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.     

Potential sources and meteorological factors affecting PM<Subscript>2.5</Subscript>-bound polycyclic aromatic hydrocarbon levels in six main cities of northeastern Italy: an assessment of the related carcinogenic and mutagenic risks

A yearlong sampling campaign (2012–2013) was conducted in six major cities of the Veneto region to investigate the spatial-temporal trends and the factors affecting the polycyclic aromatic hydrocarbon (PAHs) variations and identify the local sources. Sixty samples per city were collected for analyses in every alternate month (April, June, August, October, December, and February): 10 samples per sampling site in 10 consecutive days of the months selected. Samples were ultrasonically extracted with acetonitrile and processed through high-performance liquid chromatography. Total Σ-PAH concentrations ranged from 0.19 to 70.4 ng m^?3 with a mean concentration of 11.5 ng m^?3. The mean benzo[a]pyrene (BaP) concentration reached 2.0 ng m^?3, which is two-times higher than the limit set by the European Union. BaP contributed for 17.4% to the total concentration of PAHs, which showed the same pattern across the region with maxima during cold months and minima in the warm period. In this study, PAHs showed an inverse relationship with temperature, solar radiation, wind speed, and ozone. According to this study, biomass burning for household heating and cooking, followed by gaseous PAHs absorption on particles due to low atmospheric temperature, were the main reasons for increasing PAHs concentration in winter. Health risk, evaluated as lifetime lung cancer risk (LCR), showed a potential carcinogenic risk from the airborne BaP_TEQ six-fold higher in the cold season than in the warm one. Diagnostic ratios and conditional probability functions were used to locate the sources, and results confirmed that local emission, overall domestic heating, and road transport exhausts were responsible for higher concentration rates of PAHs as well as of PM_2.5.     

Particulate matter concentration levels during intense haze event in an urban environment

This study assessed concentration levels of particulate matter (PM) in the ambient environment of Ilorin metropolis, Nigeria, during haze episodes. Meteorological data (wind speed and direction, rainfall data, sunshine data, relative humidity and temperature) were obtained. Aerocet 531S particle counter (MetOne Instruments, USA) was used to measure four mass concentration ranges of PM (PM_1.0, PM_2.5, PM₁₀ and the total suspended particles (TSP)) in 10 locations taking into consideration land use patterns. Surfer® version 8 (Golden Software LLC, USA) was used to model the spatial variation of particulate matter concentration levels using kriging interpolation griding method. Human exposure assessment was done using the total respiratory deposition dose (TRDD) estimates and statutory limit breach (SLB) approaches. The appearance of dominating weak southern atmospheric wind flow was observed as wind speed ranged from 0 to 6.811 m/s while solar radiation periods ranged from 0.3 to 3.5 h/day. The relative humidity of the metropolis ranged between 28 and 57%, while daily temperature was 15 to 36 °C. Highest concentration levels of PM measured were 73.4, 562.7, 7066.3 and 9907.8 μg/m³ for PM_1.0, PM_2.5, PM₁₀ and TSP, respectively. Very strong negative correlations existed between the PM concentration levels and microclimatic parameters. Spatial variation of the concentration level as modelled using Surfer® version 8 indicated that particulate concentration level increases from south to north. Concentration levels of PM for the 24-h averaging period were generally above the 24-h threshold limit value set by the regulatory agencies for all the locations.     

Relationships between aquatic invertebrate communities,water-level fluctuations and different habitats in a subtropical lake

In lakes, the littoral habitat and its invertebrate communities are often exposed to water-level fluctuations. We examined the effects of seasonal changes on water level, substrata availability and benthic fauna in the littoral zone of Peri Lake, a shallow lake that has experienced a strong reduction in water level due to changes in rainfall. In this study, we also examined whether the abundance and composition of aquatic invertebrates differed among the four substrata. Our main objective was to assess the effect of seasonal changes on water level and benthic invertebrates inhabiting the different types of substrata. Benthic invertebrates were sampled four different substrata (Schoenoplectus californicus, sand and stones, allochthonous leaf litter, and macrophyte stands), and we also measured meteorological, physical and chemical variables. We found that complex habitats, such as allochthonous leaf litter and aquatic macrophyte, stand to be colonised by a larger number of macroinvertebrates because they provide more habitats or potential niches for colonisation by different species. In addition, we observed that during periods of low water level, the presence of substrata in the littoral zone decreased, as did the associated biota. Therefore, our results suggest that water level changes have a major functional impact on the littoral zone of the lake, and can affect substratum availability, which also impacts invertebrate communities.     

Water management and aquatic ecosystem services of a tropical reservoir (Itaparica,São Francisco,Brazil)

Reservoirs have a wide variety of uses that have led to frequent conflicts over ecological conservation and contamination, especially as land management has intensified. Oligotrophication must be implemented in numerous tropical reservoirs that experience advanced eutrophication to maintain aquatic ecosystem functions. To quantify impacts on ecosystem functions and to develop an adaptive management policy, multiple studies have been conducted on the Itaparica Reservoir, São Francisco River, in the semi-arid north-eastern region of Brazil. Here, we add to that existing body of knowledge through investigating how nutrient accumulation is affected by water exchange between the main river flow and Icó-Mandantes Bay. Operational water-level fluctuations in the reservoir create large desiccated littoral areas that release high amounts of nutrients when they are rewetted. In particular, water-level variation promotes proliferation of Egeria densa, a noxious weed, thus elevating trophic levels of the Itaparica Reservoir and Icó-Mandantes Bay. Analysis with a P efficiency model determined 25 μg P L^?1 to be the critical concentration and further indicated that the critical load in both bodies of water have been exceeded. Moreover, intensive fish aquaculture using net cages has led to further overtaxing of the reservoir. We conclude that an effective ecological reservoir management policy must involve oligotrophication, harvesting of noxious water weeds for use as soil amendment in agriculture or biogas production, “blue” aquaculture, and limiting hydroelectric power production based on current water availability.     

