Supramolecular chemistry—general principles and selected examples from anion recognition and metallosupramolecular chemistry

This review gives an introduction into supramolecular chemistry describing in the first part general principles, focusing on terms like noncovalent interaction, molecular recognition, self-assembly, and supramolecular function. In the second part those will be illustrated by simple examples from our laboratories. Supramolecular chemistry is the science that bridges the gap between the world of molecules and nanotechnology. In supramolecular chemistry noncovalent interactions occur between molecular building blocks, which by molecular recognition and self-assembly form (functional) supramolecular entities. It is also termed the "chemistry of the noncovalent bond." Molecular recognition is based on geometrical complementarity based on the "key-and-lock" principle with nonshape-dependent effects, e.g., solvatization, being also highly influential. Self-assembly leads to the formation of well-defined aggregates. Hereby the overall structure of the target ensemble is controlled by the symmetry features of the certain building blocks. Finally, the aggregates can possess special properties or supramolecular functions, which are only found in the ensemble but not in the participating molecules. This review gives an introduction on supramolecular chemistry and illustrates the fundamental principles by recent examples from our group.     

Predicting the sensitivity of fishes to dioxin-like compounds: possible role of the aryl hydrocarbon receptor (AhR) ligand binding domain

Dioxin-like compounds are chronically toxic to most vertebrates. However, dramatic differences in sensitivity to these chemicals exist both within and among vertebrate classes. A recent study found that in birds, critical amino acid residues in the aryl hydrocarbon receptor (AhR) ligand binding domain are predictive of sensitivity to dioxin-like compounds in a range of species. It is currently unclear whether similar predictive relationships exist for fishes, a group of animals at risk of exposure to dioxin-like compounds. Effects of dioxin-like compounds are mediated through the AhR in fishes and birds. However, AhR dynamics are more complex among fishes. Fishes possess AhRs that can be grouped within at least three distinct clades (AhR1, AhR2, AhR3) with each clade possibly containing multiple isoforms. AhR2 has been shown to be the active form in most teleosts, with AhR1 not binding dioxin-like compounds. The role of AhR3 in dioxin-like toxicity has not been established to date and this clade is only known to be expressed in some cartilaginous fishes. Furthermore, multiple mechanisms of sensitivity to dioxin-like compounds that are not relevant in birds could exist among fishes. Although, at this time, deficiencies exist for the development of such a predictive relationship for application to fishes, successfully establishing such relationships would offer a substantial improvement in assessment of risks of dioxin-like compounds for this class of vertebrates. Elucidation of such relationships would provide a mechanistic foundation for extrapolation among species to allow the identification of the most sensitive fishes, with the ultimate goal of the prediction of risk posed to endangered species that are not easily studied.     

Selenium speciation in acidic environmental samples: application to acid rain-soil interaction at Mount Etna volcano

Speciation plays a crucial role in elemental mobility. However, trace level selenium (Se) speciation analyses in aqueous samples from acidic environments are hampered due to adsorption of the analytes (i.e. selenate, selenite) on precipitates. Such solid phases can form during pH adaptation up till now necessary for chromatographic separation. Thermodynamic calculations in this study predicted that a pH < 4 is needed to prevent precipitation of Al and Fe phases. Therefore, a speciation method with a low pH eluent that matches the natural sample pH of acid rain-soil interaction samples from Etna volcano was developed. With a mobile phase containing 20 mM ammonium citrate at pH 3, selenate and selenite could be separated in different acidic media (spiked water, rain, soil leachates) in <10 min with a LOQ of 0.2 μg L⁻¹ using ⁷⁸Se for detection. Applying this speciation analysis to study acid rain-soil interaction using synthetic rain based on H₂SO₄ and soil samples collected at the flanks of Etna volcano demonstrated the dominance of selenate over selenite in leachates from samples collected close to the volcanic craters. This suggests that competitive behavior with sulfate present in acid rain might be a key factor in Se mobilization. The developed speciation method can significantly contribute to understand Se cycling in acidic, Al/Fe rich environments.     

