observed Doppler velocities and modelled mass-squared-weighted fallspeeds shows that observed fallspeeds are approximately two-thirds of the modelled values. Decreasing the modelled fallspeeds to those observed increases the modelled IWC, giving an IWP 1.6 times that observed.