Supramolecular aggregates between carboxylate anions and an octaaza macrocyclic receptor

The 28-membered octaazamacrocycle Me-2[28]py(2)N(6) was used as a receptor for the molecular recognition of aromatic and aliphatic carboxylate substrates. The receptor-substrate binding behaviour of (H6Me2[28]py(2)N(6))(6+) with an aliphatic (-O2C(CH2)(n)CO2-, n=0 to 4) and an aromatic (phthalate, isophthalate, terephthalate, 4,4'-dibenzoate, benzoate, 3- and 4-nitrobenzoate) series of carboxylate anions was evaluated by H-1 NMR spectroscopy (carried out in DMSO-d(6) at 300 K). Two association constants were found for most of the studied cases, except for 3- and 4-nitrobenzoate for which only K-1 was determined. For oxalate, malonate, benzoate and dibenzoate anions only the beta(2) constants could be obtained. The values of the first association constant cover a range from 2.86 to 3.69 (log units), and the second stepwise constant from 2.15 to 2.89 (also in log units). No special selectivity was found but the highest values were determined for adipate and the lowest for the monoprotic 3- and 4-nitrobenzoates. Single crystal X-ray structures of H6Me2[28]py(2)N(6)(6+) with terephthalate, 1, and 4,4'-dibenzoate (2) were determined showing supramolecular entities with general formula (H6Me2[28]py(2)N(6)).(substrate)(2)(PF6)(2).4H(2)O. These anions are the building blocks of an extensive 3-D network of hydrogen bonds.

Radar scattering from ice aggregates using the horizontally aligned oblate spheroid approximation

The assumed relationship between ice particle mass and size is profoundly important in radar retrievals of ice clouds, but, for millimeter-wave radars, shape and preferred orientation are important as well. In this paper the authors first examine the consequences of the fact that the widely used ‘‘Brown and Francis’’ mass–size relationship has often been applied to maximumparticle dimension observed by aircraftDmax rather than to the mean of the particle dimensions in two orthogonal directions Dmean, which was originally used by Brown and Francis. Analysis of particle images reveals that Dmax ’ 1.25Dmean, and therefore, for clouds for which this mass–size relationship holds, the consequences are overestimates of ice water content by around 53% and of Rayleigh-scattering radar reflectivity factor by 3.7 dB. Simultaneous radar and aircraft measurements demonstrate that much better agreement in reflectivity factor is provided by using this mass–size relationship with Dmean. The authors then examine the importance of particle shape and fall orientation for millimeter-wave radars. Simultaneous radar measurements and aircraft calculations of differential reflectivity and dual-wavelength ratio are presented to demonstrate that ice particles may usually be treated as horizontally aligned oblate spheroids with an axial ratio of 0.6, consistent with them being aggregates. An accurate formula is presented for the backscatter cross section apparent to a vertically pointing millimeter-wave radar on the basis of a modified version of Rayleigh–Gans theory. It is then shown that the consequence of treating ice particles as Mie-scattering spheres is to substantially underestimate millimeter-wave reflectivity factor when millimeter-sized particles are present, which can lead to retrieved ice water content being overestimated by a factor of 4.h

Death on the beach: the recycled utopia of Midnight

The chapter conducts close analysis of the film Midnight (O primeiro dia) in the light of Brazilian history and Brazilian film history

The role of information on farmers' willingness to use recycled water for irrigation

In this paper are identified several factors which affect a potential user's willingness to use recycled water for agricultural irrigation. This study is based on the results of a survey carried out among farmers in the island of Crete, Greece. It was found that a higher level of income and education are positively correlated with a respondent's willingness to use recycled water. Income and education are also positively correlated with a potential user's sensitivity to information on the advantages of using non-conventional water resources. Overall, extra information on the advantages of recycled water has a statistically significant impact on reported degrees of willingness to use recycled water.

Molecular insights into aggregates made of amphiphilic Fmoc-tetrapeptides

Pre-assembled aggregates made of Fmoc-conjugated RGDS and GRDS peptides, where Fmoc refers to fluorenylmethoxycarbonyl, have been investigated using atomistic molecular dynamics simulations. The structural characteristics of twelve different models involving two sheets packed with the Fmoc-aligned or with the charged side groups oriented face-to-face, each one containing seven explicit peptide molecules arranged in parallel or antiparallel, have been evaluated for each Fmoc-tetrapeptide. Structural criteria have been used to select the preferred assembly for each Fmoc-tetrapeptide. The two peptides have been found to prefer b-sheet assemblies with a parallel configuration under simulated low concentration conditions. Furthermore, the assembly is dominated by the interactions among Fmoc units. The overall results provide a complete atomistic view of the interactions between Fmoc-peptide molecules comprised within the same sheet or in different sheets that was not achieved experimentally.

Organic contaminant content and physico-chemical characteristics of waste materials recycled in agriculture

A range of wastes representative of materials currently applied, or with future potential to be applied, to agricultural land in the UK as fertilisers and soil improvers or used as animal bedding in livestock production, were investigated. In addition to full physico-chemical characterization, the materials were analysed for a suite of priority organic contaminants. In general, contaminants were present at relatively low concentrations. For example, polychlorinated dibenzo-p-dioxins/dibenzofurans and polychlorinated biphenyls in biosolids and compost-like-outputs (CLOs) were, in most cases, between 5-50 times lower than proposed and implemented European limit values for biosolids or composts applied to agricultural land. However, the technical basis for these limits may need to be re-evaluated. Polybrominated, and mixed halogenated, dibenzo-p-dioxins/dibenzofurans are not currently considered in risk assessments of dioxins and dioxin-like chemicals, but were detected in the biosolids and compost-like-outputs and their potential contribution to the overall toxic equivalency will be assessed. Other, ‘emerging’ contaminants such as perfluoralkyl compounds (PFCs) and organophosphate flame retardants were detected in several of the waste materials, and their potential significance is discussed. The study is part of a wider research programme that will provide evidence to improve confidence in the use of waste-derived materials in agriculture and establish guidelines to protect the food chain where necessary.