Enhanced Interfacial Adhesion and Characterisation of Recycled Natural Fibre-Filled Biodegradable Green Composites

The structural, thermal, mechanical, and biodegradable properties of composite materials made from polylactide (PLA) and agricultural residues (arrowroot (Maranta arundinacea) fibre, AF) were evaluated. Melt blended glycidyl methacrylate-grafted polylactide (PLA-g-GMA) and coupling agent-treated arrowroot fibre (TAF) formed the PLA-g-GMA/TAF composite, which had better properties than the PLA/AF composite. The water resistance of the PLA-g-GMA/TAF composite was greater than that of the PLA/AF composite; the release of PLA in water from the PLA/AF and PLA-g-GMA/TAF composites indicated good biological activity. The PLA-g-GMA/TAF material had better mechanical properties than PLA/AF. This behaviour was attributed to better compatibility between the grafted polymer and TAF. The results indicated that the T_g of PLA was increased by the addition of fibre, which may have improved the heat resistance of PLA. Furthermore, the mass losses following burial in soil compost indicated that both materials were biodegradable, especially at high levels of AF or TAF substitution.     

Systemic design for sustainability

How can we restore the ecological balance of our planet? The present article is aimed at contributing a structural framework for such a restoration. In the quest for ecological recovery, cybernetic–systemic approaches are in demand. They specialize in coping with complexity and offer new, transdisciplinary and non-reductionist ways of system design for renewing sustainability. This contribution uses a proven model from organizational cybernetics—the viable system model—as a frame for sustainable development. The model specifies how the viability of any human or social system can be achieved by means of clearly defined organizational structures. In accord with the logic of recursive organization inherent in the model, a proposal for a structural design aimed at enabling ecological recovery is formulated. That design includes all organizational levels of recursion, from individual to world. The implications of such a novel approach are far-reaching, and the impact powerful.     

Unintentional non-traffic injury and fatal events: Threats to children in and around vehicles

Objective: There have been substantial reductions in motor vehicle crash–related child fatalities due to advances in legislation, public safety campaigns, and engineering. Less is known about non-traffic injuries and fatalities to children in and around motor vehicles. The objective of this study was to describe the frequency of various non-traffic incidents, injuries, and fatalities to children using a unique surveillance system and database.

Methods: Instances of non-traffic injuries and fatalities in the United States to children 0–14 years were tracked from January 1990 to December 2014 using a compilation of sources including media reports, individual accounts from families of affected children, medical examiner reports, police reports, child death review teams, coroner reports, medical professionals, legal professionals, and other various modes of publication.

Results: Over the 25-year period, there were at least 11,759 events resulting in 3,396 deaths. The median age of the affected child was 3.7 years. The incident types included 3,115 children unattended in hot vehicles resulting in 729 deaths, 2,251 backovers resulting in 1,232 deaths, 1,439 frontovers resulting in 692 deaths, 777 vehicles knocked into motion resulting in 227 deaths, 415 underage drivers resulting in 203 deaths, 172 power window incidents resulting in 61 deaths, 134 falls resulting in 54 deaths, 79 fires resulting in 41 deaths, and 3,377 other incidents resulting in 157 deaths.

Conclusions: Non-traffic injuries and fatalities present an important threat to the safety and lives of very young children. Future efforts should consider complementary surveillance mechanisms to systematically and comprehensively capture all non-traffic incidents. Continued education, engineering modifications, advocacy, and legislation can help continue to prevent these incidents and must be incorporated in overall child vehicle safety initiatives.     

Sampling strategies in the assessment of long‐term exposures to toxic substances in air

The decision to mitigate exposures from vapor intrusion (VI) is typically based on limited data from 24‐hour air samples. It is well documented that these data do not accurately represent long‐term average exposures linked to adverse health effects. Limited decision guidance is currently available to determine the most appropriate sampling strategy, considering the cost of sampling alternatives along with the economic consequences of exposure‐related health effects. We present a decision model that introduces economic and statistical considerations in evaluating alternative VI sampling methods. The model characterizes the best sampling method by factoring economic and health consequences of exposure, the variability of exposure, the cost of sampling and mitigation, and the likelihood of false‐negatives and false‐positives. Decision‐makers can use results to select the sample size that maximizes net benefit. Conceptual and mathematical models are presented linking biological, statistical, and economic considerations to assess the cost and effectiveness of different sampling strategies. The model relates an average exposure concentration, determined statistically, to abatement costs and to the monetary value of health deterioration. The value of the information provided by different strategies is calculated and used to select the optimum sampling method. Simulations show that longer‐term sampling methods tend to be more accurate and cost‐effective than short‐term samples. The ideal sampling strategy shows significant seasonal variation (it is typically optimal to use longer samples in the winter) and also varies significantly with the stringency of regulatory standards. Longer‐term sample collection provides a more accurate representation of average VI exposure and reduces the likelihood of type I and type II errors. This reduces expected costs of mitigation and exposure (e.g., health consequences, legal and regulatory penalties), which in some cases can be quite significant. The model herein shows how these savings are balanced against the additional costs of longer‐term sampling.