Suppression of aromatase activity in populations of bream (Abramis brama) from the river Elbe, Germany

Aromatase activity was determined in brain and gonads of wild bream collected along the river Elbe, Germany, and correlated with other endocrine and reproductive endpoints such as plasma sex steroid concentrations, secondary sex characteristics (STI), plasma vitellogenin, gonad size (GSI), and maturation stages of germ cells (MS) that were reported for the same fish in a previous study. Furthermore, regional patterns of aromatase activity were correlated to a number of environmental factors such as exposure to environmental contaminants and parasitism. While aromatase activity was not detectable in the gonads of male and female fish with the assay used, fish of both genders revealed relatively great brain enzyme activities. As for most of the endocrine and reproductive parameters, with the exception of plasma testosterone (T), aromatase activities were significantly less in fish from a river stretch characterized by elevated exposures to organic contaminants and metals. Brain aromatase activity was positively and significantly correlated with plasma estradiol (E2) and MS in females, and showed a similar trend with plasma 11-ketotestosterone (11KT) and STI in males. No comparable trend occurred for T. This decrease of the reproductively relevant hormones 11KT and E2 may be indicative of a disruption of the last step in sex hormone synthesis, a hypothesis that was supported for E2 by the strong (R2=0.78, p<0.05) linear regression between aromatase activity and E2 in female bream. It is also hypothesized that the effects on brain aromatase activity were likely to be related to the disruption of other reproductive parameters including sexual maturity and expression of secondary sex characteristics. Although a number of factors such as exposure to pollutants and prevalence of the tapeworm Ligula intestinalis correlated with the suppression of aromatase activity, the exact causes for the regional decrease in brain aromatase activity remain unclear due to inconsistencies of these correlations between sampling events or gender.     

Environmental Modeling and Methods for Estimation of the Global Health Impacts of Air Pollution

Air pollution is increasingly recognized as a significant contributor to global health outcomes. A methodological framework for evaluating the global health-related outcomes of outdoor and indoor (household) air pollution is presented and validated for the year 2005. Ambient concentrations of PM2.5 are estimated with a combination of energy and atmospheric models, with detailed representation of urban and rural spatial exposures. Populations dependent on solid fuels are established with household survey data. Health impacts for outdoor and household air pollution are independently calculated using the fractions of disease that can be attributed to ambient air pollution exposure and solid fuel use. Estimated ambient pollution concentrations indicate that more than 80% of the population exceeds the WHO Air Quality Guidelines in 2005. In addition, 3.26?billion people were found to use solid fuel for cooking in three regions of Sub Saharan Africa, South Asia and Pacific Asia in 2005. Outdoor air pollution results in 2.7?million deaths or 23?million disability adjusted life years (DALYs) while household air pollution from solid fuel use and related indoor smoke results in 2.1?million deaths or 41.6?million DALYs. The higher morbidity from household air pollution can be attributed to children below the age of 5 in Sub Saharan Africa and South Asia. The burden of disease from air pollution is found to be significant, thus indicating the importance of policy interventions.     

Biogeochemical patterns in a river network along a land use gradient

The Bode catchment (Germany) shows strong land use gradients from forested parts of the National Park (23 % of total land cover) to agricultural (70 %) and urbanised areas (7 %). It is part of the Terrestrial Environmental Observatories of the German Helmholtz association. We performed a biogeochemical analysis of the entire river network. Surface water was sampled at 21 headwaters and at ten downstream sites, before (in early spring) and during the growing season (in late summer). Many parameters showed lower concentrations in headwaters than in downstream reaches, among them nutrients (ammonium, nitrate and phosphorus), dissolved copper and seston dry mass. Nitrate and phosphorus concentrations were positively related to the proportion of agricultural area within the catchment. Punctual anthropogenic loads affected some parameters such as chloride and arsenic. Chlorophyll a concentration and total phosphorus in surface waters were positively related. The concentration of dissolved organic carbon (DOC) was higher in summer than in spring, whereas the molecular size of DOC was lower in summer. The specific UV absorption at 254 nm, indicating the content of humic substances, was higher in headwaters than in downstream reaches and was positively related to the proportion of forest within the catchment. CO₂ oversaturation of the water was higher downstream compared with headwaters and was higher in summer than in spring. It was correlated negatively with oxygen saturation and positively with DOC concentration but negatively with DOC quality (molecular size and humic content). A principle component analysis clearly separated the effects of site (44 %) and season (15 %), demonstrating the strong effect of land use on biogeochemical parameters.     

