Cyclodextrin-based supramolecular assemblies: a versatile toolbox for the preparation of functional porous materials

The discovery of ordered mesoporous materials in 1992 by Mobil Oil Corporation scientists has opened great opportunities for new applications in many emerging fields such as heterogeneous catalysis, biocatalysis, energy conversion, biosensors, photocatalytic devices and environmental technologies. Porous materials are grouped by the International Union of Pure and Applied Chemistry (IUPAC) into three classes according to their pore diameter: microporous (<?2 nm), mesoporous (2–50 nm) and macroporous (>?50 nm). One of the most versatile methods for the preparation of those materials is the soft template approach which combines the sol–gel process with molecular self-assembly. While the micelles formed by ionic or nonionic surfactants, as well as amphiphilic polymers, have been extensively used as templates, the supramolecular assemblies formed between cyclodextrins and block copolymers have been less investigated, despite their large chemical and structural diversity. This review article focuses mainly on nanostructured porous inorganic materials derived from cyclodextrins or cyclodextrin-based assemblies. More than 100 references are described and discussed, in which we look both at their synthesis and characterization, as well as their applications in the emerging fields of heterogeneous catalysis and photocatalysis. A special attention is paid to the evaluation of the critical parameters that need to be controlled for improving their (photo) catalytic performances.     

Interinstrument comparison of remote-sensing devices and a new method for calculating on-road nitrogen oxides emissions and validation of vehicle-specific power

Emissions of nitrogen oxides (NOx) by vehicles in real driving environments are only partially understood. This has been brought to the attention of the world with recent revelations of the cheating of the type of approval tests exposed in the dieselgate scandal. Remote-sensing devices offer investigators an opportunity to directly measure in situ real driving emissions of tens of thousands of vehicles. Remote-sensing NO₂ measurements are not as widely available as would be desirable. The aim of this study is to improve the ability of investigators to estimate the NO₂ emissions and to improve the confidence of the total NOx results calculated from standard remote-sensing device (RSD) measurements. The accuracy of the RSD speed and acceleration module was also validated using state-of-the-art onboard global positioning system (GPS) tracking. Two RSDs used in roadside vehicle emissions surveys were tested side by side under off-carriageway conditions away from transient pollution sources to ascertain the consistency of their measurements. The speed correlation was consistent across the range of measurements at 95% confidence and the acceleration correlation was consistent at 95% confidence intervals for all but the most extreme acceleration cases. VSP was consistent at 95% confidence across all measurements except for those at VSP ≥ 15 kW t^?1, which show a small underestimate. The controlled distribution gas nitric oxide measurements follow a normal distribution with 2σ equal to 18.9% of the mean, compared to 15% observed during factory calibration indicative of additional error introduced into the system. Systematic errors of +84 ppm were observed but within the tolerance of the control gas. Interinstrument correlation was performed, with the relationship between the FEAT and the RSD4600 being linear with a gradient of 0.93 and an R² of 0.85, indicating good correlation. A new method to calculate NOx emissions using fractional NO₂ combined with NO measurements made by the RSD4600 was constructed, validated, and shown to be more accurate than previous methods.

Implications: Synchronized remote-sensing measurements of NO were taken using two different remote-sensing devices in an off-road study. It was found that the measurements taken by both instruments were well correlated. Fractional NO₂ measurements from a prior study, measurable on only one device, were used to create new NO_x emission factors for the device that could not be measured by the second device. These estimates were validated against direct measurement of total NO_x emission factors and shown to be an improvement on previous methodologies. Validation of vehicle-specific power was performed with good correlation observed.     