Ethical Discourse on the Use of Genetically Modified Crops: A Review of Academic Publications in the Fields of Ecology and Environmental Ethics

The use of genetically modified plants in agriculture (GM crops) is controversially discussed in academic publications. Important issues are whether the release of GM crops is beneficial or harmful for the environment and therefore acceptable, and whether the modification of plants is ethically permissible per se. This study provides a comprehensive overview of the moral reasoning on the use of GM crops expressed in academic publications from 1975 to 2008. Environmental ethical aspects in the publications were investigated. Overall, 113 articles from 15 ecology, environmental ethics, and multidisciplinary science journals were systematically reviewed. Three types of moral concerns were used to structure the normative statements, moral notions, and moral issues found in the articles: concerns addressing consequences of the use of GM crops, concerns addressing the act (the technique itself), and concerns addressing the virtues of an actor. Articles addressing consequences (84%) dealt with general ecological and risk concerns or discussed specific ecological issues about the use of GM crops. Articles addressing the act (57%) dealt with the value of naturalness, the value of biotic entities, and conceptual reductionism, whereas articles addressing the actor (43%) dealt with virtues related to the handling of risks and the application of GM crops. The results of this study may help to structure the academic debate and contribute to a better understanding of moral concerns that are associated with the key aspects of the ethical theories of consequentialism, deontology, and virtue ethics.     

Impact of Climate Change on Ecological Quality Indicators and Biogeochemical Fluxes in the Baltic Sea: A Multi-Model Ensemble Study

Multi-model ensemble simulations using three coupled physical-biogeochemical models were performed to calculate the combined impact of projected future climate change and plausible nutrient load changes on biogeochemical cycles in the Baltic Sea. Climate projections for 1961-2099 were combined with four nutrient load scenarios ranging from a pessimistic business-as-usual to a more optimistic case following the Helsinki Commission's (HELCOM) Baltic Sea Action Plan (BSAP). The model results suggest that in a future climate, water quality, characterized by ecological quality indicators like winter nutrient, summer bottom oxygen, and annual mean phytoplankton concentrations as well as annual mean Secchi depth (water transparency), will be deteriorated compared to present conditions. In case of nutrient load reductions required by the BSAP, water quality is only slightly improved. Based on the analysis of biogeochemical fluxes, we find that in warmer and more anoxic waters, internal feedbacks could be reinforced. Increased phosphorus fluxes out of the sediments, reduced denitrification efficiency and increased nitrogen fixation may partly counteract nutrient load abatement strategies.     

Short-Run Allocation of Emissions Allowances and Long-Term Goals for Climate Policy

We summarize the latest results on the rapid changes that are occurring to Arctic sea ice thickness and extent, the reasons for them, and the methods being used to monitor the changing ice thickness. Arctic sea ice extent had been shrinking at a relatively modest rate of 3–4% per decade (annually averaged) but after 1996 this speeded up to 10% per decade and in summer 2007 there was a massive collapse of ice extent to a new record minimum of only 4.1 million km². Thickness has been falling at a more rapid rate (43% in the 25 years from the early 1970s to late 1990s) with a specially rapid loss of mass from pressure ridges. The summer 2007 event may have arisen from an interaction between the long-term retreat and more rapid thinning rates. We review thickness monitoring techniques that show the greatest promise on different spatial and temporal scales, and for different purposes. We show results from some recent work from submarines, and speculate that the trends towards retreat and thinning will inevitably lead to an eventual loss of all ice in summer, which can be described as a ‘tipping point’ in that the former situation, of an Arctic covered with mainly multi-year ice, cannot be retrieved.