Two decision analysis approaches: Choosing a chemical analysis method

This article illustrates how two different decision analysis (DA) methods can be used to assist in making environmental remediation decisions. The two DA methods are Multiattribute Utility Theory (MAUT) and the Analytic Hierarchy Process (AHP). MAUT and AHP differ greatly in their underlying philosophies. MAUT employs an interval scale and constructs utility functions that quantify the total utility to the decision maker of each technology alternative; AHP employs a ratio scale and uses pairwise comparisons to produce a final ranking of the alternatives that reflects the decision maker's comparative preferences. In this study, the same technology was ranked first by both methods; however, the remaining rankings did not agree. Also, statistical analysis indicated that some score differences may be statistically insignificant. These results are presented and discussed along with a comparison of the features, advantages, and disadvantages of these two DA approaches.     

Is sex-biased maternal care limited by total maternal expenditure in polygynous ungulates?

We examined data on sex-specific differences in neonatal weight, litter size and adult female body weight in 32 populations of polygynous ungulates of 18 different species to test for the existence of a trade-off between sex-biased maternal care and the total amount of maternal expenditure. This corresponds to an extension of the hypothesis of Byers and Moodie (1990) that sex-biased maternal care is limited by a high level of maternal expenditure. We did not find any relationship between sex-biased care and two measures of total maternal expenditure. We highlighted high intraspecific variability in sex-biased care and very low intraspecific variability in total maternal expenditure. Even when this between-population variability in sex-biased care was accounted for, no relationship between sex-biased maternal care and maternal expenditure was detected. Apart from difficulties in finding suitable measures for both variables, two other reasons may account for the lack of a relationship between sex-biased maternal care and total maternal expenditure. Firstly, male offspring seem to be more affected than female offspring by harsh environmental conditions. This may lead to the variation observed in the extent of sex-specific differences in birth weight within a single species. If we assume that for a given maternal expenditure reproductive costs incurred by mothers are highest during harsh conditions, this could indicate the existence of a trade-off between sex-biased maternal care and maternal expenditure at the intra-specific level, thereby supporting the Byers and Moodie hypothesis. Secondly, polygyny is only a poor predictor of sex-biased care and factors such as compensatory growth or extended periods of growth may be expected to modify predictions for different species. Thus, environmental conditions and relative effects of maternal care on male and female lifetime reproductive success are better predictors of sex-biased care than total maternal expenditure.Communicated by P.M. Kappeler     

Prenatal diagnosis of Juberg–Hayward syndrome

Juberg–Hayward syndrome is a rare autosomal recessive syndrome characterised by the association of growth retardation, microcephaly, cleft lip and palate, and thumb and radial ray abnormalities. To date, no prenatal cases have been reported. Here, we report on the first prenatal case of Juberg–Hayward syndrome. The diagnosis was established following fetopathological study. Besides the cardinal features of the syndrome, this prenatal case was remarkable for the severity of the short arm malformation and by the finding of big toe agenesis and cerebral abnormalities including hydrocephalus, agenesis of corpus callosum, and cerebellar hypoplasia. We conclude that the diagnosis of Juberg–Hayward syndrome can be discussed prenatally following ultrasound diagnosis of the association of intrauterine growth restriction, microcephaly, thumb/radial anomalies, and cleft lip/palate. Copyright © 2005 John Wiley & Sons, Ltd.     

Changes in levels of organochlorines in woodcock wings from 1971 to 1975

Wings from woodcock (Philohela minor) were first monitored for organochlorine pesticides and polychlorinated biphenyls (PCBs) in the eastern U.S. in 1971. Regional differences in these compounds were clearly demonstrated and baseline residue levels were obtained for later comparisons. An expanded sampling of wings in 1972 revealed that residues in wings of adult woodcock may differ significantly from those in immatures, and that residues of several important agricultural insecticides and PCBs had declined significantly. More extensive sampling was undertaken in 1975 to determine if changes in residue levels had taken place in the intervening years. PCBs, mirex, and heptachlor epoxide increased significantly between 1972 and 1975 in adult woodcock wings. In immature woodcock wings mirex, dieldrin, and PCBs increased significantly between 1972 and 1975, but DDT residues decreased significantly.